DE2557950A1 - N- (TRICHLOROMETHYLTHIO) -, N- (TETRACHLORAETHYLTHIO) - OR N- (TETRACHLORFLUORAETHYLTHIO) -HALO-BENZOYLANILIDE AND THEIR USE AS FUNGICIDES - Google Patents

Description

Stauffer Chemical Company,. Westport

(Connecticut, USA)

N- (Trichloromethylthio) -, N- (Tetraehlorathylthio) - or N- (tetrachlorofluoroethylthio) halo-benzoylanilides and their Use as a fungicide

The invention relates to certain new N- (triehlomethylthio) -, N- (Tetraehlorathylthio) - or N- (Tetrachlorfluoräthylthio) -halo-benzoylanilide, which are useful as fungicides.

The compounds of the present invention have the formula I.

(D,

R chlorine, bromine, iodine or trifluoromethyl, where the substituents R are preferably arranged in the ortho position;

R is hydrogen, chlorine, bromine, iodine, trifluoromethyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 2 carbon atoms or alkylthio of 1 to 2 carbon atoms; and

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R ² -CCl, -CCl ₂ -CCl ₂ H ₅ or
mean.

These compounds are generally effective as fungicides. Unexpectedly it has now been discovered that they also act as a systemic poison, which makes them useful and versatile Possible uses in combating fungal infestation on field fruits greatly increased. The person skilled in the art is aware that a systemic bioeid taken up by the organism of a plant to which it is applied and deposited in the tissues where it continues to maintain its poisonous effect. If systemic poisons are used to protect crops, then these poisons are not exposed to the weather, as they are stored in the spaces between the tissues and enclosed by the cell walls are. These plants are now protected from the inside out against attack by harmful fungi, powdery mildew and the like immunized harmful microorganisms.

The compounds of the present invention are prepared by the following general procedure:

Reaction step # 1

In general, one mole of the substituted benzoyl chloride, dissolved in benzene, is added to a mixture consisting of the aniline compound and a slight excess of an HCl acceptor such as triethylamine. This mixture is refluxed for 2 hours and then cooled. The solid reaction product is dissolved in a solvent such as ethyl acetate or chloroform, twice with water and once with

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washed out with a salt solution and the solution dried over MgSO ^, filtered and evaporated to dryness.

Reaction step # 2

Close

One mole of the reaction product from reaction step # 1 is dissolved in dry tetrahydrofuran under nitrogen. Thereon a small excess of NaH is added with stirring. The mixture is refluxed for 1 hour and then cooled.

Reaction step # 3

Cl-S-R '

One mole of Cl-SR dissolved in tetrahydrofuran is added dropwise to the reaction mixture from step # 2. The mixture is refluxed for 2 hours and then a relatively large amount of methylene chloride is added to the solid. Reaction product added. The solution is washed twice with water: i _s over MgSOj, dried and then evaporated.

The preparation of the compounds according to the invention is explained by the following examples:

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ri

example 1

Preparation of 2-iodobenzoyl anilide

43.2 g (0.464 mol) of aniline and 46.9 g of triethylamine are stirred up in 930 ml of benzene. A solution of 123.7 g (0.464 mol) of 2-iodobenzoyl chloride in 450 ml of benzene is added to the above mixture from a dropping funnel. An exothermic reaction takes place. After the reaction has subsided, the mixture is refluxed for a further Y2 hours. When the solution cools, the product precipitates out. It is filtered off, poured into water and stirred up in order to dissolve the triethylamine hydrochloride formed. The product is then filtered off again and dried, 146.8 g of the desired product being obtained. , (Yield: 98 %) Mp = 141-144 ° C.

Example 2

8.075 g (0.025 mol) of the reaction product from Example 1 are dissolved in 60 ml of dry tetrahydrofuran under dry nitrogen. 0.66 g (0.0275 mol) of NaH are added to the mixture with stirring. The mixture is refluxed for one hour and then cooled. .

6 C Ö b 2 S / 10 11

Example 5
N-Trichloromethylthio-2-jcdobenzcyl-anilide

H, 65 g (0.025 mol) of ClS-CCl dissolved in 12 ml of tetrahydrofuran are added dropwise to the cooled reaction mixture from Example 2. The mixture v; ird 2 ^1/2 hours at reflux heated. 150 ml of methylene chloride are then added , and the mixture is washed twice with water, over MgSO 4. dried and evaporated to give 10.75 g (91 % yield) of the desired product. The product is washed with 8 ml of ether, with which white crystals are obtained.
Pp. = 9 * i to 101 ⁰ C.

example

N-tetrachloroethylthio-2-j ο dobenzoyl anilide

5.80 g (0.025 mol) of the compound CClSCCl -CCl H, which in 12 ml Tetrahydrofuran is dissolved, is added dropwise to the cooled reaction mixture of Example 2 and the mixture during 2] / 2 Heated at reflux for hours. 150 ml of methylene chloride are then added ^ the solution is washed twice with water, about MgSOj. dried and evaporated, leaving the desired Product is obtained.

6 G ei ο 2 8/1 0 1 1 BATH ORIGINAL

example ^r j

N-tetrachlor f 1 u ο r rn ο thy 11 h i ο -? -,; c ■ :: ο benzo y 1-anilide

0.025 mol of ClSCCl -CCl F _{5, dissolved} in 12 ml of tetrahydrofuran, is added dropwise to the cooled reaction mixture from Example 2 and the mixture is refluxed for 2 hours. 150 ml of methylene chloride are then added, and the mixture is washed twice with water, dried over MgSCv and evaporated to give the desired product as a residue.

In the following table certain selected compounds are listed which are made according to the method just described can be produced. Each connection is assigned a number, which will be used for identification purposes in the following explanations corresponding connection is used.

6 0 y ο 2 ö / 1 0 1 1 BAD ORIGINAL

Compounds of Formula I.

Table I.

(D

Number of
link I —— ι—. ■
R. R ¹ V a) Production described in Example 3
b) Production described in Example 4
c) Production described in Example 5 i ^a >
2
3
4 ^b >
5
6th
7 ^C)
8th
9 2-1
4-Cl
2-Br
2-1
4-Cl
2-Br
2-1
4-Cl
2-Br H
H
H
H
H
H
H
H
H CCl
CCl
CCl
CCl ₂ CCl ₂ H
CCl ₂ CCl ₂ H
CCl ₂ CCl ₂ H
CCl ₂ CCl ₂ P
CCl ₂ CCl ₂ P
CCl ₂ CCl ₂ F

6 0 S 3 2 3/1 0 1 1

Test method for determining the fungicidal effect on leaves

A, Determination of the preventive effect

1. Bean rust test

The test compound is dissolved in a suitable solvent and contains water, the several drops of Tween 20, a Polyoxyäthylensorbitanmonolaureat-wetting agents, ~ diluted. Test solutions with a concentration of LOGO ppm downwards are sprayed onto the primary leaves of the kidney bean (Phaseolus vulgaris L.) until they run off. After the leaves have dried, they are inoculated with an aqueous spore suspension of the bean rust fungus ( Uromyces phaseoli Arthur), after which the test plants are placed in a humid room with 100 % humidity for 24 hours. The plants are then taken out of the damp room and held until pustules from the bean rust appear on the leaves. As a measure of the fungicidal activity of a compound, the lowest concentration of the compound in the test solution is given in ppm, with which a 50 # reduction in the formation of pustules is achieved compared with untreated plants inoculated with spores.
The values obtained are shown in Table II.

2. Bean powdery mildew test

The compound to be tested is applied to the leaves in the same way as in the bean rust test. As the plants are dry again, the leaves are dusted with powdery mildew spores (Erysiphe polygoni De Candolle) and the plants are kept in the greenhouse until the fungus has spread on the leaf surface. As a measure of the fungicidal effectiveness of the compound, the lowest

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Specified concentration of the compound in the test solution with which a 50 % reduction in mycelium formation is achieved compared with untreated, but inoculated with spores plants.

The values obtained are shown in Table II.

3. Tomato dry spot disease

The compound to be investigated is dissolved analogously to the bean rust test and sprayed onto the leaves of 4-week-old tomato plants ( Lycopersicon esculentum ) as the host plant. As soon as the leaves are dry, they are inoculated with an aqueous suspension of spores of the dry spot fungus ( Alternaria solani Ellis and Martin) and the plants are placed in a humid room with 100% moisture for 48 hours. The plants are then taken out of the damp room and kept in the greenhouse until the damage to the leaves by the disease becomes visible. As a measure of the fungicidal effectiveness of a compound, the lowest concentration of the compound in the test solution is given in ppm with which a 50% reduction in the formation of leaf injuries due to the disease compared to plants that have been treated with urine but have been inoculated with spores is achieved will. The values obtained are given in Table II.

4. Blue grass leaf spots

The compound to be investigated is dissolved analogously to the bean rust test and sprayed onto the leaves of 4-week-old Kentucky meadow rasp plants (Poa pratensis ) as the host plant. As soon as the leaves are dry, they are inoculated with an aqueous suspension of spores of the blue grass leaf spot fungus (Helminthosporium sativum ) and the plants are placed in a damp room for 48 hours.

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- ίο -

The plants are then taken out of the damp room and kept in the greenhouse until the damage to the leaves by the disease becomes visible. As hate the lowest concentration of the compound in the test solution is used for the fungicidal activity of a compound given in ppm, with a 50% reduction in the development of leaf injuries caused by the disease, compared to untreated but spore-inoculated plants. The values obtained are given in Table II.

B. Determination of the killing effect

1. Bean rust test

Untreated kidney bean plants ( Phaseolus vulgaris L.) are inoculated with spores of the bean rust fungus (Uromyces phaseoli. Arthur) and placed in a damp room with 100 % moisture for 48 hours. The plants are then taken out of the damp room and kept in the greenhouse until the fungus has settled on the host. The compound to be examined is then applied to the leaves in solution as in the bean rust test under A 1. As a measure of the killing effectiveness of a compound, the lowest concentration of the compound in the test solution is given in ppm, with which a 50 # reduction in the formation of pustules is achieved compared with untreated plants inoculated with spores.

The values obtained are shown in Table II.

2. Bean powdery mildew test

Untreated bean plants are dusted with spores of the powdery mildew fungus (Erysiphe polygoni De Candolle) and kept in the greenhouse until mycelia are visible on the leaves. The connection to be examined now becomes analog

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as in the bean rust test in solution and applied to the leaves. Four days later, the degree of the reduction in further growth of the mycelium is determined on the leaves. As a measure of the killing effectiveness, the lowest concentration of the compound in the test solution is given in ppm, with which a 50 % reduction in the formation of viable spore-forming myeel compared with untreated plants inoculated with the fungus is achieved. The values obtained are given in Table II.

Table II A. Preventive effect

Number of Bean grate Bean flour tomatoes Blue grass leaf link dew drought stains 1 10 500 500 100 2 3 4th 5 6th 7th CXD 9

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B- killing effect

Number of
link Blue grass leaf
stains Bean grate Bean powdery mildew 1 100 2 3
4th 5
6th 7th
8th 9

C. Determination of the systemic effect in the test tube 1. Bean rust test

The compound to be examined is dissolved in a suitable solvent and gradually diluted with well water, starting with a concentration of 50 ppm. 60 ml of the solutions of each concentration of the dilution series are placed in a test glass. A bean plant (Phaseolus vulgaris L.) is placed in each test glass and fixed with a cotton ball in such a way that only the roots and the lower part of the stem are immersed in the test solution. 48 hours later, the leaves are inoculated with an aqueous suspension of spores of the bean rust fungus ( Uromyces phaseoli Arthur) and the plants are placed in a damp room for 24 hours. The plants are then kept in the greenhouse until the rust pustules are visible on the leaves. As a measure of the effectiveness of a compound, the lowest concentration of the compound in the test solution is given in ppm with the still

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a 50 % reduction in pustular formation is achieved compared with untreated, but spore-inoculated plants. The values obtained are shown in Table III.

2. Bean powdery mildew test

The compound to be examined is applied to the roots of the plants in the same way as in the bean rust test. After two days, the leaves are dusted with spores of the bean powdery mildew fungus (Erysiphe polygone De Candolle) and kept in the greenhouse until mycelium is visible on the leaves. As a measure of the systemic effectiveness of the compound, the lowest concentration of the compound in the test solution is given, with which a 50 % reduction in mycelial formation is achieved compared with untreated plants inoculated with spores.

The values obtained are shown in Table III.

D. Determination of the systemic effect in wetted soil 1. Bean rust test

Kidney bean plants ( Phaseolus vulgaris L.) are grown in "- 0.55 ^ ice cream cups, each containing 454 g of soil. Aliquots of the compound to be examined are dissolved in a suitable solvent, diluted with 25 ml of water and poured onto the surface of the soil. two days later, the bean leaves with an aqueous suspension of the bean rust fungus (Uromyces phaseoli Arthur) -geimpft and asked the plants for 24 hours in a humid chamber with 100% humidity. the plants are taken out from the damp room and kept in a greenhouse until pustules become visible on the leaves as a measure for

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the effectiveness of a compound is given as the lowest concentration of the compound in the test solution in ppm with which a 50 % reduction in the formation of pustules is achieved compared with untreated plants inoculated with spores.

The values obtained are shown in Table III.

2. Bean powdery mildew test

The compound to be investigated is used in the same way as in the bean rust test under D 1. After 10 days, the leaves of the bean plant ( Phaseolus vulgaris L.) are dusted with spores of the powdery mildew fungus (Erysiphe phaseoli Arthur) and the plants are kept in the greenhouse until the mycelium is visible on the leaf surface. As a measure of the systemic effectiveness of the compound, the lowest concentration of the compound in the test solution is given, with which a 50 # reduction in mycelial formation is achieved compared with untreated plants inoculated with spores.

The values obtained are shown in Table III.

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Table III

Number of
link C. Systemic effect
in the test glass Bean meal
dew D. Systemic effect in
wetted soil Bean powdery mildew 1
2
3
4th
5
6th
7th
8th
.9 Bean grate 25th Bean grate 1 3

The compounds according to the invention can be brought into any useful application form. For example, you can use pesticides Preparations in the form of emulsions, suspensions, solutions, dusts and pressure sprays are produced. Generally included Such preparations, in addition to the active component, also include adjuvants such as are generally found in pesticidal preparations are. In these preparations, the active component according to the invention can be the only active component s-a, or it can be used in conjunction with other compounds with similar potency. Pesticide preparations can as adjuvants, organic solvents such as sesame oil, xylene-type solvents, heavy gasoline and the like, water, Emulsifiers, surfactants, talc, pyrophyllite, diatomaceous earth, gypsum, clay and propellants such as dichlorodifluoromethane etc. be. ,

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If necessary, the active ingredients can be applied directly to the host plant that is attacked by the pest. For purposes of this kind, it is advantageous to use non-volatile preparations. With regard to the activity of the present pesticidal preparations, it will be understood that it is not necessary that the preparation be active as such. It is completely sufficient if it is activated by external influences such as light or by physiological processes that take place in the pest's body when the preparation is consumed by it. The most advantageous mode of application for the pesticide according to the invention in each individual case can easily be determined in each case by the person skilled in the art. In general, the active pesticidal preparation will be in the form of a liquid, for example an emulsion, suspension or pressure spray. Although the concentration of the active component in the present preparation can vary within fairly wide limits, the pesticidal preparation will usually not contain more than 15.0% by weight of the active component. Preferably the fungicidal composition is in the form of a solution or suspension according to this invention, the 0.1 to 1 wt -.% Containing the active components.

6 0 9 8 28/1011

Claims (6)

Claims worm R chlorine, bromine or iodine or trifluoromethyl; R hydrogen, chlorine, bromine, iodine, trifluoro, alkyl with 1 up to 5 carbon atoms, alkoxy with 1 to 2 carbon 2. substance atoms or alkylthio with 1 to / carbon atoms; and R ² -CCl, -CCl ₂ -CCl ₂ H or CCl ₂ -CCl P mean. 2. Compound according to claim 1 of the formula I, wherein R 1 2 2-iodine, R is hydrogen and R -CCl. 3. Compound according to claim 1 of the formula I, wherein R i \ - is chlorine, R ^{1 is} hydrogen and R ^{2 is} -CCl. 4. Compound according to claim 1 of the formula I, in which 1 2 R is 2-bromine, R is hydrogen and R is -CCl. 5. A method of combating fungi, characterized in that a fungicidally effective amount of one is applied to the fungi Compound of formula I. 809828/1011 (D ₃ worxn R chlorine, bromine, iodine or trifluoromethyl; R hydrogen, chlorine, bromine, iodine, trifluoromethyl, alkyl 1 to 5 carbon atoms, alkoxy with 1 to 2 carbon atoms or alkylthio with 1 to 2 carbon atoms; and
R ² -CCl, -CCl ₂ CCl ₂ H or mean, brings up. 6. The method according to claim 5, characterized in that that a compound of the formula I, wherein R 2-iodine, R 2
Hydrogen and R -CCl are used. 609828/1011