DD298097A5 - SUBSTITUTED CARBOXANILIDTHIAZOLE AND THEIR USE AS FUNGICIDES - Google Patents

Abstract

The invention relates to certain substituted 5-carboxanilidothiazoles and their use as fungicides. {Substituted carboxanilidothiazoles; Use; fungicides}

Description

(III)

wherein each E is independently chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy. A method for controlling the growth of fungal diseases on a plant, characterized in that an effective amount of a compound selected from the compounds represented by formula IV and agronomically acceptable salts thereof is applied to the plant site,

(IV)

wherein each W is independently chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy. 33. The method according to claim 32, characterized in that W is chlorine.

Field of application of the invention

The invention relates to certain substituted 5-carboxanilidothiazoles and their use as fungicides.

Characteristic of the known state of the art

Various substituted carboxanilidothiazoles are known in the art as fungicides. A known fungicide, 2-amino-4-methyl-5- (carboxyanilide) thiazole, is sold under the tradename Seedvax. However, there is still a need in the art for fungicides which have the advantage of being safe for field crops and of being effective in reducing costs and reducing the environmental burden of pesticides at low application levels.

Explanation of the invention

The invention relates to certain substituted 5-carboxanilidothiazoles and their use in the control of fungal diseases in plants such as Basidiomycetes. Dio inventive Caboxanilidthiazole are substituted as follows on the thiazole ring (the sulfur atom is in the 1-position): in the 2-Steliung on Thiazolring a halogen substituent, preferably a chlorine, bromine or iodine substituent, preferably a chlorine substituent; in the 4-step on the thiazole ring, a Dihalogenmethyl- or Trihalogenmethyl-, preferably a Trihalogenmethylrest, most preferably a Trifluormethylrpst; in the 5-position on the thiazole a Carboxanilidsubstituent with at least three electron-withdrawing substituents on the phenyl ring. The electron attracting substituents are selected from a halo (preferably chloro, iodo or bromo), C, _ ₂ haloalkyl (preferably perhaloalkyl, preferably trifluoromethyl), C 1-4 haloalkoxyl (preferably halomethoxyl, preferably trifluoromethoxyl) ), Ci-2-alkoxyl, cyano and nitro group. Preferred electron-attracting groups are chloro, bromo, iodo, ci ₂ -perhaloalkyl and halo-methoxyl groups. When there are only three electron withdrawing substituents on the phenyl ring, the substituents are in the ortho and para positions. The para substituent, if present, preferably also has lipophilic character.

The open positions on the phenyl ring of the carboxanilide group may also be substituted by a variety of substituents other than the hydride radical that do not unacceptably affect the fungicidal activity of the molecule. Such substituents are preferably in the meta position. Suitable substituents are lower alkyl, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl and similar groups. Other types of suitable substituents will be known to those skilled in the art.

The degree of substitution on the phenyl ring of the carboxanilide group will be between three and five, but unstable molecules such as those with trinitro substitution or tetra- or penta-aloxide substitution are outside the scope of this invention. The compounds of the invention have a low fungicidal activity for example Basidiomycetes and are generally harmless to the host plant. The following is a more detailed description of the invention:

The invention relates to certain substituted 5-Carboxanilidthiazole, compositions thereof and their use in the control of pandemic diseases in plants such as Basidiomycetes, z. Rhizoctonia, Sclerotium and Corticium and other fungi such as Botrytis, Colletotrichum, Fusarium, Gaeumannomyces and Sclerotium.

A preferred embodiment of the unique class of 5-carboxanilide thiazoles of the invention are compounds represented by the formula I and agronomically acceptable salts thereof:

(I)

wherein A is dihalomethyl or trihalomethyl; Your halogen is; X is a halogen, C 1-5 haloalkyl, C ,. ₂ alkoxyl, C | _ ₂ -Halogenalkoxyl-, cyano or nitro; Y is chlorine, bromine, iodine, C ,. _{2 is} perhaloalkyl, dihalomethoxyl or trihalomethoxy; each Z is independently a halogen, C, _2 haloalkyl or Ct- ₂ haloalkoxy radical and η is an integer of 1 to 3, provided that when η is 1, Z is in the 4 position. A is preferably trihalomethyl, most preferably trifluoromethyl. D is preferably chlorine. X and Z as Ci_ ₂ -haloalkyl or Ci-rHalogenalkoxyl have at least two halogen substituents and most preferably 3 or more halogen substituents. X, Y and Z are independently of each other preferably chlorine, bromine, iodine, C |. ₂ perhaloalkyl (preferably trifluoromethyl) or trihalomethoxy (preferably trifluoromethoxy).

The term "carboxanilide" - means C ₈ H ₀ NHCO-.

The term "halogen" means fluorine, chlorine, bromine or iodine.

The term "lower alkyl" means Cn-alkyl.

Open positions on the phenyl ring of formula I which do not have a Z substituent may be substituted with other substituents which either increase the efficiency of the molecule or do not unacceptably affect it. Molecules having such substituents are considered to be equivalents of the compounds of the invention. Such substituents include the electronegative substituent clay described herein or substituents such as

a lower alkylthio, lower alkyl, lower alkoxyl, lower alkylcarbonyl or lower alkoxycarbonyl group. One skilled in the art will be able to select other types of suitable substituents.

Another preferred embodiment of the unique class of the 5-carboxanilidothiazoles according to the invention are compounds represented by the formula II and agronomically acceptable salts thereof:

wherein X is a halogen, trihalomethyl trihalomethoxyl, nitro or cyano radical; Y and Z are independently chlorine, bromine, iodine, trihalomethyl (preferably trifluoromethyl), dihalomethoxyl (preferably difluoromethoxyl) or trihalomethoxyl (preferably trifluoromethoxyl) radical.

Open positions on the phenyl ring of formula II may be substituted by other substituents which either increase the efficiency of the molecule or do not unacceptably affect it; Examples thereof are electronegative substituents described herein or substituents such as a lower alkyl, lower alkoxyl, lower alkylthio, lower alkylcarbonyl or lower alkoxycarbonyl group. Compounds having such substituents are considered to be equivalents of the compounds of the invention.

Another preferred embodiment of the unique class of the 5-carboxanilidothiazoles according to the invention are compounds represented by the formula III and agronomically acceptable salts thereof:

CNM

(Hl)

wherein each E is independently chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy.

The open positions on the phenyl ring of formula III may be replaced by other substituents that either increase the efficiency of the molecule or do not unacceptably affect it, such as electronegative substituents described herein, or a substituent such as a lower alkyl, lower alkoxyl, lower alkylthio, lower alkylcarbonyl or lower alkoxycarbonyl be substituted. Compounds having such substituents are considered to be equivalents of the compounds of the invention.

Another preferred embodiment of the unique class of the 5-carboxanilidothiazoles according to the invention are compounds represented by the formula IV and agronomically acceptable salts thereof:

(IV)

wherein each W is independently chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy. W is preferably chlorine.

Agronomically acceptable salts according to the invention are alkali metal, alkaline earth metal, acid addition, base addition and alkylation salts.

Other suitable electron-attracting ring substituents for compounds according to the invention are pentahalogensulfuryl, preferably pentafluorosulfuric, halomethylthio, haloethylthio, (C 1 -C 4 -alkyl or C 1 -C 4 -halogenoalkylsulfinyl) or (C 1 -C 2 -alkyl or C 1 -C 2 -alkyl) groups. Compounds which according to the invention have such electron-withdrawing substituents on the phenyl ring are considered as equivalents of the compounds according to the invention The procedures described below are suitable methods according to which the compounds according to the invention can be prepared by known chemical methods from compounds which are known in the art and / or These procedures described below are merely illustrative, and those skilled in the art will be aware of a variety of other procedures suitable for the preparation of the compounds of this invention.

Compounds of the invention may be prepared by reacting an appropriately substituted thiazole with a 5-carbonyl chloride substituent with an appropriately substituted aniline in suitable or suitable solvent (s) at elevated temperature. Suitable solvents are xylene, THF, toluene, chlorobenzene, collidine and 2,6-di-t-butyl-4-methylpyridine. In some cases, acid acceptors such as tertiary amines and pyridines may be used to accelerate the reaction rate. The acid acceptor may also function as a solvent. Correspondingly substituted anilines are commercially available or can be prepared by standard chemical procedures. Halogen-substituted anilines can be prepared, for example, by halogenation of appropriately substituted anilines by standard methods.

The thiazoles are conveniently prepared by the following sequential reactions: (i) reaction of ethyl 4,4,4-trifluoro-2-chloroacetate with thiourea in a suitable solvent, preferably DMF, to give ethyl 2-amino-4- trifluoromethyl-5-thiazolecarboxylate; (ii) reaction of the product of (i) with HCl and sodium nitrite (or with amyl nitride and copper (I) chloride to form 2-chloro-4-trifluoromethyl-5-thiazole-carboxylate and (iii) conversion of the product of (ii) into the corresponding acid chloride with subsequent hydrolysis with base and reaction with thionyl chloride.

embodiments

The following Examples 1 to 5 are detailed descriptions of preparation methods for certain compounds of the invention. These detailed preparations are within the scope of the preparation methods more generally described above. These examples are intended to help illustrate and not limit the scope of the invention.

example 1

2-chloro-4-trifluoromethyl-5- (pentachlorcarboxanilid) thiazole

To a solution of 5.31 g (0.02 mol) of pentachloroaniline in 50 ml of xylene was added 5.0 g (0.02 mol) of 2-chloro-4-trifluoromethyl-5-chlorocarbonylthiazole. The resulting solution was refluxed for 4 days. The mixture was cooled and petroleum ether was added to precipitate a white solid. The solid was purified by thin layer chromatography in ethyl acetate: hexane at 30:70 to give 5.14 g of a solid with a melting point

of 237-238 ° C cleaned.

Elemental analysis for CnHNaSCI ₆ OF ₃

C H N calculated: 27.59 0.21 5.85 detected: 27.68 0.37 6.01

Example 2

Cl

γΊγ-'ι

CF ₃

2-Chloro-4-trifluoromethyl-5- (2 ', 6'-dichloro-4-iodo-carboxanilide) -thiazole A solution of 2.9 g (0.01 mol) of 2', 6'-dichloro-4-iodoaniline was added 2.5g (0.01mil) of 2-chloro-4-trifluoromethyl-5-chlorocarbonylthiazole was added and the mixture was refluxed for 12 hours. The mixture was cooled to room temperature and cyclohexane was added to precipitate 3.1 g of a white crystalline product having a melting point of 20O-202 ° C (yield 62%).

Elemental analysis for C _n HaCUFaINiOS

calculated: determined:

Example 3

26,34 25,89

0.6 0.64

5.59

5.47

2-Chloro-4-trifluoromethyl-5- (2 ', 6'-dibromo-4-trifluoromethylcarboxanilide) thiazole To a solution of 3.2 g (0.01 mol) of 2', 6'-bromo-4-trifluoromethylaniline was added 2 , 5g (0.01 mol) of 2-chloro-4-trifluoromethyl-5-chlorocarbonylthiazole and 70ml of xylene, and the mixture was refluxed for 18 hours. The mixture was cooled to room temperature, evaporated to a small volume, and cyclohexane was added to precipitate 2.8 g of a white crystalline product having a melting point of 178-180 ° C (53% yield). Elemental analysis for C ₁₂ H ₃ CIBR ₂ F ₆ N ₂ OS

calculated: determined:

Example 4

27.07 28.13

0.57 0.83

5.26

5.19

2-Chloro-4-trifluoromethyl-5- (2 ', 6'-dibromo-3', 5'-di-trifluoromethyl] -carboxanilide) -thiazole 2.33g (0.005mol (2 ', 6'-dibromo-3'5 '-di [trifluoromethyl] aniline was mixed with 1.5 g (0.006 mol) of 2-chloro-4-trifluoromethyl-5-chlorocarbonylthiazole and 1.44 g (0.007 mol) of 2,6-di-tert-butyl-2-methylpyridine, and 3 heated hours at 12O ⁰ C. the mixture was cooled to room temperature, dissolved in ethyl acetate and water and transferred to a separatory funnel. sodium bicarbonate was added and the organic layer separated, dried and until the formation of crystals

evaporated. Heptane was added and the crystals were spotted to give 1.81 g of a white crystalline solid having a melting point of 226-227 ° C.

Elemental analysis

C H

calculated: 26.0 0.34

determined: 26.05 0.41

Example 5

0 Br

F ₃ C p = | C

Cl

2-Chloro-4-trifluoromethyl-5- (2 ', 6'-dibromo-4-tri (methoxycarboxanilide) thiazole To a solution of 3.35 g (0.01 mol) of 2', 6'-dibromo-4-trifluoromethoxyaniline 2.5 g (0.01 mol) of 2-chloro-4-trifluoromethyl-5-chlorocarbonylthiazole and 70 ml of toluene were added and the mixture was refluxed for 18 hours The mixture was cooled to room temperature, evaporated to a low volume and treated with cyclohexane was added, so that 4.2 g of a white crystalline product having a melting point of 138-140 ° C (yield 76%) were precipitated.

Elemental analysis for C ₁₂ H ₃ BR ₂ CIFeN ₂ O ₂ S

C H N calculated: 26.28 0.55 5.11 detected: 27.8 0.93 4.97

Using procedures similar to those set forth in detail above, further compounds of the invention have been prepared, which are set forth in Table I below.

example

Connection (name) structure

Analysis C%)

set

do not calculate

5-Thiazolecarboxamide, 2-chloro-N- / 2,4-dibromo-6- (trifluoromethyl) phenyl / -4- (trifluoromethyl) melting point: 180.0-181, O ⁰ C CF ₁

Ar ^!

br

Cl

27.07 0.57

30.01 6.66

21.41 5.26 6.02

26.75 0.75

5-thiazolecarboxamide, 2-chloro-N- (2,4,6-trichlorophenyl) -4- (trifluoromethyl) -

Melting point: 167.0 to 168.0 ⁰ C

H Cl

F N S

32.22

0.74

34.59

13.90

6.S3

7.82

32.41 0.79

5-thiazolecarboxamide, 2-chloro-N- (2,4,6-tribromophenyl) -4- (trifluoromethyl) -

Melting point: 208.0 to 209.0 ⁰ C

br

Cl

24.31 0.56

44.12 6.52

10.49 5.16 5.90

24.46 0.61

5-thiazolecarboxamide, N- (4-bromo-2,6-dichlorophenyl) -2-chloro-4- (trifluorovethyl) -

Melting point: 170.0 to 172.0 ⁰ C

C H Br Cl

F N S

29.07

0.67

17:58

23:40

12:54

6.16

7:05

28.65 0.83

example Connection (name) .Structure br r \ II CF ₃ C Analysis C%) calculated 26.73 Αγ-ΝΗ- Il -C- δγΝ H 26.48 12:59 5-thiazolecarboxamide, 2-chloro-1 - (-> ¹ , 4- JLvJv Cl Br Cl 0.61 η η dibromo-6-chlorophenyl) -4- Br ^ Ci F 32.03 14.21 1 U (tri-fluorine-thyl) - N 11:42 5:41 Br I O SsyfN S 5.61 Melting point: 188.0 to 190.0 ⁰ C Il Cl C H 6:43 29.21 0.72 5-thiazolecarboxamide, li-2-bromo-4,6- Χα ^νη br 29.07 0.67 dichlorophenyl) -2-chloro-4- Cl Cl Cl F 17:58 1 1 (trif luormüthyl) - br O I! -a S _n ^ N N S 23.40 12.54 6.16 Melting point: 169.0-171.0 ° c S ^ r NH Il - Γ I Cl C u 6.16 7.05 26.87 D fi? 5-thiazolecarboxamide, N- (4-chloro-2,6- AA br 26.48 O RI 12 dibromophenyl) -2-chloro-4- Cl Br Cl F 32.03 (Trifluoromethyl) - -T "" "nr ~~ CF. N 14:21 11.42 5.69 Melting point: 192.0 to 194.0 ⁰ C NO ₂ η S ^ N S 5.61 r ^ v -NH- c- Cl C H 6:43 28.86 0.73 5-thiazolecarboxamide, C F C Br br 28.91 0.61 K / 2-bromo-6-nitro-4- (trifluoromethyl) - Cl F 3.16 13 pheny] _v 7-2-chloro-4- (trifluoromethyl) - N 7:11 22.86 8:41 Melting point: 183.0 to 184.0 ⁰ C S 8:43 6:43

IO CO OO

example

Connection (name) structure

Analysis C%) calculated fesf- net Busy

5-thiazolecarboxamide, 2-chloro-N- ^ 2-chloro-6-nitro-4- (trifluoromethyl) phenyl / -4- (trifluoromethyl) -

Melting point: 164.0 to 165.0 ⁰ C

Cl

31.74

0.67

15.61

25.10

9.25

7:06

31.76 0.68

5-thiazolecarboxamide, N- (2-bromo-4,6-difluorophenyl) -2-chloro-4- (trifluoromethyl) -

Melting point: 158.0 to 160.0 ⁰ C

^{NH c}

ι-ι

Cl

br

Cl

31.34 0.72

18.95 8.41

22.53 6.64 7.61

31.71 0.78

5-thiazolecarboxamide, N- (2-bromo-6-chloro-4-fluorophenyl) -2-chloro-4- (trifluoromethyl) -

Melting point: 180.0 to 182.0 ⁰ C

br

CI

30.16

0.69

18:24

16:19

17:35

6:40

7:32

30.24 0.73

5-thiazolecarboxamide, 2-chloro-N- (2,6-dibromo-4-iodophenyl) 4- (trifluoromethyl) -

Melting point: 199.0 to 203.0 ⁰ C

br

Cl

22.38 0.51

27.07 6.00 9.65

21.49 4.74 5.43

24.07 0.66

example

Connection (name) Strukiur

Anafyse C%) faercchfesf net Busy

5-thiazolecarboxamide, 2-chloro-H- (2,4-dichloro-6-iodophenyl) -4- (trifluoromethyl) -

Melting point: 194.0 ⁰ C

C 26.35 26.67

H 0.60 0.77

Cl 21, 21

F 11:37

I 25.31

N 5.59 5.61

S 6.39

5-thiazolecarboxamide, 2-chloro-N- (2,6-dibromo-3-chloro-4-fluorophenyl) -4- (trifluoromethyl) -

Melting point: 181.0 to 183.0 ⁰ C

C 25.56 25.66

H 0.39 0.61

Br 30.92

Cl 13.72

F 14.70

N 5.42 5.41

S 6.20

5-thiazolecarboxamide, 2-chloro-N- (2,3,5,6-tetrachlorophenyl) -4- (trifluoromethyl) -

Melting point: 224.0 to 225.0 ⁰ C

Cl

C 29.72 29.77 H 0.45 0.48

Cl 39.88

F 12.82 N 6.30 S 7.21

5-thiazolecarboxamide, 2-chloro-W- / 2,4-dibromo-6- (2,2,2-trifluoro-thoxy) -phenyl-4-4- (trifluoromethyl) -

Or.

Melting point: 171.0-173.0 C

ι ι

Cl

br

CH j-CF,

br

C 27.76 27.63

H 0.90 0.92

Br 28.41

Cl 6.30

F 20.27

N 4.98 5.00

S 5.70

example Connection (name) structure Analysis C%) calculated 22 5-thiazolecarboxamide, 2-chloro-N- (2,4,6-tribromo-3,5-chlorophenyl) -4- (trifluoro methyl) - Melting point: 282.0 to 285.0 ⁰ C Brx_H-C- _r jC F ₃ Cl Cl C 21.58 21.5: H 0.16 0.32 Br 39.15 Cl 17.37 F 9.31 N 4.58 4.5i S 5.24 23 5-thiazolecarboxamide, N- (4-bromo-2,3,5,6-tetrachlorophenyl) -2-chloro-4- (trifluoromethyl) - Melting point: 248.0 to 250.0 ⁰ C Cl Cl I ° \ J Il] * || NH-C-ρ-η-CF ₃ AA v ^N T ^N Br CI I Cl Cl C 25.24 24.6: H 0.19 0.3ί Br 15.27 Cl 33.87 F 10.89 N 5.35 5.24 S 6.13 24 5-thiazolecarboxamide, 2-chloro-W- (2,4-dibromo-6 ~ ni trophenyl) - 4- (trifluoromethyl) - Melting point: 176.0 to 177.0 ⁰ C 8 ² 8 _Br / ^ A _r ^ f " Cl C 25.93 25.66 H 0.59 0.61 Br 31.37 Cl 6.96 F 11.19 N 8.25 8.18 S 6.29 25 5-thiazolecarboxamide, 2-chloro-N- (2,4-dichloro-6-nitrophenyl) - 4- (trifluoromethyl) - Melting point: 150.0 ⁰ C r ^ S-NH-C [ιn CF ₃ ¹ ΛΛ v ^N er ^x ci T Cl C 31 .41 31.45 H 0.72 0.74 Cl 25.29 F 13.55 N 9.99 S 7.62

M CO OO

example Connection (name) structure Ana Iy se C%) Calculated - Occupied 26 5-thiazolecarboxamide, N- (2-bromo-4-fluoro-2-nitrophenyl) -2-chloro-4- (trifluoromethyl) - Melting point: 184.0 to 185.0 ⁰ C NO, 1 U r ^ ip- NH- C- | ii ι CF ₃ Cl C 29.45 29.29 H 0.67 0.92 Br 17.81 Cl 7.90 F 16.94 N 9.37 9.27 S 7.15 27 5-thiazolecarboxamide, N- (2-bromo-4-chloro-6-nitrophenyl) -2-chloro-4 - (! Trifluoromethyl) - Melting point: 172.0 to 173.0 ⁰ C NO ₂ ^ V-Nhf- C [ι. CF ₃ Cr ^X Br T Cl C 28.41 28.39 H 0.65 0.63 Br 17. 18 Cl 15.25 F 12.26 N 9.04 9.06 S 6.89 28 5-Thiazolcerboxamid, 2-chloro-N- (4,6-dibromo-2-cyano-3-fluorophenyl) -A- (trifluoromethyl) - Melting point: 160.0 to 161.0 ⁰ C CN Tf ^FjC v ^c Z £ \. Cl C 28.40 28.4 £ H 0.40 0.44 Br 31.49 Cl 6.99 F 14.98 N 8.28 8.21 S 6.32 29 5-thiazolecarboxamide, 2-chloro-N- / 2,6-dibromo-4- (2,2,2-trifluore thoxy) phenyl / - A- (trifluoromethyl) - Melting point: 147.0 to 149.0 ⁰ C 0 Br F ₂ C j ι-C-NM-ji ^ H ^^ 8> - OCH £ C ^ Cl C 27.76 28.26 H 0.90 0.82 Br 28.41 Cl 6.30 F 20.27 N 4.98 4.8i S 5.70

example

Connection (name) structure

Analysis C%)

calculated ηcf busy

5-thiazolecarboxamide, 2-chloro-li- (2,3-4 »5-tetrachloro-6-methoxyphenyl) - Melting point: 226.0 to 227.0 ⁰ C) -CH

C 30.38 30.39

H 0.85 0.89

Cl 37.36

F 12.01

Cl

5.90 6.76

5-Thiazolecarboxamide. J 2-Chloro-1-l- (2,4,6-tribromo-3-nitrophenyl) -4- (trifluoromethyl) m.p .: 235.0-237.0 ^{0 Br}

br

SyN

CF,

Cl

C 22.45 22.46

H 0.34 0.50

Br 40.74

Cl 6.03

F 9.69

N 7.14 7.15

S 5.45

5-thiazolecarboxamide, 2-chloro-N- (2,4,6-tribromo-3-cyanophenyl) -4- (trifluoromethyl) - Melting point: 220.0 to 221.0 ⁰ C

C 25.36 25.52

H 0.35 0.62

Br 42.17

Cl 6.24

F 10.03

N 7.39 7.19

S 5.64

5-thiazolecarboxamide, N- (3-acetyl-2,4,6-tribromophenyl) -2-chloro-4- (trifluoromethyl) - Melting point: 187.0 to 189.0 ⁰ C Br

Νγ <Cl

C-NH-r ^ S

br

br

CH

C 26.67 26.74

H 0.86 0.81

Br 40.95

Cl 6.06

F 9.74

N 4.79 4.75

S 5.48

example

Connection (name)

Benzoic acid, 2,4,6-tribromo-3/7/2-chloro-4- (trifluoromethyl) -5-thiazolyl / carbonyl / amino_7-, methyl ester

Melting point: 178.0 to 179.0 ⁰ C S rukiur

C-O-CH

Analysis C%)

Calculated net occupied

C 25.96 26.04

H 0.84 0.89

Br 39.86

Cl 5.89

F 9.48

N 4.66

S 5.33

5-thiazolecarboxamide, 2-chloro-N- (2,4,6-tribromo-3,5-dimethylphenyl) -4- (trifluoromethyl) -

Melting point: 266.0 to 268.0 ⁰ C

C 27.32 27.20

H 1.23 1.26

Br 41.95

C) 6.20

F 9,97

N 4.90 4.85

S 5.61

5-thiazolecarboxamide, 2-chloro-N- (2,4,6-tribromo-3-methoxyphenyl) -4- (trifluoromethyl) -

Melting point: 218.0-220.0 ⁰ C 25.14 25.53

H 0.88

Br 41.81

Cl 6.18

F 9.94

N 4.89

S 5.59

1

4.84

5-thiazolecarboxamide, 2-chloro-N- / 2,6 · dibromo-4-chloro-3- (trifluoromethyl) -phenyl-4-4- (trifluoromethyl) -

Melting point: 195.0 to 197.0 ⁰ C Br

Cl

C 25.42 25.31

H 0.36 0.48

Br 28:19

Cl 12:51

F 20.1 1

N 4.94 4.88

P 5.66

example Connection (name) .Structure Analysis C%) calculated fßSf - ncf peietzt 38 5-thiazolecarboxamide, 2-chloro-N - (2,4-dibromo-6-cyanophenyl) - 4- (trifluoromethyl) - Melting point: 166.0 to 167.0 ⁰ C CN 1 f> - NH-C j ι CF ₃ Br VT Cl C 29.44 29.33 H 0.62 0.64 Br 32.65 Cl 7.24 F 11.64 N 8.58 8.50 S 6.55 39 2-chloro-4-trifluoromethyl-5- (2 ^1, 6-4 Wibrom ^f -difluormetho: cy- carboxanilide) thiazole Melting point: 153-155 ⁰ C. Br CF ₃ CONH \ VoCHF ₁ Ct 40 2-chloro-4-trifluoromethyl-5- (2 ^1, 4'-dibromo-6 '-difluormethoxy- carboxanilide) thiazole Melting point: 163-165 ⁰ C. OCHF ₂ Cf, CONH-y-Br / \ Br O

ro co oo

Basic test for the effectiveness be! Brown rot of the rice sheath

Rhizoctonia solani is grown in rice grain seed culture at room temperature in the dark in Lsbor. The seed culture is prepared by mixing one part rice grain, one part chopped rice grain and one part water. The mixture is autoclaved twice before being soaked. Sclerotia of the fungus was added to each flask and the seed culture is ready for use when mycelia from Rhizoctonia solani have branched through the medium and new sclerotia have formed (generally in about 4 to 8 weeks).

Rice plant seeds (16-18) are placed in the middle of a 7.62 cm ² pot and covered with steam sterilized soil (silt loam, red earth and osmocote). The pots are placed at 25-3O ⁰ C in the greenhouse with a lighting time of 14 hours. In about 11-15 days, the plants are in the second to third leaf stage and are ready for testing. ,

The test compounds are diluted to a 1% solution in acetone. Before application, the test solutions are prepared in concentrations of 0.5, 0, 1 and 0.02 mg / ml with a formulation of 40% acetone, 0.4% Tween-20 and 59.6% water.

The plants are sprayed at the second to third leaf stage. Two milliliters of the recipe are placed on the pot with the soil, about 1.5ml / pot are then sprayed with the help of a nebulizer "Devilbiss 152" in addition to the leaves.

Between treatments, the nebulizer is rinsed with acetone.

Before the rice plants are returned to the greenhouse, they can be air-dried at room temperature. The pots are placed in a specially made plastic skimmer. There are no drain holes in the bowls, so the water is retained in the system.

All pots are kept in these trays, which are filled with water to the ground line before vaccination. After two days, about 2 g of the seed culture is applied to each pot at the foot of the rice plant group. The dishes are then placed in a dark growth room with 100% relative humidity and a temperature of 25 ° C. After at least 24 hours of darkness, the lamps are switched to a 12-hour light cycle. The plants are left undisturbed for 4 to 7 days and then assessed for the control of the disease. The assessment of disease control is based on the presence and severity of brown rot damage compared to control pots. For each treatment (four pots) a rating is made.

The following rating scale is used:

0 = no effectiveness

1 = low efficiency

2 = moderate effectiveness

3 = high effectiveness

Table II summarizes the results of the tests carried out to determine the fungicidal activity of the compounds of the invention.

tables Concentration of Review of Trial solution (mg / ml) effectiveness example 0.5 / 0.1 / 0.02 3/3/2 1 0.5 / 0.1 / 0.05 3.3 "/ 2" 2 0.5 / 0.1 / 0.05 2 / 2.5V2 3 0.5 / 0.1 / 0.02 3 / 3V3 4 0.5 / 0.1 / 0.02 3/3/3 5 0.5 / 0.1 / 0.05 3/3/3 6 0.5 / 0.1 3/0 7 0.5 / 0.1 / 0.02 3 / 2,3VO CX) 0.5 / 0.1 / 0.05 3 / 0,5VO 9 0.5 / 0.1 / 0.05 3 / 1.5v1 10 0.5 / 0.1 3.1 11 0.5 / 0.1 3/0 12 0.5 13 0.1 / 0.02 1/0 "· 14 0.5 / 0.1 2/0 15 0.5 / 0.1 3/0 16 0.5 / 0.1 / 0.05 2/3/3 17 0.5 / 0.1 / 0.05 3 / 2.5 "/ 1 18 0.5 / 0.1 / 0.02 3/1/2 19 0.5 / 0.1 3.1 20 0.5 / 0.1 3/0 21 0.5 / 0.1 / 0.05 3/3 "/ 2 22 0.5 / 0.1 / 0.05 3 / 3V3 23 0.5 / 0.1 / 0.05 1/2/3 24 0.1 / 0.05 3.1 25 0.5 / 0.1 2/0 26 0.1 / 0.05 2.7V2 27 0.1 / 0.02 0/2 28 0.5 / 0.1 / 0.02 3/2/0 29 0.5 / 0.1 / 0.05 3 / 2V2 30

-20- 298 097 Continued from Table II

0.5 / 0.1 Review of Concentration of 0.5 / 0.1 / 0.05 effectiveness Example of test solution (mg / ml) 0.5 / 0.1 / 0.02 2.2 31 0.5 / 0.1 / 0.02 3 / 2,5V2 32 0.5 / 0.1 3/2/3 33 0.5 / 0.1 3/3/1 34 0.5 / 0.1 / 0.05 2/0 35 0.5 2/0 36 0.5 / 0.1 / 0.02 3/3/3 37 0.5 / 0.1 / 0.02 1 38 Average of 2 or more retakes. 3/3/2 39 Plant injury. 3/3/1 40

Further developed to study the efficacy of brown rot of the rice leaf scab The host seeds are inserted and R. solani is bred as described above. The plants are vaccinated at the three-leaf stage. To inoculate the plants, the inoculum is removed from the flasks, broken into small bits or individual grains and a small amount (1 cm ³⁾ is added to each group of rice plants on the foot. After seeding, the plants are placed in a dark growth room set to fog and 25 ^° C. After 24 hours. In darkness, the lamps are reset to a 12-hour day-night cycle. The test solutions are prepared in the same way as in the basic test. At leaf application the plants are sprayed when the third leaf has fully developed, but the fourth leaf has not yet appeared. The surface of all pots is covered with a vermiculite layer prior to chemical application, which is removed immediately after application in all foliar spray tests. The compounds were applied using a DeVilbiss airbrush sprayer. It is applied 2 ml / pot, which is sufficient to cover all plant surfaces to moisture, but so that no substance drips from the leaves. After spraying, the plants are brought into the drying room (very low light conditions) and transferred after 3-4 hours in the greenhouse. If plants have been planted on day "0", the chemical is typically applied on the 14th day, and the pathogen will then be on day 16. The disease will be assessed on the 26th to the 30th day. The disease is assessed by estimating the amount of stalk tissue covered by symptoms (water penetration, chlorosis and necrosis) and converting to% of the control compared to the control sample treated with the formulation The test solutions are prepared and applied to the surface of the earth with a pipette (1 ml / pot) and the plants are brought to the greenhouse within 30 minutes of treatment They are watered immediately with sufficient water to the edge of the pot and saturated soil for 2 days Vaccination, storage in the brood chamber and evaluation are carried out in the same way as in the foliar protection test.

Table III summarizes the results of the experiments conducted to determine the fungicidal activity of the compounds of this invention.

Table III

Example trial

1 sheet

earth

2 sheets

3 sheets

4 sheets of earth

5 sheets

6 sheets

Concentration of fight Test solution * in% 0.1 92 * 0.05 86 * 0.02 68 * 0.01 50 * 0.20 78 * 0.04 32 * 0.05 68 0.02 63 0.05 56 0.02 86 0.1 100 0.02 100 1.0 100 0.2 85 0.04 35 0.1 96 0.05 72 0.02 99 0.01 36 0.05 83 0.02 64

Continuation of Table III

Concentration of control Example Experiment Experimental solution *

89 14 25 8

63 '95 17 59 36 59 40 42 42 31 15 93 95 94 80 77 55 97 92 78 80 81

100 85

100 97 74 52 57 29 53 51 41 36

100 85 *

100 37 ⁺

100 38 58

100 83 99 89 10 99 67 40 7

96 99 85 ⁺ 93 66

* for leaf treatment mg / ml -for soil penetration mg / pot.

* Average of * white or more attempts.

7 sheet 0.1 0.05 0.02 0.01 8th sheet 0.05 0.02 0.01 9 sheet 0.05 0.02 10 sheet 0.05 0.02 11 sheet 0.05 0.02 12 sheet 0.05 0.02 13 sheet 0.05 0.02 17 sheet 0.05 0.02 18 blue 0.05 0.02 19 sheet 0.5 0.1 0.02 20 sheet 0.05 0.02 22 sheet 0.05 0.02 23 sheet 0.05 0.02 24 sheet 0.05 0.02 25 sheet 0.05 0.02 27 sheet 0.05 0.02 30 sheet 0.05 0.02 31 sheet 0.1 0.05 0.02 0.01 earth 1.0 0.2 0.04 32 sheet 0.05 0.02 33 sheet 0.5 0.1 0.02 34 Flat 0.1 0.02 earth 0.2 0.04 37 sheet 0.1 0.05 0.02 38 sheet 0.05 0.02

Test for efficacy in brown spot

Lichengrassgrass was grown in the greenhouse in PlasUöpfoiwiiit with a diameter of 12.7 cm over a period of 6 weeks. One day before the start of the experiment, the lawn turf was mowed to a height of approx. 2.54 cm. The test compounds were formulated as flowable substances. The properly prepared substances were dissolved in an appropriate amount of water so that Enclansuchslösungen with concentrations of 1.0.2 and 0.04 mg / ml of active ingredient emerged.

Four pots were used for each treatment, with each test pot containing 5ml of test solution. The solution was applied to the grass blades with a DeVilbiss sprayer. The pots were placed prc square in the growth chamber at 28 ⁰ C, 9C and 12% humidity U reasons illumination at 40OuE.

The pathogen Rhizoctonia solani intended for the experiment was cultured on sterilized seedlings three weeks before the start of the test. Two days after the chemical treatment, the pots were closed by adding ten rhizoctonia-infected sorghumsamon to each pot. The vaccinated pots were returned to the growth chamber again, and to promote infection with Rhizoctonia and development of brown spot symptoms, the duration of the day was reduced to 8 hours.

Ten days after inoculation, the experimental pots were removed from the growth chamber and evaluated for disease and phytotoxicity. Each pot was evaluated for infection with Rhizoctonia brown spot in percent.

The test results are shown in Table IV.

Table IV

Compound from concentration of control

Example of test solution (mg / ml) in%

1 1 91

1 0.2 92

1 0.04 22

Peanut white mold effectiveness test

Peanuts are grown in the field at 91.5cm row spacing using normal agronomic practices. Individual plots consisted of two adjacent rows, which were divided into 15.25m long sections with a total length of 30.5m per plot. The test compounds were prepared as fluid substances and used in amounts in which the amount of active ingredient per acre was varied. The amounts were calculated area by area, while the test solutions were applied in a 30 cm strip in the middle of the plant row. The spray rate was 2331 / hA and the test solutions were applied through uniform flat fan nozzle ports. Four parcels were used for each treatment. The trial patches each received three treatments: one in stapling, one four weeks after stapling, and one eight weeks after stapling. The experimental pathogen Sclerotium rolfsii was bred for 21 days on sterilized oat seeds. The mushroom and oat seed mixture was removed from the culture flasks, air-dried for 3 days and then stored at room temperature until use (within 30 days). Approximately Seventy days after planting, 250 ml of the fungal and oat seed inoculum were applied to each plot by finely distributing the seed mixture along the middle of both rows of plots. The artificial seed culture was used as a supplement to the natural pathogen population present at the experimental site. Trial treatments were assessed for disease and phytotoxicity by counting total disease sites in the treated rows of plots. A disease site was a dead plant or up to about 30 linear centimeters long row of dead plants. Evaluations were made 130 days after planting. The test results are shown in Table V.

Table V

Application control

Example quantity (g / A) in%

1 226.4 69

1 452.8 94

1 905.6 97

As can be seen from the above values, the compounds of the present invention have good fungicidal efficacy at low application rates and consequent cost savings and lower environmental pesticide load. The compounds according to the invention generally have a good fungus control generally without injury to the plant or in the case of short-term damage to the plant.

The fungicidal compositions of the present invention, including the concentrates which must be diluted before use, contain at least one active ingredient and one additive in liquid or solid form. The compositions are prepared by admixing the active ingredient with an additive including diluents, extenders, carriers and fillers to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. It can therefore be considered that the active ingredient could be used with an additive such as a finely divided solid, an organic liquid, a wetting agent, a dispersing agent, an emulsifier or a suitable combination of these.

Suitable wetting agents include alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylene glycols, polyoxyethylene derivatives of alkylphenols (especially isooctylphenol and nonylphenol), and polyoxyethylene derivatives of higher Monofnttsäureester of Hexitolanhydriden (eg sorbites).

Suitable dispersants are methyl, cellulose, polyvinyl alcohol, sodium lignosulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate, and polyethylene oxide-polypropylene oxide copolymers.

Spray powders are water-dispersible compositions containing one or more active agents, an inert solid extender and one or more wetting and dispersing agents. The inert solid diluents are usually of mineral origin such as natural clays, diatomaceous earth and silica derived synthetic minerals and the like. Examples of such extenders are kaolinites, att'ipulgittone and synthetic magnesium silicate. The wettable powder compositions according to the invention usually contain 0.5 to 60 parts (preferably 5-20 parts) of active ingredient, about 0.25 to 25 parts? (preferably 1-15 parts) of wetting agent , about 0.2b to 25 parts (preferably 1.0-15 parts) of dispersing agent and about 5 to 95 parts (preferably 5-50 parts) of inert solid diluent, the data being in parts by mass are made based on the total composition. If necessary, about 0.1 to 2.0 parts of the solid inert diluent may be replaced by a corrosion inhibitor or antifoam, or both.

Other formulations include dust concentrates containing 0.1 to 60% by weight of active ingredient with a suitable diluent.

These dust concentrates may be diluted to concentrations in the range of about 0.1 to 10 mass% for use.

Aqueous suspensions or emulsions may be prepared by stirring a non-aqueous solution of a water-insoluble active agent and an emulsifying agent with water until uniform and then homogenizing to form a stable emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that a very uniform hiding power is achieved during dilution and spraying.

Suitable concentrations of these formulations contain about 0.1-60, preferably 5-50 wt.% Of active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent.

Concentrates are usually solutions of an active ingredient in water-insoluble or partially water-insoluble solvents together with a surfactant. Suitable solvents for the active ingredient according to the invention are dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and water-insoluble ethers, esters or ketones. However, other highly concentrated liquid concentrates may be prepared by dissolving the active ingredient in a solvent and then diluting, e.g. As with kerosene, be prepared to spray concentration.

The concentrate compositions according to the invention generally contain about 0.1 to 95 parts (preferably 5 to 60 parts) of active ingredient, about 0.25 to 50 parts (preferably 1 to 25 parts) of surfactant and, if necessary, about 4 to 94 Parts of solvent, all parts given are parts by weight based on the total mass of the emulsifiable oil.

Grains are physically stable, particulate compositions containing an active ingredient which adheres to or is distributed throughout a matrix of an inert, finely divided particulate extender. To facilitate leaching of the active ingredient from the particulate extender, a surfactant such as one of those listed above may be included in the composition.

Natural clays, pyrophyllites, lllites and vermiculite are examples of useful classes of particulate mineral extenders.

The preferred extenders are the porous, absorptive, preformed particles such as preformed and sieved particulate attapulgite or heat stretched particulate vermiculite and the finely divided clays such as kaolin clay species, hydrogenated attapulgite or bentonite clay. These extenders are sprayed or mixed with the active ingredient so that the herbicidal grains form.

The granulated compositions of the present invention may contain between about 0.1 and about 30 parts by weight of active ingredient per 100 parts by weight of clay and between 0 and about 5 parts by weight of surfactant per 100 parts by weight particulate clay.

Suitable recipe types are emulsifiable concentrates, flowable substances, wettable powders, dusts and granules. A suitable formulation for a flowable substance is the following (0.35kg / L):

Ingredients Ma .-%

Compound of Example 1 31.14 xanthan gum 1.25 Block copolymers of propylene oxide and ethylene oxide 2.50 Magnesium aluminum silicate 1.00 Lignosulfonatdispergiermittel 2.00 Anti-foaming agents 0.25 water 61.86 100.00

The compounds of the present invention generally appear to have the greatest activity when used as a foliar spray.

The compositions of the invention may also contain other additives, e.g. As other fungicides, fertilizers, insecticides, herbicides, other pesticides, additives that prevent reactions between ingredients of drug mixtures and similar substances that may be used as additives or in combination with one of the additives described above. Other fungicides may be used in combination with the active ingredients of the invention including fungicides having activity on Rhizoctonia. The following fungicides may be suitable in combination with compounds according to the invention:

Tricyclazole propiconazole

Pyroquilon Procliloraz

Chlorothalonil Maneb / Mancozeb

Triadimenol lprodione

Fenpropimorph thiabendazole

Carbendazim, trialuazole

Triadphone Edifenphos

Flusilazole IBP

Mdtalaxyl isoprothiolane

The skilled person will be aware of other suitable fungicides.

In accordance with the present invention, effective amounts of the compounds of this invention are applied to the leaves or vegetative propagules, or may be conveniently introduced into the bubbles or water around the leaves. The liquid and particulate solid compositions may be prepared by conventional methods, e.g. B. with Pulververstäubern, field spray pipes and Handsprühgeräten and Sprühzerstäubern be applied to the ground. The compositions may also be effective at low dosages from the aircraft as dust or spray.

The exact amount of active ingredient to be used depends on various factors such as plant species, stage of development of plants and disease, nature and condition of the soil, amount of precipitation and the specific compounds used. In the selective foliar application, a dosage of about 30 to about 500 g / h j, preferably from about to about 250 g / ha is normally used. In Bodenanwendi'ng usually a dosage of about 100 to about 1000 g / ha, preferably from about 250 to about 500 g / ha applied. In some cases, smaller or larger quantities may be required. The person skilled in the art can easily determine the optimum amount to be used in a particular case by means of this specification including the above examples.

While the invention has been described with reference to the specific modifications set forth herein, the details thereof are not to be construed as limiting, for it is apparent that various embodiments, changes, and modifications may be practiced without departing from the spirit and scope of the invention it is to be understood that such equivalent embodiments are within the scope of the invention.

Claims (31)

and agronomically acceptable salts thereof, characterized in that A is dihalomethyl or trihalomethyl; D is a halogen; X is a halogen, Ci ₂ haloalkyl, C, _ ₂ alkoxyl, C ^ ₂ -Halogenalkoxyl-, cyano or nitro radical; Y is chlorine, bromine, iodine, Ci_ ₂ perhaloalkyl, dihalomethoxy or trihalomethoxy; each Z is independently a halogen, C, _ ₂ haloalkyl or C ^ -Halogenalkoxylrest and η is an integer of 1 to 3, provided that when η 1, Z is in the 4-position. 2. A compound according to claim 1, characterized in that D is chlorine. 3. A compound according to claim 2, characterized in that A is trihalomethyl. 4. A compound according to claim 3, characterized in that A is trifluoromethyl. 5. A compound according to claim 4, characterized in that X, Y and Z are independently chlorine, bromine, iodine, C ^ rPerhalogenalkyl- or Trihalogenmethoxylrest. 6. A compound according to claim 5, characterized in that X, Y and Z are independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. 7. A compound selected from the compounds represented by formula II, X 0 (ID Cl and agronomically acceptable salts thereof, characterized in that X is a halogen, trihalomethyl, trihalomethoxyl, nitro or cyano radical; Y and Z are independently chlorine, bromine, iodine, trihalomethyl or Trihalogenmethoxylrest. 8. A compound according to claim 7, characterized in that Y and Z are independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. 9. A compound selected from the compounds represented by formula III, (III) and agronomically acceptable salts thereof, characterized in that E is independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. 10. A compound selected from compounds represented by Formula IV, W W rc »/ N 5 VV \ V and agronomically acceptable salts thereof, characterized in that W is independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. 11. A compound according to claim 10, characterized in that W is chlorine. A fungicidal composition, characterized in that it contains a fungicidally effective amount of a compound selected from the compounds represented by formula I and agronomically acceptable salts thereof, CNH (D wherein A is dihalomethyl or trihalomethyl; D is a halogen; X is a halogen, C ^ ₂ haloalkyl, CI_ ₂ alkoxyl, Ci_2-Halogenalkoxyl-, cyano or nitro radical; Y is chlorine, bromine, iodine, C 1 -C 2 -haloalkyl, dihalomethoxy or trihalomethoxy; each Z is independently a halogen, C ₁ _ ₂ haloalkyl or C 1 haloalkoxy radical and η is an integer from 1 to 3, provided that when η 1 Z is in the 4 position. 13. The composition according to claim 12, characterized in that D is chlorine. 14. A composition according to claim 13, characterized in that A is trihalomethyl. 15. A composition according to claim 14, characterized in that ATrifluoromethyl is. 16. The composition according to claim 15, characterized in that X, Y and Z are independently chlorine, bromine, iodine, Ct_ ₂ perhalhalalkyl or Trihalogenmethoxylrest. 17. A composition according to claim 16, characterized in that X, Y and Z are independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. A fungicidal composition, characterized in that it contains a fungicidally effective amount of a compound selected from the compounds represented by formula II and agronomically acceptable salts thereof, wherein X is a halogen, trihalomethyl, Trihalogenmethoxyl-, nitro or cyano radical; Y and Z are independently chlorine, bromine, iodine, trihalomethyl or Trihalogenmethoxylrest. 19. The composition according to claim 18, characterized in that Y and Z are independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. A fungicidal composition, characterized in that it contains a fungicidally effective amount of a compound selected from the compounds represented by formula III and agronomically acceptable salts thereof, E.E. £ t wherein each E is independently chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy. A fungicidal composition, characterized in that it contains a fungicidally effective amount of a compound selected from the compounds represented by formula IV and agronomically acceptable salts thereof, W W 0 M- > W (IV) wherein each W is independently chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy. 22. The composition according to claim 21, characterized in that W is chlorine. A method of controlling the growth of fungal diseases on a plant, characterized by applying to the plant site an effective amount of a compound selected from the compounds represented by formula I and agronomically acceptable salts thereof; (D wherein A is dihalomethyl or trihalomethyl; D is a halogen; X is a halogen, C ^ ₂ haloalkyl, C, _ ₂ alkoxyl, C ^ -Halogenalkoxyl-, cyano or nitro radical; Y is chlorine, bromine, iodine, C 1-4 perhaloalkyl, dihalomethoxyl or trihalomethoxy; each Z is independently a halogen, CI_ ₂ haloalkyl or C ^ -Halogenalkoxylrest and η is an integer of 1 to 3, provided that when η 1, Z is in the 4-position. 24. The method according to claim 23, characterized in that D is chlorine. 25. The method according to claim 24, characterized in that ATrihalogenmethyl. 26. The method according to claim 25, characterized in that A is trifluoromethyl. 27. The method according to claim 26, characterized in that X, Y and Z are each independently chlorine, bromine, iodine, C ₁ _ ₂ -Perhalogenalkyl- or Trihalogenmethoxylrest. 28. The method according to claim 27, characterized in that X, Y and Z are each independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. 29. A method for controlling the growth of fungal diseases on a plant, characterized in that an effective amount of a compound selected from the compounds represented by the formula II and agronomically acceptable salts thereof is applied to the plant site, (ID wherein X is a halogen, Trihalogenmethyl-, Trihalogenmethoxyl-, nitro or cyano radical; Y and Z are independently chlorine, bromine, iodine, trihalomethyl or Trihalogenmethoxylrest. 30. The method according to claim 29, characterized in that Y and Z are independently chlorine, bromine, iodine, trifluoromethyl or Trifluormethoxylrest. A method of controlling the growth of fungal diseases on a plant, characterized by applying to the plant site an effective amount of a compound selected from the compounds represented by Formula III and agronomically acceptable salts thereof;