BG60369B2 - Substituted thiazoles and their usage as fungicides - Google Patents

Abstract

The invention relates to substituted 5-carboxylidothiothiazoles and their use against plant fungicidal diseases such as vasodomycetes. The carboxanilidothiazoles are substituted on the thiazole ring.

Description

Technical field

The present invention relates to certain substituted 5-carboxanilidothiazoles for use as fungicides.

BACKGROUND OF THE INVENTION

Various substituted carboxanilidothiazoles are known as fungicides. The known fungicide 2-amino-4-methyl-5- (carboxanilido) thiazole is marketed under the trademark Seedvan. European Patent No. 276,166 discloses certain N- (indanyl) carboxamidothiazoles, such as fungicides, including 2-methyl-4-trifluoromethyl-5- (N- [1,3 trimethylindan-4-yl] -carboxamido / thiazole. However, there is still a need for new fungicides that are safe for crops and effective at low doses of application to reduce costs and pesticide pollution.

Summary of the invention

The invention relates to certain substituted 5-carboxanilidothiazoles and their use in the control of plant fungicidal diseases, for example Basidiomyiites. The carboxanilidothiazoles according to the invention are substituted on the thiazole ring (sulfur atom comes first) as follows:

2-position of the thiazole ring - C _{f 2} haloalkyl or a lower alkyd substituent, preferably C ₂ alkyl and most preferably methyl as a substituent, (n) in the 4-position of the thiazole ring - low alkyl such as C ₂ alkyl or C, ₂ haloalkyl, preferably halomethyl, preferably perhalomethyl, and most preferably trifluoromethyl. Condition is thiazolyl ring has at least one C ₂ haloalkyl as a substituent, preferably a halomethyl;

at the 2-position or at the 4-position and (III) at the 5-position of the thiazole ring carboxanilido substituent. With at least one electron-releasing substituent on the phenyl ring, preferably two to four electron-withdrawing groups and most preferably three to four. Preferably the electron-withdrawing groups are selected from halogen (preferably chlorine, iodine or bromine), low haloalkyl (preferably halo C _1-4 alkyl, more preferably perhalomethyl or trifluoromethyl) or low haloalkoxy / preferably halo C ₁₂ alkoxy, more preferably perhalomethoxy or trifluoromethoxy. Other suitable electron-releasable ring substituents for the compounds of the invention include nitro, cyano, pentahalosor, pentafluorosil, halomethylthio, haloethylthio, (C ₁₂ alkyl or C _1-2 haloalkyl) sulfinyl or (C _1-2 alkyl or C ₁₂ haloalkyl) sulfonyl. Haloethyl, haloethoxy, haloethylthio, haloethylsulfinyl and haloethylsulfonyl electron-withdrawing substituents preferably have at least one halo substituent on the I-carbon atom and most preferably two halo substituents on the 1-carbon atom. Preferably, the electron-withdrawing substituents are located at ortho or parapositions, and most preferably at orthos. Preferably, the para-substituent, if any, is also lipophilic. Nitro and permissible cyano substituents are not optimal as para substituents.

The open positions of the phenyl ring and the N atoms of the carboxanilide group may also be substituted by a variety of substituents other than hydrogen, which do not undesirably interfere with the fengicidal action of the molecule. Such substituents are preferably (preferably) in the meta position and include lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl and the like.

The degree of substitution of the phenyl ring of the carboxanilide group ranges from 1 to 5, with unstable molecules such as those with trinitro substitution or pentioid substitution being outside the scope of the present invention. The compounds of the invention have good fungicidal action at low levels of application, especially on Basidiomyietes, and are generally safe for the environment, including the plant to which they are applied, and the animal world, such as fish, with which the compound may come into contact during use. Description

The invention relates to certain substituted 5-carboxanilidothiazoles and their use in the control of plant fungicidal diseases, for example Basidionyietes, such as Rhizootonia, Sclertium, Corticium.

A preferred embodiment of the unique class of 5- carboxanilidothiazoles according to the invention includes compounds of formula I and their agronomically acceptable salts

Oh

R, I in which each R is independently halogen, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio, pentafluorocarb, halomethylsulfinyl, 1-haloethylsulfinyl, halomethylsulfonyl or 1-haloethylethyl; R 1 and R ₂ are independently methyl, ethyl or halomethyl, provided that at least one of R or R 1 is halomethyl and η is from 1 to 5. Preferably R is selected from chlorine, bromine iodine, trihalomethyl, / most preferably trifluoromethyl (or trihalomethoxy) (preferably trifluoromethoxy). Preferably, η is 2 to 5, more preferably η is 3 to 5, and most preferably η is 3-4. The R-substituents are preferably of ortho and / or para-positions, and preferably the two ortho-positions have an R-substituent. In one preferred class of compounds R 1 is methyl and R 1 is perhalomethyl and most preferably trifluoromethyl. In another preferred class of compounds R1 and R1 are perhalomethyl and most preferably trifluoromethyl. In another preferred class R 1 is difluoromethyl and R ₂ is trifluoromethyl.

The terms in the description have the following meanings: the term "carboxanilido" means C 1 H 2 NHCO-; the term "1-haloethyl" means CX _with H ₃ - _with -CHCH _{2 d} -, where X is halogen, c is 0-3 and d is 1 or 2; "1-haloethoxy" means 1-haloethyl-O-; "1-haloethylsulfonyl" means 1-haloethyl-BO ₂ -; "Lower alkyl" means C _1-3 alkyl.

The open positions of the phenyl ring of formula I which do not have an R substituent may be substituted by other substituents that either increase the activity of the molecule or undesirably affect its activity. Molecules with such substituents are considered as equivalents of the compounds claimed in the invention and which may include nitro, cyano, alkylthio, C ₍₂ alkylsulfinyl, lower alkyl, lower alkoxy, lower alkylcarbonyl or lower alkoxycarbonyl.

Those skilled in the art will also be able to select other types of suitable substituents.

Another preferred embodiment of the unique class of 5-carboxyanilidothiazoles according to the present invention includes compounds of formula II and their agronomically acceptable salts:

CH ₃ n in which X is halo, trihalomethyl or trihalomethoxy, Y is halo, trihalomethyl, trihalomethoxy, nitro or cyano, each Z is independently halogen, trihalomethyl, trihalomethoxy, nitro or cyano and η has a value of 0 to 3.

Preferably, X, Υ and Ζ are independently halogen, trifluoromethyl or trifluoromethoxy, especially for the para-substituent. Preferred halogens for X, W and Ζ are chlorine, bromine, iodine and η is preferably 2.

The open positions of the phenyl ring of formula II which do not have a substituent thereof may be substituted by other suitable substituents that either enhance the activity of the molecule or do not unduly affect it, such as electronegative substituents as indicated or substituents such as lower alkyl, lower alkoxy , lower alkylthio, lower alkylcarbonyl, or lower alkoxycarbonyl. Compounds with similar substituents are regarded as equivalents of the compounds of the invention.

Another preferred embodiment of the unique class of 5-carboxyanilidothiazoles according to the invention include compounds of formula III and their agronomically acceptable salts:

wherein each A is independently selected from halogen, trifluoromethyl, or trifluoromethoxy. And halogen is preferably chlorine, bromine or iodine.

The open positions of the phenyl ring of formula III may be substituted by other substituents that either enhance the activity of the molecules or undesirably affect its activity, such as electronegative substituents as indicated, or substituents such as lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl or lower alkoxycarbonyl. Compounds with such substituents are regarded as equivalents of the compounds claimed herein.

Another preferred embodiment of the class 5-carboxyanilidothiazoles according to the invention include compounds of formula IV and their agronomically acceptable salts:

wherein each B is independently halogen, trifluoromethyl or trifluoromethoxy. The halogen is preferably chlorine or bromine.

The open positions of the phenyl ring of formula IV may be substituted by other substituents that either increase the activity of the molecules or undesirably affect the activity, such as electronegative substituents as indicated, or substituents such as lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl or lower alkoxycarbonyl. Compounds with similar substituents are considered equivalent to compounds of the invention.

Agronomically acceptable salts of the invention include alkali, alkaline earth metal oxides, acid additives, basic additives, and alkyl salts.

The following procedures disclose suitable methods where the compounds of the present invention may be prepared by known chemical procedures from compounds known to those skilled in the art and / or commercially available. They are merely illustrative, and those skilled in the art will be able to use other ones suitable for the preparation of the compounds of the invention.

The compounds of the invention can be prepared by reaction of suitably substituted thiazoles with a 5-carboxy chloride substituent with appropriately substituted aniline in a suitable solvent (s) at elevated temperature. Suitable solvents include xylene, THG, toluene, chlorobenzene, colidine and

2,6-di-1-butyl-4-methylpyridine. In some cases, acid acceptors, such as tertiary amines and pyridines, can be used to accelerate the reaction.

Suitably substituted anilines are commercially available or can be prepared by standard chemical procedures. For example halosubstituted anilines can be prepared by standard techniques.

Thiazoles are readily prepared by reaction of ethyl 4,4,4 trifluoro-2-chloroacetoacetate with thioacetamide in a suitable solvent, preferably DMF, to form ethyl 2-methyl-4-trifluoromethyl-5-thiazolecarboxylate, which can be converted to the corresponding acid chloride by successive hydrolysis with a base and reaction with thionyl chloride.

2-Haloalkyl thiazoles are readily prepared by the following reactions: (1) reaction of readily available amides, for example with the Laveson reagent, to give the corresponding thioamide. Thioamide may be unstable and is best stored in the cold and used for several days; (2) reaction of thioamide with ethyl 4,4,4, trifluoromethyl-2-chloroacetoamide in a suitable solvent such as DMF or THG in the presence of a base, for example sodium bicarbonate or potassium carbonate, to form ethyl 2-haloalkyl-4-trifluoromethyl -5-thiazole-carboxylate, and (3) converting the above product into acid chloride by saponification with sodium hydroxide, followed by reaction with oxalyl chloride.

The following examples describe methods for preparing certain compounds of the invention, which are within the scope of the invention and serve to illustrate the known methods described. The examples are for illustrative purposes only and do not limit the scope of the invention.

Example 1.

2 = methyl-4-trifluoromethyl-5- (2 ', 6-dibromo-4'-trifluoromethoxy carboxanilido / thiazole a) 21.8 g (0.1 mol) 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 brine (brine), dried over magnesium sulfate, filtered through silica gel, and distilled (Kgelrohr) to give 9.0 g (38%) of a tan solid - 2-methyl - 4- Trifluoromethyl -5-ethoxycarbonylthiazole.

b) 9.0 g (0.038 mol) of ester in step a) was stirred overnight with 1.6 g (0.04 mol) of sodium hydroxide in 50 ml of water. The mixture was cooled with ice water and 10% HCl was added dropwise to pH 1. The mixture was extracted with ether. The ether was washed with water and brine, dried over magnesium sulfate and evaporated by rotation to give 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 of step b) is combined with 30 ml of thionyl chloride. The mixture was cooled, evaporated to remove excess thionyl chloride and distilled (Kygelrohr) to give 5 g (61%) of a yellow oil -2-methyl-4-trifluoromethyl-chlorocarbonylthiazole, b.p. 50-52 ° C at 20.05 torus.

g / 8.85 g / 0.05 mol / 4-trifluoromethoxy aniline was combined with 8.4 g /0.10 mol / bromine and heated at 60 ° C for 2 hours.

The mixture was stirred at room temperature overnight. Water was added and the mixture filtered to give 16.0 g of a very light crystalline solid, m.p. - 6567 ° C - 2,6-dibromo-4-trifluoromethoxy aniline.

g (2.07 g (0.002 mol) of the product of step c) is combined with 2.68 g (0.08 mol) of the product of step d) in 100 ml of xylene and refluxed for 24 hours. The mixture was then extracted sequentially with 10% HCl and water, dried over magnesium sulfate and concentrated in vacuo to give a solid. The solid was recrystallized from ethyl acetate / cyclohexane to give 2.54 g (53%) of a white solid, m.p. 172-173 ° C.

Elemental analysis for c ₁₃ h ₄ n ₂ o ₂ sf ₆ br ₂ Η N p Calculated 29.57 1.15 5.30 Found Example 2 29.50 1.15 5.26 -Ch-d ⁴ Br A ^FiC r i I N S t .A HH ^ O-CFj

dream,

2-methyl-4-trifluoromethyl-5- (2 ', 4', 6'-tribromo-3'-nitrocarboxanilido / thiazole a) 6.9 g / 0.05 mol / m-nitroaniline, 12.6 g / 0.15 mol / sodium acetate, 24.0 g / 0.15 mol / bromine in 120 ml of crystalline acetic acid was refluxed for 6 hours. The mixture was then added to water and filtered to give 15.1 g of a pale yellow solid, -2,4,6 tribromo-3-nitroaniline, m.p. 101 ° -103 ° C.

b) 3.75 g (0.008 mol) of the product of step a) is combined with 2.3 g (0.01 mol) of 2-methyl-4trifluoromethyl-5-chlorocarbonylthiazole and 2.05 g (0.01 mol). 2,6 di-1-butyl-4-methylpyridine and heated with stirring for 2 hours. The mixture was then dissolved in ethyl acetate, extracted with 10% HCl and water, dried over magnesium sulfate and evaporated to remove ethyl acetate. The solid was recrystallized from ethyl acetate / hexane to give 3.5 g (77%) of a tan solid, m.p. 244 ° -246 ° C.

Elemental analysis for C _{12 H 3} N ₃ O ₃ SF ₃ Br ₃

With ΗN

Calculated 25.38 0.897.40

Found 25.46 0.927.37

Using procedures similar to the above, other compounds of the present invention are prepared and similar to the above, as shown in the following Table 1.

Table 1

Example Name

formula

5-Thiazole carboxamide-2-methylN- (pentafluorophenyl) -4- (trifluoromethyl)

mp 111.0-120.0 nD

4.

5-Thiazolecarboxamide-2-methyl-N (2,4,6-trichlorophenyl) -4- (trifluoromethyl)

mp 167.0-169.0 nD

SI)

5.

6.

7.

8.

5-triazolecarboxamide-N- (2,4-dibromo-6-nitrophenyl) -2-methyl-

4- (trifluoromethyl)

mp. 203.0-204.0 nD

5- triazolecarboxamide-N- (2,4-dichloro-6-nitrophenyl) -2-methyl-4 (trifluoromethyl)

mp 167.0-169.0 nD

5-triazolecarboxamide-N- (2-bromo-4-chloro-6-nitrophenyl) -2-methyl- /

4- (trifluoromethyl)

mp 180-181.0 nD

5-Thiazole carboxamide-2-methyl-

N- (pentachlorophenyl) -4- (trifluoromethyl)

mp 229.00-231.00 nD

CH)

sn.

9. 5-Thiazolecarboxamide-N- [2,6-dibromo-4-chloro-3- (trifluoromethyl)] -2-methyl-4- (trifluoromethyl) m.p. 188.-190.0 nD

10. 5-Thiazole carboxamide-2-methyl-

4- (trifluoromethyl)

mp 232..0-234.0 nD

11.

5-Thiazolecarboxamide-N- [2,6-dibromo-4- (trifluoromethyl) phenyl] -2methyl-4- (trifluoromethyl)

mp 190.0-193.0 nD

5-Thiazolecarboxamide-M- (4,6-dibromo-

2-cyano-3-fluorophenyl-2-methyl-4 (trifluoromethyl)

mp 183.0-185.0 nD

13.

14.

5-Thiazolecarboxamide-N- [2-chloro-

4- (Trifluoromethyl) -6-nitrophenyl] -2methyl-4- (trifluoromethyl)

mp 179.0-184.0 nD

5- Thiazolecarboxamide-2-N- (2,4,6tibromophenyl) -4- (trifluoromethyl)

mp 208.0-210.0 nD

16.

17.

5-Thiazolecarboxamide-N- (2,6-dichloro-4-iodophenyl) -2-methyl-4- (trifluoromethyl)

mp 197.0-199.0 nD

5-Thiazolecarboxamide-N- (2,4-dibromo-6-cyanophenyl) -2-methyl-4- (trifluoromethyl)

mp 182.0-184.0 nD

5- Thiazolecarboxamide-N- [2-bromo-

6- nitro-4- (trifluoromethyl) phenyl] -2 (methyl)

mp 196.0-197.0 nD

5- Thiazolecarboxamide-N- [2,4-dibromo-

6- (trifluoromethyl) phenyl] -2-methyl-

4- (trifluoromethyl)

mp 232.0-234.0 nD

5- Thiazolecarboxamide-2-methyl-N (2,3,5,6-tetrachlorophenyl) -4- (trifluoromethyl) mp 232.0-234.0 nD

19.

20.

5-Thiazolecarboxamide-N- (2,6-bromo-4-iodophenyl) -2-methyl-4- (trifluoromethyl) m.p. 221.0-223.0 nD

21.

22.

23.

24.

25.

5-Thiazolecarboxamide-N- (2,4-dibromo-3,6-cyanophenyl) -2-methyl-

4- (trifluoromethyl)

so. 211.0-213.0 nD

5-Thiazolecarboxamide-N- [2,6-dichloro-4- (trifluoromethyl) phenyl] 2-methyl-4- (trifluoromethyl)

mp 162.0-163.0 nD

5-Thiazolecarboxamide-N - (2-acetyl-4,6-dibromophenyl) -2-methyl -

4- (trifluoromethyl)

mp 164.0-166.0 nD

5-Thiazolecarboxamide-N- [2,6-dichloro-4- (trifluoromethoxy) phenyl] -2-methyl-4- (trifluoromethyl)

mp 151.0-152.0 nD

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

mp 127-130.0 nD

sn.

CH)

26.

5-Thiazolecarboxamide-N- (4-bromo-2,6-dicyanophenyl) -2-methyl-4 (trifluoromethyl)

mp 217-219.0 nD

27.

5-Thiazolecarboxamide-4- (difluoromethyl) -2-methyl-N - (2,4,6-tribromophenyl)

mp 163-165.0 nD

5-Thiazolecarboxamide-N- [2,6-dibromo- (trifluoromethoxy) phenyl] -4-difluoromethyl) -2-methyl

mp 160-162.0 nD

CH)

28.

29.

30.

31.

32.

33.

Sulfur- [3,5-dibromo-4- [[[[2-methyl-4- (trifluoromethyl) -5-thiazolyl] carbonyl] amino] phenyl] pentafluoro]

mp 174-176.0 nD

5-Thiazolecarboxamide-N- (2,4,6-trichlorophenyl) -2,4-bis (trifluoromethyl) m.p. 180-181,0 nD

5-Thiazolecarboxamide-N- (pentachlorophenyl) -2,4-bis (trifluoromethyl)

mp 230.0-231.0 nD

5-Thiazole carboxamide-N- (2,4,6-tribromophenyl) -2,4-bis (trifluoromethyl) m.p. 204-205.0 nD

5-Thiazolecarboxamide-N- (pentafluorophenyl) -2,4-bis (trifluoromethyl)

mp 143.0-145.0 nD

34.

35.

5-Thiazolecarboxamide-N- [2,6-dibromo-

4- (trifluoromethoxy) phenyl] -2,4 (trifluoromethyl) m.p. 167.0-168.5 nD

5- Thiazolecarboxamide-2- (difluoromethyl)

N- (2,4,6-tribromophenyl) -4- (trifluoromethyl)

mp 215.0-217.0 nD

36.

5-Thiazolecarboxamide-N- [2,6-dibromo-

4- (trifluoromethoxy) phenyl] -2- (difluoromethyl) -4- (trifluoromethyl)

mp 196.0-198.0 nD

5- Thiazolecarboxamide-4-M-

2,4,6-tribromophenyl) -2- (trifluoromethyl)

mp 200.0 - 201.0

37.

38.

39.

40.

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

4- methyl-2- (trifluoromethyl)

mp 162-16900 nD

5- Thiazolecarboxamide-2- (dibromophenyl-

4- methyl-N- (2,4,6-tribromophenyl) m.p. 188-189.0

5-Thiazolecarboxamide-N- [2,6-dibromo-4- (trifluoromethoxy) phenyl] 2- (difluoromethyl) -4-methyl

mp 150.0-151.0

CF; -H

Rice Sheath Bliichlt Primary Rice Test

Rhizoctonia solanie is cultivated on rice grain inoculum at room temperature in the dark under laboratory conditions. The inoculum is obtained by mixing one part rice grain, one part chopped rice grain and one part water. Sclerotia is added to each flask and the inoculum is ready for use when a mycelium of Rhizoctomia solani develops in the medium and new sclerotia develops (usually within soldni and new sclerots form (usually within four to eight weeks).

16-18 rice seeds are sown in the center of a 7.62 cm square pan and covered with steam-sterilized soil (silt, red soil and octagon). The vessels are placed in a greenhouse at 25-30 ° C or 14 hours illumination. After about 11 to 15 days, the plants are in the second to third leaf stage and are ready for testing.

The test compounds were diluted to 1% by weight of the solution in acetone. Prior to administration, the test solutions were adjusted to a concentration of 0.5, 0.1 and 0.02 mg / ml with 40% acetone, 0.4% Tween-20 and 59.6% water.

The plants are sprayed in the second to third leaf stage. Two ml of the composition was irrigated with the soil of the vessel, after which approximately 1.5 ml / vessel was applied to the foliage using a "Devilbiss 152" nebulizer. During the treatments, the atomizer was rinsed with acetone.

The rice plants are allowed to air dry at room temperature before being returned to the greenhouse. The containers are placed in specially prepared plastic ³ θ watering cans. They do not have drainage holes, so water is contained in the system.

All vessels are kept in watering cans that are filled with water up to the finger line before inoculation. After two days, approximately two grams of inoculum is placed in each vessel at the base of the rice planted. The trays were then left in a dark growth room at approximately 100% humidity and 25 ° C. At least after 24 hours darkness turns on the light at a 12 hour light cycle. Plants are left alone for 4 to 7 days, after which they are evaluated for disease control. Morbidity control is evaluated based on the presence and severity of Sheath Blight lesions compared to control vessels. One grade is taken for each treatment (four ppm &).

The following scale is used:

** no activity = low activity

- moderate activity = high activity

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

Table 2

Example Test solution concentration (mg / ml) Degree of activity 1 0.5 / 0.1 / 0.02 3/3/2 2 0.5 / 0.1 / 0.02 3/2/2 4 0.5 / 0.1 / 0.02 3/2/1 * 8 0.5 / 0.1 / 0.02 3/3/3 10 0.5 / 0.1 / 0.02 3/3/3 11 0.5 / 0.1 / 0.02 3/3/0 14 0.5 / 0.1 / 0.02 2.66 * / 3/3 15 0.5 / 0.1 / 0.02 1.66 * / 1 * / 0 16 0.5 / 0.1 / 0.02 3/2/3 17 0.5 / 0.1 / 0.02 1.3 * / 1/0 19 0.5 / 0.1 / 0.02 3/3/3 20 0.5 / 0.1 / 0.02 3 * / 2 * / 2 * 21 0.5 / 0.1 / 0.02 0/1/0 22 0.1 / 0.02 3/3 23 0.5 / 0.1 / 0.02 3/3/3 24 0.5 / 0.1 / 0.02 3/3/2 27 0.5 / 0.1 / 0.02 3/1/0 28 0.5 / 0.1 / 0.02 3/2/0 29 0.5 / 0.1 / 0.02 3/0/0 30 0.5 / 0.1 / 0.02 3/3/0 31 0.5 / 0.1 / 0.02 1/1/1 32 0.5 / 0.1 / 0.02 3/3/1 33 0.5 / 0.1 / 0.02 + 34 0.5 / 0.1 / 0.02 3/3/1 35 0.5 / 0.1 / 0.02 2/2/2 36 0.5 / 0.1 / 0.02 3/3/3 37 0.5 / 0.1 / 0.02 3/3/3 38 0.5 / 0.1 / 0.02 3/2/2 39 0.5 / 0.1 / 0.02 3/2/2 40 0.5 / 0.1 / 0.02 3/3/2

Subsequent Rice Sheath Blight Activity Testing

The seeds are planted and R. splani cultivated as indicated. Plants are inoculated at the third leaf stage and inoculated to remove the inoculum from the flasks, break into small pieces or individual grains and add a small amount (1 cm ') to the base of each planted rice plant. After inoculation, the plants were placed in a dark growth room at a 12 hour day / night cycle.

The test solutions were prepared in the same manner as in the original test.

For application to the leaves, the plants are sprayed when the third leaf is fully expanded, but the fourth leaf is not shown. The surface of all vessels is covered prior to the chemical treatment with a layer of vermiculite, which is removed immediately after application in all spray tests on the leaves. The compounds were (sprayed) using a DeVilbiss atomizer. Two ml / container is sufficient to cover the entire surface of the plant to humidity, but not sufficient to cause the leaf material to fall. After spraying the plants are applied in a drying room (in very low light) and after 3-4 hours they are taken in greenhouse conditions. If the plants are planted on day “O”, the chemical is usually applied at 14 days and pathogenic inoculation occurs at day 16. The disease is evaluated every 26 to 30 days. The disease is evaluated by determining the amount of stem tissue covered by the symptoms of water absorption, chlorination and necrosis, and becomes a percentage of control compared to those treated with the composition.

The procedure of the soil penetration test is identical to that of the leaf protection test5, except for the chemical application method. Chemical test solutions were prepared and applied to the soil surface with a pipette (1 ml / vessel). Plants are sown in the greenhouse 30 minutes after treatment, irrigated immediately with enough water to cover the end of the container and kept for 2 days with moist soil. The inoculation, incubation and evaluation are done in the same scheme and in the same way as for the test of protection applied to the leaf mass.

Table 3 summarizes the results of the tests performed to determine the fungicidal activity of the compounds according to the invention

Table 3

Example Test

Concentration of the solution mg / ml

Degree of activity

1 Leaves 0.1 98 005 100 0.02 59 ⁺ Soil 0.01 32- 1.00 67 0.20 37 2 Leaves 01 87 0.05 97 0.02 84 0.01 64 Soil 1.00 47 0.20 8 3 Leaves 0.1 15 4 Leaves 0.02 3 0.05 29+ 0.02 17 0.01 15 5 Leaves 0.1 58 0.02 6 6 Leaves 0.1 15 0.02 15 7 Leaves 0.5 94 0.1 72

Soil 0.02 27 1.00 85 0.20 10 0.04 23 8 Leaves 0.5 100 0.1 100 0.05 98 0.023 97 ⁺ 0.01 86 0.002 71 8 Soil 1.00 39 0.20 65 004 -1 9 Leaves 0.02 99 0.01 93 0.002 95 Soil 0.04 41 0.02 11 10 Leaves 0.1 93 0.05 98 0.02 85 0.01 45 Soil 1.00 38 0.20 18 11 Leaves 0.5 99 0.1 90 0.02 43 Soil 1.00 71 0.20 57 0.04 8 12 Leaves 0.1 42 0.02 30 13 Leaves 0.02 21 0.01 6 14 Leaves 0.5 91 0.1 93 0.05 70 0.02 10 0.01 20 16 Leaves 0.1 84 0.02 24 1.00 58 0.20 20 17 Leaves 0.1 81 0.02 38 18 Leaves 0.02 71 0.01 30 19 Leaves 0.5 100 0.01 72 0.02 96 0.005 44

Soil 1.00 18 0.20 11 0.04 -3 20 Leaves 0.5 100 0.1 97 0.02 41 Soil 0.005 13 1.00 36 0.20 12 0.04 13 24 Leaves 0.5 100 0.1 97 0.02 59 Soil 1.00 91 0.20 52 0.04 26 25 Leaves 1.0 87 0.5 32 0.1 8 Soil 2.0 23 1.0 12 26 Leaves 0.5 72 0.1 66 0.02 40 Soil 2.0 0 1.0 60 30 Leaves 0.5 98 0.1 64 0.02 20 Soil 1.00 75 0.20 73 0.04 27 31 Leaves 0.5 83 0.1 87 0.02 63 Soil 1.00 40 0.20 47 0.04 28 32 Leaves 0.5 99 0.1 100 0.02 79 Soil 1.00 49 0.20 20 0.04 28 34 Leaves 0.5 99 0.1 96 0.02 54 Soil 1.00 67 0.20 69 0.04 14 36 Leaves 0.1 100

0.02 97 Soil 1.00 84 0.20 71 Leaves 0.5 100 0.1 96+ 0.02 68+ Soil 1.00 25+ 0.20 16+ 0.04 12 Leaves 0.1 85 0.02 25 Soil 1.00 48 0.20 -4 Leaves 0.1 87 0.02 30 1.00 21 0.20 21 Leaves 0.1 95 0.02 21 Soil 1.00 70 0.20 21

Brown patch activity test

Seedlings are sown under greenhouse conditions at 12.7 cm in diameter plastic container and remain to grow for 6 weeks. One day before the experiment, the grass is cut to approximately 1 inch in height. The test compounds are prepared in liquid form. The prepared substances / materials / were dissolved in an appropriate amount of water to give the final test compounds at a concentration of 1, 0.2 and 0.04 mg / ml of active ingredient.

Four vessels were used for each treatment, each test vessel containing 5 ml of test solution. The treatment of the lawn is done using DeVilbiss type of sprayers. The vessels were placed in a growth room at 28 ° C, 95% humidity and 12 h light at 400 uE / m ³ .

Three weeks before the start of the experiment on sterilized sorghum seeds, pathogenic Rhizoctonia solani was cultivated. After chemical treatment, the two vessels were inoculated by placing ten sorghum seeds abundant in Rhizoctomia in each vessel. The inoculated vessels are placed back in the growth room and the duration of light is reduced to 8 hours to aid the spread of Rhizoctonia and the onset of Brown patch symptoms.

Ten days after inoculation, the vessels are removed from the growth room and the morbidity and phytotoxicosis are evaluated. The rate of Rhizoctonia infection is estimated for each vessel.

The test results are listed in Table IV

Table 4

Example Concentration of the test solution Degree of activity 1 1 94 0.2 87 0.04 59 2 1 81 0.2 49 0.04 0 9 1 97 0.2 94 0.04 78 19 1 66 0.2 50 0.04 0

Table 5

One grade is taken for each treatment (four vessels)

Example Amount of compound from the test Degree of activity 1 1 / .2 / .04 1.0 / 1.0 / 2.0 2 1 / .2 / .04 1.0 / 2.5 / 4.0 3 1 / .2 / .04 1.0 / 3.5 / 4.0 4 1 / .2 / .04 2.0 / 2.25 / 3.25 8 1 / .2 / .04 2.0 / 2.25 / 4.0 11 1 / .2 / .04 1.25 / 1.0 / 1.5 12 1 / .2 / .04 2.75 / 4.5 / 4.75 28 1 / .2 / .04 1.0 / 1.75 / 4.25 34 1 / .2 / .04 1.0 / 1.0 / 2.75 38 1 / .2 / .04 1.5 / 1.0 / 2.25 2.8 / 2.94 / 4.66 *

Green peanut activity test

Experimental pathogenic Sclerotium rolfsii was cultured on sterile oat grains for 21 days.

The fungicidal / oat seed mixture was removed from the culture flasks, air-dried for 3 days and then stored at room temperature until use (up to 30 days). Subject to the above laboratory procedures peanut plants are grown individually in 7.62 cm ² containers for 12-14 days. To the lower part of the stem, the leaf mass and soil surface of each vessel was applied 2 ml of the test compound in acetone, water and Tween 20. After 24 hours, 2 g of oat seed inoculum was applied to the soil surface of each vessel. The vessels were then incubated for 10 days in a growth room at 25-28 ° C, 100% humidity with 12 hours light / 12 hours dark photoperiod. The incidence rate for each plant is evaluated and graded as follows:

1. No illness.

2. Mild illness - mild mycelium - no lesions.

3. Moderate illness - mycelium and mild lesions.

4. Moderate / severe illness - mycelium and lesions.

5. Severe illness - the plant fades from the disease.

As can be seen from the above data, the compounds of the invention have good fungicidal action. Some of the compounds have high fungicidal action (Examples 1, 2, 8, 19 and 36) at low doses of administration and reduced costs and little pesticidal pollution. The compounds of the present invention generally show good fungicidal control without or with very little transient plant damage. The compounds also show that they are safe for animals, such as fish, which may have access to it when administered.

The fungicidal substances of the invention, including the concentrates to be diluted prior to administration, may contain at least one active ingredient and additive in liquid or solid form. Substances are prepared by mixing the active ingredient and additives, including diluents, fillers, carriers and other substances, depending on the conditions that make the substances in the form of finely divided small and solids, granules, pellets, solutions, dispersions, or emulsions. It is believed that the active ingredient can be used with additives such as finely divided solids, liquids of organic origin, water, moisturizing, dispersing or emulsifying agents, or any suitable combination thereof.

Suitable wetting agents include alkyl gasoline, and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain sodium isotonic acid esters, sodium sulfosuccinate esters, sulfated or sulfonyl sulfonated oils, sulfated sulfonyl oils, sulfated sulfonyl oils, acetylene glycols, polyoxyethylene derivatives of alkylphenols (especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives of mono-high fatty acid esters of hexitol anhydrides (e.g. sorbitan.

Suitable dispersants are methyl, cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polymetallic binaphalinsulfonate and polyethylene oxide polypropylene oxide copolymers.

Moisturizing powders are water-dispersing substances containing one or more active ingredients, an inert solid filler and one or more moisturizing and dispersing agents. Inert solid fillers are generally of mineral origin, for example natural clays, infuser soil and synthetic minerals derived from quartz and the like. Examples of such fillers include kaolinite, attapulgite clay and synthetic magnesium silicate. The moisturizing substances according to the invention typically include more than 0.5 to 60 parts / preferably from 5 to 20 parts / active ingredient about 0.25 to 25 parts / preferably from 1 to 15 parts / wetting agent, about 0.25 up to 25 parts / preferably from 1.0 to 15 parts / dispersant and from 5 to 95 parts / preferably from 5 to 50 parts / inert solid filler, the weight of all parts giving the weight of the whole substance. Where necessary, about 0.1 - 2.0 parts of the solid excipient may be replaced by a corrosion inhibitor or a foaming agent, or both.

Other compositions include powdered concentrates consisting of 0.1% to 60% by weight of the active ingredient on a suitable excipient, these powdered compositions may be diluted for use at concentrations within 0.1-10% by weight.

Aqueous suspensions or emulsions may be obtained by stirring an anhydrous solution of the water-insoluble active ingredient and an emulsifying agent with water to obtain a homogeneous mass and then homogenizing to obtain a stable emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by an extremely small particle size, so that when it is thinned and sprayed the coating is very uniform. Suitable concentrations for these compositions contain from 0.1 to 60%, preferably from 5 to 50%, by weight of the active ingredient, the upper limit being determined by the solubility limit of the active ingredient of the solvent.

Concentrates are usually solutions of the active ingredient in water-immiscible or partially water-immiscible solvents together with a surfactant. Suitable solvents for the active ingredients of the invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, and water-immiscible ethers, esters or ketones. Other very strong liquid concentrates can be obtained by dissolving the active ingredient in a solvent after dilution, for example with kerosene, to form a spray concentrate.

According to the present invention, the concentrate compositions typically contain from 0.1 to 95 parts / preferably from 5 to 60 parts / active ingredient, about 0.25 to 50 parts / preferably from 25 parts / surfactant and when necessary about 4 up to 94 parts of solvent, all parts by weight based on the total weight of the emulsifying oil.

Granules are physically stable particulate matter containing an active ingredient attached or distributed to the bulk (matrix) of an inert, finely divided particulate filler. In order to assist in the extraction of the active ingredient from the particulate filler, a surfactant may be present in the substance, as indicated above. Examples of possible classes of particular mineral fillers are natural clays, pyrophyllites, illite, and verticulitis. Preferred fillers are porous, absorbent, preformed particles such as preformed and sorted particulate attapulgitis or hot stretched particulate vermiculitis and finely divided clays such as kaolin clays, hydrated attapulgite or bentonite clays. These fillers are sprayed or mixed with the active ingredient to form the herbicidal granules.

The granular substances according to the invention may contain from 0.1 to 30 particles by weight of the active ingredient per 100 particles by weight of clay and from 0 to 5 particles by weight of the surfactant per 100 particles by weight of particulate clay.

Suitable types of compositions are emulsifiable concentrates, flowable and moisturizing powders, powders and granules. A suitable flowable composition (31 b / gal) / 0.35 kg / I / is as follows: Ingredients Weight%

Compound of Example 9 31.14

Xanthan gum 1.25 block copolymers of propylene oxide and ethylene oxide magnesium aluminum silicate1.00 ligninsulphonate dispersant 2.00 dehumidifier 0.25 water61.84

100.00

The compounds according to the invention exhibit the highest activity when applied as a spray on the leaf mass.

The compositions of the invention may also contain other additives, for example other fungicides, fertilizers, insecticides, herbicides, other pesticides, insecticides and the like, used as additives or in combination with any of the above additives. Useful In combination with the active ingredients of the invention, for example, the following fungicides are useful:

Tricyclazole Tricyclazole roquilon

Chlorothalonil

Triads omenfl

Fenpoimorph Carbendazim Triadimefon Flusilazol Metalaxyl Ha Other suitable fungicides are known in the art.

When using the compounds of the invention, effective amounts are applied to the leaf mass or plant propagation material, or applied to the soil or water around the leaf mass in the most convenient manner. Liquid or particulate solids can be applied to the soil by conventional means, such as mechanical sieves, hand sprays and spray sieves. Substances may also be administered by aircraft such as dust or spray due to their low dose efficacy.

The exact amount of active ingredient to be administered depends on various factors, including the plant species, the degree of plant development and disease, the specific compounds applied, the type and conditions of the soil, the amount of rain. When applied to the leaf mass, a dose of 30 to 500 g / ha is usually used, preferably about 60 to 250 g / ha. For soil application, doses of 100 to 1000 g / ha, preferably 250 to 500 g / ha, are generally used. In some cases, lower or higher doses may be required. One skilled in the art can readily determine, depending on the specifics, the optimal ratio, using the above examples, which ratio should be used in each case.

Claims (25)

1. Compound with formula O ^R i in which each R is independently halogen, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio, pentafluorosulfur, halomethylsulfinyl, 1-haloethylsulfinyl, halomethylsulfonyl or 1-haloethylsulfonyl, R ₁ and R j are independently methyl, ethyl or fluoromethyl, provided that at least R j or R j is difluoromethyl and N is an integer from 3 to 5, or agronomically acceptable salts thereof. 2. A compound according to claim 1, wherein R ₍ is methyl. A compound according to claim 2 wherein R ₂ is trifluoromethyl. 4. A compound according to claim 3, wherein each R is halogen, halomethyl or halomethoxy. 5. A compound according to claim 4, wherein each is chlorine, bromine, iodine, trihalomethoxy. 6. A compound according to claim 4, wherein each R is chloro, bromo trifluoromethyl or trifluoromethoxy. 7. A compound according to claim 5, wherein η is an integer from 3 to 4. 8. Compound with formula CH ₃ in which X is halogen, trihalomethyl or trihalomethoxy, Υ is halogen, trihalomethyl, trihalomethoxy, nitro or cyano each Ζ is independently halogen, trihalomethyl, trihalomethoxy, nitro or cyano and N is an integer from 1 to 3, or agronomically acceptable salts thereof. 9. A compound according to claim 8, wherein X is halogen, trifluoromethyl or trifluoromethoxy, Y is halogen, trifluoromethyl, trifluoromethoxy, nitro or cyano and each Z is independently halogen, trifluoromethyl, trifluoromethoxy, nitro or cyano. 10. A compound according to claim 9, wherein N is from 1 to 2. 11. Compound with formula CH ₃ in which each A is independently halogen, trifluoromethyl or difluoromethoxy or an agronomically acceptable salt thereof. 12. Compound with formula CH ₃ in which each B is independently halogen, trifluoromethyl or trifluoromethoxy or an agronomically acceptable salt thereof. 123. Compound with general formula O ^R 1 in which each R is independently halogen, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, pentafluorosulfur, halomethylsulfinyl, 1-haloethylsulfinyl, haloethylsulfonyl, 1-haloethylsulfonyl, nitro, cyano, halomethylthio, 1-haloethylthio, methylsulfinyl, ethylsulfonyl, lower alkyl carbonyl or lower alkoxycarbonyl, R 1 is methyl or ethyl, 1% is difluoromethyl or trifluoromethyl, and η is an integer from 3 to 5 or agronomically acceptable salts thereof. 14. A substance containing a fungicidally active amount of a compound of general formula 20 ^R i in which each R is independently halogen, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio, pentafluorosulfur, halomethylsulfinyl, 1-haloethylsulfinyl, R1 and R2 are independently methyl, ethyl or fluoromethyl provided that at least Rj or R ₂ is difluoromethyl or trifluoromethyl, and η is an integer from 3 to 5, or an agronomically acceptable salt thereof. 15. A compound according to claim 14, wherein _R1 is methyl. 16. A substance according to claim 15, wherein 1% is trifluoromethyl. 40 17. A compound according to claim 16, wherein R is chlorine, bromine, trifluoromethyl or trifluoromethoxy. 18. A compound according to claim 17, wherein N is 3 or 4. 45 19. A method for controlling the growth of fungicidal diseases in plants, characterized in that an effective amount of a compound of the general formula is applied to the plant O ^R i in which each R is independently halogen, halomethyl, 1-haloethyl, halomethoxy, 1-haloethoxy, halomethylthio, 1-haloethylthio, pentafluorosulfur, halomethylsulfinyl, 1-haloethylsulfinyl, halomethylsulfonyl or 1-haloethylsulfonyl, R, and 1% are independently methyl, ethyl or fluoromethyl provided that at least Rj or 1% is difluoromethyl or trifluoromethyl, and is an integer from 3 to 5, or agronomically acceptable salts thereof. 20. A method according to claim 19, wherein R 1 is methyl. 21. A method according to claim 22, wherein R ₂ is trifluoromethyl. 22. A method according to claim 21, wherein R is chlorine, bromine, trifluoromethyl or trifluoromethoxy. 23. The method of claim 22, wherein η is 3 or 4. 24. Chemical compound 2-methyl-4-trifluoromethyl-5-[2', 6'-dibromo-4'-trifluoromethoxy carboxanilid]thiazole. 25. A substance characterized in that it contains a fungicidally effective amount of the chemical compound 2-methyl-4-trifluoromethyl-5/2',6'-dibromo-4'-trifluoromethoxy carboxanilid/thiazole. 26. A method for controlling the growth of a fungicidal disease in plants, characterized in that an effective amount of the chemical compound 2-methyl-4-trifluoromethyl 5-(2',6'-dibromo-4-trifluoromethoxy carboxanilid) thiazole is applied to the plant.