BR112020004750B1 - FUNGICIDAL COMPOSITION AND METHOD FOR CONTROL OR PREVENTION OF PHYTOPATHOGENIC DISEASES - Google Patents

Abstract

Fungicide composition comprising a mixture of components (A) and (B), wherein component (A) is a quinoline-3-carboxamide of formula (I) and component (B) is selected from the group consisting of pyriflumetofen , benzovindiflupyr, difenoconazole, hexaconazole, azoxystrobin, fludioxonil, cyprodinil, fluazinam, isoprazam, pyroquilone, tricyclazole, chorothalonil, propiconazole, aminopyrifene, penconazole, prothioconazole, mancozeb, fenpropimorph, fenpropidine, sulfur, and a biofungicide comprising a strain of Bacillus subtilis, as well such as the use of the compositions in agriculture or horticulture to control or prevent infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

[0001] The present invention relates to new fungicidal compositions, their use in agriculture or horticulture to control diseases caused by phytopathogens, especially phytopathogenic fungi, and to methods of controlling diseases in useful plants, especially fruits and vegetables.

[0002] Certain quinoline (thio)carboxamide compounds have been proposed in the literature as microbicidal active ingredients in pesticides. For example, WO04039783 discloses quinoline (thio)carboxamide compounds which are described as being useful as a fungicide. Additionally, while many fungicidal compounds and compositions, belonging to several different chemical classes, have been/are being developed for use as fungicides on useful plant crops, crop tolerance and activity against particular pathogenic fungi do not always meet the needs of agricultural practice. in many aspects.

[0003] There is, therefore, a continued need to find new compounds and new compositions having superior biological properties for use in controlling or preventing infestation of plants by phytopathogenic fungi; for example, compounds having greater biological activity, an advantageous spectrum of activity, an improved safety profile, improved physicochemical properties, increased biodegradability, or compositions having a broader spectrum of activity, improved crop tolerance, synergistic interactions or potentiating properties, or compositions that exhibit a faster onset of action or that have longer lasting residual activity or that allow a reduction in the number of applications and/or a reduction in the rate of application of compounds and compositions required for effective control of a phytopathogen, thereby enabling beneficial resistance management practices, reduced environmental impact and reduced operator exposure.

[0004] The use of compositions comprising mixtures of different fungicidal compounds having different modes of action can meet some of these needs (for example, combination of fungicides with different spectrums of activity).

[0005] The present invention therefore provides new fungicidal compositions comprising as active ingredients a mixture of component (A) and component (B), wherein component (A) is a compound of formula (I) wherein R1 is hydrogen, fluorine, chlorine or methyl; R2 is hydrogen or fluorine; R3 is -C(Cl)=CH2, isopropyl, 1-methylcyclopropyl, trifluoromethyl, -C(CH3)=CH2, 1-fluorocyclopropyl, -CF2CH3, -CF(CH3)CH3 or tert-butyl; R4 is hydrogen or fluorine; or its salts, enantiomers and/or N-oxides; and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Pyroquilone, Tricyclazole, Chlorothalonil, Propiconazole, Aminopirifen, Penconazole , Fenpropimorph, Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising strain FZB24 of Bacillus subtilis var. amyloliquefaciens strain FZB24, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153 , USA), Serenade® (based on strain QST713) or Subtilex® (based on strain MBI600), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40 .

[0006] In general, the weight ratio between component (A) and component (B) is from 20:1 to 1:40, especially from 15:1 to 1:30, more especially in a ratio of 12: 1 to 1:25, even more especially in a ratio of 10:1 to 1:20 and very especially from 5:1 to 1:20.

[0007] The benefits provided by certain mixing compositions according to the invention may also include, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (e.g. example, greater biological activity, an advantageous spectrum of activity, an increased safety profile, improved physicochemical properties or increased biodegradability).

[0008] The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds can occur in optically isomeric forms, that is, enantiomeric or diastereoisomeric forms. The specific substitution pattern on the carbon atom to which R2 is attached means that the compounds of formula (I) occur in (at least) two enantiomeric forms. Atropisomers can also occur as a result of restricted rotation around a single bond. The present invention includes all such possible isomeric forms (e.g., geometric isomers) and mixtures thereof for a compound of formula (I). Likewise, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for a compound of formula (I), and also a racemic compound, that is, a mixture of at least two enantiomers in a ratio of substantially 50:50.

[0009] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide or in salt form, for example, an agronomically usable salt form.

[0010] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described for example in the book “Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0011] More preferably, component (A) is a compound selected from compound No. .008, X.009, X.010, X.011, X.012, X.013, X.014, X.015, X.016, , or one of the (S) or (R) enantiomers as defined in Table X below: Table

[0012] Preferably, component (B) is a compound selected from the group consisting of pyriflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isoprazam, Propiconazole, Aminopirifen, Pyroquilone, Tricyclazole, Chlorothalonil, Penconazole, Fenpropimorph, Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem , VA 24153, USA).

[0013] More preferably, component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone , Tricyclazole and Chlorothalonil.

[0014] The compounds of component (B) are referred to herein above by a so-called “ISO common name” or another “common name” being used in individual cases or a registered trademark name. The compounds of component (B) are known and are commercially available and/or can be prepared using procedures known in the art and/or procedures reported in the literature.

[0015] In a preferred composition according to the invention, component (A) is compound No. -fluoro-quinoline-3- carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole , Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0016] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.001, or a salt and/or N-oxide thereof.

[0017] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.001, or a salt and/or N-oxide thereof.

[0018] In another preferred composition according to the invention, component (A) is compound No. -carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil , Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0019] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.002, or a salt and/or N-oxide thereof.

[0020] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.002, or a salt and/or N-oxide thereof.

[0021] In another preferred composition according to the invention, component (A) is compound No. fluoroquinoline-3-carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [107295771-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens , available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0022] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.003, or a salt and/or N-oxide thereof.

[0023] Alternatively, in a preferred embodiment, this composition comprises the (R) enantiomer of compound No. X.003, or a salt and/or N-oxide thereof.

[0024] In another preferred composition according to the invention, component (A) is compound No. -methyl-quinoline-3- carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole , Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0025] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.004, or a salt and/or N-oxide thereof.

[0026] Alternatively, in a preferred embodiment, this composition comprises the (R) enantiomer of compound No. X.004, or a salt and/or N-oxide thereof.

[0027] In another preferred composition according to the invention, component (A) is compound No. -chloro-quinoline-3- carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole , Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0028] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.005, or a salt and/or N-oxide thereof.

[0029] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.005, or a salt and/or N-oxide thereof.

[0030] In another preferred composition according to the invention, component (A) is compound No. -fluoro-quinoline- 3-carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole , Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0031] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.006, or a salt and/or N-oxide thereof.

[0032] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.006, or a salt and/or N-oxide thereof.

[0033] In another preferred composition according to the invention, component (A) is compound No. ,8-difluoroquinoline-3-carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [107295771-1], Difenoconazole, Hexaconazole , Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0034] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.007, or a salt and/or N-oxide thereof.

[0035] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.007, or a salt and/or N-oxide thereof.

[0036] In another preferred composition according to the invention, component (A) is compound No. -3- carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available at Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0037] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.008, or a salt and/or N-oxide thereof.

[0038] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.008, or a salt and/or N-oxide thereof.

[0039] In another preferred composition according to the invention, component (A) is compound No. -quinoline-3- carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens , available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0040] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.009, or a salt and/or N-oxide thereof.

[0041] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.009, or a salt and/or N-oxide thereof.

[0042] In another preferred composition according to the invention, component (A) is compound No. -difluoro-quinoline-3- carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var .

[0043] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.010, or a salt and/or N-oxide thereof.

[0044] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.010, or a salt and/or N-oxide thereof.

[0045] In another preferred composition according to the invention, component (A) is compound No. -butyl]quinoline-3- carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var .

[0046] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.011, or a salt and/or N-oxide thereof.

[0047] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.011, or a salt and/or N-oxide thereof.

[0048] In another preferred composition according to the invention, component (A) is compound No. methyl]-1-methyl-propyl]quinoline-3-carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [107295771-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Tricyclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the strain of FZB24 Bacillus subtilis var. amyloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1 :40.

[0049] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.012, or a salt and/or N-oxide thereof.

[0050] Alternatively, in a preferred embodiment, this composition comprises the (R) enantiomer of compound No. X.012, or a salt and/or N-oxide thereof.

[0051] In another preferred composition according to the invention, component (A) is compound No. -fluoro-quinoline-3-carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [107295771-1], Difenoconazole, Hexaconazole, Azoxystrobin , Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Tricyclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0052] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.013, or a salt and/or N-oxide thereof.

[0053] Alternatively, in a preferred embodiment, this composition comprises the (R) enantiomer of compound No. X.013, or a salt and/or N-oxide thereof.

[0054] In another preferred composition according to the invention, component (A) is compound No. -quinoline-3- carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin , Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Tricyclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0055] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.014, or a salt and/or N-oxide thereof.

[0056] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.014, or a salt and/or N-oxide thereof.

[0057] In another preferred composition according to the invention, component (A) is compound No. -quinoline-3- carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens , available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0058] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.015, or a salt and/or N-oxide thereof.

[0059] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.015, or a salt and/or N-oxide thereof.

[0060] In another preferred composition according to the invention, component (A) is compound No. -3- carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available at Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0061] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.016, or a salt and/or N-oxide thereof.

[0062] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.016, or a salt and/or N-oxide thereof.

[0063] In another preferred composition according to the invention, component (A) is compound No. -carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0064] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.017, or a salt and/or N-oxide thereof.

[0065] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.017, or a salt and/or N-oxide thereof.

[0066] In another preferred composition according to the invention, component (A) is compound No. -carboxamide, or a salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetophene, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0067] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.018, or a salt and/or N-oxide thereof.

[0068] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.018, or a salt and/or N-oxide thereof.

[0069] In another preferred composition according to the invention, component (A) is compound No. salt and/or N-oxide, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole , Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0070] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.019, or a salt and/or N-oxide thereof.

[0071] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.019, or a salt and/or N-oxide thereof.

[0072] In another preferred composition according to the invention, component (A) is compound No. 3- carboxamide, or a salt and/or N-oxide thereof, and component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Triciclol, Chlorothalonil, Penconazole, Fenpropimorph Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis, such as Taegro® (a biofungicide comprising the FZB24 strain Bacillus subtilis var. amiloliquefaciens, available at Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A.), wherein the weight ratio of component (A) to component (B) is 20:1 to 1:40.

[0073] In a preferred embodiment, this composition comprises the enantiomer (S) of compound No. X.020, or a salt and/or N-oxide thereof.

[0074] Alternatively, in a preferred embodiment, this composition comprises the enantiomer (R) of compound No. X.020, or a salt and/or N-oxide thereof.

[0075] The preferred ratios of compounds of formula (I) described in Table X (above) [as component (A)]: mixing partner [component (B)] are given in the Table below for certain preferred mixing partners :

[0076] The term “fungicide” as used here means a compound that controls, modifies or prevents the growth of fungi. The term "fungicide-effective amount" means the amount of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviations from natural development, such as death, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.

[0077] The term “plants” refers to all physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stems, foliage and fruits.

[0078] The term “plant propagation material” denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. This includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes and parts of plants.

[0079] The term “site” as used herein designates fields in which, or upon which, plants are cultivated or where seeds of cultivated plants are sown or where the seed will be placed in the soil. Includes soil, seeds and seedlings, as well as established vegetation.

[0080] Throughout this document, the expression “composition” represents the various mixtures or combinations of components (A) and (B) (including the modalities defined above), for example in a simple “ready mix” form, in a combined spray mixture composed of separate formulations of the individual active ingredient components, such as a “tank mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e., one after the other over a relatively short period of time, such as a few hours or days. The order of application of components (A) and (B) is not essential to the operation of the present invention.

[0081] The composition according to the invention is effective against harmful microorganisms, such as microorganisms that cause phytopathogenic diseases, in particular against phytopathogenic bacteria and fungi.

[0082] The composition of the invention can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the classes of Basidiomycetes, Ascomycetes, Oomycetes and/or Deuteromycetes, Blasocladiomycetes, Critidiomycetes, Glomeromycetes and/or Mucoromycetes.

[0083] The composition is effective in controlling a wide spectrum of plant diseases, such as foliar pathogens of ornamental crops, grasses, vegetables, fields, cereals and fruits.

[0084] These pathogens may include: Oomycetes, including Phytophthora diseases, such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora soyae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and erythroseptica; Pythium diseases, such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales, such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida, Sclerophthora macrospora and Bremia lactucae; and others, such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and Sclerospora graminicola; Ascomycetes, including spot, spot, blast or rust diseases and/or rots, for example those caused by Pleosporales, such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides , Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis , Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales, such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, now fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis Bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales, such as Ga eumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales, such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and others, such such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp. ., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides bras iliensis, Penicillium expansum, Pestalotia rhododendri , Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis , Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew diseases, for example those caused by Erysihales, such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis; molds, for example, those caused by Botryosphaeriales, such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta cucurbitacearum; anthracnoses, for example, those caused by Glommerelales, such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and wilting or molds, for example, those caused by Hypocreales, such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae; Basidiomycetes, including sooty molds, for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts, for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia uvatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis, Pucciniastrum coryli, or Uredinales, such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmer is , Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries; Blastocladiomycetes, such as Physoderma maydis; Mucoromycetes, such as Choanephora cucurbitarum; Mucor spp.; Rhizopus arrhizus; as well as diseases caused by other species and genera closely related to those listed above.

[0085] In addition to their fungicidal activity, the compositions may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.

[0086] The composition according to the invention is particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (for example, Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g., the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Imperfect fungi (also known as Deuteromycetes; e.g., Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia, and Pseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).

[0087] Useful plant crops in which the composition according to the invention can be used include perennial and annual crops, such as berry plants, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, corn, millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar and fodder beet, coffee, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example, apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses, for example Bermuda grass, blue grass, agrostis, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; aromatic herbs, such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes, for example beans, lentils, peas and soybeans; dried fruits, for example almonds, cashews, arachids, hazelnuts, peanuts, pecans, pistachios and walnuts; palms, e.g. palm oil; ornamental plants, for example flowers, shrubs and trees; other trees, for example cocoa, coconut, olive and rubber; vegetables, for example asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, pumpkin, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines, for example grapes.

[0088] Crops are to be understood as those that occur naturally, obtained by conventional breeding methods or obtained by genetic engineering. These include crops that contain so-called resulting traits (e.g. improved storage stability, higher nutritional value and improved taste).

[0089] Crops are to be understood as also including those crops that have been made tolerant to herbicides such as bromoxynil or to classes of herbicides such as ALS, EPSPS, GS, HPPD and PPO inhibitors. An example of a crop that has been made tolerant to imidazolinones, for example imazamox, by conventional breeding methods is Clearfield® summer canola. Examples of crops that have been made tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant apple varieties, commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0090] Crops are also to be understood as being those that are naturally or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesizing one or more toxins with selective action, such as those known, for example, from toxin-producing bacteria. Examples of toxins that may be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode-colonizing bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi.

[0091] An example of a culture that has been modified to express the Bacillus thuringiensis toxin is Bt KnockOut® maize (Syngenta Seeds). An example of a crop comprising more than one gene encoding insecticide resistance and thus expressing more than one toxin is VipCot ® (Syngenta Seeds). Crops or their seed material can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant may have the ability to express an insecticidal protein, while at the same time being tolerant to herbicides, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0092] Preferred examples of compositions according to the invention are as follows (wherein the term “TX1” represents a compound selected from compounds No. 005, X.006, X.007, X.008, X.009, X.010, X.011, X.012, X.018, X.019 and X.020, or one of their (S) or (R) enantiomers, as defined in Table + Azoxystrobin, TX1 + Fludioxonil, TX1 + Ciprodinil, TX1 + Fluazinam, TX1 + Isopyrazam, TX1 + Pyroquilone, TX1 + Tricyclazole, TX1 + Chlorothalonil, TX1 + Propiconazole, TX1 + Penconazole, TX1 + Fenpropimorph, TX1 + Fenpropidine, TX1 + Sulfur , TX1 + Aminopyrifen and TX1 + Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A. and known under the trade name Taegro®), wherein the weight ratio between component (A) [TX1] and component (B) [partner] is 20:1 to 1:40.

[0093] Compounds of formula (I) are a specific subset of compounds of formula (X) and can be made according to the processes for preparing compounds of formula (X) as described below.

[0094] Compounds of formula (X) are defined as follows: where X is O or S; R1 is hydrogen, halogen, methyl, methoxy or cyano; R2 and R3 are each independently hydrogen, halogen or methyl; R4 is hydrogen, cyano, C1-C4 alkyl or C3C4 cycloalkyl, wherein the alkyl, cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1C3 alkoxy and C1-C3 alkylthio; R5 and R6 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 alkylthio; or R5 and R6 together with the carbon atom to which they are attached represent C=O, C=NORc, C3-C5 cycloalkyl or C2-C5 alkenyl, where the cycloalkyl or alkenyl can be optionally substituted with 1 to 3 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio; R7 is hydrogen, C1-C5 alkyl, C3-C5 cycloalkyl, C2-C5 alkenyl, C3-C5 cycloalkenyl, or C2-C5 alkynyl, in which the alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl groups may be optionally substituted with 1 to 4 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy, hydroxyl and C1-C3 alkylthio; R8 and R9 are each independently selected from hydrogen, halogen, C1-C4 alkyl and C1-C4 alkoxy; or R8 and R9 together with the carbon atom to which they are attached represent a C3-C5 cycloalkyl group, in which the cycloalkyl may be optionally substituted with 1 to 3 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1 alkoxy -C3 and C1-C3 alkylthio; each R10 independently represents halogen, nitro, cyano, formyl, C1-C5 alkyl, C2-C5 alkenyl, C2C5 alkynyl, C3-C6 cycloalkyl, C1-C5 alkoxy, C3-C5 alkenyloxy, C3-C5 alkynyloxy, C1-C5 alkylthio, -C(=NORc)C1-C5 alkyl or C1-C5 alkylcarbonyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy and alkylthio may be optionally substituted by 1 to 5 independently selected halogen, C1 alkyl substituents -C3, C1-C3 alkoxy, cyano and C1-C3 alkylthio; n is 0, 1, 2, 3, 4 or 5; each Rc is independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C3-C4 alkynyl, C3-C4 cycloalkyl (C1-C2) and C3-C4 cycloalkyl, in which alkyl, cycloalkyl, alkenyl and alkynyl groups can be optionally substituted by 1 to 3 independently selected halogen and cyano substituents; R11 is hydrogen, halogen, methyl, methoxy or cyano; and R12 and R13 are each independently selected from hydrogen, halogen, methyl, methoxy or hydroxyl; and its salts and/or N-oxides.

[0095] Compounds of formula (X) can be prepared as shown in the following schemes, in which, unless otherwise shown, the definition of each variable is as defined above for a compound of formula (X). As mentioned above, compounds of formula (I) are made in the same or analogous manner as compounds of formula (X).

[0096] As shown in scheme 1, compounds of general formula (Xa) in which R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and n are as defined for compounds of formula (X) and ) wherein R4, R5, R6, R7, R8, R9, R10 and n are as defined for compounds of formula (X). Scheme 1

[0097] Among the various methods reported for this transformation, the most widely applied involves the treatment of carboxylic acid (II) with an activating agent such as thionyl chloride or an amide coupling reagent such as dicyclohexylcarbodiimide in an inert organic solvent such as tetrahydrofuran (THF) or dimethylformamide (DMF) and reaction with amine (III) in the presence of a catalyst such as dimethylaminopyridine as described in Chem. Soc. Rev., 2009, 606-631 or Tetrahedron 2005, 1082710852.

[0098] As shown in scheme 2, compounds of general formula (Xa), where X is O, can also be prepared by reacting compounds of formulas (IV) and (V) in the presence of a Bronsted acid as acid sulfuric acid or trifluoromethanesulfonic acid, in a solvent such as dichloromethane or acetic acid at temperatures between -20 °C and +50 °C as described in Eur. J. Org. Chem. 2015, 2727-2732 Scheme 2

[0099] Alternatively, compounds of general formula (Xa) wherein X is O can also be prepared by reacting compounds of formula (VI) with amines of formula (III), carbon monoxide, a base such as triethylamine or potassium carbonate and a suitably supported transient metal catalyst such as palladium in an inert organic solvent such as 1,4-dioxane at a temperature between 20°C and 110°C as described in Org. Lett., 2014, 4296-4299 (references mentioned therein) and shown in diagram 3. Scheme 3

[0100] Alternatively, compounds of general formula (Xa) in which X is O can also be prepared by reacting organometallic compounds of formula (VIa) with isocyanates of formula (IIIa) in an inert organic solvent such as diethyl ether or THF a temperatures between -78 °C and +40 °C, as described in Angew. Chem. Int. Ed. 2012, 9173 - 9175 and shown in diagram 4. Scheme 4

[0101] The preparation of organometallic compounds of formula (VIa) from compounds of formula (VI) by lithium-halogen exchange with an alkyllithium reagent such as s-butyl lithium or magnesium-halogen exchange with trimagnesate n-butyl, in an ethereal solvent such as THF at temperatures between -90 ° C and + 20 ° C, is generally known to one skilled in the art, and is described in synthetic chemistry texts such as March's Advanced Organic Chemistry.

[0102] As shown in scheme 5, carboxylic acids of formula (II) can be prepared by various methods and many are commercially available. Among the many methods reported for its preparation, the following have been widely applied: Scheme 5

[0103] 1) Transformation of anilines of formula (VII) into quinolones of formula (VIIb) by reaction with a malonate derivative of formula (VIIa) in an inert solvent such as diphenyl ether at temperatures between 100 °C and 260 °C as described in US 20070015758, followed by well-known functional group interconversion that is generally known to one skilled in the art and also described in WO 2007133637.

[0104] 2) Transformation of compounds of formula (VI) into organometallic intermediates of formula (VIa) by lithium-halogen exchange with an alkyllithium reagent such as s-butyl lithium or magnesium-halogen exchange with n-trimagnesate -butyl, in an ethereal solvent such as THF at temperatures between -90 °C and + 20 °C and subsequent reaction with CO2.

[0105] 3) Transformation of compounds of formula (VI) in the presence of a source of carbon monoxide, a base such as triethylamine, water or an equivalent thereof and a suitably bound transition metal catalyst containing for example palladium as described in J Am. Chem. Soc. 2013, 2891-2894 (and references therein) or Tetrahedron 2003, 8629-8640.

[0106] As shown in scheme 6, compounds of formula (IV) can be prepared from compounds of formula (VI) by treatment with a cyanide source such as zinc cyanide in the presence of a palladium, nickel or copper catalyst and a solvent inert as DMF at temperatures between 20°C and 150°C as described in J. Org. Chem. 2011, 665-668 or Bull. Chem. Soc. Jpn. 1993, 2776-8. Scheme 6

[0107] As shown in scheme 7, compounds of formula (VI) can be prepared by treating compounds of formula (VIa) with a halogenating agent such as N-iodosuccinimide, bromine or chlorine, in an inert solvent such as described in WO 2005113539 or JP 2001322979. Alternatively, compounds of formula (VI) can be prepared by treating propargylated anilines of formula (VIb) with a halogenating agent such as iodine in an inert solvent such as acetonitrile and a base such as sodium hydrogen carbonate at temperatures between 0°C and 80°C as described in Org. Lett. 2005, 763-766. Scheme 7.

[0108] The preparation of propargylated anilines of formula (VIb) from the corresponding commercially available anilines is trivial for one skilled in the art and described in March's Advanced Organic Chemistry, Smith and March, 6th edition, Wiley, 2007.

[0109] The synthesis of compounds of formula (VIa) is generally known to one skilled in the art and a wide variety of compounds are commercially available.

[0110] As shown in scheme 8, compounds of formula (V) can be prepared from carbonyl compounds of formula (Va) or (Vc) by treatment with an organometallic species of formula (Vb) or (Vd) respectively where is lithium, an aluminum salt or a magnesium salt, in an inert solvent such as diethyl ether at temperatures between -90 °C and 60 °C. Scheme 8

[0111] The preparation, general manipulation and reactivity (Vb) and (Vd) is described in March's Smith and March, 6th edition, Wiley, 2007, and is generally known to one skilled in the art. A large selection of compounds of formula (Va) and (Vc), where R4, R5, R6, R7, R8, R9 and R10 as defined above, are also commercially available and their syntheses are well described in scientific literature and literature texts. synthetic chemistry (such as March's Advanced Organic Chemistry) and, in addition, are generally known to one skilled in the art.

[0112] As shown in Scheme 9, amines of formula (III) can be prepared from compounds of formula (Vc) by condensation with tert-butyl sulfinamide in the presence of a dehydrating agent such as Ti(OEt)4 to form sulfimines of formula (Ve), which can then be treated with an organometallic reagent of formula (Vd), where X is lithium, an aluminum or magnesium salt, in an inert solvent such as THF at temperatures between -78°C and +70° C, followed by an acid hydrolysis of the sulfonamide; a sequence generally known to one skilled in the art and also described in Chem. Rev. 2010, 3600-3740.

[0113] Alternatively, amines of formula (III) can be prepared from compounds of formula (Vcc) by condensation with tert-butyl sulfinamide in the presence of a dehydrating agent such as Ti(OEt)4 to form sulfimines of formula (Vee), which can then be treated with an organometallic reagent of formula (Vdd), where X is lithium, an aluminum or magnesium salt, in an inert solvent such as THF at temperatures between -78 °C and + 70 °C, followed by a acid hydrolysis of sulfonamide. Scheme 9

[0114] Alternatively, amines of formula (III) can also be prepared from alcohols of formula (V) by treatment with a strong acid such as sulfuric acid in the presence of chloro-acetonitrile in an organic solvent such as acetic acid at temperatures between -10 °C and 50 °C to obtain amides of formula (IIIb), which can be deprotected with thiourea in an organic solvent such as ethanol or acetic acid, at temperatures between 20 °C and 100 C, as described in Synthesis 2000, 1709-1712 and shown in diagram 10. Scheme 10

[0115] Alternatively, amines of formula (III) can also be prepared from carboxylic acids of formula (IX) through an isocyanate intermediate of formula (IIIa) or a carbamate of formula (IIIc), where R14 is C1-alkyl C4, which can be hydrolyzed with acid or aqueous base at temperatures between 0 °C and 100 °C, as shown in scheme 11. Scheme 11

[0116] Among the various protocols reported for the transformation of acid (IX) into isocyanate (IIIa), the following have found wide application: 1) Treatment of acid (IX) with diphenylphosphorylazide and an amine base such as tributylamine, in an organic solvent inert such as toluene at temperatures between 50 °C and 120 °C to obtain isocyanate (IIIa), as described in Aust. J. Chem., 1973, 1591-3. 2) Treatment of acid (IX) with an activating agent such as thionyl chloride or propylphosphonic anhydride in the presence of an azide source such as sodium azide and an amine base such as triethylamine in an inert solvent such as THF at temperatures between 20 °C and 100 °C, as described in Synthesis 2011, 1477-1483. 3) Conversion of the acid (IX) to the corresponding hydroxamic acids which can then be treated with a dehydrating agent such as para-toluenesulfonyl chloride and a base such as triethylamine in an inert organic solvent such as toluene, at temperatures between 20 °C and 120 °C. 4) Conversion of the acid (IX) to the corresponding primary carboxamide which can then be treated with an oxidizing agent such as diacetoxyiodobenzene and an acid such as trifluoroacetic acid or para-toluenesulfonic acid in a solvent such as acetonitrile at temperatures between 0°C and 100° C, as described in J. Org. Chem. 1984, 4212-4216. 5) Conversion of the acid (IX) to the corresponding primary carboxamide, which can then be treated with an oxidizing agent such as bromine and a base such as sodium hydroxide in a solvent such as water or methanol, at temperatures between 0 °C and 100°C.

[0117] One skilled in the art will appreciate that the carboxylic acids of formula (IX) can be prepared from the corresponding esters. Similarly, one skilled in the art will appreciate that the alpha position of these esters can be functionalized by deprotonation with a strong base such as lithium diisopropylamine in an inert solvent such as THF at temperatures between -78°C and 20°C followed by reaction with an electrophilic reagent such as an alkyl iodide as described in March's Advanced Organic Chemistry, Smith and March, 6th edition, Wiley, 2007. This reaction can be repeated to prepare acids of formula (IX) from commercially available esters.

[0118] Alternatively, amines of formula (III) can also be prepared by reducing nitro compounds of formula (Za) with a reducing agent, such as iron in an organic solvent such as acetic acid, at temperatures between 20 ° C and 120 °C, as shown in Scheme 12. Nitro compounds of formula (Za), in turn, can be prepared from simple nitro compounds of formula (Z) by treatment with a benzyl bromide and a base, such as tert. -sodium butoxide, in the presence of a copper catalyst in an inert solvent, such as hexane, at temperatures between 20 °C and 100 °C, as described in J. Am. Chem. Soc. 2012, 9942-9945. Scheme 12

[0119] The synthesis of compounds of formula (Z) is generally known to one skilled in the art and a wide variety is commercially available.

[0120] Alternatively, amines of formula (III) can also be prepared by treating compounds of formula (V) with trimethylsilylazide and a Lewis acid catalyst of type B(C6F6)3 in an inert solvent such as toluene at temperatures between 0 °C and 100 °C, as described in J. Am. Chem. Soc. 2015, 9555-9558, followed by reduction of the azide intermediates of formula (XI) with a reducing agent such as hydrogen/palladium in an organic solvent such as methanol at temperatures between 0 °C and 80 °C, as shown in scheme 13. Scheme 13

[0121] Examples of intermediates of formula III (where R5, R6, R8 and R9 are all hydrogen) are:

[0122] One skilled in the art will recognize that compounds of formula (III) may have a center of chirality and that individual enantiomers may be prepared by i) enantioselective transformation of a suitable precursor, ii) resolution of a racemic or partially enriched mixture by fractional crystallization with an enantiomerically enriched acid or metal complex, iii) chromatographic separation of the enantiomers using an enantiomerically enriched stationary phase. Some representative protocols can be found in Chiral Amine Synthesis: Methods, Developments and Applications, Wiley, 2010.

[0123] As shown in scheme 14, compounds of general formula (Xb) where X is S can be prepared from compounds of general formula (Xa) where X is O by treatment with a deoxothionating agent such as P4S10 or reagent of Lawesson in an inert organic solvent such as toluene at temperatures between 20 °C and 150 °C.

[0124] Alternatively, compounds of formula (Xa), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and n are as defined for compounds of formula (X ) and defined for formula (X) and X is O and Z represents chlorine, bromine or iodine in a solvent, in the presence or absence of a base, and in the presence of a couplant reagent and a metal catalyst. There are no particular limitations on coupling agent, catalyst, solvent and bases, as long as they are used in standard coupling reactions, such as those described in “Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry)”, edited by Norio Miyaura and SL Buchwald (Springer editions) or “Metal-Catalyzed CrossCoupling Reactions”, edited by Armin de Meijere and François Diederich (WILEY-VCH editions). This is shown in Scheme 15. Scheme 15

[0125] Alternatively, compounds of formula (X-a), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and n are as defined for compounds of formula (X ) and X is O, can be obtained by transforming another closely related compound of formula (X-a) using standard synthetic techniques known to the person skilled in the art. Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, nucleophilic or electrophilic aromatic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions, and halogenation reactions.

[0126] Certain intermediates described in the schemes above are new and as such form an additional aspect of the invention.

[0127] The fungicidal quinoline (thio)carboxamide compounds disclosed and described in WO2017/153380 and compounds X.001, X.002, X.003, X.004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, X.012, X.013, X.014, X.015, 020, and each of its (S) or (R) enantiomers (in particular compounds F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8 , F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F -21, F-22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33 , F-34, F-35 and F-36, as defined in Table F below), and the fungicidal compositions disclosed and described above and below, in particular the binary compositions and ternary compositions (disclosed herein) can be used in controlling or prevention of phytopathogenic diseases, especially phytopathogenic fungi, as disclosed and described above and below.

[0128] Additionally, to date, no cross-resistance has been observed between the quinoline (thio)carboxamide fungicidal compounds disclosed and described in WO2017/153380 and compounds X.001, X.002, X.003, X.004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, X.012, 017, X.018, X.019 and , F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F -18, F-19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30 , F-31, F-32, F-33, F-34, F-35 and F-36, as defined in Table F below) and current commercial fungicides.

[0129] In fact, fungicide-resistant strains of many target pathogens have been reported in the scientific literature, with pathogen strains resistant to one or more fungicides of at least each of the following classes of fungicidal action being observed: sterol demethylation inhibitors (DMI ), external quinone inhibitors (QoI) and succinate dehydrogenase inhibitors (SDHI), anilinopyrimidine (AP), phenylpyrrole (PP) and hydroxyanilide fungicides, dicarboximides and methyl benzimidazole carbamate (MBC) fungicides.

[0130] See for example: "The rising threat of fungicide resistance in plant pathogenic fungi: Botrytis as a case study." M Hahn, J Chem Biol (2014) 7:133-141. Other citations from the literature are presented in the table below:

[0131] Thus, in a preferred embodiment, the quinoline (thio)carboxamide fungicidal fungicidal compounds disclosed and described in WO2017/153380 and compounds X.001, X.002, X.003, X.004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, X.012, X.013, 018, X.019 and , F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F -19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31 , F-32, F-33, F-34, F-35 and F-36, as defined in Table F below) and the fungicidal compositions disclosed and described above and below, in particular the binary compositions and ternary compositions (disclosed herein ), are used to control plant pathogenic fungi, especially Venturia, Sclerotinia, Botrytis, and Fusarium, that are resistant to one or more fungicides from any of the following MoA fungicide classes: sterol demethylation inhibitors (DMI), external inhibitors of quinone (QoI) and succinate dehydrogenase inhibitors (SDHI), anilinopyrimidine (AP), phenylpyrrole (PP) fungicides and hydroxyanilide fungicides, dicarboximides and benzimidazole methyl carbamate (MBC) fungicides.

[0132] Furthermore, it is preferred that in the application of the quinoline (thio)carboxamide fungicidal compounds disclosed and described in WO2017/153380 and compounds X.001, X.002, X.003, X.004, X.005, .006, X.007, X.008, X.009, X.010, X.011, X.012, X.013, , X.019 and X.020, and each of their (S) or (R) enantiomers (in particular compounds F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F- 17, F-18, F- 19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F- 27, F-28, F-29, F-30, F-31, F-32, F-33, F-34, F-35 and F-36, as defined in Table F below), and the fungicidal compositions disclosed and described above and below, in particular the binary compositions and ternary compositions (disclosed herein ), an adjuvant is applied and used in combination. Preferred adjuvants are: - Polyethylene oxide/polypropylene oxide copolymers (di- and triblocks) - Ethoxylated alkylsiloxanes or polysiloxanes - Alkylsulfosuccinate salts - Alkyl fatty acid esters - Ethoxylated alcohols/sorbitan fatty acids - Ethoxylated alcohols/fatty acids - Alcohols /ethoxylated fatty acids coated at the end with alkyl - Alcohols/ethoxylated propoxylated fatty acids - Alkylated vegetable oils - Aromatic mineral oils

[0133] Thus, in an additional preferred embodiment, the quinoline (thio)carboxamide fungicidal compounds disclosed and described in WO2017/153380 and compounds X.001, X.002, X.003, X.004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, X.012, X.013, 018, X.019 and X.020, and each of their (S) or (R) enantiomers (in particular compounds F-1, F-2, F-3, F-4, F-5, F-6 , F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F -19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F- 27, F-28, F-29, F-30, F-31 , F-32, F-33, F-34, F-35 and F-36, as defined in Table F below), and the fungicidal compositions disclosed and described above and below, in particular the binary compositions and ternary compositions (herein disclosed), are applied to a plant, its site or propagation material, in combination (separately or as a single composition) with an adjuvant selected from: Polyethylene oxide/polypropylene oxide copolymers (di- and triblocks), alkylsiloxanes or ethoxylated polysiloxanes, alkylsulfosuccinate salts, alkyl fatty acid esters, ethoxylated sorbitan alcohols/fatty acids, ethoxylated alcohols/fatty acids, ethoxylated alcohols/fatty acids end capped with alkyl, ethoxylated propoxylated alcohols/fatty acids, alkylated vegetable oils and aromatic mineral oils.

[0134] The compositions of the present invention, including all the modalities disclosed above and their preferred examples, can be mixed with one or more additional pesticides including fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, additional attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of crop protection.

[0135] Examples of such agricultural protectants with which the composition of the present invention can be formulated are:

[0136] Fungicides such as etridiazole, fluaziname, benalaxyl, benalaxyl-M (chiralaxyl), furalaxyl, metalaxyl, metalaxyl-M (mefenoxam), dodicine, N'-(2,5-Dimethyl-4-phenoxy-phenyl)-N -ethyl-N-methyl-formamidine, N'-[4-(4,5-Dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, N' -[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine , ethyrimole, 3'-chloro-2-methoxy-N-[(3RS)-tetrahydro-2-oxofuran-3-yl]aceto—2',6'-xylidide (clozilacone), cyprodinil, mepanipyrim, pyrimethanil, dithianone, aureofungin, blasticidin-S, biphenyl, chloroneb, dichlorane, hexachlorobenzene, quintazene, technazene, (TCNB), tolclophos-methyl, metrafenone, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, fluopicolide (flupicolide) , thioximide, flusulfamide, benomyl, carbendazime, carbendazim hydrochloride, chlorphenazole, fuberidazole, thiabendazole, thiophanate-methyl, bentiavalicarb, clobenthiazone, probenazole, acibenzolar, bethoxazine, pyriophenone (IKF-309), acibenzolar-S-methyl, piribencarb (KIF- 7767), butylamine, 3-iodo-2-propynyl n-butylcarbamate (IPBC), iodocarb (deisopropanyl butylcarbamate), isopropanyl butylcarbamate (iodocarb), picarbutrazox, polycarbamate, propamocarb, tolprocarb, 3-(difluoromethyl)-N-( 7-fluoro-1,1,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazol-4-carboxamide diclocymet, N-[(5-chloro-2-isopropyl-phenyl)methyl]-N -cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazol-4-carboxamide, N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1- methyl-pyrazole-4-carboxamide, carpropamide, chlorothalonil, flumorph, copper oxine, cymoxanil, fenamacryl, cyazofamide, flutianil, ticiophene, clozolinate, iprodione, procymidone, vinclozoline, bupyrimate, dinoctone, dinopentone, dinobutone, dinocape, meptildinocape, diphenylamine, phosdiphene, 2,6-dimethyl-[1,4]dithi-ino[2,3-c:5,6- c']dipyrrole-1,3,5,7(2H,6H)-tetraone, azitiram, eteme , ferbame, mancozeb, maneb, metam, metiram (polyrame), metiram-zinc, nabame, propineb, thiram, vapame (sodium metam), zineb, ziram, dithioether, isoprothiolane, etaboxam, fosetyl, fosetyl-Al (fosetyl-al ), methyl bromide, methyl iodide, methyl isothiocyanate, cyclafuramide, fenfuram, validamycin, streptomycin, (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonyl), dodine, doguadine, guazatine, iminoctadine, triacetate iminoctadine, 2,4-D, 2,4-DB, kasugamycin, dimetirimol, fenhexamide, himexazole, hydroxyisoxazole, imazalyl, imazalyl sulfate, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenamidone, Bordeaux mixture, polysulfide calcium, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulfate, copper thallate, cuprous oxide, sulfur, carbaryl, phthalide (phthalide), dingjunezuo (Jun Si Qi), oxathiapiproline, fluoroimide, mandipropamide, KSF-1002, benzamorph, dimethomorph, fenpropimorph, tridemorph, dodemorph, diethofencarb, fentin acetate, fentin hydroxide, carboxin, oxycarboxine, drazoloxone, famoxadone, m - phenylphenol, p-phenylphenol, tribromophenol (TBP), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2- [2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol cyflufenamide, ofurace, oxadixyl, flutolanil, mepronil, isofetamide, fenpiclonil, fludioxonil, pencicurone, edifenphos, iprobenfos, pyrazophos, phosphorus acids, teclophthalam, Captafol, Captan, Ditalymphos, Triforin, Fenpropidine, Piperaline, Ostol, 1-methylcyclopropene, 4-CPA, Chlormequat, Clofencet, Dichlorprop, Dimethipine, Endothal, Ethephone, Flumetralin, Forchlorfenurone, Gibberellic Acid , gibberellins, himexazole, maleic hydrazide, mepiquat, naphthalene acetamide, paclobutrazol, prohexadione, prohexadione-calcium, thidiazurone, tribuphos (tributyl phosphorotrithioate), trinexapace, uniconazole, acetic acid, α-naphthalene, polyoxin D (polyoxrime) , BLAD, chitosan, fenoxanil, folpet, 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazol-4-carboxamide, bixaphene , fluxapyroxad, furamethpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, fenpyrazamine, diclomezine, pyrifenox, boscalid, fluopyram, diflumetorime, fenarimol, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine ferinzone, dimethaclone (dimethaclone), pyroquilone, proquinazide, ethoxyquin, quinoxyphene, 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(3-quinolyl) isoquinoline, 5-fluoro-3,3,4,4-tetramethyl-1-(3-quinolyl)isoquinoline, 9-fluoro-2,2-dimethyl-5-(3-quinolyl)- 3H-1,4-benzoxazepine , tebufloquine, oxolinic acid, cinomethionate (oxythioquinox, quinoxymethionate), spiroxamine, (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetamide, (mandestrobin), azoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin, fenamistrobin, fluphenoxystrobin, fluoxastrobin, cresoxime-methyl, mandestrobin, metaminostrobin, metominostrobin, orisastrobin, picoxystrobin, pyraclostrobin, pyramethostrobin, pyraoxystrobin, triclopiricarb, trifloxystrobin, amisulbrom, diclofluanid, , N-[6-[ But-3-ynyl [(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, dazomet, isothianyl, thiadinyl, thifluzamide, bentiazole (TCMTB), Silthiofame, Zoxamide, Anilazine, Tricyclazole, (.+-.)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol (huanjunzuo), 1-(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1,1-difluoro-3-(1,2,4-triazol-1-yl)propan-2-ol, 2 -(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol (TCDP), azaconazole, bitertanol (biloxazole), bromuconazole , climbazole, cyproconazole, difenoconazole, dimetconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimephone , triadimenol, triazoxide, triticonazole, Mefentrifluconazole, 2-[[(1R,5S)- 5-[(4-fluorophenyl)methyl]-1-hydroxy-2,2-dimethyl-cyclopentyl]methyl]-4H-1,2 ,4-triazol-3-thione, 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H- 1,2,4-triazol-3 -thione, ametoctradine (imidium), iprovalicarb, valifenalate, 2-benzyl-4-chlorophenol (Chlorophene), allyl alcohol, azafenidine, benzalkonium chloride, chloropicrin, cresol, daracid, dichlorophene (dichlorophene), diphenzoquat, dipyrythion, N chloride -(2- p-chlorobenzoylethyl)hexamino, NNF-0721, octilinone, oxasulfurone, propamidine and propionic acid.

[0137] Insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartape, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafentiurone, diazinone, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diophenolan, emamectin, endosulfan, , etiprol, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamide, flubendiamide, flucitrinate, tau-fluvalinate, flufenerime (UR-50701), flufenoxurone, fonofos, halofenozide, hexaflumurone, hydramethylnone, imidacloprid, indoxacarb, isofenphos, lufenurone, malathion, mizona , metaldehyde, methamidophos, methidathione, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novalurone, noviflumurone (XDE-007), oxamyl, parathione, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosfamidone, pirimicarb, profenophos, profluthrin, pymetrozine, pyrafluprol, pyrethrin, pyridalyl, pyrifluquinazone, pyriprol, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramate, sulprophos, tebufenozide, teflubenzurone, , terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultape-sodium, tralomethrin, triazamate, trichlorphone and triflumurone; Bactericides such as streptomycin; Acaricides such as amitraz, quinomethionate, chlorobenzylate, cyenopyrafen, cyhexatin, dicofol, dienochlor, ethoxazole, fenazaquine, fenbutatin oxide, fenpropathrin, fenpyroximate, hexithiazox, propargite, pyridabene and tebufenpyrad; and Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, viruses and fungi. Other examples of mixtures of “reference” compositions are as follows (wherein the term “TX” represents a compound selected from compounds No. X.006, X.007, X.008, X.009, X.010, X.011, X.012, X.013, 018, X.019 and X.020, or one of their (S) or (R) enantiomers, as defined in Table 628) + TX, an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical name Abstracts) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX , acequinocil (3) + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumeth [CCN] + TX, amidothioate (872) + TX, amitone (875) + TX, amitone hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenic oxide (882 ) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotine (46) + TX, nitrogenate (889) + TX, benomyl (62) + TX, benoxaphos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [ CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacril (907) + TX, brofenvalerate (alternative name) + TX, bromocyclene (918) + TX, bromophos (920) + TX, bromophos- ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxym (103) + TX, butoxycarboxym (104) + TX, butylpyridabene (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX, camfeclor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothione (947) + TX, CGA 50'439 (development code) (125) + TX, quinomethionate (126) + TX, chlorbenside (959) + TX, chlorodimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorphenetol (968) + TX, chlorofensone (970) + TX, chlorfensulphide (971) + TX, chlorfenvinphos (131) + TX, chlorobenzylate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamitone (alternative name) [CCN] + TX, crotoxiphos (1010) + TX, kofraneb (1013) + TX, cyanhoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion-S (1037) + TX, demethone (1038) + TX, demethone-methyl (224) + TX, demethone-O (1038) + TX, demetone-O-methyl (224) + TX, demetone-S (1038) + TX, demetone-S- methyl (224) + TX, demetone-S-methylsulfone (1039) + TX, diafenthiuron ( 226) + TX, dialiphos (1042) + TX, diazinone (227) + TX, diclofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos ( 243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dynactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexin (1089) + TX, dinobutone (269) + TX, dinocape (270) + TX, dinocape-4 [CCN] + TX, dinocape-6 [CCN] + TX, dinoctone (1090) + TX, dinopentone (1092) + TX, dinosulfone (1097) + TX, dinoterbone (1098) + TX, dioxathione (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfotone (278) + TX, DNOC (282) + TX, dofenapine (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothione (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethione (309) + TX, ethoate-methyl (1134) + TX, ethoxazole (320) + TX, ethrimphos (1142) + TX, fenazaflor (1147) + TX, fenazaquine (328) + TX, fenbutatin oxide (330) + TX, phenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, phensone (1157) + TX, fentriphanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacripyrim (360) + TX, fluazurone (1166) + TX, flubenzimine (1167) + TX, flucicloxurone (366) + TX, flucitrinate (367) + TX , fluenethyl (1169) + TX, flufenoxurone (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotiona (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, gliodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexithiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) (473 ) + TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenfos (1248) + TX, lindane (430) + TX, lufenurone (490) + TX, malathion (492) + TX, malonobene (1254) + TX, mecarbam (502) + TX, mephospholane (1261) + TX, mesulfen ( alternative name) [CCN] + TX, methacryphos (1266) + TX, methamidophos (527) + TX, methidathione (529) + TX, methiocarb (530) + TX, methomyl (531) + TX methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, nalede (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309) + TX, nicomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride (1313) + TX, NNI-0101 (compound code ) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxideprophos (1324) + TX, oxydisulfotone (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phencaptone (1330) + TX, phentoate (631) + TX, phorate (636) + TX , phosalone (637) + TX, phospholan (1338) + TX, phosmet (638) + TX, phosfamidone (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, pollinactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacil (1354) + TX, propargite (671) + TX, propetanphos (673) + TX, propoxur (678) + TX, protidathion (1360) + TX, protoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridabene (699) + TX, pyridafenthion (701) + TX, pyrimidifene (706) + TX, pyrimitate (1370) + TX, quinalfos (711) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, escradane (1389) + TX, sebuphos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI -0009 (compound code) + TX, sofamide (1402) + TX, spirodiclofen (738) + TX, spiromesifene (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramide (750) + TX, sulfotepe (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifone (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425 ) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometone (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX , triamiphos (1441) + TX, triaratene (1443) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, trichlorphone (824) + TX, tripenophos (1455) + TX, trinactin (alternative name) ( 653) + TX, vamidothione (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX, an algaecide selected from the group of substances consisting of bethoxazine [CCN] + TX, copper dioctanoate (IUPAC name ) (170) + TX, copper sulfate (172) + TX, cybutrin [CCN] + TX, diclone (1052) + TX, dichlorophene (232) + TX, endotal (295) + TX, fentin (347) + TX , hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, phenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1 -hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX , bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophene (232) + TX, dipyrithione ( 1105) + TX, dodicine (1112) + TX, phenaminosulfe (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + TX, kasugamycin (483) + TX, hydrated kasugamycin hydrochloride (483 ) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octylinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, sulfate potassium hydroxyquinoline (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX, a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani ( alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide ( scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri ( alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (name scientific) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX , Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX , Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542 ) and methyl bromide (537) + TX, a chemosterilant selected from the group of substances consisting of afolate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzurone (250) + TX, dimatife (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl afolate [CCN ] + TX, morzide [CCN] + TX, penflurone (alternative name) [CCN] + TX, tepa [CCN] + TX, thio-hempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX, an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E )-6-methyl-hept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779 ) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-11-enal (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl (IUPAC name) (437) + TX, (Z)-hexadec-13-en-11-en-1-yl acetate (IUPAC name) (438) + TX, (Z)-icos- 13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1- al (IUPAC name) (782) + TX, (Z )-tetradec-9-en-1-ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E) acetate ,9Z)-dodeca-7,9-dien-1-yl (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780 ) + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemon (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN ] + TX, gossiplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) alternative) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatina (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) ( 588) + TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, orictalure (alternative name) (317) + TX, ostramon (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidine (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-11-en-1- acetate ila (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure B1 (alternative name) (839) + TX, trimedlure B2 (alternative name) (839 ) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (name IUPAC) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methochin -butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX, an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2 acetate -trichloro-1-(3,4-dichlorophenyl)ethyl (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl-methyl phosphate (IUPAC name) (1066) + TX, 2-(dimethylcarbamate 1,3-dithiolan-2-yl)phenyl (IUPAC/Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935) + TX, 2-methylcarbamate -(4,5-dimethyl-1,3-dioxolan-2- yl)phenyl (IUPAC/Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, diethyl 2-chlorovinyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindane-1,3-dione (IUPAC name) (1246 ) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop- 1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-methylcarbamate 3,5-xylyl (IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethione (alternative name) [CCN] + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidine (alternative name) [CCN] + TX, alixicarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminum phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873 ) + TX, amitone (875) + TX, amitone hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, atidathione (883) + TX, AVI 382 (compound code) + TX , AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, nitrogenate (889 ) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892) + TX, barthrin [ CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultape (66 ) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioalethrin (78) + TX, S-cyclopentenyl isomer of bioalethrin (alternative name) (79) + TX, bioethanometrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistriflurone (83) + TX, borax (86 ) + TX, brofenvalerate (alternative name) + TX, bronfenvinphos (914) + TX, bromocyclene (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl ( 921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiophos (927) + TX, butocarboxym (103) + TX, butonate (932) + TX, butoxycarboxym (104 ) + TX, butylpyridabene (alternative name) + TX, cadusaphos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camfeclor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name ) (946) + TX, carbofenothione (947) + TX, carbosulfan (119) + TX, Cartape (123) + TX, Cartape hydrochloride (123) + TX, Cevadine (alternative name) (725) + TX, Chlorbicyclene ( 960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyphos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazurone (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorfoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos ( 145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX , cis-resmethrin (alternative name) + TX, cismethrin (80) + TX, clocitrin (alternative name) + TX, cloetocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX , copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumitoate (1006) + TX, crotamitone (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos ( 184) + TX, cyantoate (1020) + TX, cyclothrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206 ) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d-tetramethrin (alternative name) (788) + TX, DAEP ( 1031) + TX, dazometh (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demefion (1037) + TX, demefion-O (1037) + TX, demefion -S (1037) + TX, demetone (1038) + TX, demetone-methyl (224) + TX, demetone-O (1038) + TX, demetone-O-methyl (224) + TX, demetone-S (1038) + TX, demetone-S-methyl (224) + TX, demetone-S-methylsulfone (1039) + TX, diafentiurone (226) + TX, dialiphos (1042) + TX, diamidaphos (1044) + TX, diazinone (227) + TX, dicaptone (1050) + TX, diclofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanyl (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzurone (250) + TX, dilor (alternative name) [CCN] + TX, dimefluthrin [CCN] + TX, dimefox (1081) + TX, dimethane (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimethylane (1086) + TX , dinex (1089) + TX, dinex-diclexin (1089) + TX, dinoprope (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diophenolan (1099) + TX, dioxabenzophos (1100) + TX, dioxacarb (1101) + TX, dioxathione (1102) + TX, disulfotone (278) + TX, diticrophos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [ CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothione (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX , epofenonan (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etafos (alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX , etiprol (310) + TX, ethoate-methyl (1134) + TX, etoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrymphos (1142) + TX, EXD (1143) + TX, famfur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenetacarb (1149) + TX, fenfluthrin (1150) + TX, fenitrothion (335) + TX , fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpyrithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothione (1158) + TX , phenthion (346) + TX, phenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamide (358) + TX, flubendiamide (CAS Reg. No.: 272451-65 -7) + TX, flucofurone (1168) + TX, flucicloxurone (366) + TX, flucitrinate (367) + TX, fluenethyl (1169) + TX, flufenerim [CCN] + TX, flufenoxurone (370) + TX, flufenprox ( 1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, phonofos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride ( 405) + TX, formotiona (1192) + TX, formparanate (1193) + TX, fosmethylane (1194) + TX, fospirate (1195) + TX, fosthiazate (408) + TX, fosthiethane (1196) + TX, furathiocarb (412 ) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (code development) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptaclor (1211) + TX, heptenophos (432) + TX , heterophos [CCN] + TX, hexaflumurone (439) + TX, HHDN (864) + TX, hydramethylnone (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprotrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazophos (1231) + TX, isobenzane ( 1232) + TX, isocarbophos (alternative name) (473) + TX, isodrine (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, O-(methoxyaminothiophosphoryl)salicylate isopropyl (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathione (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolina II (696) + TX, jodfenfós (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, chelevane (1249) + TX, quinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250 ) + TX, lindane (430) + TX, lirinfos (1251) + TX, lufenurone (490) + TX, litidathione (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonobene (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarfone (1258) + TX, menazone (1260) + TX, mephospholane (1261) + TX, mercurous chloride (513) + TX, mesulfenphos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX , methamsodium (519) + TX, methacryphos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathione (529) + TX, methiocarb (530 ) + TX, methocrotophos (1273) + TX, methomyl (531) + TX methoprene (532) + TX, methoxychlor-butyl (1276) + TX, metothrin (alternative name) (533) + TX, methoxychlor (534) + TX , methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofluthrin [CCN] + TX, metolcarb (550) + TX, methoxadiazone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphthalophos (alternative name) [CCN] + TX, nalede (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride ( 1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, noviflumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, O-4-methyl-2-oxo-2H-chromen-7-yl O,O-diethyl phosphorothioate (IUPAC name) (1074) + TX, O-6-methyl-2-propylpyrimidin-4-yl O,O-diethyl phosphorothioate (IUPAC name) (1075) + TX, O,O,O',O dithiopyrophosphate '-tetrapropyl (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemetone-methyl (609) + TX, oxideprophos ( 1324) + TX, oxydisulfotone (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penflurone (name alternative) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60 -38 (development code) (1328) + TX, fencaptone (1330) + TX, phenothrin (630) + TX, phentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phospholane ( 1338) + TX, phosmet (638) + TX, fosnichlor (1339) + TX, phosfamidone (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pyrimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes ( traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, pralethrin (655) + TX, precoten I (alternative name) [CCN] + TX, precone II (name alternative) [CCN] + TX, precocin III (alternative name) [CCN] + TX, primidofos (1349) + TX, profenophos (662) + TX, profluthrin [CCN] + TX, promacil (1354) + TX, promecarb ( 1355) + TX, propaphos (1356) + TX, propetanphos (673) + TX, propoxur (678) + TX, protidathion (1360) + TX, prothiophos (686) + TX, protoate (1362) + TX, protrifenbut ] + TX, pymetrozine (688) + TX, pyraclophos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins ( 696) + TX, pyridabene (699) + TX, pyridalyl (700) + TX, pyridafenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quasia (name alternative) [CCN] + TX, quinalfos (711) + TX, quinalfos-methyl (1376) + TX, quinothione (1380) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, riânia (alternative name) (1387) + TX, ryanodina (traditional name) (1387) + TX, sabadila (alternative name) (725) + TX, escradano (1389) + TX, sebufós (alternative name) + TX , selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (code of the compound) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC name /Chemical Abstracts) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sofamide (1402) + TX, spinosad (737) + TX, spiromesifene (739) + TX, spirotetramate (CCN) + TX, sulcofurone (746) + TX, sulcofurone-sodium (746) + TX, sulfluramide (750) + TX , sulfothepe (753) + TX, sulfuryl fluoride (756) + TX, sulprophos (1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupyrimphos (764) + TX, teflubenzurone (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, teralethrin (1418) + TX, terbam (alternative name) + TX, terbufós (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, ticrophos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798 ) + TX, thiocyclam hydrogen-oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometone (801) + TX, thionazine (1434) + TX, thiosultape (803) + TX, thiosultape-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos ( 1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorphone (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronate (1452 ) + TX, tripenophos (1455) + TX, triflumurone (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidothione (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name ) (725) + TX, veratrin (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprophos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [ 500008-45-7] + TX, cyenopirafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazone [337458-27-2] + TX, spinetoram [187166-401 + 187166- 15-0] + TX, spirotetramate [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprol [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX , tetramethylfluthrin [84937-88-2] + TX, triflumezopyrime (disclosed in WO 2012/092115) + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloetocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate ( IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide ( 623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimetacarb (840) + TX, triphenyltin acetate (IUPAC name) ( 347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1 ,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3- dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- ( 4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thidiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6- isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprol [CCN] + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (code of the compound) + TX, benclotiaz [CCN] + TX, benomyl (62) + TX, butylpyridabene (alternative name) + TX, cadusaphos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX , carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chloretocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045 ) + TX, DCIP (218) + TX, diamidaphos (1044) + TX, diclofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX , emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, etoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX , fenpyrad (alternative name) + TX, fensulfothione (1158) + TX, fosthiazate (408) + TX, fosthiethane (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) ( 423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX, isazophos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin ( alternative name) (210) + TX, mecarphone (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537 ) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, composition of Myrothecium verrucaria (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosfamidone (639) + TX, phosphocarb [CCN] + TX, sebuphos (alternative name) + TX, selamectin (name alternative) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazine (1434) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code), and zeatin (alternative name) (210) + TX , fluensulfone [318290-98-1] + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar ( 6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and extract of Reynoutria sachalinensis (alternative name) (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan- 1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide ( 640) + TX, antu (880) + TX, arsenic oxide (882) + TX, barium carbonate (891) + TX, bistiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumaclor (1004) + TX, coumafuril ( 1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difetialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumafen (357 ) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, fosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinurone (1371) + TX, sciliroside (1390 ) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851 ) and zinc phosphide (640) + TX, a synergistic agent selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol- 5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX , MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX , sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN ] + TX, copper oxychloride (171) + TX, diazinone (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530 ) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX, a selected virucide from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX, a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octilinone (590 ) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole [60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [114369 -43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole [125116-23-6] + TX, myclobutanil [88671- 89-0] + TX, pefurazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-706] + TX, pyrifenox [88283-41-4] + TX, prochloraz [67747-095] + TX, propiconazole [60207-90-1] + TX, simeconazole [14950890-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771-68- 5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupyrimate [41483-43-6] + TX, dimethyrimole [5221-53-4] + TX, ethyrimole [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8 ] + TX, tridemorph [81412-433] + TX, cyprodinil [121552-61-2] + TX, mepanipyrim [11023547-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17- 3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxil [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R -metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21 -7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878-19-1] + TX, thiabendazole [148-79-8] + TX, clozolinate [84332-86-5] + TX, diclozolin [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozolin [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozolin [50471-44- 8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7] + TX, guazatine [108173-90-6 ] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [ 149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [14339089-0] + TX, metominostrobin [133408-50-1] + TX , trifloxystrobin [141517-21-7] + TX, orisastrobin [24859316-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1 ] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, tiram [ 137-26-8] + TX, zinebe [12122-67-7] + TX, ziram [137-30-4] + TX, Captafol [2425-06-1] + TX, Captano [133-06-2] + TX, diclofluanid [1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3] + TX, tolylfluanide [731-27-1] + TX, Bordeaux mixture [8011-63-0] + TX, copper hydroxide [20427-59-2] + TX, copper oxychloride [1332-40-7] + TX, copper sulfate [7758-98-7] + TX, oxide copper [1317-391] + TX, mancobre [53988-93-5] + TX, oxina-copper [10380-286] + TX, dinocape [131-72-6] + TX, nitrotal-isopropyl [10552-74 -6] + TX, edifenfos [17109-49-8] + TX, iprobenfos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdifen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclophos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anylazine [101-05-3] + TX, bentiavalicarb [413615-35-7] + TX, blasticidin-S [2079-007] + TX, quinomethionate [2439-01-2] + TX, chloroneb [267577-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamide [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, diclone [117-80-6] + TX, diclocimet [139920-32-4] + TX, diclomezine [62865 -36-5] + TX, dichloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867- 47-9] + TX, dithianone [3347-22-6] + TX, etaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX , fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59 -6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-526] + TX, fenhexamide [126833-17-8] + TX, fosetyl aluminum [39148-24-8] + TX, himexazole [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Ciazofamide) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX , metasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencicurone [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80 -7] + TX, probenazole [27605-761] + TX, propamocarb [25606-41-1] + TX, proquinazide [189278-12-4] + TX, pyroquilone [57369-32-1] + TX, quinoxifen [ 124495-18-7] + TX, quintazene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiadinyl [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforin [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamide [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, (9-dichloromethylene-1,2,3,4-tetrahydro- 3-Difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid 1,4-methane-naphthalen-5-yl)-amide (disclosed in WO 2007/048556) + TX, (3',4',5 3-difluoromethyl-1-methyl-1H-pyrazol-4-carboxylic acid '-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343) + TX, [(3S,4R,4aR,6S, 6aS,12R,12aS,12bS)-3- [(cyclopropylcarbonyl)oxy]- 1,3,4,4a,5,6,6a,12,12a,12b- decahydro-6,12-dihydroxy- 4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972- 17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1 -methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H- pyrazol-4-carboxamide [926914-55-8] + TX, or a biologically active compound selected from the group consisting of N-[(5-chloro-2- isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazol-4-carboxamide + TX, 2,6-Dimethyl-1H,5H-[1,4]diti- ino[2,3- c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX, 6-ethyl-5,7- dioxo-pyrrolo[4,5] [1,4]dithi-ino[1,2-c]isothiazol-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine- 3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1 ,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)- N-(2-chloro-6-fluoro-phenyl)-2,5 -dimethyl-pyrazol-3-amine + TX, 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazol-4-carboxamide + TX , CAS 850881-30-0 + TX, 3-(3,4-dichloro-1,2-thiazol-5-ylmethoxy)-1,2-benzothiazole 1,1-dioxide + TX, 2-[2-[ (2,5-dimethylphenoxy)methyl]phenyl]-2-methoxy-N-methyl-acetamide + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl )quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, Oxathiapiproline + TX, N-[6-[ tert-butyl [[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, N-[2-(3,4-difluorophenyl)phenyl]-3- (trifluoromethyl)pyrazine-2-carboxamide + TX, 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide + TX, N- 2,2,2-Trifluoroethyl [2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate + TX, (2RS)-2-[4-(4-chlorophenoxy)-α,α ,α-trifluoro-o-tolyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol + TX, (2RS)-2-[4-(4-chlorophenoxy)- α,α,α-trifluoro-o-tolyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol + TX, 2- (difluoromethyl)-N- [(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl- N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2 -[3-[2-[1-[2-[3,5- bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol- 4-yl]-4,5-dihydroisoxazole- 5-yl]-3-chlorophenyl]methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl] but-3-ynyl carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro -6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3 -yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4- (3,4 ,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, Aminopirifen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy -2-methoxy-imino-N,3-dimethyl-pent-3-enamide + TX, (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX, Florylpicoxamide (CAS 1961312-55 -9, IUPAC name [(1S)-2,2-bis(4-fluorophenyl)-1-methyl-ethyl] (2S)-2-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino ]propanoate; known from WO 2016/109257) + TX, and

[0138] References in square brackets after active ingredients, for example, [3878-19-1] refer to the Chemical Abstracts Registration Number. The mixing partners described above are known. Where active ingredients are included in “The Pesticide Manual” [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council] are described therein under the entry number given in curly brackets above for the particular compound; for example, the compound “abamectin” is described under accession number (1). When "[CCN]" is added herein above to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessed via the internet [A. Wood; "Compendium of Pesticide Common Names", Copyright© 1995-2004]; for example, the compound "acetoprol" is described at http://www.alanwood.net/pesticides/acetoprole.html

[0139] Most of the active ingredients described above are referred to hereinbefore by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a “common name,” the nature of the alternative designation used is given in parentheses for the particular compound; in this case the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditional name”, a “compound name” or a “development code” is used or, if neither of these designations nor a “common name”, an “alternative name” is used. “No CAS Reg” means the Chemical Abstracts Registration Number.

[0140] In the “reference” mixture compositions, mixtures of compounds of formula (I) [selected from Table X (above)] with active ingredients described above comprise a compound selected from Table X (above) and an active ingredient such as described above preferably in a mixing ratio of 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of 20:1 to 1:20, even more especially from 10:1 to 1 :10, most especially 5:1 and 1:5, with special preference being given to a ratio of 2:1 to 1:2, and a ratio of 4:1 to 2:1 being similarly preferred, above all in a ratio of 1:1 or 5:1 or 5:2 or 5:3 or 5:4 or 4:1 or 4:2 or 4:3 or 3:1 or 3:2 or 2:1 or 1: 5 or 2:5 or 3:5 or 4:5 or 1:4 or 2:4 or 3:4 or 1:3 or 2:3 or 1:2 or 1:600 or 1:300 or 1:150 or 1:35 or 2:35 or 4:35 or 1:75 or 2:75 or 4:75 or 1:6000 or 1:3000 or 1:1500 or 1:350 or 2:350 or 4:350 or 1: 750 or 2:750 or 4:750. These mixing ratios are by weight.

[0141] Mixture compositions as described above (both according to the invention and the “reference” mixture compositions) can be used in a method for controlling pests, which comprises applying a composition comprising a mixture such as described above to pests or their environment.

[0142] Mixtures comprising a compound of formula (I) selected from Table X (above) and one or more active ingredients as described above, can be applied, for example, in a simple "ready-mix" form , in a combined spray mixture prepared from separate formulations of the single active ingredient components, such as a "tank mix", and in a combined use of the individual active ingredients when applied in a sequential manner, i.e. one after the other. another in a relatively short period of time, such as a few hours or days. The order of application of the compounds of formula (I) selected from Table X (above) and the active ingredients as described above is not essential for carrying out the present invention.

[0143] The compositions of the present invention can also be used in crop intensification.

[0144] According to the present invention, “crop intensification” means an improvement in plant vigor, an improvement in plant quality, improved tolerance to stress factors and/or improved resource use efficiency by plants.

[0145] According to the present invention, an “improvement in plant vigor” means that certain strains are improved qualitatively or quantitatively compared to the same strain in a control plant that was grown under the same conditions in the absence of the method of invention. Such strains include, but are not limited to, earlier and/or improved germination, improved emergence, the ability to use fewer seeds, increased root growth, a more developed root system, increased root nodulation, increased shoot growth, increased tillering, stronger shoots, more productive shoots, increased or improved ability to remain upright, less leaning (lodging) of plants, an increase and/or improvement in plant height, an increase in the weight (fresh or dry) of plants, larger leaf blades , greener leaf color, increased pigment content, increased photosynthetic activity, earlier flowering, longer panicles, earlier grain maturity, increased size of seeds, fruits or pods, increased number of pods or ears, increased number of seeds per pod or ear, increased seed mass, enhanced seed filling, fewer dead basal leaves, delayed senescence, improved plant vitality, increased amino acid levels in storage tissues, and/or fewer resources needed (e.g., less fertilizer, water and /or labor required). A plant with improved vigor may have an increase in any one of the above-mentioned traits or any combination of two or more of the above-mentioned traits.

[0146] According to the present invention, an “improvement in plant quality” means that certain traits are improved qualitatively or quantitatively compared to the same trait in a control plant that was grown under the same conditions in the absence of the method of invention. Such traits include, but are not limited to, improved visual appearance of the plant, reduced ethylene (reduced production and/or inhibition of reception), improved quality of collected material, e.g., seeds, fruits, leaves, legumes and vegetables (such quality improved may manifest as improved visual appearance of the collected material), improved carbohydrate content (e.g. increased amounts of sugar and/or starch, improved sugar to acid ratio, reduction of reducing sugars, increased rate of sugar development), improved protein content, improved oil content and composition, improved nutritional value, reduction in anti-nutritional compounds, improved organoleptic properties (e.g. improved taste) and/or improved consumer health benefits (e.g. increased levels of vitamins and antioxidants), improved post-harvest characteristics (e.g. enhanced shelf life and/or storage stability, easier processability, easier extraction of compounds), more homogeneous crop development (e.g. germination, flowering and/or production of synchronized plant fruits), and/or improved seed quality (e.g. for use in subsequent seasons). A quality-improved plant may have an increase in any one of the above-mentioned traits or any combination of two or more of the above-mentioned traits.

[0147] According to the present invention, an “improved tolerance to stress factors” means that certain traits are improved qualitatively or quantitatively compared to the same trait in a control plant that was grown under the same conditions in the absence of the method of the invention. Such traits include, but are not limited to, an increased tolerance and/or resistance to abiotic stress factors that cause suboptimal growth conditions, such as drought (e.g., any stress that leads to an absence of water content in plants, an absence of water uptake potential or a reduction in water supply to plants), cold exposure, heat exposure, osmotic stress, UV stress, waterlogging, increased salinity (e.g. in soil), mineral exposure increased, ozone exposure, high light exposure and/or limited nutrient availability (e.g. nutrients containing nitrogen and/or phosphorus). A plant with improved tolerance to stress factors may have an increase in any one of the above-mentioned traits or any combination of two or more of the above-mentioned traits. In the case of drought and nutrient stress, such improved tolerances may be due, for example, to more efficient capture, use or retention of water and nutrients.

[0148] According to the present invention, an “improved resource use efficiency” means that plants are able to grow more efficiently using given resource levels compared to the growth of control plants that are grown under the same conditions in the absence of the method of the invention. In particular, the resources include, but are not limited to, fertilizer (such as nitrogen, phosphorus, potassium, micronutrients), light and water. A plant with improved resource use efficiency may have a use. enhanced of any of the above-mentioned features or any combination of two or more of the above-mentioned features.

[0149] Other crop intensifications of the present invention include a decrease in plant height, or reduction in tillering, which are beneficial characteristics in crops or conditions where it is desirable to have less biomass and fewer shoots.

[0150] Any or all of the above crop intensifications can lead to improved yield by improving, for example, plant physiology, plant growth and development and/or plant architecture. In the context of the present invention, “yield” includes, but is not limited to: (i) an increase in biomass production, grain yield, starch content, oil content and/or protein content, which may result from (a) an increase in the amount produced by the plant per se or (b) an improved ability to harvest plant matter, (ii) an improvement in the composition of the harvested material (e.g., better acid to sugar ratios, better oil composition , greater nutritional value, reduction of anti-nutritional compounds, greater benefits for the health of the consumer) and/or (iii) greater capacity, or easier, to harvest the crop, better processability of the crop and/or better storage stability/shelf life validity. Increased yield of an agricultural plant means that, where a quantitative measurement is possible, the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions but without application of the present invention. According to the present invention, it is preferred that the yield is increased by at least 0.5%, more preferred by at least 1%, even more preferred by at least 2%, even more preferred by at least 4%, preferably 5 % or even more.

[0151] Any or all of the above crop intensifications may also lead to improved land utilization, i.e., land that was previously unavailable or suboptimal for cultivation may become available. For example, it may be possible to grow plants that exhibit an increased ability to survive drought conditions in areas of suboptimal rainfall, for example, perhaps on the edges of a desert or even in the desert itself.

[0152] In one aspect of the present invention, crop intensifications are carried out in the substantial absence of pest and/or disease pressure and/or abiotic stress. In a further aspect of the present invention, improvements in plant vigor, stress tolerance, quality and/or yield are made in the substantial absence of pest and/or disease pressure. For example, pests and/or diseases can be controlled by a pesticide treatment that is applied prior to or at the same time as the method of the present invention. In a still further aspect of the present invention, improvements in plant vigor, stress tolerance, quality and/or yield are made in the absence of pest and/or disease pressure. In a further embodiment, improvements in plant vigor, quality and/or yield are made in the absence, or substantial absence, of abiotic stress.

[0153] The compositions of the present invention can also be used in the area of protecting storage goods against fungal attack. According to the present invention, the term “storage goods” is understood to denote natural substances of plant and/or animal origin and their processed forms, which have been removed from the natural life cycle and for which long-term protection is desirable. term. Storage goods of plant origin, such as plants or parts thereof, e.g. stems, leaves, tubers, seeds, fruits or grains, may be protected in the freshly collected state or in the processed form, such as pre-dried, moistened , crushed, ground, pressed or roasted. Also included in the definition of storage goods is wood, either in the form of raw wood, such as construction lumber, electricity poles and barriers, or in the form of finished articles, such as furniture or objects made from wood. Storage goods of animal origin are skins, leather, fur, fur and the like. The composition according to the present invention can prevent disadvantageous effects such as degradation, discoloration or mold. Preferably, “storage goods” are understood to denote natural substances of plant origin and/or their processed forms, more preferably fruits and their processed forms, such as pome fruits, stone fruits, soft fruits and citrus fruits and their processed forms. In another preferred embodiment of the invention, "storage goods" are understood to denote wood.

[0154] Therefore, a further aspect of the present invention is a method of protecting storage goods, which comprises applying to the storage goods a composition according to the invention.

[0155] The composition of the present invention can also be used in the area of protecting technical material against fungal attack. According to the present invention, the term “technical material” includes paper; carpets; constructions; cooling and heating systems; wall panels; air conditioning and ventilation systems and similar; Preferably, “technical material” is understood to denote wall panels. The composition according to the present invention can prevent disadvantageous effects such as degradation, discoloration or mold.

[0156] The composition according to the invention is generally formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations may be in various physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent granules, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other known forms , for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

[0157] Formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

[0158] The active ingredients can also be contained in microcapsules. Microcapsules contain the active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled quantities (e.g. slow release). Microcapsules usually have a diameter of 0.1 to 500 microns. They contain active ingredients in an amount of approximately 25 to 95% by weight of the capsule weight. The active ingredients may be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion, or in the form of a suitable solution. Encapsulation membranes may comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers which are known to the skilled artisan. in technique. Alternatively, very fine microcapsules may be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

[0159] Formulation adjuvants that are suitable for preparing the formulations according to the invention are known per se. As liquid carriers can be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abiethate, diethylene glycol butyl ether, diethylene glycolethyl ether, diethylene glycol methyl ether, N,N- dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene , d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane , isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methylisoamylketone, methylisobutylketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n- octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetra alcohol -hydrofurfuryl, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

[0160] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, flour. wheat, soy flour, pumice, wood flour, crushed walnut shells, lignin and similar substances.

[0161] A large number of surface-active substances can be advantageously used in solid and liquid formulations, especially in those formulations that can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric, and can be used as emulsifiers, wetting agents or suspending agents, or for other purposes. Typical surface-active substances include, for example, alkyl sulfate salts, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide, and salts of mono- and di-alkylphosphate esters, and also additional substances described, e.g., in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey, (1981).

[0162] Additional adjuvants that can be used in pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, colorants, antioxidants, foaming agents, light absorbers, mixing aids, antifoams, complexing agents, substances pH neutralizers or modifiers and buffers, corrosion inhibitors, fragrances, wetting agents, adhesion enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides and liquid and solid fertilizers.

[0163] The formulations according to the invention may include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the formulation according to the invention is generally 0.01 to 10%, based on the mixture to be applied. For example, the oil additive may be added to a spray tank at the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example methyl derivatives or an oil of vegetable origin. animal, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example, the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the "Compendium of Herbicide Adjuvants", 10th Edition, Southern Illinois University, 2010.

[0164] The formulations generally comprise from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of compounds of formulas (I) and (II) and from 1 to 99.9% by weight of a formulation adjuvant that preferably includes 0 to 25% by weight of a surfactant substance. Although commercial products may preferably be formulated as concentrates, the end user will typically employ diluted formulations.

[0165] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions and other factors controlled by the method of application, the time of application and target culture. As a general guideline, compounds can be applied at a rate of 1 to 2000 L/ha, especially 10 to 1000 L/ha.

[0166] Certain mixture compositions comprising a compound of formula (I) described above may show a synergistic effect. This occurs whenever the action of a combination of active ingredients is greater than the sum of the actions of the individual components. The action to be expected E for a given combination of active ingredients obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20 -22; 1967): ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture ppm of active ingredient.

[0167] According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is:

[0168] If the actually observed action (O) is greater than the expected action (E), then the action of the combination is super additive, that is, there is a synergistic effect. In mathematical terms, synergy corresponds to a positive value for the difference of (O-E). In the case of adding purely complementary activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.

[0169] However, in addition to the actual synergistic action with regard to fungicidal activity, the composition according to the invention may also have additional surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageous degradability; improved toxicological and/or ecotoxicological behavior; or improved useful plant characteristics including: emergence, crop yields, more developed root system, increased tillering, increased plant height, larger leaf blade, fewer dead basal leaves, stronger shoots, greener leaf color, less fertilizer needed, fewer seeds needed, more productive shoots, earlier flowering, earlier grain maturity, less plant lodging, increased shoot growth, improved plant vigor and early germination.

[0170] The composition according to the invention can be applied to phytopathogenic microorganisms, useful plants, their locus, their propagation material, storage goods or technical materials threatened by attack by microorganisms.

[0171] The composition according to the invention can be applied before or after infection of useful plants, their propagation material, storage goods or technical materials by microorganisms.

[0172] The amount of a composition according to the invention to be applied will depend on several factors, such as the compounds used; the subject of the treatment, such as, for example, plants, soil or seeds; the type of treatment, such as, for example, spraying, dusting or seed covering; the purpose of the treatment, such as, for example, prophylactic or therapeutic; the type of fungi to be controlled or the moment of application.

[0173] When applied to useful plants, component (A) is typically applied at a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, for example, 50, 75, 100 or 200 g a.i. /ha, typically in association with 1 to 5000 g a.i./ha, particularly 2 to 2000 g a.i./ha, for example 100, 250, 500, 800, 1000, 1500 g a.i./ha of component (B).

[0174] In agricultural practice, application rates of the composition according to the invention depend on the type of effect desired and typically range from 20 to 4000 g of the total composition per hectare.

[0175] When the composition according to the invention is used for seed treatment, rates of 0.001 to 50 g of a compound of component (A) per kg of seed, preferably 0.01 to 10 g per kg of seed, are generally sufficient. seed and 0.001 to 50 g of a compound of component (B) per kg of seed, preferably 0.01 to 10 g per kg of seed.

[0176] For the avoidance of doubt, where a literary reference, patent application or patent is cited within the text of this application, the entire text of said citation is incorporated herein by reference.

EXAMPLES

[0177] The following Examples serve to illustrate the invention. Certain compounds and compositions of the invention can be distinguished from known compounds and compositions by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, if required, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0178] Throughout this description, temperatures are presented in degrees Celsius and "pf" means melting point. LC/MS stands for Liquid Chromatography coupled to Mass Spectroscopy, and the description of the devices and method is as follows: Method G: Spectra were recorded on a Waters Mass Spectrometer (ACQUITY UPLC) (SQD Single Quadrupole Mass Spectrometer , SQDII or ZQ) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/h, Mass Range: 100 to 900 Da) and a Waters Acquity UPLC: Binary pump, housing heated column and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, Temp: 60 °C, DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + MeOH 5% + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 10-100% B in 1.2 min; Flow (mL/min) 0.85 Method H: Spectra were recorded on a Waters Mass Spectrometer (ACQUITY UPLC) (SQD, SQDII or ZQ Single Quadrupole Mass Spectrometer) equipped with an electrospray source (Polarity: ions positive or negative, Capillary: 3.00 kV, Cone Range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/h, Mass Range: 100 to 900 Da) and a Waters Acquity UPLC: Binary pump, heated column compartment and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, Temp: 60 °C, DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + MeOH 5% + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 10-100% B in 2.7 min; Flow (mL/min) 0.85 Formulation Examples

[0179] The active ingredient is extensively mixed with the adjuvants and the mixture is extensively crushed in a suitable mill, yielding wettable powders that can be diluted with water to yield suspensions with the desired concentration.

[0180] The active ingredient is extensively mixed with the adjuvants and the mixture is extensively crushed in a suitable mill, resulting in powders that can be used directly for seed treatment.

[0181] Emulsions of any required dilution, which can be used in plant protection, with water. can be obtained from this concentrate by dilution with water.

[0182] Ready-to-use dusts are obtained by mixing in a suitable mill. Such powders can also be used for dry coatings for seeds.

[0183] The active ingredient is mixed and crushed with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0184] The finely crushed active ingredient is uniformly applied, in a mixer, to kaolin moistened with polyethylene glycol. Dust-free coated granules are thus obtained.

[0185] The finely crushed active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms by spraying, pouring or immersing.

[0186] The finely crushed active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, live plants as well as plant propagation material can be treated and protected against infestation by microorganisms by spraying, pouring or immersing.

Suspension of Slow Release Capsules

[0187] 28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene polyphenylisocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water until the desired particle size is obtained. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% active ingredients. The average capsule diameter is 8 to 15 microns.

[0188] The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for this purpose. Preparation Examples Preparation of enatiomerically pure compounds of formula (I) can be achieved by chiral resolution of racemic mixture, for example, using chiral chromatography, or by coupling a carboxylic acid or carboxylic acid derivative with an enantiopure chiral amine. Examples of both possible synthetic approaches are reported below Example 1: Preparation of N-(1-benzyl-1,3-dimethyl-butyl)quinoline-3-carboxamide Step 1: Preparation of 2,4-dimethyl-1-phenyl- pentan-2-ol

[0189] A solution of 4-methyl-2-pentanone (3.0 g, 29.4 mmol) in diethyl ether (25 mL) was added dropwise to benzylmagnesium chloride in tetrahydrofuran (2 M in tetrahydrofuran). hydrofuran, 22 mL, 44 mmol) at RT. The reaction mixture was then heated to 35 °C and aged for 3 h at this temperature. After cooling to RT, aqueous HCl (2 M) was added to the reaction and the mixture was partitioned between water and ethyl acetate. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography to provide the title compound as a colorless liquid.

[0190] 1H NMR (400 MHz, CDCl3) δ 7.18-7.34 (m, 5H), 2.65 2.85 (m, 2H), 1.81-1.99 (m, 1H), 1.42 (dd, 2H), 1.15 (s, 3H), 0.98 (dd, 6H). Step 2: Preparation of N-(1-benzyl-1,3-dimethyl-butyl)-2-chloroacetamide

[0191] To a solution of 2,4-dimethyl-1-phenyl-pentan-2-ol (3.6 g, 19 mmol) and chloroacetonitrile (2.4 mL, 37 mmol) in acetic acid (11 mL ) cooled to 0-5°C concentrated sulfuric acid (3.1 mL, 56 mmol) was added dropwise. The resulting slurry was heated to 20°C and stirred for 3 h at this temperature. The reaction mixture was then diluted with water and extracted with ethyl acetate. The organic layer was washed with aqueous NaHCO3, brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography to provide the title compound as a colorless solid.

[0192] 1H NMR (400 MHz, CDCl3) δ 7.20-7.34 (m, 3H), 7.087.16 (m, 2H), 6.13 (sl, 1H), 3.94 (s, 2H ), 3.21 (d, 1H), 2.90 (d, 1H), 1.86-1.95 (m, 1H), 1.73-1.86 (m, 1H), 1.54 ( dd, 1H), 1.31 (s, 3H), 0.96 (dd, 6H). Step 3: Preparation of 2,4-dimethyl-1-phenyl-pentan-2-amine

[0193] To a solution of N-(1-benzyl-1,3-dimethyl-butyl)-2-chloro-acetamide (3.0 g, 11.2 mmol), acetic acid (3.9 mL, 67 mmol ) and thiourea (1.02 g, 13.4 mmol) in ethanol (30 mL) was heated to 80 °C and stirred for 18 h at this temperature. The reaction mixture was then cooled to 20°C, diluted with aqueous HCl (0.5 M), filtered through a small pad of Celite. The filtrate was washed with ethyl acetate; the aqueous layer was then basified with 4 M NaOH and extracted with n-hexanes. The n-hexanes layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to provide the title compound as a light brown oil.

[0194] 1H NMR (400 MHz, CDCl3) δ 7.14-7.34 (m, 5H), 2.592.71 (m, 2H), 1.78-1.94 (m, 1H), 1.26 -1.41 (m, 2H), 1.05 (s, 3H), 1.03 (sl, 2H), 0.98 (dd, 6H). Step 4: Preparation of N-(1-benzyl-1,3-dimethyl-butyl)quinoline-3-carboxamide

[0195] To a solution of quinoline-3-carboxylic acid (0.20 g, 1.15 mmol), 2,4-dimethyl-1-phenyl-pentan-2-amine (0.22 g, 1.15 mmol ), triethylamine (0.14 g, 1.4 mmol) and 1-hydroxy-7-azabenzotriazole (0.16 g, 1.15 mmol) and dry dimethylformamide (5 mL) was added N-(3-dimethylaminopropyl)- N'-ethyl-carbodiimide HCl (0.22 g, 1.15 mmol) at RT and the resulting solution was aged for 18 h at 20 °C. Water was added and the mixture was extracted with ethyl acetate. The organic phase was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography to provide the title compound as a white solid, m.p. 121°C.

[0196] 1H NMR (400 MHz, CDCl3) δ 9.12 (d, 1H), 8.40 (d, 1H), 8.13 (d, 1H), 7.86 (d, 1H), 7, 74-7.82 (m, 1H), 7,567.64 (m, 1H), 7.16-7.30 (m, 5H), 5.73 (s, 1H), 3.46 (d, 1H) , 2.98 (d, 1H), 2.17 (dd, 1H), 1.84-1.99 (m, 1H), 1.67 (dd, 1H), 1.43 (s, 3H), 1.02 (d, 6H). Example 2: Preparation of N-(1-benzyl-1,3-dimethyl-butyl)-8-fluoro-quinoline-3-carboxamide

[0197] Example 2 was prepared in analogy to example 1 using 8-fluoro-quinoline-3-carboxylic acid instead of quinoline-3-carboxylic acid in step 4. The title compound was obtained as a white solid.

[0198] 1H NMR (400 MHz, CDCl3) δ 9.16 (s, 1H), 8.47 (d, 1H), 7.70 (d, 1H), 7.43-7.63 (m, 2H ), 7.09-7.37 (m, 5H), 5.74 (sl, 1H), 3.46 (d, 1H), 3.02 (d, 1H), 2.17 (dd, 1H) , 1.82-2.04 (m, 1H), 1.71 (dd, 1H), 1.47 (s, 3H), 1.05 (d, 6H). 19F NMR (377 MHz, CDCl3) δ -124.64 (s) Example 3: Preparation of N-(1-benzyl-1,3-dimethyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide Step 1: Preparation of 2-methyl-N-(1-methyl-2-phenyl-ethylidene)propane-2-sulfinamide

[0199] 1-Phenylpropan-2-one (8.30 g, 61.9 mmol) was dissolved in tetrahydrofuran (75 mL), titanium (IV) ethoxide (32.6 g, 92.8 mmol) and 2-Methylpropan-2-sulfinamide (7.50 g, 61.9 mmol) was added sequentially at room temperature and the resulting mixture was heated to 60 °C. After stirring for 2 h at 60 °C, the reaction was cooled to room temperature and quenched with aqueous NaHCO3. The resulting mixture was filtered and the filter cake was washed with ethyl acetate. The combined filtrates were extracted with ethyl acetate, the organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to provide the title compound as a light yellow oil (purity > 80%, about 4: 1 cis-trans isomer ratio) which was used as such for the next step.

[0200] 1H NMR (400 MHz, CDCl3, larger rotamer) δ 7.17-7.43 (m, 5H), 3.72 (d, 1H), 3.70 (d, 1H), 2.32 ( s, 3H), 1.23 (s, 9H) Step 2: Preparation of N-(1-benzyl-1,3-dimethyl-but-3-enyl)-2-methyl-propane-2-sulfinamide

[0201] A solution of crude 2-methyl-N-(1-methyl-2-phenyl-ethylidene)propane-2-sulfinamide (80% purity, 7.4 g, 24.9 mmol) in dichloromethane (100 mL) was slowly added to a solution of commercially available 2-methylallylmagnesium chloride in THF (0.5 M, 75 mL, 37.4 mmol) maintained at -50 °C. The reaction mixture was gradually heated to 20 °C over 4 h and stirred overnight at 20 °C. Saturated NH4Cl solution was then added, the mixture was extracted with ethyl acetate and the organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to provide the title compound as a mixture of diastereoisomers.

[0202] 1H NMR (400 MHz, CDCl3, larger rotamer) δ 6.94-7.18 (m, 5H), 4.82 (s, 1H), 4.71 (s, 1H), 3.39 ( s, 1H), 2.76 (d, 1H), 2.55 (d, 1H), 2.21 (d, 2H), 1.63 (s, 3H), 1.06 (s, 3H), 0.94 (s, 9H). Step 3: Preparation of N-(1-benzyl-1,3-dimethyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide

[0203] To an ice-cold solution of N-(1-benzyl-1,3-dimethyl-but-3-enyl)-2-methyl-propane-2-sulfinamide (5.2 g, 15.9 mmol) in methanol (16 mL) HCl in 1,4-dioxane (4 M, 6 mL, 24 mmol) was added and the resulting solution was stirred for 2 h at 0 - 5 °C. All volatiles were then removed in vacuum to give a brown gummy residue which was triturated with a diethyl ether/heptane mixture. The resulting light brown solid was dried under vacuum and used as such in the next step.

[0204] A part of the solid hydrochloride salt obtained above (2 g, 8.0 mmol) was suspended in dichloromethane (40 ml) and 8-fluoroquinoline-3-carboxylic acid (1.68 g, 8.8 mmol), triethylamine (2.8 mL, 19.9 mmol), 1-hydroxy-7-azabenzotriazole (1.2 g, 8.8 mmol) and N-(3-dimethylaminopropyl)-N'-ethyl-carbodiimide-HCl (1. 72 g, 8.8 mmol) was added sequentially at room temperature. The resulting mixture was aged for 2 h at 20 °C. Water was then added and the mixture was extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to provide the title compound as a white solid, m.p. 115-117°C

[0205] 1H NMR (400 MHz, CDCl3) δ 9.11-9.26 (m, 1H), 8.50 (s, 1H), 7.72 (d, 1H), 7.45-7.64 (m, 2H), 7.19-7.37 (m, 5H), 5.96 (s, 1H), 5.01 (s, 1H), 4.84 (s, 1H), 3.57 ( d, 1H), 3.08 (dd, 2H), 2.46 (d, 1H), 1.89 (s, 3H), 1.47 (s, 3H). 19F NMR (377 MHz, CDCl3) δ -124.64 (s). Example 4: N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamide Step 1: preparation of 2-benzyl-4,4,4 ethyl-trifluoro-2-methyl-butanoate

[0206] n-Butyl lithium (2.5 M in hexanes, 100 mL, 248.9 mmol) was slowly added to a solution of diisopropylamine (35.2 mL, 248.9 mmol) in tetrahydrofuran ( 400 mL) at -70 °C. The resulting solution was aged for 30 min at -70 °C and then ethyl 4,4,4-trifluorobutyrate (36 g, 207.4 mmol) was added dropwise. The reaction was stirred for 2 h at -70 °C, benzyl bromide (43.2 g, 248.9 mmol) was added and the reaction mixture was gradually warmed to room temperature over ca. 2 h. Saturated NH4Cl solution was added and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed with water, brine, dried over MgSO4, filtered and concentrated in vacuo. The residual oil was passed through a small pad of silica gel, the pad was rinsed with cyclohexane:ethyl acetate (2:1) and the filtrate was concentrated in vacuo, yielding 4,4,4-trifluoro-2- ethyl methyl butanoate as light orange oil.

[0207] n-Butyl lithium (2.5 M in hexanes, 99 mL, 247.2 mmol) was slowly added to a solution of diisopropylamine (35 mL, 247.2 mmol) in tetrahydrofuran (380 mL ) at -70 °C. The resulting solution was aged for 30 min at -70 °C and then the crude product obtained above (49.5 g, 190.2 mmol, diluted with tetrahydrofuran (30 mL)) was added slowly at -70 °C . The resulting dark solution was stirred for 2 h at -70 °C before methyl iodide (13.1 mL, 209.3 mmol) was added. The reaction mixture was gradually heated to 20°C over ca. 3 h, then quenched with saturated NH4Cl solution and extracted with methyl tert-butyl ether. The organic layer was washed with water, brine, dried over MgSO4, filtered and concentrated in vacuo. The residual oil was passed through a small pad of silica gel, the pad was rinsed with cyclohexane:ethyl acetate (2:1) and the filtrate was concentrated in vacuo, yielding the title compound as a light brown oil. (ca. 80% pure).

[0208] 1H NMR (400 MHz, CDCl3) δ 7.05-7.33 (m, 5H), 4.13 (q, 2H), 2.98 (d, 1H), 2.81-2.72 (m, 2H), 2.11-2.32 (m, 1H), 1.28 (s, 3H), 1.21 (t, 3H). Step 2: preparation of 2-benzyl-4,4,4-trifluoro-2-methyl-butanamide

[0209] A solution of ethyl 2-benzyl-4,4,4-trifluoro-2-methyl-butanoate (25.5 g, 93.0 mmol) in 1,4-dioxane (45 mL)/ethanol (45 mL) was treated with NaOH (7.6 g, 186 mmol) at room temperature, the resulting solution was heated to 90 °C and aged for 1 h at 90 °C. After cooling to room temperature, the reaction mixture was concentrated to approximately 50% of the original volume. The residue was diluted with water and washed with cyclohexane. The water layer was then acidified with HCl (concentrated) under ice cooling to temp < 25 °C and the mixture was extracted with DCM. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to provide 2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid as a dark yellow oil.

[0210] To a solution of crude 2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid (6.7 g, 27.2 mmol) and dimethylformamide (0.1 mL, 1.4 mmol ) in dichloromethane (25 mL) was slowly added oxalyl chloride (2.5 mL, 28.6 mmol) at 20 °C. The resulting solution was stirred for 1 h at 20 °C and then all volatiles were removed under vacuum. The residue was dissolved in dichloromethane (25 mL) and the resulting solution was slowly added to ice-cold, rapidly stirred aqueous ammonia solution (25 wt%, 21 mL). The resulting mixture was gradually warmed to room temperature and stirred for 30 min. Water was then added and the mixture was extracted with dichloromethane. The organic layer was washed with water, brine, dried over Na2SO4, filtered and concentrated in vacuo to provide the title compound as a light brown oil.

[0211] 1H NMR (400 MHz, CDCl3) δ 7.13-7.44 (m, 5H), 5.42 (sl, 2H), 3.13 (d, 1H), 2.97-3.09 (m, 1H), 2.67 (d, 1H), 2.18 (qd, 1H), 1.33 (s, 3H). Step 3: Preparation of 4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine

[0212] To a solution of 2-benzyl-4,4,4-trifluoro-2-methyl-butanamide (6.6 g, 26.9 mmol) in acetonitrile (25 mL) / water (25 mL) was added diacetoxyiodobenzene (9.73 g, 29.6 mmol) and trifluoroacetic acid (4.6 mL, 59.2 mmol) at room temperature and the resulting mixture was stirred for 18 h at room temperature. The acetonitrile was then removed under vacuum, the remaining aqueous emulsion was adjusted to pH 1 with concentrated HCl and washed with methyl tert-butyl ether. The aqueous layer was basified to pH 12 with NaOH (8 M) and extracted with methyl tert-butyl ether. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to provide the title product as a yellow oil.

[0213] 1H NMR (400 MHz, CDCl3) δ 7.16-7.50 (m, 5H), 2.81 (s, 2H), 2.13-2.41 (m, 2H), 1.28 (s, 3H). Step 4: Preparation of N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamide

[0214] To a solution of 7,8-difluoroquinoline-3-carboxylic acid (0.35 g, 1.67 mmol), 4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine (0.40 g, 0.84 mmol), triethylamine (0.6 mL, 4.2 mmol) and 1-hydroxy-7-azabenzotriazole (0.27 g, 2.0 mmol) in dichloromethane (10 mL) was N-(3-dimethylaminopropyl)-N'-ethyl-carbodiimide-HCl (0.39 g, 2.0 mmol) was added at room temperature. The resulting mixture was stirred for 15 h at room temperature and then quenched with water. The mixture was extracted with dichloromethane, the organic layer was washed with water, brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel to provide the title compound as a white solid, m.p. 158-160°C.

[0215] 1H NMR (400 MHz, CDCl3) δ 9.07 (d, 1H), 8.38 (t, 1H), 7.62 (ddd, 1H), 7.47 (dt, 1H), 7, 11-7.38 (m, 5H), 6.14 (s, 1H), 3.62 (d, 1H), 3.46 (dd, 1H), 2.96 (d, 1H), 2.58 (qd, 1H), 1.50 (s, 3H).

[0216] 19F NMR (377 MHz, CDCl3) δ -59.75 (s), -132.03 (d), -150.23 (d). Example 5: Preparation of N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-8-fluoro-quinoline-3-carboxamide

[0217] Example 5 was prepared in analogy to example 4 using 8-fluoro-quinoline-3-carboxylic acid instead of 7,8-difluoroquinoline-3-carboxylic acid in step 4. The title compound was obtained in the form of a white solid.

[0218] 1H NMR (400 MHz, CDCl3) δ 9.14 (d, 1H), 8.44 (t, 1H), 7.69 (d, 1H), 7.57 (dt, 1H), 7, 45-7.53 (m, 1H), 7.16-7.35 (m, 5H), 5.88 (s, 1H), 3.65 (d, 1H), 3.46 (qd, 1H) , 2.97 (d, 1H), 2.61 (qd, 1H), 1.52 (s, 3H). 19F NMR (377 MHz, CDCl3) δ -59.73 (s), -124.46 (s). Example 6: Preparation of (S)-4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine

[0219] To a solution of 4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine (5.0 g, 23 mmol) in propionitrile (230 mL) was added acid L-(- )-malic (1.62 g, 11.5 mmol) and the resulting mixture was heated to 90 °C. The white paste that formed was stirred for 2 h at 90°C, cooled to room temperature and the solid was collected by suction filtration. The filtrate cake was washed with propionitrile and dried in vacuo until a white powder. (In cases where enantiomeric purity was not satisfactory after the first pass, the solid was triturated with propionitrile at 90 °C)

[0220] The white powder obtained above was suspended in tert-butyl methyl ether and stirred with aq. NaOH (1 M) until all solids dissolve. The layers were separated and the organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give the title compound (enantiomeric ratio > 98:2) as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.16-7.50 (m, 5H), 2.81 (s, 2H), 2.13-2.41 (m, 2H), 1.28 (s, 3H). [α]20D : - 2.9° (CHCl3, c= 1.47)

[0221] The enantiomeric ratio was measured according to the following method: SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® IF 3 μm, 0.3 cm x 10 cm, 40 ° C Mobile phase: A: CO2 B: MeOH gradient: 3% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 220 nm Sample concentration: 1 mg/mL in ACN/iPr 50 /50 Injection: 1 μL Peak 1: 0.99 min (R amine) Peak 2: 1.36 min (S amine) Example 7: Preparation of N-[(1S)-1-benzyl-3,3,3- trifluoro-1-methyl-propyl)-8-fluoro-quinoline-3-carboxamide

[0222] To a suspension of 8-fluoroquinoline-3-carboxylic acid (3 g, 14.9 mmol) in dichloromethane (37 mL), N,N-dimethylformamide (0.1 mL) was added followed by oxalyl chloride ( 1.4 mL, 15.5 mmol) over a period of 30 minutes at room temperature. A vigorous release of gases was observed. The white suspension was stirred for 4 h until the gas release completely came to an end. The pale yellow suspension was verified by LCMS of a small sample (quenched with EtNH2) still showing traces of acid (M+H+= 192) and amide (M+H+= 219). Crude NMR analysis of acid chloride was performed: 1H NMR (400 MHz, CDCl3) δ ppm 9.50 - 9.63 (m, 1 H), 9.06 - 9.20 (m, 1 H), 7.87 - 7.98 (m, 1 H), 7.75 (s, 1 H), 7.64 - 7.83 (m, 2 H).

[0223] A pale yellow solution of (2S)-4,4,4-trifluoro-2-methyl-1-phenyl-butan-2-amine (3 g, 14 mmol) in dichloromethane (7 mL) and triethylamine (5 mL) was added in parallel dropwise, over a period of 20 min, to the acid chloride suspension. Then, the pale brown suspension was stirred overnight at room temperature.

[0224] The reaction mixture was diluted with additional dichloromethane and washed with saturated aqueous NaHCO3, water and brine. The organic layer was dried with Na2SO4, filtered and concentrated in vacuo to give 5.3 g of a yellow resin. The residue was purified by flash chromatography on silica gel to provide the title compound as an off-white solid.

[0225] 1H NMR (400 MHz, CDCl3) δ 9.14 (d, 1H), 8.44 (t, 1H), 7.69 (d, 1H), 7.57 (dt, 1H), 7, 45-7.53 (m, 1H), 7.16-7.35 (m, 5H), 5.88 (s, 1H), 3.65 (d, 1H), 3.46 (qd, 1H) , 2.97 (d, 1H), 2.61 (qd, 1H), 1.52 (s, 3H).

[0226] 19F NMR (377 MHz, CDCl3) δ -59.73 (s), -124.46 (s). The enantiomeric ratio was measured according to the following method: SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® ID 3 μm, 0.3 cm x 10 cm, 40 °C Mobile phase : A: CO2 B: iPr gradient: 15% B in 2.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 234 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection : 1 μL Peak 1 (tr: 1.46 min): N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide Peak 2 (tr: 1.83 min): N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide Example 8: Preparation of (R)-2,4-dimethyl-1-phenyl-pentan-2-amine

[0227] To a solution of 2,4-dimethyl-1-phenyl-pentan-2-amine (1.0 g, 5.2 mmol) in acetonitrile (25 mL) was added acid (S)-2-acetamido- 4-methyl-pentanoic acid (0.45 g, 4.6 mmol) and the resulting mixture was heated to reflux. The white paste that formed was stirred for 2 h at reflux, cooled to room temperature and the solid was collected by suction filtration. The filtrate cake was washed with acetonitrile and dried in vacuo. The white powder obtained above was suspended in methyl tert-butyl ether and stirred with aq. NaOH (1 M) until all solids dissolve. The layers were separated and the organic layer was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give the title compound (enantiomeric ratio > 94:6) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.14-7.34 (m, 5H), 2.59-2.71 (m, 2H), 1.78-1.94 (m, 1H), 1, 26-1.41 (m, 2H), 1.05 (s, 3H), 1.03 (sl, 2H), 0.98 (dd, 6H). [α]20D : -9.769° (CHCl3, c=1.25) The enantiomeric ratio and/or enantiomeric excess was measured according to the following method: HPLC:Waters UPLC - HClass Waters DAD detector UPLC Column: Daicel CHIRALPAK ® ID, 3 μm, 0.46 cm x 10 cm Mobile phase: Hept/iPr/DEA 90/10/0.1% Flow rate: 1.0 mL/min Detection: 265 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 2 μL Peak 1: 1.92 min (S enantiomer) Peak 2: 2.98 min (R enantiomer) Example 9: Preparation of N-[(1R)-1-benzyl-1, 3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide

[0228] To a suspension of 8-fluoroquinoline-3-carboxylic acid (32 g, 167 mmol) in dichloromethane (420 mL), N,N-dimethylformamide (3 mL) was added followed by oxalyl chloride (17 mL, 201 mmol) over a period of 2 h at room temperature. A vigorous release of gases was observed. The white suspension was stirred for 2 h until the gas release completely came to an end. The volatiles were removed in vacuo and dichloromethane (350 mL) was added to the white residue obtained after evaporation to form a white suspension.

[0229] The suspension was added over a period of 30 minutes to a solution of (R)-2,4-dimethyl-1-phenyl-pentan-2-amine (26.7 g, 140 mmol) in dichloromethane (300 ml ) containing triethylamine (98 ml, 700 mmol) and 4-dimethylamino pyridine (0.86 g, 7 mmol). The orange solution was stirred at room temperature for 2 hours.

[0230] The reaction mixture was diluted with additional dichloromethane and washed with saturated aqueous NaHCO3, water and brine. The organic layer was dried with Na2SO4, filtered and concentrated in vacuo to give 52 g of crude material. The residue was purified by flash chromatography on silica gel (ethyl acetate and cyclohexane as solvents) to provide the title compound as a white solid, m.p. 139-141°C.

[0231] 1H NMR (400 MHz, CDCl3) δ 9.16 (s, 1H), 8.47 (d, 1H), 7.70 (d, 1H), 7.43-7.63 (m, 2H ), 7.09-7.37 (m, 5H), 5.74 (s l, 1H), 3.46 (d, 1H), 3.02 (d, 1H), 2.17 (dd, 1H) , 1.82-2.04 (m, 1H), 1.71 (dd, 1H), 1.47 (s, 3H), 1.05 (d, 6H). 19F NMR (377 MHz, CDCl3) δ -124.67 (s) The enantiomeric ratio was measured according to the following method: SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® IA 3 μm, 0.3 cm x 10 cm, 40 °C Mobile phase: A: CO2 B: MeOH gradient: 25% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 235 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 μL Peak 1 (tr: 0.99 min): N-[(1S)-1-benzyl-1,3-dimethyl-butyl]- 8-fluoro-quinoline-3-carboxamide Peak 2 (tr: 1.36 min): N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide Example 10: Preparation of individual isomers: N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide and N-[(1R )-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline-3-carboxamide

[0232] The racemic mixture of N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamide was subjected to chiral resolution by HPLC preparative chromatography using the conditions described below. Analytical HPLC Method SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® OZ, 3 μm, 0.3 cm x 10 cm, 40 °C Mobile phase: A: CO2 B: iPr gradient : 10% B in 2.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 233 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 μL Preparative HPLC method:

[0233] Waters Autopurification System: 2767 Sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module. Column: Daicel CHIRALPAK® IF, 5 μm, 1.0 cm x 25 cm Mobile phase: TBME/EtOH 98/02 Flow rate: 10 mL/min Detection: UV 265 nm Sample concentration: 165 mg/mL in EE/ACN Injection: 30-90 μL, 5-15 mg Results:

[0234] The compound with the elution time of 1.05 minutes is N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline- 3-carboxamide, corresponding to compound F-22.

[0235] The compound with the elution time of 1.51 minutes is N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-7,8-difluoro-quinoline- 3-carboxamide, corresponding to compound F-21. Example 11: Preparation of individual isomers: N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide N-[(1R)- 1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoroquinoline-3-carboxamide

[0236] The racemic mixture of N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-8-fluoro-quinoline-3-carboxamide was subjected to chiral resolution by HPLC preparative chromatography using the conditions described below. Analytical HPLC Method SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® ID, 3 μm, 0.3 cm x 10 cm, 40 °C Mobile phase: A: CO2 B: iPr gradient : 15% B in 2.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 235 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 μL Preparative HPLC method:

[0237] Waters Autopurification System: 2767 Sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module. Column: Daicel CHIRALPAK® IF, 5 μm, 1.0 cm x 25 cm Mobile phase: Hept/EtOH 95/05 Flow rate: 10 mL/min Detection: UV 265 nm Sample concentration: 10 mg/mL in MeOH/DCM (1/1) Injection: 500 μL Results:

[0238] The compound with the elution time of 1.49 minutes is N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3- carboxamide, corresponding to compound F-7.

[0239] The compound with the elution time of 1.88 minutes is N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3- carboxamide, corresponding to compound F-8. Example 12: Preparation of individual isomers: N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide and N-[(1S)-1-benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide

[0240] The racemic mixture of N-(1-benzyl-1,3-dimethyl-butyl)-8-fluoro-quinoline-3-carboxamide was subjected to chiral resolution by HPLC preparative chromatography using the conditions described below. Analytical HPLC Method: SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40 °C Mobile phase: A: CO2 B: MeOH gradient: 25% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 240 nm Sample concentration: 1 mg/mL in Hept/EtOH 90/10 Injection: 3 μL Preparative HPLC method :

[0241] Waters Autopurification System: 2767 Sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module. Column: Daicel CHIRALPAK® IE, 5 μm, 1.0 cm x 25 cm Mobile phase: Hept/EtOH 90/10 Flow rate: 10 mL/min Detection: UV 265 nm Sample concentration: 100 mg/mL in MeOH/DCM (1/3) (filtered) Injection: 150 μL - 250 μL

[0242] The compound with the elution time of 0.97 minutes is N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, corresponding to compound F -1.

[0243] The compound with the elution time of 1.88 minutes is N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, corresponding to compound F -two. Example 13: Preparation of individual isomers: N-[(1R)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide and N-[(1S)-1 -benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide A racemic mixture of N-(1-benzyl-3-fluoro-1,3-dimethyl-butyl)-8 -fluoro-quinoline-3-carboxamide was subjected to chiral resolution by HPLC preparative chromatography using the conditions described below. Analytical HPLC Method: SFC: Waters Acquity UPC2/QDa Waters Acquity UPC2 PDA Detector Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40 °C Mobile phase: A: CO2 B: MeOH gradient: 30% B in 1.8 min ABPR: 1800 psi Flow rate: 2.0 mL/min Detection: 230 nm Sample concentration: 1 mg/mL in ACN/iPr 50/50 Injection: 1 μLMepparative HPLC method: System Waters Self-Purification Unit: 2767 Sample Manager, 2489 UV/Visible Detector, 2545 Quaternary Gradient Module. Column: Daicel CHIRALPAK® IA, 5 μm, 1.0 cm x 25 cm Mobile Phase: Hept/EtOH 90/10 Flow Rate : 10 mL/min Detection: UV 265 nm Sample concentration: 127 mg/mL in EE Injection: 40-160 μL, 5-20 mg

[0244] The compound with the elution time of 0.88 minutes is N-[(1R)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, corresponding to the F-15 compound.

[0245] The compound with the elution time of 1.51 minutes is N-[(1S)-1-benzyl-3-fluoro-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, corresponding to the F-16 compound. Table E: Physical data of compounds of formula I Table F: Physical data of compounds of formula (I) as individual enantiomers

Biological examples Alternaria solani / tomato / leaf disc (early blight)

[0246] Leaf discs of tomato cv. Babies are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf discs are inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf discs are incubated at 23°C/21°C (day/night) and 80% RH under a 12/12 h light regime (light/dark) in a climate-controlled chamber, and the activity of a compound is assessed as percentage of disease control compared to no treatment when an appropriate level of disease damage appears on untreated control leaf discs (5 - 7 days after application).

[0247] The following compounds gave at least 80% control of Alternaria solani at 200 ppm compared to untreated control under the same conditions, which showed extensive disease development:

Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Grey rot)

[0248] Cryogenic storage fungus conidia are directly mixed into nutrient broth (Vogels broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.

[0249] The following compounds gave at least 80% control of Botryotinia fuckeliana at 200 ppm compared to untreated controls under the same conditions, which exhibit extensive disease development: X.001, X.002, X.003, X. 004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, X.017, X.018, X.019 , F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F-21, F -22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33, F-34 , F-35, F-36

Glomerella lagenarium (Colletotrichum lagenarium)/liquid culture (Anthracnose)

[0250] Cryogenic storage fungus conidia are directly mixed into nutrient broth (potato broth and PBD dextrose). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is measured photometrically 3-4 days after application.

[0251] The following compounds gave at least 80% control of Glomerella lagenarium at 200 ppm when compared to untreated controls under the same conditions, which showed extensive development of the disease: .004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, , X.017, X.018, X.019, -9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F-21 , F-22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33, F -34, F-35, F-36

Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) / wheat / preventive on leaf discs (Powdery mildew on wheat)

[0252] Leaf segments of wheat cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs are inoculated by shaking powdery mildew-infected plants over the test plates 1 day after application. The inoculated leaf discs are incubated at 20 °C and 60% RH under a light regime of 24 h dark followed by 12 h light/12 h dark in a climate-controlled chamber and the activity of a compound is evaluated as a percentage. of disease control compared to no treatment when an appropriate level of disease damage appears on untreated control leaf segments (6 - 8 days after application).

[0253] The following compounds gave control of at least 80% of Blumeria graminis f. sp. tritici at 200 ppm compared to untreated control leaf discs under the same conditions, which showed extensive disease development: X.0010

Fusarium culmorum / liquid culture (Fusarium)

[0254] Cryogenic storage fungus conidia are directly mixed into nutrient broth (potato broth and PBD dextrose). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.

[0255] The following compounds resulted in at least 80% control of Fusarium culmorum at 200 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: X.001, X.002, X.003, X. 004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, X.017, X.018, X.019, 9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F-21, F-22, F-23, F-24, F-25, F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-33, F- 34, F-35, F-36

Fusarium culmorum/wheat/preventative in spikelets (Fusarium)

[0256] Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a suspension of fungal spores 1 day after application. The inoculated spikelets are incubated at 20 °C and 60% RH under a light regime of 72 h semi-darkness followed by 12 h light/12 h dark in a climate-controlled chamber and the activity of a compound is evaluated as percentage of disease control compared to no treatment when an appropriate level of disease damage appears in untreated control spikelets (6 - 8 days after application).

[0257] The following compounds resulted in at least 80% control of Fusarium culmorum at 200 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: X.001, X.002, X.004, X. 005, X.006, X.007, X.008, X.009, X.010, X.011, X.012, F- 1, F-2, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F- 13, F- 15, F-16, F-17, F-18, F-19, F-20, F-21, F — 23, F-24, F-25, F-27, F-28, F-29, F-30, F-32, F-33, F-34, F-35

Gaeumannomyces graminis/liquid culture (foot disease)

[0258] Mycelial fragments of the cryogenic storage fungus were directly mixed in nutrient broth (potato broth and PDB dextrose). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 4-5 days after application.

[0259] The following compounds resulted in at least 80% control of Gaeumannomyces graminis at 20 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: X.002, X.003, X.006, X. 008, X009, X011, X017, X018, X019, F-1, F-2, F-3, F-4, F-6, F-9, F-10

Gibberella zeae (Fusarium graminearum)/wheat/preventative in spikelets (Fusarium)

[0260] Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the spikelets are inoculated with a suspension of fungus spores. Inoculated test leaf discs are incubated at 20°C and 60% RH under a light regime of 72 h semi-darkness followed by 12 h light/12 h dark in a climate-controlled chamber, the activity of a compound is assessed. as percentage of disease control compared to no treatment when an appropriate level of disease damage appears in untreated control spikelets (6 - 8 days after application).

[0261] The following compounds gave at least 80% control of Gibberella zeae at 200 ppm compared to untreated control under the same conditions, which showed extensive disease development: .005, X.006, X.007, X.008, X.009, X.010, X.012, X.014, , F-5, F-6, F-7, F-9, F-10, F-11, F-13, F-15, F-16, F-19, F-22, F-24, F -25, F-27, F-28, F-29, F-31, F-32, F-34, F-35

Phaeosphaeria nodorum (Septorda nodorum) / wheat / leaf disc preventative (glume spot):

[0262] Leaf segments of wheat cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf discs are inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf discs are incubated at 20 °C and 75% RH under a light regime of 12 h light/12 h dark in a climate-controlled chamber and the activity of a compound is evaluated as percent control of the disease compared to untreated when an appropriate level of disease damage appears on untreated control leaf segments (5 - 7 days after application).

[0263] The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm compared to untreated control under the same conditions, which showed extensive disease development: X.0010, F-2

Monographella nivalis (Microdochium nivale) / liquid culture (cereal stem rot)

[0264] Cryogenic storage fungus conidia are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 4-5 days after application.

[0265] The following compounds gave at least 80% control of Monographella nivalis at 20 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: X.001, X.002, X.004, X. 005, X.008, X.009, X.010, X.011, X.012, X.013, X.015, F-2, F-3, F-5, F-6, F-9, F-12, F-15, F-16, F-17, F-23, F-24, F-26, F- 27, F-30, F-31, F-34, F-35

Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf necrosis):

[0266] Conidia of the cryogenic storage fungus are directly mixed into nutrient broth (potato dextrose broth PDB). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 4-5 days after application.

[0267] The following compounds resulted in at least 80% control of Mycosphaerella arachidis at 20 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: X.009, X.010

Puccinia recondita f. sp. tritici / wheat / dressing on leaf discs (Brown Rust)

[0268] Leaf segments of wheat cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a suspension of fungal spores. Plates are stored in darkness at 19°C and 75% RH. The formulated test compound diluted in water is applied 1 day after inoculation. Leaf segments are incubated at 19 °C and 75% RH under a 12 h light/12 h dark light regime in a climate-controlled chamber, and the activity of a compound is assessed as the percentage of disease control in compared to no treatment when an appropriate level of disease damage appears on untreated control leaf segments (6 - 8 days after application).

[0269] The following compounds gave control of at least 80% of Puccinia recondita f. sp. tritici at 200 ppm compared to untreated control under the same conditions, which showed extensive disease development: X.010

Puccinia recondita f. sp. tritici / wheat / preventive on leaf discs (Brown Rust)

[0270] Leaf segments of wheat cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs are inoculated with a suspension of fungal spores 1 day after application. Inoculated leaf segments are incubated at 19 °C and 75% RH under a 12 h light/12 h dark light regime in a climate-controlled chamber, and the activity of a compound is assessed as the percentage of disease control. compared to no treatment when an appropriate level of disease damage appears on untreated control leaf segments (7 - 9 days after application).

[0271] The following compounds gave control of at least 80% of Puccinia recondita f. sp. tritici at 200 ppm compared to untreated control under the same conditions, which showed extensive disease development: X.010

Magnaporthe grisea (Pyricularia oryzae) / liquid culture (Rice Bruzone)

[0272] Conidia of the cryogenic storage fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.

[0273] The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: .004, X.005, X.006, X.007, X.008, X.009, X.010, X.011, , X.017, X.018, -13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F- 21, F-22, F-23, F-24, F-25 , F-26, F-27, F-28, F-29, F-30, F-31, F-32, F-34, F-35

Magnaporthe grisea (Pyricularia oryzae) / rice / preventive on leaf discs (rice bruzone)

[0274] Leaf segments of rice cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf segments are inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf segments are incubated at 22 °C and 80% RH under a light regime of 24 h dark followed by 12 h light/12 h dark in a climate-controlled chamber, and the activity of a compound is evaluated as percentage of disease control compared to no treatment when an appropriate level of disease damage appears on untreated control leaf segments (5 - 7 days after application).

[0275] The following compounds gave at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: X.015, X.020, F-2, F -21, F-22, F-23, F-31, F-32, F-35

Pyrenophora teres / barley / preventative on leaf discs (Reticular spot)

[0276] Leaf segments of barley cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf segments are inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf segments are incubated at 20 °C and 65% RH under a light regime of 12 h light/12 h dark in a climate-controlled chamber and the activity of a compound is evaluated as a percentage of disease control compared with no treatment when an appropriate level of disease damage appears on untreated control leaf segments (5 - 7 days after application).

[0277] The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm compared to untreated control under the same conditions, which showed extensive disease development: .018, F-2, F-6, F-12, F-24

Sclerotinia sclerotiorum/liquid culture (white rot)

[0278] Mycelial fragments from a freshly grown liquid culture of the fungus are directly mixed into nutrient broth (Vogels broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), nutrient broth containing the fungal material is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.

[0279] The following compounds resulted in at least 80% control of Sclerotinia sclerotiorum at 20 ppm compared to untreated controls under the same conditions, which exhibit extensive disease development: X.001, X.002, X.003, X. 006, X.007, X.009, X.011, X.012, X.013, X.016, X.017, F-17, F-19, F-21, F-24, F-25, F-28, F-29, F-32, F-34, F-35

Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria stain)

[0280] Conidia of the cryogenic storage fungus are directly mixed into nutrient broth (potato dextrose broth PDB). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 4-5 days after application.

[0281] The following compounds resulted in at least 80% control of Mycosphaerella graminicola at 20 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: 3, F-16, F-35

Additional examples of biological tests: Example B1: Pyricularia orzyae (rice bruzone):

[0282] Cryogenic storage fungus conidia were directly mixed into nutrient broth (potato broth and PDB dextrose). After placing a solution (DMSO) of the test compounds in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. Test plates were incubated at 24 C and growth inhibition was determined photometrically after 72 hrs.

[0283] The following mixture compositions (B:A) at the reported concentration (in ppm) gave disease control of at least 80% in this test:

Example B2: Botrytis cinerea (Grey mold):

[0284] Conidia of the cryogenic storage fungus were directly mixed into nutrient broth (potato broth and PDB dextrose). After placing a solution (DMSO) of the test compounds in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. Test plates were incubated at 24 C and growth inhibition was determined photometrically after 72 hrs.

[0285] The following mixture compositions (B:A) at the reported concentration (in ppm) gave disease control of at least 80% in this test:

Example B3: Glomerella lagenarium (syn. Colletotrichum lagenarium), Cucurbit anthracnose:

[0286] Cryogenic storage fungus conidia were directly mixed into nutrient broth (potato broth and PDB dextrose). After placing a solution (DMSO) of the test compounds in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. Test plates were incubated at 24 C and growth inhibition was determined photometrically after 72 hrs at 620 nm.

[0287] The following mixture compositions (B:A) at the reported concentration (in ppm) gave disease control of at least 80% in this test:

Example B4: Septoria tritici (leaf spot):

[0288] Cryogenic storage fungus conidia were directly mixed into nutrient broth (potato broth and PDB dextrose). A DMSO solution of the test compounds was placed in a microtiter plate (96-well format) and nutrient broth containing the fungal spores was added thereto. Test plates were incubated at 24 C and growth inhibition was determined photometrically after 72 hrs.

[0289] The following mixture compositions (B:A) at the reported concentration (in ppm) gave disease control of at least 80% in this test:

Example B5: Fusarium culmorum (root rot):

[0290] Cryogenic storage fungus conidia were directly mixed into nutrient broth (potato broth and PDB dextrose). A DMSO solution of the test compounds was placed in a microtiter plate (96-well format) and nutrient broth containing the fungal spores was added thereto. Test plates were incubated at 24 C and growth inhibition was determined photometrically after 48 hrs.

[0291] The following mixture compositions (B:A) at the reported concentration (in ppm) gave disease control of at least 80% in this test:

Example B6: Venturia inequalis (Apple scab):

[0292] Cryogenic storage fungus conidia were directly mixed into nutrient broth (potato broth and PDB dextrose). A DMSO solution of the test compounds was placed in a microtiter plate (96-well format) and nutrient broth containing the fungal spores was added thereto. Test plates were incubated at 24 C and growth inhibition was determined photometrically after 7 days at 620 nm.

[0293] The following mixture compositions (B:A) at the reported concentration (in ppm) gave disease control of at least 80% in this test:

Claims (13)

1. Fungicide composition characterized by the fact that it comprises a mixture of components (A) and (B), wherein component (A) is a compound of formula (I) wherein R1 is hydrogen, fluorine, chlorine or methyl; R2 is hydrogen or fluorine; R3 is -C(Cl)=CH2, isopropyl, 1-methylcyclopropyl, trifluoromethyl, -C(CH3)=CH2, 1-fluorocyclopropyl, -CF2CH3, -CF(CH3)CH3 or tert-butyl; R4 is hydrogen or fluorine; and salts, enantiomers and/or N-oxides thereof; and component (B) is a compound selected from the group consisting of: pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Pyroquilone, Tricyclazole, Chlorothalonil, Propiconazole, Aminopirifen, Penconazole, Fenpropimorph, Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis in which the weight ratio of component (A) to component (B) is 20:1 to 1:40. 2. Fungicide composition according to claim 1, characterized by the fact that component (A) is a compound selected from: N-(1-benzyl-3-chloro-1-methyl-but-3-enyl)- 8-fluoro-quinoline-3-carboxamide (compound X.001), N-(1-benzyl-1,3-dimethyl-butyl)-8-fluoro-quinoline-3-carboxamide (compound X.002), N- [1-benzyl-1-methyl-2-(1-methylcyclopropyl)ethyl]-8-fluoro-quinoline-3-carboxamide (compound X.003), N-(1-benzyl-3,3,3-trifluoro- 1-methyl-propyl)-8-methyl-quinoline-3-carboxamide (compound X.004), N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-8-chloroquinoline -3-carboxamide (compound X.005), N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-8-fluoro-quinoline-3-carboxamide (compound X.006), N -(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8-difluoro-quinoline-3-carboxamide (compound X.007), N-(1-benzyl-1,3- dimethyl-butyl)-7,8-difluoro-quinoline- 3-carboxamide (compound X.008), N-(1-benzyl-1,3-dimethyl-but-3-enyl)-8-fluoro-quinoline- 3 -carboxamide (compound X.009), N-(1-benzyl-1,3-dimethyl-but-3-enyl)-7,8-difluoro-quinoline-3-carboxamide (compound -N-[1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide (compound X.011), 8-fluoro-N-[3,3,3-trifluoro- 1-[(3-fluorophenyl)methyl]-1-methyl-propyl]quinoline-3-carboxamide (compound X.012), N-[1-benzyl-2-(1-fluorocyclopropyl)-1-methyl-ethyl] -8-fluoro-quinoline-3-carboxamide (compound X.013), N-(1-benzyl-3,3-difluoro-1-methyl-butyl)-8-fluoro-quinoline-3-carboxamide (compound X. 014), N-(1-benzyl-3-fluoro-1,3-dimethyl-butyl)-8-fluoroquinoline-3-carboxamide (compound X.015), N-(1-benzyl-1,3, 3-trimethyl-butyl)-8-fluoro-quinoline-3-carboxamide (compound X.017), N-(1-benzyl-1,3-dimethyl-butyl)-8-chloro-quinoline-3-carboxamide (compound X.018), N-(1-benzyl-1,3-dimethyl- butyl)quinoline-3-carboxamide (compound X.019), and N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)quinoline-3-carboxamide (compound X.020), or a salt, enantiomer or N-oxide thereof; and component (B) is a compound selected from the group consisting of: pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Ciprodinil, Fluazinam, Isopyrazam, Pyroquilone, Tricyclazole, Chlorothalonil, Propiconazole, Aminopirifen , Prothioconazole, Mancozeb, Penconazole, Fenpropimorph, Fenpropidine, Sulfur, and a biofungicide comprising strains of Bacillus subtilis in which the weight ratio of component (A) to component (B) is 20:1 to 1:40. 3. Fungicidal composition according to claim 1 or 2, characterized by the fact that component (A) is N-(1-benzyl-1,3-dimethyl-butyl)-8-fluoro-quinoline-3-carboxamide (compound X.002); or a salt, enantiomer or N-oxide thereof. 4. Fungicidal composition according to claim 1 or 2, characterized by the fact that component (A) is N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-8-fluoro - quinoline-3-carboxamide (compound X.006); or a salt, enantiomer or N-oxide thereof. 5. Fungicide composition according to claim 1 or 2, characterized by the fact that component (A) is N-(1-benzyl-3,3,3-trifluoro-1-methyl-propyl)-7,8 - difluoro-quinoline-3-carboxamide (compound X.007); or a salt, enantiomer or N-oxide thereof. 6. Fungicidal composition according to any one of claims 1 to 5, characterized by the fact that component (A) is present as the enantiomer (S), or a salt or N-oxide thereof. 7. Fungicidal composition according to any one of claims 1 to 6, characterized by the fact that component (A) is present as the enantiomer (R), or a salt or N-oxide thereof. 8. Fungicidal composition according to any one of claims 1 to 7, characterized by the fact that component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopyrifen, Pyroquilone, Tricyclazole, Chlorothalonil, Penconazole, Fenpropimorph, Fenpropidine, Sulfur and a biofungicide comprising strains of Bacillus subtilis. 9. Fungicidal composition according to any one of claims 1 to 8, characterized by the fact that component (B) is a compound selected from the group consisting of pidiflumetofen, benzovindiflupyr [1072957-71-1], Difenoconazole, Hexaconazole, Azoxystrobin, Fludioxonil, Cyprodinil, Fluazinam, Isopyrazam, Propiconazole, Aminopirifen, Pyroquilone, Tricyclazole and Chlorothalonil. 10. Fungicide composition according to any one of claims 1 to 9, characterized in that the composition comprises one or more additional pesticides selected from the group consisting of: a fungicide, selected from etridiazole, fluazinam, benalaxyl, benalaxyl- M (chiralaxyl), furalaxyl, metalaxyl, metalaxyl-M (mefenoxam), dodicine, N'-(2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4 -(4,5-Dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, N'-[4-[[3-[(4-chlorophenyl) methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, ethyrimole, 3'-chloro-2-methoxy-N- [(3RS)-tetrahydro-2-oxofuran-3-yl]acet-2',6'-xylidide (clozilacone), cyprodinil, mepanipyrim, pyrimethanil, dithianone, aureofungin, blasticidin-S, biphenyl, chloroneb, dichlorane, hexachlorobenzene, quintazene, technazene, (TCNB), tolclofos-methyl, aminopyrifen, metrafenone, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, fluopicolide (flupicolide), thioximide, flusulfamide, benomyl, carbendazim, carbendazim hydrochloride , chlorphenazole, fuberidazole, thiabendazole, thiophanate-methyl, bentiavalicarb, clobenthiazone, probenazole, acibenzolar, betoxazine, pyriophenone (IKF-309), acibenzolar-S-methyl, piribencarb (KIF-7767), butylamine, 3-iodine n-butylcarbamate -2-propynyl (IPBC), iodocarb (isopropanyl butylcarbamate), isopropanyl butylcarbamate (iodocarb), picarbutrazox, polycarbamate, propamocarb, tolprocarb, 3-(difluoromethyl)-N-(7-fluoro-1,1,3,3 -tetramethyl-indan-4-yl)- 1-methyl-pyrazol-4-carboxamide diclocymet, N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5- fluoro-1-methyl-pyrazol-4-carboxamide, N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1-methyl-pyrazol-4-carboxamide, carpropamide, chlorothalonil , flumorph, copper oxina, cymoxanil, fenamacril, cyazofamide, flutianil, ticiophene, clozolinate, iprodione, procymidone, vinclozolin, bupyrimate, dinoctone, dinopentone, dinobutone, dinocape, meptildinocape, diphenylamine, phosdiphene, 2,6-dimethyl-[1, 4]diti-ino[2,3-c:5,6- c']dipyrrole-1,3,5,7(2H,6H)-tetraone, azitiram, etem, ferbam, mancozeb, maneb, metam, metiram ( polished), metiram-zinc, nabame, propineb, thiram, vapam (sodium metam), zineb, ziram, dithioether, isoprothiolane, etaboxam, fosetyl, fosetyl-Al (fosetyl-al), methyl bromide, methyl iodide, isothiocyanate methyl, cyclafuramide, fenfuram, validamycin, streptomycin, (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonil), dodine, doguadine, guazatine, iminoctadine, iminoctadine triacetate, 2,4-D, 2,4 -DB, kasugamycin, dimetirimol, fenhexamide, himexazole, hydroxyisoxazole, imazalil, imazalil sulfate, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenamidone, Bordeaux mixture, calcium polysulfide, copper acetate, copper carbonate, hydroxide copper, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulfate, copper thallate, cuprous oxide, sulfur, carbaryl, phthalide (phthalide), dingjunezuo (Jun Si Qi), oxathiapiproline, fluoroimide, mandipropamide, KSF-1002, benzamorph, dimethomorph, fenpropimorph, tridemorph, dodemorph, diethofencarb, fentin acetate, fentin hydroxide, carboxine, oxycarboxine, drazoxolone, famoxadone, m-phenylphenol, p-phenylphenol, tribromophenol (TBP) , 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8- fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, ciflufenamide, ofurace, oxadixyl, flutolanil, mepronil, isofetamide, fenpiclonil, fludioxonil, pencicurone, edifenfos, iprobenfos, pyrazofos, phosphorus acids, teclophthalam, Captafol, Captan, Dittalymphos, Triforin, Fenpropidine, Piperaline, Ostol, 1-Methylcyclopropene, 4-CPA, Chlormequat, Clofencet, Dichlorprop, Dimethipine, Endothal, Ethephone, Flumetralin, Forchlorfenurone, Gibberellic Acid, Gibberellins, Himexazole, Maleic Hydrazide, Mepiquat, naphthalene acetamide, paclobutrazol, prohexadione, prohexadione-calcium, thidiazurone, tribuphos (tributyl phosphorotrithioate), trinexapace, uniconazole, a-naphthaleneacetic acid, polyoxin D (polyoxrim), BLAD, chitosan, fenoxanil, folpet, 3- (difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazol-4-carboxamide, bixaphene, fluxapyroxad, furamethpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, fenpyrazamine, diclomezine, pyrifenox, boscalid, fluopyram, diflumetrim, fenarimol, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, ferimzone, dimethaclone (dimethaclone), pyroquilone, proquinazide, ethoxyquin, quinoxyfen, 4, 4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline, 5-fluoro-3,3, 4,4-tetramethyl-1-(3-quinolyl)isoquinoline, 9-fluoro-2,2-dimethyl-5-(3-quinolyl)- 3H-1,4-benzoxazepine, tebufloquine, oxolinic acid, cinomethionate (oxythioquinox, quinoxymethionate), spiroxamine, (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetamide, (mandestrobin), azoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, enoxastrobin phenamistrobin, fluphenoxystrobin , fluoxastrobin, kresoxim-methyl, mandestrobin, metaminostrobin, metominostrobin, orisastrobin, picoxystrobin, pyraclostrobin, pyramethostrobin, pyraoxystrobin, triclopiricarb, trifloxystrobin, amisulbrom, diclofluanid, tolylfluanid, N-[6-[[(Z)-[(1-methyltetrazol- (±) -cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol (huanjunzuo), 1-(5-bromo-2-pyridyl)-2- (2,4-difluorophenyl)-1,1-difluoro-3-(1,2,4-triazol-1-yl)propan-2-ol 2-(1-tert-butyl)-1-(2-chlorophenyl )-3-(1,2,4-triazol-1-yl)-propan-2-ol (TCDP), azaconazole, bitertanol (biloxazole), bromuconazole, climbazole, cyproconazole, difenoconazole, dimetconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, mefentrifluconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triazoxide, triticonazole, 2-[[(1R ,5S)-5-[(4-fluorophenyl)methyl]-1-hydroxy-2,2-dimethyl-cyclopentyl]methyl]-4H-1,2,4-triazol-3-thione, 2-[[3- (2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H- 1,2,4-triazol-3-thione, ametoctradine (imidium), iprovalicarb, valifenalate, 2-benzyl -4-chlorophenol (Chlorophene), allyl alcohol, azafenidine, benzalkonium chloride, chloropicrin, cresol, daracid, dichlorophene (dichlorophene), diphenzoquat, dipyrithione, N-(2-p-chlorobenzoylethyl)-hexamine chloride, NNF-0721 , octilinone, oxasulfuron, propamidine and propionic acid; or an insecticide selected from abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartape, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazurone, chlorpyrifos, s -methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafentiurone, diazinone, dieldrin, diflubenzurone, dimefluthrin, dimethoate, dinotefuran, diophenolan, emamectin, endosulfan, esfenvalerate, etiprol , fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamide, flubendiamide, flucitrinate, tau-fluvalinate, flufenerime (UR-50701), flufenoxurone, phonofos, halofenozide, hexaflumurone, hydramethylnone, imidacloprid, indoxacarb, isofenphos, lufenurone, metaflumizo, na, metaldehyde, methamidophos, methidathione, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novalurone, noviflumurone (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosfamidone, pirimicarb , profenophos, profluthrin, pymetrozine, pyrafluprol, pyrethrin, pyridalyl, pyrifluquinazone, pyriprol, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramate, sulprophos, tebufenozide, teflubenzuron, tefluthrin, os, tetrachlorvinphos, thiacloprid , thiamethoxam, thiodicarb, thiosultape-sodium, tralomethrin, triazamate, trichlorphone and triflumurone; or a bactericide selected from streptomycin; or an acaricide selected from amitraz, quinomethionate, chlorobenzylate, cyenopirafen, ciexatin, dicofol, dienochlor, etoxazole, fenazaquine, fenbutatin oxide, fenpropathrin, fenpyroximate, hexithiazox, propargite, pyridabene and tebufenpyrad; or a biological agent selected from Bacillus thuringiensis, Bacillus thuringiensis delta-endotoxin, baculovirus and entomopathogenic bacteria, viruses and fungi. 11. Fungicidal composition according to any one of claims 1 to 10, characterized in that the composition additionally comprises an agriculturally acceptable carrier and, optionally, a surfactant and/or formulation adjuvants. 12. Method of controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, on useful plants or their propagating material, characterized by the fact that it comprises the application to the useful plants, their location or their propagating material of a composition fungicide as defined in any one of claims 1 to 11. 13. Method according to claim 12, characterized by the fact that components (A) and (B) of the composition are applied in a sequential manner.