DD289695A5 - SUBSTITUTED THIAZOLE AND THEIR USE AS FUNGICIDES - Google Patents

Abstract

The invention relates to a fungicidal composition and a method for controlling fungal diseases on a plant. The compositions contain as active ingredient certain substituted 5-carboxanilidothiazoles, for example * formula {fungicidal composition; Method; combating; Fungal diseases; Plant; active ingredient; substituted 5-carboxanilidothiazoles}

Description

For this 1 page formulas

Field of application of the invention The invention relates to a fungicidal composition and a method for controlling fungal diseases on a plant, Characteristic of the known state of the art

The prior art discloses various substituted carboxanilidothiazoles as fungicides. A known fungicide, 2-amino-4-methyl-5- (carboxyanilide) thiazole, is sold under the trademark "Seadvax." EP-PA 276177 relates to certain NMndany D-carboxamidolthiazole.

Object of the invention

The aim of the invention is to combine the advantage of safety in the cultivation areas and the effectiveness at low application rates as cost savings with the advantage of low environmental impact when using fungicides.

Explanation of the essence of the invention

The present invention relates to a fungicidal composition containing certain substituted 5-carboxanilide thiazole 3 as the active ingredient. It also relates to a method for controlling plant fungal diseases such. B. caused by Basidiomycetes. The carboxanilide thiazoles provided as active ingredient according to the present invention are substituted on the thiazole ring as follows (the sulfur atom is the 1-position):

a) in the 2-position on the thiazole ring a C ₁ -C ₂ -HaIOaIkYl or a lower alkyl radical, preferably C ₁ -C ₂ -alkyl and in particular a methyl radical;

b) in the 4-position of the thiazole ring, a lower alkyl radical, such as C ₁ -C ₂ alkyl or a Ct-CrHaloalkylrest, preferably halomethyl, in particular perhalomethyl, especially trifluoromethyl, provided, however, the thiazole ring has at least one halomethyl substituent in the 2-position or in 4 -Position; and

c) in the 5-position of the thiazole a Carboxanilidrest having exclusively at least one electron-withdrawing substituent on the phenyl ring, preferably two to four electron-attracting groups.

The electron withdrawing groups are preferably selected from halogen (preferably chloro, iodo or bromo), lower haloalkyl (preferably halo-C | -C _r alkyl, in particular perhalomethyl or trifluoromethyl) or lower haloalkoxy (preferably halo-Ci-Cj-alkoxy, insbesonder Perhalomethoxy or trifluoromethoxy ). Other suitable electron-attracting ring substituents for the compounds according to the invention are nitro, cyano, pentahalolohio, preferably pentafluorio, halomethylthio, haloethylthio, (C ₁ -C ₂ -alkyl- or C ₁ -C ₂ -haloalkyl) -sulfinyl or (C ₁ -C ₂₎ Alkyl or C, -C ₂ haloalkyl) sulfonyl.

Haloethyl, haloethoxy, haloethylthio, haloethylsulfinyl and haloethylsulfonyl as electron-attracting substituents have at least one halogen substituent on the 1-carbon atom, in particular two halogen substituents on the 1-carbon atom. The electron attracting substituents are preferably located in ortho or para positions, especially in ortho positions. If a para substituent is present, it also has a lipophilic character. Nitro and cyano are not optimal para substituents.

The open positions on the phenyl ring and on the N-Atrom or carboxanilide group may also be substituted by a number of other substituents other than hydrogen, if they do not unduly interfere with the fungicidal activity of the molecule. Such substituents are preferably in the meta position and include lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl and the like. Other suitable substituents are known to those skilled in the art.

The degree of substitution on the phenyl ring of the carboxanilide group varies between 1 and 5, but such unstable molecules as those with trinitro substitution or tetra- or penta-iodo substitution are outside the Schutium range of the invention. The compounds of the present invention have good fungicidal activity at low rates of application, particularly against basidiomycetes, and are generally safe in terms of host plant and animal life damage, as well as fish with which the compounds may come into contact in use. Further details of the disclosure of the present invention can be found in the following detailed description. The present invention relates to a fungicidal composition containing certain substituted 5-carboxanilidothiazoles as the active ingredient. It can be used to advantage in combating plant fungal diseases such as Basidiomycetes such as Rhizoctonia, Scleroticum and Corticium. In addition to the active ingredient, it contains usual excipients and carriers.

A preferred embodiment of the noteworthy class of 5-carboxanilide thiazoles of the present invention covers compounds of formula I (see formula sheet) and their agriculturally acceptable salts. Wherein R independently is halogen, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio, pentafluorothio, halomethylsulfinyl, 1-haloethylsulfinyl, halomethylsulfonyl or 1-haloethylsulfonyl; R ₁ and R ₂ are independently methyl, ethyl or halomethyl, with the proviso that one of Ri or R _{2 is} halomethyl; and η is 1 to 5. Preferably, R is selected from chlorine, bromine, iodine, trihalomethyl (most preferably trifluoromethyl) or trihalomethoxy (most preferably trifluoromethyl). Preferably, η is 2 to 5, more preferably 3 to 5, and most preferably η is 3 to 4. The R substituents are preferably in ortho or para positions, and preferably at both ortho positions there is an R- substituent. In a preferred linking group, R _{1 is} methyl and R; is perhalomethyl (most preferably trifluoromethyl). In another preferred linking group, R ₁ and R _{2 are} each perhalomethyl and most preferably trifluoromethyl. In another preferred group R _{1 is} difluoromethyl and R _{2 is} trifluoromethyl. The term "carboxanilide" means C ₆ H ₆ NHCO- The term "1-haloethyl" means CXcH ₃ . _c -CX _d H ₂ . << -, wherein X is halogen, c is O to 3 and d is 1 or 2. The term "1-haloethoxy" means 1-haloethyl-O-. The term "1-haloethylsulfonyl" means 1-haloethyl-SOz- , The term "lower alkyl" means C ₁ -C ₅ alkyl.

Open positions on the phenyl ring of formula I which do not have an R substituent may be substituted by other substituents which either do not unacceptably interfere with the activity. Molecules having such substituents are considered to be equivalents of the compounds claimed herein. Such substituents may include nitro, Cy <n, lower alkylthio, Ci-C ₂ alkylsulfinyl, C ^ Cralkylsulfonyl, lower alkyl, lower alkoxy, lower alkylcarbonyl or lower alkoxycarbonyl.

Those skilled in the art will be able to select other suitable substituents. Another preferred embodiment of the notable class of 5-carboxanilide thiazoles of the present invention includes compounds represented by the general formula II (see formula sheet) and agriculturally acceptable salts thereof. In formula II, X is halogen, trihalomethyl, trihalomethoxy; Y is halo, trihalomethyl, triisomethoxy, nitro, or cyano; each Z is independently halo, trihalomethyl, trihalomethoxy, nitro or cyano; and η is 0 to 3.

Preferably, X, Y and Z are independently halogen, trifluoromethyl or trifluoromethoxy, especially for a Z substituent in the para position. Preferred halogens for X, Y and Z are chlorine, bromine or iodine, and η is preferably 1 or 2.

Open positions on the phenyl ring of formula II which do not have a Z substituent may be substituted by other substituents which either enhance the activity of the molecule or unacceptably interfere with the efficacy, such as the electronegative substituents or lower alkyl, lower alkoxy, lower alkylthio described herein , Lower alkylcarbonyl or lower alkoxycarbonyl. Compounds having such substituents are contemplated as equivalents of the compounds claimed herein.

Another preferred embodiment of the noteworthy class of 5-carboxanilide thiazoles of the present invention includes compounds represented by the general formula III (see formula sheet) as well as agriculturally acceptable salts thereof. In formula III, each A is independently halogen, trifluoromethyl or trifluoromethoxy. As the halogen, chlorine, bromine or iodine is preferred.

Open positions on the phenyl ring of formula III may be substituted by other substituents which either enhance the activity of the molecule or not unacceptably interfere with the efficacy, such as the electronegative substituents or lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl or lower alkoxycarbonyl described herein. Compounds having such substituents are contemplated as equivalents of the compounds claimed herein.

Another preferred embodiment of the remarkable class of 5-carboxanilide thiazoles of the present invention

includes compounds represented by the general formula IV (formula, see formula sheet), which are agriculturally acceptable salts thereof. In formula IV, each B is independently halogen, trifluoromethyl or trifluoromethoxy. B as halogen is preferably chlorine or bromine.

The open positions on the phenyl ring of formula IV may be substituted by other substituents which are either the Enhance the efficacy of the molecule or not unacceptably interfere with the efficacy, such as those described herein

electronegative substituents or lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl or

Lower alkoxycarbonyl. Compounds having such substituents are considered to be equivalents of the compounds claimed herein

to consider.

Agriculturally acceptable salts of the present invention include alkali, alkaline earth, acid addition, Base addition and alkylation salts. The practice described describes suitable methods, the compounds of the invention according to known

chemical processes can be prepared from those compounds which are known from the prior art and / or are readily available commercially. These methods described below are more illustrative, and the

A person skilled in the art knows a number of other processes which are suitable for the preparation of the compounds according to the invention. The compounds of the present invention can be prepared by reacting an appropriately substituted one Thiazole having a 5-carbonyl chloride substituent with an appropriately substituted aniline in suitable (n) Solvent (s) at elevated temperature. Suitable solvents include 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

Speeding up the reaction rate can be used. Correspondingly substituted anilines are commercially available or can be prepared by standard chemical procedures

become. For example, halo-substituted anilines can be prepared by halogenation of anilines under standard conditions.

The thiazoles are usually prepared by reacting EthyM, 4,4-trifluoro-2-chloroacetoacetate with thioacetamide

a suitable solvent, preferably DMF, until ethyl 1-methyl-trifluoromethyl-S-thiazole carboxylate is formed, which is converted to the corresponding acid chloride by sequential hydrolysis with a base and reaction with thionyl chloride.

The 2-haloalkylthiazoles are usually prepared by the following successive reactions:

a) Reaction of an easily available amide with, for example, Lawesson's reagent to obtain the corresponding thioamide. The thioamide can be unstable, so it is generally best to store it cold and consume it within a few days.

b) reacting the thioamide with EthyM ^^ - trifluoromethyl ^ -chloroacetoacetate in a suitable solvent such as TMF or THF in the presence of a base such as sodium bicarbonate or potassium carbonate to form the ethyl 2-haloalkyl-4-trifluoromethyl-5-thiazolecarboxylate, and

c) Conversion of the above product to the acid chloride by saponification with sodium hydroxide, followed by reaction with oxalyl chloride.

embodiments

The following Examples 1 and 2 are detailed descriptions of the method of preparation of certain compounds of the invention. These preparations described in detail fall within the scope of protection and serve to explain the manufacturing processes already described above in more general terms. These examples are therefore illustrative only and in no way limit the scope of the invention.

example 1

(Formula see formula sheet)

2-methyl-4-trifluoromethyl-5- (2 ', 6'-dibromo-4'-trifluoromethoxy-carboxanilide) thiazole

a) 2l, 8g (0.1 mol) of ethyl 4,4,4-trifluoro-2-chloroacetoacetate were combined with 7.5 g (0.1 mol) of thioacetamide in 200 ml of DMF and refluxed overnight. The mixture was then mixed with water and extracted with ether. The ether extracts were washed with water and with brine, dried over magnesium sulfate, filtered through silica gel, rotary evaporated and distilled (Kugelrohr). This gave 9.0 g of a tan solid, 2-methyl-4-trifluoromethyl-5-ethoxvcarbonylthiazol.

b) 3.0 g (0.038 mol) of the ester of step a) were stirred overnight with 1.6 g (0.04 mol) of sodium hydroxide in 50 ml of water. This mixture was cooled with ice-water and 10% HCl was added dropwise until pH 1 was reached. The mixture was extracted with ether. The ether was washed with water and brine, dried over magnesium sulfate and rotary evaporated. This gave 7.5 g (93.5%) of a white solid, 2-methyl-4-trifluoromethyl-5-thiazolecarboxylic acid.

c) 7.5 g (0.0355 mol) of the product from step b) were combined and heated overnight with 30 ml of thionyl chloride. The mixture was cooled, rotary evaporated to remove excess thionyl chloride and distilled (Kugelrohr). There were obtained 5 g (61%) of a yellow oil, 2-methyl-4 · trifluoromethyl-5-chlorcarbonylthiazol melting point 50-52 ⁰ C at 0.05 Torr.

d) 8.85 g (0.05 mol) of 4-trifluoromethoxyaniline were combined with 8.4 g (0.10 mol) of sodium acetate, 90 ml of glacial acetic acid and 16 g (0.10 mol) of bromine and heated to 60 ° C for 2 hours.

The mixture was stirred at room temperature overnight. Water was added to the mixture, and the mixture was filtered. This gave 16.0 g of a bright white crystalline solid, mp 65-67 ⁰ C, 2,6-dibromo-4-trifluoromethoxyaniiin.

e) 2.07 g (0.009 mol) of the product of step c) were combined with 2.68 g (0.008 mol) of the product of step d) in 100 ml of xylenes and refluxed for 24 hours. The mixture was then extracted sequentially with 10% HCl and water, dried over magnesium sulfate and evaporated in vacuo. The resulting solid was recrystallized from ethyl acetate / cyclohexane. There was obtained 2.54 g (53%) of a white solid, melting point 172-173 ⁰ C.

Elemental analysis for C) ₃ H ₆ N] O ₂ SFeBr ₂

C H N calculated 29.57 1.15 5.30 found 29,50 1.15 5.26

Example 2

(Formula see formula sheet)

2-methyl-4-trifluoromethyl-5- (2 ', 4', 6'-tribromo-3'-nitrocarboxanilid) thiazole

a) 6.9 g (0.05 mol) of m-nitroaniline, 12.6 g (0.15 mol) of sodium acetate, 24.0 g (0.15 mol) of bromine in 120 ml of glacial acetic acid were heated at reflux for 6 hours. The mixture was then poured into water and filtered. This gave 15.1 g of a pale yellow solid, 2,4,6-tribromo-3-n-troaniline, melting point 101-103 ⁰ C.

b) 3.75 g (0.008 mol) of the product of step a) were mixed with 2.3 g (0.01 mol) of 2-methyl-4-trifluoromethyl-5-chlorocarbonylthiazole and 2.05 g (0.01 mol) of 2,6 -Di-t-butyl-4-methylpyridine combined and heated with stirring for 2 hours. The mixture was then dissolved in ethyl acetate, extracted with 10% HCl and water, dried over MgSO ₄ and rotary evaporated to remove the ethyl acetate. The solid was recrystallized from ethylacetate / hexane to give a tan solid 3.5 g (77%), melting point 244-246 ⁰ C.

Elemental analysis for C ₁₂ HeN ₃ O ₃ SF ₃ Br ₃

C H N calculated 25.38 0.89 7.70 found 25.46 0.92 7.37

Under the above procedures, further compounds of the present invention were prepared. They are listed in the following Table I (MP = melting point, Ex = example).

Ex CP i

Nune structure

2-methyl-N-

(pentafluorophyl) -4- (trifluoromethyl) -MP: 111.0-112.0 nD:

Il

NH-C

CH,

5-thiol ~ c & rbox & nrid., 2-methyl-N- (2,4,6 ·

trichlorophenyl) -4- (trifluoromethyl) -

MP: 107.0-169.0

nD: Λ-NH-C-

he ^x ci

CH

5-thiol-c & rboxamide., N- (2,4-dibromo-6-

nitrophenyl) -2-methyl-4- (trifluoromethyl) -

MP: 203.0-204.0

n D:

5-thiol-arboxamide, N- (2,4-dichloro- (J-)

nitrophenyl) -2-methyl-4- (trifluoromethyl) -

MP: 167.0-169.0

n D:

5-Thiol-carboxamide, N- (2-bromo-4-chloro-6-nitrophenyl) -2-methyl-4- (trifluoromethyl) .F ₃ C

Il

-C-N

br

MP: 180.0-181 ^ 0

nD: CH,

5-thiol-arboxunidv, 2-methyl-N-

(Pentachlorophenyl) -4 ~ (trifluoromethyl) ·

MP: 229.0-231.0

n D:

Ex CP 4

NameStruktv

5-thiaiohcarboxamide., N- [2,6-dibromo-4-chloro-3 · (trifluoromethyl) phenyl] -2-methyl-4- (trifluoromethyl) -

^f jC-

C-N

br

MP: 188.0-190.0

nD: CH,

br

Cl

5-thiol-carboxamido, 2-methyl-N- (2,4,6-

tribromoS-cyanophenyl) -4- (trifluoromethyl) ·

F ₃ C-

-C-Nl

MP: 232.0-234.0

nD: CH,

br

C-N

br

5-Thiaiokcarboxamidv :,

N- [2,6-dibromo-4- (trifluoromethyl) phinyl] -2-

methyl-4- (trifluoromethyl) ·

F ₃ C-

0 it

-C-N

br

MP: 190.0-193.0

nD: CH,

br

CF

S-thiaiole-carboxamide, N- (4,6-dibromo-2-cyano-3-fluoroph nyl) -2-methyl-4- (trifluoromethyl) .C-Nl

C-N

MP: 183.0-185.0

nD: 1

CH,

br

5-Thiajol-carboxajnid * '

N- | 2-chloro-4- (trifluoromethyl) -ft-nitrophenyl] -2-methyl-4- (trifluoromethyl) -

F, C

Il

C-N

NO,

MP: 179.0-181.0

nD: NyS CH ₃

5-thiolcarboxamide, tribromophenyl) -4- (trifluoromethyl)

MP: 208.0-210.0

nD: Ji

C-NH-r ^

Br ^N Br

CH ₃

NtmeStruktur

5-thi & zol-.c & rbox & mid.-, N- (2, ft-dichloro-4-

iodophenyl) -2-methyl-4- (tri8uoromethyl) -

F ₃ C-

Il

Cl

MP: 197.0-199.0

nD: CH

Cl

5-1hi & iolrc & rboxamid j, N- (2,4-dibromo (J)

cyanophenyl) -2-methyl-4- (trifluoromethyl) -

MP: 182.0-184.0

nD: CH

C-N

br

C-N

5-Thiaiol-carboxamide.,

N- [2-bromo-e-nitro-4- (trifluoromethyl) phenyl] -2-

methyl-4- (trifluoromethyl) -

-C-N

MP: 190.0-197.0

n D:

CH,

CF

5-thiol-cajboxamide., N- [2,4-dibromo-6- (trifluoromethyl) phenyl] J-methyl-4- (tifluoromethyl) -C-N

MP: 202.0-204.0

n D:

CH,

br

CF,

5-thiol-cuboxunid :, 2-methyl-N- (2,3,5,6 ·

tetrachlorophenyl) -4- (trifluoromcthyl) -

 C-N

MPi 232.0-234.0

nD: CH

Cl

Cl

Cl

5-ihiaiol - <& rboxamid, N- (2,6-broin <x4-

iodophenyl) -2-methyl-4- (tri6uoromethyi) ·

-C-Nl

MP: 221.0-22S ₁ O

nD: S CH ₃

br

Ex CP 4

NameStrufctur.

5-thiazole ~ carboxamide, N '- (2,4-dibromo-3,6-

dicyanophenyl) -2-meth> l-4- (trifluoromethyl) -

MP: 211.0-213.0

n D:

Il

-C-Ni

br

C-N

CH,

• Br

C-N

5-Thiaiol-) carboxamide.,

N! 2,6-dichloro-4- (trifluoromethyl) phenyl] -2-

methyl-4- (trifluoromethyl) -

F ₃ C

-C-N

Cl

MP: 162.0-165.0

dd: Kyi

CH,

CF,

5-thiolcarboxamide., N- (2-acetyl-4,6-

dibromophenyl) -2-methyl-4- (trifluoromethyl) ·

F ₃ C-

-C-N

MP: 164.0-166.0

nD: CH

Il

5-thiajolcarboxamide -

N-j2,6-dichloro-4- (trifluorometl, oxy) phenyl] -2-

methyl-4- (trifluoromethyl) -

F, C-

MP: 151.0-152.0

n D:

CH,

Cl ^'N O-CF

2-ethyl-N- (2,4,6-trichlorophenyl) -4- (trifluoromethyl) -

F j C

MP: 127.0-130.0

nD: O η

-C-Nl

CH ₂ -CH ₃

Cl

5-ihiMoKctrboxajnid :, N- (4-bromo-2,6-

dicyajiophenyl) -2-methyl-4- (trifluoromethyl) -

F, C-

Il

-C-Nl

MP: 217.0-219.0

nD: V N- / CH,

Ex CP *

name structure

5-thiaiolecarboxamide, 4- (difluoromethyl) -2-

methyl-N- (2,4, e-thbromopbenyl) · H-CF.

-C-N

br

MP: 168.0-165.0

n D:

CH,

br

5-T) iiasul'-earboxajnid.,

N- (2,6-dibromo-4- (trifluoromethoxy) phenyl | -4-

(Difluoromethyl) -? - methyl ·

MP: 160.0-162.0

n D:

0-CF,

sulfur, [S, 5-dibromo-4 - ([[2-methyl-4- (trifluoromethyl) -S-thiaiolyljcarbonyljamlnojphenyllpentafluoro-fl

br

MP: 174.0-176.0

n D:

CH,

br

5-thiazole-carboxunide, N- (2,4,6-trichlorophenyl) 2,4-bis (trifluoromethyl)

Il

-C-N

Cl

MP: 180.0-181.0

n D: CF.

Cl

5-thiajolcarboxamide ·, N- (pentachlorophenyl) -2,4-bu (trifluoromethyl) -

MP: 230.0-251.0

nD: C-NH- | * Ύ

V ^s ΛΑ

T he T ^N ci

CF, Cl

idj, N- (2,4,6-tribromophenyl) 2,4-bij (trifluoromethyl) -F ₃ C-

-C-N

MP: 204.0-205.0

n D: Br

NameStructur

5-thimol-cirboxamide, N- (pentafluorophenyl) -2,4-bis (trifluoromethyl) ·

Il

-C-N

MP: 143.0-145.0

n D: CF.

S-thiaioHcarboxamid\ N- [2,6-dibromo-4-

(trifluoromethoxy) phenyl] -2,4-bis (trifluoromethyl) -F ₃ C-

-C-Nl

MP: 167.0-168.5

n D:

CF ₃

O-CF.

idL, 2- (difluoromethyl) -N- (2 ₁ 4, -6-tribromophenyl) -4- (trifluoromethyl) -F j C

MP: 215.0-217.0

nD: ^ A

CF, -H

Br '

5-Thiajol-cafboxamid.,

N- (2, ft-dibromo-4- (trifluoromethoxy) phenyl) -2-

(difluoromethyl) -4- (trifluoromethyl) -F ₃ C-

Il

-C-f

br

MP: 196.0-198.0

nD: ¹ V ⁵ ,, Μ «,

CF ₂ -H

5-ihiaiol caiboxamide ;, 4-methyl-N- (2,4,6-

tribromophenyl) -2- (trifluoromethyl) -H ₃ C-

Il

-C-N

br

MP: 200.0-201.0

n D:

CF.

5-1niasols: urboxunid '.

N- [2,6-dibromo-4- (trifluoromethoxy) phenyl) -4-

methyl-2- (triflaoromethyl) ·

MP: 16 ^ 0-169,0

n D:

0-CF ₃

nime

structure

S-ihiazolyl cwboxamide, 2- (difluoromethyl) -4-

methyl-N- (2,4, e-tribromophenyl) ·

MP: 188.0-189.0

n D:

N- [2, e-dibromo-4- (trifluorometlioxy) phenyl] -2 * (difluoro-omethyl) -4-methyl

H, C ·

MP: 150.0-151.0

n D:

) -CF ₃

First activity test on rice leaf fire

Rhizoctonia solani was cultured on a grain of rice inoculum at room temperature in the dark in the laboratory. The inoculum was prepared by mixing a portion of rice grains, a portion of husked rice grains and a portion of water.

Before use, the mixture was autoclaved twice. Sclerotia was added to each flask and the inoculum was considered ready after Rhizoctonia solani mycelium was distributed in the medium and new sclerotia had formed (generally about four to eight weeks).

16 to 18 rice seedlings were planted in the center of a square pot (7.62 cm side) and covered with steam-sterilized soil (sandy loam, ready soil and osmocote). The pots were kept at 25 to 30 ° C at 14 hours brightness in the greenhouse. After about 11 to 15 days, the plants were in the second to third leaf stage and used for the test.

The test compounds were diluted to a 1% solution (parts by weight) in acetone. Before application, the test solutions were in concentrations of 0.5; 0.1; and 0.02 mg / ml prepared in a formulation of 40% acetone, 0.4% Tween-20 and 59.6% water.

In the second to third leaf stage, the plants were sprayed. Two milliliters of the formulation was placed on the bottom of the pot, approximately 1.5 ml / pot was applied to the leaves using a "Devilbiss 152" sprayer The sprayer was rinsed with acetone between treatments.

The rice plants were allowed to air dry at room temperature before being returned to the greenhouse. The TÖDs were placed in specially made plastic irrigation pans. There were no drainage holes in these tubs so that the water was kept in the system.

All pots were kept in the irrigation tubs that were filled with water to the top of the soil (in the pots) prior to inoculation. After two days, approximately 2 grams of the inoculum in each pot was applied to the base of the rice plant piling. The trays were then placed in a dark room at 100% relative humidity and 25 ^° C. After at least 24 hours darkness began the 1? Siündige light-dark cycle. Then the plants were left undisturbed for 4 to 7 days and then the affection was determined. This infestation control took place in the presence of rice leaf fire damage in comparison with Kontroütöpfen. An activity rate was set for each treatment (four pots).

The following rating scale was used

0 = no activity

1 = low activity

2 = mean activity

3 = high activity

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

example Concentration of the test solution -12- 289 695 activity review Table II 1 (Mg / ml) 2 0.5 / 0.1 / 0.02 3/3/2 4 0.5 / 0.1 / 0.02 3/3/2 8th 0.5 / 0.1 / 0.02 3/2/1 " 10 0.5 / 0.1 / 0.02 3/3/3 • 11 0.5 / 0.1 / 0.02 3/3/3 14 0.5 / 0.1 / 0.02 3/3/0 15 0.5 / 0.1 / 0.02 2.66V3 / 3 16 0.5 / 0.1 / 0.02 1.66V1 / 0 17 0.5 / 0.1 / 0.02 3/2/3 19 0.5 / 0.1 / 0.02 1.5v1 / 0 20 0.5 / 0.1 / 0.02 3/3/3 21 0.5 / 0.1 / 0.02 3V3V1.5 " 22 0.5 / 0.1 / 0.02 0/1/0 23 0.1 / 0.02 3.3 24 0.5 / 0.1 / 0.02 3/3/3 27 0.5 / 0.1 / 0.02 3/3/2 28 0.5 / 0.1 / 0.02 3/1/0 29 0.5 / 0.1 / 0.02 3/2/0 30 0.5 / 0.1 / 0.02 3/0/0 31 0.5 / 0.1 / 0.02 3/3/0 32 0.5 / 0.1 / 0.02 1/1/1 33 0.5 / 0.1 / 0.02 3/3/1 34 0.5 / 0.1 / 0.02 phytotoxicity 35 0.5 / 0.1 / 0.02 3/3/1 36 0.5 / 0.1 / 0.02 2/2/2 37 0.5 / 0.1 / 0.02 3/3/3 38 0.5 / 0.1 / 0.02 3/3/3 39 0.5 / 0.1 / 0.02 3/2/2 40 0.5 / 0.1 / 0.02 3/2/2 0.5 / 0.1 / 0.02 3/3/2

* Average of two or more test repeats

Another test for rice leaf fire activity Host plants were grown and R. solani cultured as previously described. The plants were in the three-leaf stage

inoculated. To inoculate the plants, the inoculum was removed from the flask in small bits or individual grains and broken a small amount (1 cm ³⁾ to the base of each of the rice plants Anhäufelung added. After Inokulierungwurden the plants into a dark growth room housed, maintained under 100% humidity, and at 25 ⁰ C. After 24 hours of darkness, the 12-hour day / night cycle began.

The test solutions were prepared in the same manner as in the first activity test. For application on leaves the plants were sprayed, when the third leaf fully developed, the fourth leaf however still

had not emerged. The surface of all pots was covered with a layer of vermiculite prior to chemical application, which was removed again immediately after application in all foliar spray tests. The compounds were under

Use of a DeVilbriss airbrush sprinkler applied. The applied volume of two ml / pot was sufficient, the

However, to cover said surface of the plants to moisture was not sufficient for dripping the material from the leaves. After spraying, the plants were placed in a drying room (very low exposure to light) and then placed in trays in the greenhouse after 3 to 4 hours. When the plants were planted on day "0", the chemicals were applied on day 14 and pathogenic inoculation was made on day 16. The affection was assessed on days 26 to 30. The numerical evaluation of the disease was made by estimating the amount on

Stem tissue (stern tissue), the symptoms occurred due to Wassertränkung, chlorosis and necrosis. This was after Comparison with the control value of the plants treated with the formulation in a percentage (% control)

transformed.

The procedure of the soil dryness protection test was identical to that of the foliar protection test, with the exception of the application

the chemicals. The chemical test pieces were prepared and applied to the soil surface with a pipette (ImIpro pot). The plants were brought to the greenhouse within 30 minutes of the treatment. The plants were watered immediately with sufficient water so that they were filled to the top of the pot and the soil was saturated in water for 2 days. The inoculation, incubation and assessment are carried out according to the same procedure and in the same

As in the case of the blade protection test. Table III summarizes the results of the tests used to determine the fungicidal activity of the present invention Connections were performed. Table III example

Type of test

Concentration of the test solution

% Combat

sheet

Ground sheet

ground

sheet

sheet

Leaf leaf leaf

Ground sheet

Ground sheet

Ground sheet

Ground sheet

ground

Leaf leaf leaf

sheet

0.1

0.05

0.02

0.01

1.00

0.20

0.1

0.05

0.02

0.01

1.00

0.20

0.1

0.02

0.05

0.02

0.01

0.1

0.02

0.1

0.02

0.5

0.1

0.02

1.00

0.20

0.04

0.5

0.1

0.05

0.02

0.01

0,002

1.00

0.20

0.04

0.02

0.01

0,002

0.04

0.02

0.01

0.02

0.05

0.1

1.00

0.20

0.5

0.1

0.02

1.00

0.20

0.04

0.1

0.02

0.02

0.01

0.5

0.1

0.05

0.02

0.01

0.1

0.02

98 100 59 · 32 * 67 37 87 97 84 64 47 8 15

29 · 17 15 58 6 15 15 94 72 27 85 10 23 100 100 98 97 * 86 71 39 65 -1 99 93 95 41 11 45 85 98 93 38 18 99 90 43 71 57 8 42 30 21

6 91 93 70 10 20 84 24

Table III (continued) Type of test concentration % Combat ground derTestlösung 58 example 1.00 20 sheet 0.20 81 0.1 38 17 sheet 0.02 71 0.02 30 .18 sheet 0.01 100 0.5 72 19 0.01 96 0.02 44 ground 0.005 18 1.00 11 0.20 -3 sheet 0.04 100 0.5 97 20 0.1 41 0.02 13 ground 0.005 36 1.00 12 0.20 13 sheet 0.04 100 0.5 97 24 0.1 59 ground 0.02 91 1.00 52 0.20 26 sheet 0.04 87 1.0 32 25 0.5 8th ground 0.1 23 2.0 12 sheet 1.0 73 0.5 66 26 0.1 40 ground 0.02 0 2.0 60 sheet 1.0 98 0.5 64 30 0.1 20 ground 0.02 75 1.00 73 0.20 27 sheet 0.04 83 0.5 87 31 0.1 63 ground 0.02 40 1.00 47 0.20 28 sheet 0.04 99 0.5 100 32 0.1 79 ground 0.02 49 1.00 20 0.20 28 sheet 0.04 99 0.5 96 34 0.1 54 ground 0.02 67 1.00 69 0.20 14 sheet 0.04 100 0.1 97 36 ground 0.02 84 1.00 71 0.20

Table III (continued) example

37

concentration % Combat Type of test the test solution 100 sheet 0.5 96 » 0.1 68 » 0.02 25 » ground 1.00 16 » 0.20 12 0.04 85 sheet 0.1 25 0.02 48 ground 1.00 -4 0.20 87 sheet 0.1 30 0.02 21 ground 1.00 21 0.20 35 sheet 0.1 21 0.02 70 ground 1.00 21 0.20

38

39

40

Concentration of the test solution: In foliar treatment mg / ml at soil saturation mg / pot * average of 2 or more tests

Activity test at Braunf lickigkeit

Creeping ostrich grass was grown in the greenhouse in 12.7 cm diameter plastic pots over a period of 6 weeks. One day before the test began, this was cut back to a height of about 25 mm. The test compounds were formulated fluidity. The formulated materials were dissolved in an appropriate amount of water to yield a test solution at concentrations of 1.0; 0.2 and 0.04 mg / ml of active ingredient.

Four pots were used for repetitions of each treatment, each containing 5 ml of the test solution.

The treatments were done on the blades of grass using a DeVilbiss sprayer. The pots were kept in a growth chamber at 28 ° C, 95% humidity and 12 hours brightness at 400uE / square meter.

The test agent Rhizoctonia solani was cultured on sterilized sorghum seed three weeks before the start of the test. Two days after the chemical treatment, the pots were inoculated by placing ten rhizoctonia-infested sorghum seeds in each pot. The inoculated pots were returned to the growth chamber and the daylight length was reduced to eight hours to promote rhizoctonia infestation on the brown rot symptoms.

Ten days after inoculation, the test pots were removed from the growth chamber and assessed for disease and phytotoxicity. Percent infection of Rhizoctonia brown spot was estimated for each pot.

The test results are listed in Table IV.

Table VI example

concentration % Combat the test solution (mg / ml) 94 1 87 0.2 59 0.04 81 1 49 0.2 0 0.04 97 1 94 0.2 78 0.04 66 1 50 0.2 0 0.04

19

Greenhouse test for activity on peanut white mold

The investigator Sclerotium rolfsii was cultured on sterilized oat seeds (grains) for 21 days. The mushroom / oat grain mixture was removed from the culture flasks, air-dried for 3 days and then stored at room temperature until use (within 30 days). The following laboratory procedures were continued on peanut plants, each growing in pots of 7.62 cm ² size over a period of 12 to 14 days. Then, 2 milliliters of solution of the test compound in acetone, water and Tween-20 were added to the bottom trunk, foliage and bottom surface of each pot. After twenty-four hours, two grams of oat grains of inoculum were added to the bottom surface of each pot. The pots were then maintained for 10 hours in a growth chamber at 25-28 ⁰ C, 100% humidity mii 12 hour light / dark periods 12.Stunden. The degree of infestation was assessed for each plant and evaluated as follows:

1. no infestation

2. mild infestation - low mycelium - no damage

3. medium infestation - mycelium and minor damage

4. moderate to severe infestation - mycelium and damage

5. severe infestation - plant collapse by infestation

Table V

For each treatment (four pots), a rating was made

Example amount of test compound (mg / pot)

activity review

1 1 / 0.2 / 0.04 2 1 / 0.2 / 0.04 3 1 / 0.2 / 0.04 4 1 / 0.2 / 0.04 8th 1 / 0.2 / 0.04 11 1 / 0.2 / 0.04 12 1 / 0.2 / 0.04 28 1 / 0.2 / 0.04 34 1 / 0.2 / 0.04 38 1 / 0.2 / 0.04 Example 10 EP-OS 276277

1.0 / 1.0 / 2.0 1.0 / 2.5 / 4.0 1.0 / 3.5 / 4.0 1.0 / 2.25 / 3.25 2.0 / 2, 25 / 4.0 1.25 / 1.0 / 1.5 2.75 / 4.5 / 4.75 1.0 / 1.75 / 4.25 1.0 / 1.0 / 2.75 1 , 5 / 1.0 / 2.25

2.8 / 2.94 / 4.66 *

* Average of 2 or more test repeats

As can be seen from the above data, the compounds of the present invention show good fungicidal activity. Certain compounds of the invention have high fungicidal activity (Examples 1,2,8,19 and 36) at low application rates, resulting in a cost reduction and a low environmental impact of pesticides. The compounds of the invention generally show good fungicidal control with little or no transient plant damage. The compounds are also safe against animals, such as fish, which may come in contact with the compounds when they are used.

The fungicidal compounds of the invention in their compositions, including concentrates which must be diluted before use, may contain at least one active ingredient and one companion in liquid or solid form. The compositions are prepared by mixing the active ingredient with an adjunct such as diluents, extenders, carriers, and conditioning agents to obtain compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions, or emulsions. The active ingredient may therefore be employed with an adjunct such as a finely divided solid, an organic-based liquid, water, a wetting agent, a dispersing agent, an emulsifying agent or a suitable combination of these substances.

Suitable wetting agents include alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty acid 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 acetylenic glycols, polyoxyethylene derivatives of alkylphenols (especially isooctyl). and nonylphenol) and folyoxyethylene derivatives of the mono-halo fatty acid esters of hexitol anhydrides (eg sorbitan).

Suitable dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonate, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylenebis naphthalene sulfonate and polyethylene oxide-polypropylene oxide copolymers. Wettable powders are water-dispersible compositions containing one or more active ingredients, as well as an inert solid extender and one or more wetting and dispersing agents. The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica, and the like. Examples of such extenders are kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powder compositions according to the invention usually contain about 0.5 to 60 parts (preferably 5 to 20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1 to 15 parts) of wetting agent, about 0.25 to 25 parts (preferably 1, 0 to 15 parts) of dispersant and 5 to about 95 parts »(preferably 5 to 50 parts) of inert solid extender. All parts mentioned are parts by weight of the total composition. If necessary, about 0.1 to 2.0 parts of the solid inert extender can be replaced by a corrosion inhibitor or antifoam, or both.

Other formulations are dust concentrates containing from 0.1 to 60 parts by weight of active ingredient on a suitable extender. In the case of application, these dusts can be diluted to concentrations in the range from 0.1 to 10 parts by weight in%.

Aqueous suspensions or emulsions can be prepared by stirring a non-aqueous solution of a water-insoluble active ingredient and an emulsifier with water until evenly distributed and then homogenizing to obtain a stable emulsion of finely divided particles. The resulting concentrated suspension is characterized by its extremely small particle size, so that when diluted and sprayed, the distribution is very uniform.

Suitable concentrations of these formulations contain about 0.1 to 60 parts by mass in%, preferably 5 to 50% active ingredient, the upper limit being determined by the solubility of the active ingredient in the solvent. Concentrates are typically solutions of the active ingredient in water-immiscible or partially water-miscible solvents along with a surfactant. Suitable solvents for the active ingredient of this invention are dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons and water immiscible ethers, esters and ketones. However, other very strong liquid concentrates may be formulated by dissolving the active ingredient in a solvent, followed by dilution to spray concentration, e.g. With kerosene.

The concentrate compositions generally contain from about 0.1 to 25 parts (preferably 5 to 60 parts) of the active ingredient, about 0.25 to 50 parts (preferably 1 to 25 parts) of surfactant, and, where necessary, about 4 to 94 parts of solvent. All parts mentioned are parts by weight, based on the total mass of emulsifiable oil. Granules are physically stable particulate compositions that contain the active ingredient coupled to or distributed throughout a matrix of an inert finely divided extender. To aid in "leaching" the active ingredient from the particulate extender, a surface active agent from said group may be present in the composition Naturtone, pyrophillites, lllite, and vermiculite are examples of a functional group of particulate mineral extenders The preferred extenders are porous Absorptive preformed particles such as preformed and sieved particulate attapulgite or hot expanded particulate vermiculite and finely divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays These extenders are sprayed or mixed with the active ingredient to form herbicidal granules.

The granulated compositions of this invention may contain from about 0.1 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and from 0 to about 5 parts by weight of surfactant per 100 parts by weight of particulate clay. Suitable types of formulations are emulsifiable concentrates, flowable wettable powders, dusts and granules. A flowable formulation (3 pounds / gallon = 0.35 kg / l) is as follows:

ingredients Masseteilein% Compound of Example 9 31.14 xanthan gum 1.25 Block copolymers of propylene oxide and ethylene oxide 2.50 Magnesium aluminum silicate 1.00 Lignosulfonate dispersant 2.00 defoamers 0.25 water 61.86 100.00

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

The compositions of the present invention may also contain other additives, for example other fungicides, fertilizers, insecticides, herbicides, other pesticides, safeners and the like, as adjuncts or in combination with any of the above-mentioned concomitants. Fungicides which may be combined with the active ingredients of the present invention include, for example

tricyclazole

pyroquilon

chlorothalonil

triadimenol

fenpropimorph

carbendazim

Triadimethon

flusilazole

metalaxyl

Other suitable fungicides are known to the person skilled in the art.

When it is desired to operate in accordance with the present invention, effective amounts of the compound of the present invention are applied to the foliage or growth shoots, or may be introduced into the soil or into the water around any foliage in any conventional form. The application of liquid and particulate solid compositions on the ground .'ann be done by conventional methods, for example by means of pressure atomizer, tree and hand sprayer, spray mist. The compositions can also be applied from aircraft as a mist or spray, as they are effective at low dosages.

The exact amount of active ingredient to be employed will depend on several factors, including plant species, the stage of development of plants and disease, the nature and condition of the soil, the amount of rainfall and the particular compounds used. In the selective application on the foliage is usually a dosage of

from about 30 to about 500 g / ha, preferably from about 60 to 250 g / ha. For soil application, a dosage of about 100 to about 100 g / ha will be required, preferably about 250 to about 500 g / ha. In some cases, lower or higher rates may be required. One skilled in the art can determine from the description, including examples, the optimum rate to be used in the particular case.

Although the invention has been described in terms of specific embodiments, the details thereof are not to be construed as limitations. It will be understood that various embodiments, changes, and modifications may be made without departing from the spirit and scope of the invention, and it is to be understood that such equivalent embodiments are within the scope thereof.

FO ^ / ^ e /. "T-ΛΤΤ

8 9 6 9

Il

«> .. sC-W

O "3

CH- ^A

CF "

CH ₁

MH

(H

ß. y8

ß Ö

CH,

Sr

^C _X ^F 3, C-WH

CH ^

or

Cfa X-WH

He 111

Example I

BecspieL ^

Claims (12)

V r. 1. Fungicidal composition, characterized in that it contains a fungicidally effective amount of the general formula I in which each R is independently halo, halomethyl, 1-haloethyl, halomeihoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio, pentafluorothio, halomethylsulfinyl, 1- Haloethylsulfinyl, halomethylsulfonyl or 1-haloethylsulfonyl; R ₁ and R _{2 are} independently methyl, ethyl or halomethyl, with the proviso that at least R ₁ or R _{2 is} halomethyl; and η is an integer of 1 to 5; or an agriculturally acceptable salt thereof, as well as suitable excipients and carriers. 2. Composition according to claim 1, characterized in that R _{1 represents} methyl. 3. Composition according to claim 2, characterized in that R _{2 represents} trihalomethyl. 4. The composition according to claim 3, characterized in that R _{2 represents} trifluoromethyl. Composition according to Claim 4, characterized in that R is chlorine, bromine, trifluoromethyl or trifluoromethoxy. 6. The composition according to claim 5, characterized in that η is three or four. 7. A method for controlling fungal diseases on a plant, characterized by applying to the plant location of an effective amount of a compound of general formula I, wherein R is independently halo, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio Pentafluorothio, halomethylsulfinyl, 1-haloethylsulfinyl, halomethylsulfonyl or 1-haloethylsulfonyl; R ₁ and R _{2 are} independently methyl, ethyl or halomethyl, with the proviso that at least R ₁ or R _{2 is} halomethyl; and η is an integer of 1 to 5 or an agriculturally acceptable salt thereof. 8. The method according to claim 7, characterized in that R _{1 represents} methyl. 9. The method according to claim 8, characterized in that R _{2 represents} trihalomethyl. 10. The method according to claim 9, characterized in that R _{2 represents} trifluoromethyl. 11. The method according to claim 10, characterized in that R represents chlorine, bromine, trifluoromethyl or trifluoromethoxy. 12. The method according to claim 11, characterized in that η is three or four.