DE3147156A1 - 3- (N-ACYL-N-ARYLAMINO) LACTONE, THIS CONTAINING FUNGICIDE AGENT AND APPLICATION FOR CONTROLLING VINEYARD LEAF - Google Patents

Description

U.S. Patents 3,933,860; 4,012,519 / 4,107,323 and 4,141,938 disclose the use of a large class of 3- {N-acyl-N-arylamino) lactones and 3- (N-acyl-N-arylamino ) lactams are described as protective fungicides.
5

US-PS & 034 108 and 4015 648 discloses the use of Ai- (Methoxy carbony Ie thy 1) -N-haiogenacetylanilineii. as preventive and curative fungicides.

10 DE-OS 26 43 403 and 26 43 445 describe the use of N- (alkylthio-carbonylethyl) acetanilides for combating fungi, especially fungi of the class Phycomycetes.

15 NL-OS 152 849 has the use of N- (alkoxymethyl) acetanilides as fungicides to the content.

BE-PS 867 556 describes 3- (N-cyclopropylcarbonyl-N-arylamino) - } f -butyrolactones. »0

BE-PS 863 615 describes fungicidal 3- (N-acyl-N-arylamino) - X -butyrolactones.

In the aforementioned US Pat. No. 3,933,860, 3- (N-acyl-N-Ϊ5 arylamino) lactones and lactams of the formula (I)

^Ar -

C-R

CH ₃ - (CH ₂ ) _n (I)

Io I η

O = CT CH-R ^

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in which Ar is substituted for phenyl or phenyl with 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atom (s), alkoxy with 1 to 4 carbon atom (s) or nitro, while R is alkyl with 1 to 6

2
Carbon atom (s) etc., R is hydrogen or alkyl

with 1 to 6 carbon atom (s), Y is oxygen and NR ² and η is 1 or 2.

In the aforementioned US Pat. No. 4,107,323 it is stated that compounds of the formula (I) in which R represents halomethyl Y is oxygen and Ar is 2,6-dialkylphenyl are particularly preferred because of their high eradication and healing activity Fungal infestation, especially grapevine dew and tomato dry rot.

It has also been found that subsequent generations of the powdery mildew-producing fungi treated with a fungicide have been treated as it is most commonly used to combat this disease (namely N-methoxyacetyl-N- (1-methoxycarbonylethyl) -2,6-dimethylaniline) ,. »A resistance to this fungicide to develop. This resilience also increases the resistance of such fungi to a number newer aniline derivative fungicides. If this resilience spreads further, the fight will this disease is very problematic.

The invention is based on the knowledge that of the Compounds of the formula (I) in which Ar is 2,6-dialkylphenyl, Y is oxygen, η Ο is and R is alkyl of 1 to 6 carbon atom (s), the compound in which R is propyl or butyl has an unexpectedly high fungicidal activity against grapevine dew owns. This is unexpected as the connec-

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fertilize in which R contains fewer than 3 carbon atoms or more than 4 carbon atoms up to 6 carbon atoms / shows a significantly poorer activity in terms of combating powdery mildew as well as significantly higher ED ₅₀ , "" values. Recent fungicide agar investigations using N-methoxyacety1-N- (1-methoxycarbonylethyl) -2,6-dimethylaniline-resistant mutant strains of Pythium ultimum or Pythium vexans have shown that the fungicidal activity of the compounds in which R is propyl or butyl, Significantly better ED _n values compared to resistant fungi

gen than the compounds in which R is less than 3 carbon contains atoms. The compounds in which R has more than 4 carbon atoms are also opposite this acquired resilience less effective, with their activity compared to the original Fungi is already too low compared to the compounds in which R stands for propyl or butyl.

The invention relates to 3- (N-butyryl-N-arylamino) lactones and thiolactones of the formula

If

Ar-

_C-2 CH {CH _{2) m} CH ₃ NR

W = C ²

wherein Ar is phenyl or phenyl, substituted with 1 to 3 alkyl group (s) with 1 to 4 carbon atom (s),

R is identical or different and represents hydrogen or

2 3

Alkyl with 1 to 6 carbon atom (s), R and R

individually hydrogen or alkyl of 1 to 6 carbon atom ten), m is 1 or 2, η is 1 or 2, and W, Y and Z are oxygen or sulfur.

I SUITABLE

2 3

Representative alkyl groups that R / R and R represent can are methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, isohexyl etc.

Representative substituted phenyl groups for which Ar are 2-methylphenyl, 4-methylphenyl, 2,6-diethy! phenyl, 2,6-dimethylphenyl etc. In particular

2 Ar stands for 2,6-dialkylphenyl. Preferably R, R are and R is hydrogen .. Preferably Y and Z are oxygen and W is oxygen or sulfur, preferably oxygen, while η is 1.

The lactone and thiolactone compounds according to the present invention can be described by the methods as disclosed in DE-OS 2,845,454.8, by alkylating an aniline (II) with an OC-halogen-iT-butyrolactone or öf-halogen- <Jf-thiobutyrolactone (III) and by subsequent acylation of the 0C- (N-arylamino) -üf * -butyrolactons or -thiobutyrolactons with an acyl halide (V) to obtain the 3- (N-acyl-N-arylamino) -ίΤ-butyrolactone or thiobutyrolactone product (IB) according to the following equations:

ArNH,

X-CH-

i W = C

CH

Ar-NH-CH-

CH,

(III)

Ar-NH-CH CH ₀ 0

Il

(IV)

W = C CH _n + XC-CH ₀ (CH,) _ CH

CH CH,

W = C CH,

(IB)

ff # 4

10

IB

P_S. (0OCH-J

AJL

Il

-R ¹

, C-R

(IC)

15th

wherein Ar, m, W, Ϊ and Z have the same meanings as above and X is chlorine or bromine. The compounds for which η has a meaning other than 1 and

2 3
R, R and R have a meaning other than hydrogen can be prepared by methods which are analogous to reactions (1) and (2).

20th

fs ¹

25th

3ö

35

The alkylation reaction (1) is carried out in the presence of a base. Suitable bases are inorganic alkali metal carbonates, such as sodium carbonate or potassium carbonate, or organic amines, such as trialkylamines, for example triethylamine, or pyridine compounds, for example pyridine or 2,6-dimethylpyridine. In general, essentially equimolar amounts of reactants (II) and (III) and of the base are used. According to a modification of the reaction, a molar excess of the aniline reactant (II) is used as the base, no more base being used. The reaction is carried out in an inert organic solvent, for example an apolar diprotic solvent such as dimethylformamide or acetonitrile, or in aromatic hydrocarbons such as benzene or toluene, at reaction ^{temperatures between 25 and 150 °} C. and preferably 50 and 150 ^° C. Water can be used as a cosolvent. The reaction pressure

• C W €

C I · C t

can be atmospheric pressure, below atmospheric pressure or above atmospheric pressure. In view of the easiness of carrying out the reaction, the pressure is generally atmospheric pressure. The reaction time naturally depends on the Reaktan- i th and the reaction temperature. In general, \ varies the response time of 0.25 to 24 h. The product (IV) |

Γ is generally cleaned using conventional methods / » for example by extraction, distillation or crystal | ! isation before it is used to carry out the acylation reaction (2).

Preferred alkylation reaction conditions become more specific by Richard N. Reynolds, Jr. entitled "Alkylation of Aniline with a Lactone in the Presence of Water" in the ÖS-PS 4 165 322 described.

The acylation reaction (2) is carried out according to conventional methods. The reactants (IV) and (V) are contacted in general in substantially äquiiaolaren amounts in an inert organic solvent at a temperature of 0 to 100 ⁰ C. Suitable inert organic solvents are ethyl acetate, methylene dichloride, dimethoxyethane, benzene etc. The product is isolated and purified by conventional methods, for example by extraction, distillation, chromatography, crystallization etc.

For the preparation of a butyrolactone product {compounds of formula (IA), where Y = 0) can be an organic amine, such as a trialkylamine or a pyridine compound, as Säuxacceptor are used, however, a biaryrothiolactone product (Compounds of the formula IA}, where Y = S), then no organic amine should be used will.

Preferred acylation reaction conditions become more specific by Richard N. Reynolds / Jr./ Stephen D. Z! man and David C. K. Chan under the title "Acylation of Lactone-Substituted Aniline Compound in the Absence of an Acid Acceptor "in DS-PS 4,224,453.

The conversion of the carbonyl compound (IB) into the corresponding Thiono compound (IC) according to reaction (2 ^) can be carried out under the conditions / those of Shridhar et al. in "Organic Preparations and Procedures International ", Volume 12, pages 203-206 (1980) will.

The preferred method for the preparation of compounds of the formula (IA) in which Y is S corresponds to the following Reaction scheme:

# φ Τ · ·

f * Ο * 4 < €

· » Qt ·

Ar-N

a) RS Na ⁺

b) H ⁺

Ar-N

SR
(3)

PCI

Ar-N

(VII)

(4a)

(4b)

The compound of formula (IC) is first treated with the salt, preferably the sodium salt of an alkyl mercaptan, RSNa, where R contains 1 to 10 carbon atoms. Even if the sodium salt of the alkyl mercaptan is preferred, other monovalent cation salts can also be used be, for example the potassium, lithium or ammonium salt. The acidic product of this first reaction will be

»T M

■ 6 ·

314/156

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then with a reagent, such as phosphorus trichloride, which is able to have a carboxylic acid in it corresponding To convert acid halide, treated.

The reaction (3), in a suitable inert solvent at ⁰ to 100 Approx- Π C and preferably between 40 and 80 ⁰ C are durchaezührt. Essentially equimolar amounts of the butyrolactone (IC) and the salt of the alkylmsrcaptan i? SI * a} are used. Suitable solvents are diitietixoxyethane, chlorinated hydrocarbons, dioxane and tetrahydrofuran. The reaction pressure is not critical and can be selected accordingly. In general, atmospheric pressure is maintained. The reaction is generally complete within 1 hour. The acid (VI) occurring as the product can be isolated by conventional methods, for example by extraction, filtration, chromatography, etc. The nature of the salt of the alkyl mercaptan, RSNa, is not particularly critical. Tertiary alkyl mercaptans are preferred over secondary and primary alkyl mercaptans.

Reaction (4a) is carried out above using phosphorus trichloride described, but you can use any reagent that is capable of a carboxylic acid in to convert an acid halide. Examples of such reagents are thionyl chloride, phosphorus pentachloride as well Oxalyl chloride. The reaction (4a) can also be carried out with the corresponding acidic salt of the free acid (VI).

A are kctnn in an inert solvent between 0 and 20 ⁰ C is executed (4 </. By operating at ambient temperature, the reaction mixture is heated after the addition of PCl ₃ to about 4O ⁰ C. An excess of the stoichiometric amount of PCl ₃ is used .

ti «···

- 12 -

After the addition of PCI., The mixture to effect the cleavage reaction (4b) is stirred * This reaction may be between about -6 ° C and about 80 ⁰ C / preferably at 8 to 14 ° C performed werden- The Thiolactonprodukt (ID) separated from the reaction mixture by conventional methods, for example by extraction / filtration / chromatography / crystallization etc.

Particularly preferred solvents for carrying out processes (4a and 4b) are dialkyl glycols / preferably dimethoxyethane and chlorinated hydrogens, preferably methylene chloride. Reactions (4a) and (4b) can be carried out under any conventional pressure, preferably atmospheric pressure.
15th

Although the use of a solvent is preferred to carry out reaction (4a) and (4b), according to another embodiment, the PCl ₃ can be added directly to the acid (VI), in particular when the acid is a liquid. The thiolactone product (ID) can then be isolated using conventional purification methods.

The preferred molar ratio for reaction (3) is 1: 1 for the starting lactone (IC) and the mercaptide salt. To carry out reaction (4a), if phosphorus trichloride is used, the stoichiometric molar ratio of 3: 1 of the acid (VI) to PCl _{3 can be} maintained. An iodol ratio of acid (VI) to PCl ₃ of 3.2 is preferred.

The compounds according to the invention are suitable for combating of fungi, especially fungal attack on plants. For example, the activity is preferred according to the invention Compounds extremely specific to certain fungal diseases, such as powdery mildew diseases, such as. B. Plasmopara viticola (grapes) and Peronospora parasitica

C (Ct · ill · »·

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- 13 (cabbage).

The compounds according to the invention are particularly suitable Fungicides as they fight established fungal infestations. This allows an economical use of the invention Fungicides, as they are only applied to the plants when a fungal attack has actually occurred is. A preventive program using fungicides against a potential fungal infection is not 10 necessary.

When used as fungicides, the compounds according to the invention can be applied to fungi in fungicidally effective amounts and / or their growth sites are applied, for example the plant hosts and offspring, for example Animal products. The amount used depends of course on various factors, such as the host, the Mushroom type and the one used in each case according to the invention Link. As is the case with most pesticidal compounds, the fungicides of the invention are common not applied as such, but generally in conventional biological inert extenders or Carriers introduced as they normally would to facilitate the dispersion of active fungicidal effects

25 are used, the formulation and the type of application affect the activity of the fungicide. The fungicides according to the invention can therefore be in the form of Granules, powdery dusts, wettable powders, emulsifiable concentrates, as solutions or in the form

30 of other known formulations can be formulated and used depending on the desired type of application.

Wettable powders are in the form of finely divided particles that are easily dispersed in water or other dispersants Disperse 35. These preparations usually contain 5 to 80% fungicide and the remainder inert material such as dispersants, emulsifiers and wetting agents.

SJI · fl ti · I

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The powder can be applied to the soil in the form of a dry substance or, preferably, in the form of a suspension in water. Typical carriers are Fuller's earth, kaolin clays, silica and other highly absorbent, wettable inorganic diluents. Typical wetting, dispersing or emulsifying agents are for example the following: the aryl and alkylaryl sulfonates and their sodium salts, alkylamide sulfonates, for example Fettmethyltauride, alkylaryl polyether alcohols ₇ sulfated higher alcohols and polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, sulfonated petroleum oils, fatty acid ester of polyhydric alcohols and the ethylene oxide such esters, as well as the addition products of long-chain mercaptans with ethylene oxide. Many other types of suitable surfactants are commercially available. The surfactant is normally used in an amount between 1 and 15% by weight, based on the fungicidal agent /.

Dusts are free-flowing mixtures of the active fungicide with finely divided solids, such as talc, natural shades, Kieselguhr, pyrophyllite, lime / diatomaceous earth, calcium phosphates, Calcium and magnesium carbonate / sulfur / lime, flour and other organic and inorganic solids, which serve as dispersants and carriers for the active ingredient. These finely divided solids have a average particle size less than about 50 microns. A typical dust formulation contains 75%

30 silica and 25% of the active ingredient.

Suitable liquid concentrates are the emulsifiable concentrates which are homogeneous liquids or pastes and are easily dispersed in water or other dispersants and completely out of the fungicide with a liquid or solid emulsifying agent. They can also use a liquid carrier such as xylene,

IB t * ■ · ·

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Contains heavy aromatic naphthas, isophorone and other non-volatile organic solvents. To the application these concentrates are dispersed in water or other liquid carriers and usually in the form of a Sprays applied to the area to be treated.

Other suitable formulations for fungicidal application are simple solutions of the active fungicide in a dispersant in which it is completely soluble in the desired concentration, using as a solvent Acetone, alkylated naphthalenes, xylene and other organic solvents may be mentioned. Granular formulations, in which the fungicide sits on relatively coarse particles are of particular value for distribution the air odor for penetration into cover crops. Pressurized sprays, typically aerosols, in which the active ingredient in finely divided form as a result of evaporation of a low boiling dispersant as Solvent carrier distributed, mentioning the freons, can also be used. All to Formulation and application of fungicides known methods can be used.

The percentages by weight of the fungicide can be depending on the type / according to which the preparation is applied, as well as depending on the respective Formulation type vary, in general the formulations contain 0.5 to 95% of the active ingredient, based on the weight of the fungicidal agent. 30th

The fungicidal agents can be formulated and applied with other active ingredients, for example other fungicides, Insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc. 35

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Examples

The preparation and use of the compounds according to the invention can be seen from the following examples.

example 1

Production of 3- (N-butyryl-N-2,6-dimethyIphenylamino) -Q-butyrolactone

A slurry of 12.2 g (0/1 mole) 2,6-dimethylaniline, 16.5 g (0.1 mole) Oi-bromo-J-butyrolactone, 10.6 g (0.1 mole) sodium carbonate and 150 nJ. Dimethylformamide is heated to 125 to 140 ^° C. for 21 h. The reaction mixture is then diluted with water and extracted with benzene. D: Benzene extracts are washed with water, dried over magnesium sulfate and evaporated to give an oil. The oil is chromatographed on a silica gel column. 3 = {N = 2.6 = Dijnethyipheriylaiai: no} * = ÜT-butyrölaefcön with a P. of 85 to 87 ⁰ C is eluted from the column using hexane / ether (50:50).

A solution of 6.2 g (0.03 mol) of 3- (N-2,6-dimethylphenylainino) - <3f-butyrolactone, 3.5 g (0.033 mol) of butyryl chloride, 2.6 g (0.033 mol) of fyridine and 150 ml ethyl acetate is stirred overnight at 25 ° C and then at 50 to 75 ⁰ C during the third After cooling, the reaction mixture is washed with water, diluted with methylene chloride, washed with water _f a 10% aqueous sodium bicarbonate solution and then with water, dried over magnesium sulfate and evaporated to give a solid residue. The residue is crystallized from ethyl ether to obtain the desired compound. If the butyryl chloride is replaced by valeryl chloride, the corresponding valeryl homolog of the product is obtained.

»» * Eoc

ο 1 47 1

- 17 -

Example 2 Production of 2- (N-butyryl-2,6-dimethylanilino) -4-

(tert-butylthio) butyric acid

To 952 g (17.02 mol) of sodium methoxide in 3.8 l of dimethoxyethane, 1590 g (17.62 mol) of tert-butyl mercaptan and 3.8 l of dimethoxyethane are added in portions. The mixture is stirred until it has cooled to about 40 ⁰ C.

10

4443 g {16.0 mol) 3- (N-Butyry1-2,6-dimethylphenylanilino) butyrolactone according to Example 1 are added in portions to the reaction mixture which is heated from the outside 60 to 80 ⁰ C. The mixture is stirred and ^{allowed to cool to 60 °} C. and then poured into 2.8 l of ice water.

The mixture is extracted with toluene and the extracts are backwashed with water. Any water backwash is added again to the aqueous phase. The aqueous phase is acidified with 19% HCl (pH 1), then twice extracted with methylene chloride. The organic phases (CH2Cl2) are combined, washed with water and dried (MgSO ^), filtered and stripped to give the sought product in the form of an oil.

25th

Example 3

Preparation of 3- (N-butyryl-2, 6-dimethylanilino) -butyrothiolacton
30th

T) io rromSß Roioniol 9 or7onnfa Gänro t »ri ττΛ ΐ« 9 1 Mof l «; 1 on-

- _, _E - -,, - _ - _Λ

chloride dissolved in a flask, which is provided with a cooler, and ^{cooled to 5 0} C in a dry ice / acetone bath. Then 256 g of PCl _{3 are} added dropwise. The temperature is kept below 10 ^° C. during the addition. The mixture is stirred at room temperature overnight.

It t *

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The mixture is poured into 7.7 liters of ice water, collecting 2 liters of methylene chloride and the organic layer. After two further extractions with methylene chloride, the organic phases are combined, washed with a 50% mixture of saturated NaCl solution and water, dried (MgSO ₂ I, silica gel), filtered and stripped. The oil obtained is slurried in isopropyl alcohol, filtered and the solid washed with isopropyl alcohol and then with hexane to give the sought product.

Example 4 Preventive powdery mildew control

The compounds according to the invention are used for combating powdery mildew organisms, Plasmopara viticola examined. Plucked leaves with a diameter between 70 and 85 mm of 7 week old Vitis vinifera cultivar Emperor seedlings are used as hosts. The leaves are sprayed with a solution of the test compound in acetone in various concentrations. The sprayed Leaves are dried, inoculated with a suspension of spores of the organism, in a chamber with a humid atmosphere introduced and incubated at 18 to 22 ° C and a relative humidity of about 100%. 7 to 9 days after inoculation, the extent to which the disease has been combated is determined. The percentage of disease control that by the compound of Example 1 is based on the percentage of disease reduction compared to non-treated reference plants. The connection of the Example 1 gives 99% control at 250 ppm, 82% control at 100 ppm and no control at 40 ppm. The loss of control at 40 ppm is believed to be due to an accidental loss of the Connection when performing this test. Subsequent tests {s. Example 6) result in a 96% loading

ce β e * c

st »cea

- 19 -

fighting at 40 ppm.

Example 5 Eradicating powdery mildew control

Compounds according to the invention are examined with regard to their eradicating efficacy of the powdery mildew organisms Plasmopara viticola. Plucked leaves with a diameter of 70 and 80 mm from 7-week-old Vitis vinifera ei'ltivar Emperor seedlings are used as the shepherd inoculated into the organism and placed in a chamber with a temperature between 18 and 22 ° C and a relative humidity of approximately 100% for 1 to 2 day (s) The leaves are then treated with a solution of the test compound in acetone / water and a small amount a nonionic emulsifying agent sprayed. the sprayed sheets are then maintained at 18 to 22 ⁰ C and at a relative humidity of about 100%. Seven to nine days after the Eeimpfung the extent of disease control is calculated. the percentage of disease control obtained by the example 1 is achieved based on the percentage disease reduction in the comparison ch to non-treated reference plants. The compound of Example 1 gives 100% control at 250, 100 and 40 ppm. The compound 3- (N-valeryl-N-2,6 ~ dimethylphenylamino) -. ^ - butyrolactone shows 100% control at 100 ppm and 92% control at 40 ppm.

In the following Table I, the fungicidal activity isc a homologous and isomeric series of Verbindvngen shown, the only difference between the compounds in length and in the Verzweigungsgrac ¹ is the carbon chain of the R substituents.

The tests are related to that in Example 4 carried out in the manner described with the control of powdery mildew. The test connections are applied

■ "" 20 "*

in an amount of 250 ppm / unless otherwise in brackets Quantities are given.

The tests to determine the control of tomato rot are carried out according to the following method:

Five to six week old tomato seedlings (variety Bonny Best) are used. The tomato plants are sprayed with a 250 ppm suspension of the test compound in acetone / water and a small amount of a nonionic emulsifier. The sprayed plants are then inoculated 1 day later with the organism, placed in a chamber and ^{incubated at a temperature of 19 to 20 °} C. and a relative humidity of 100% for at least 16 h. Following cultivation, the plants are kept in a greenhouse at a relative humidity of 60 to 80% for approximately 7 days. The percentage disease control by a given test compound is based on the percentage disease reduction compared to untreated control plants.

Table I Fungicidal activity at 250 ppm

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υ O O CH ₃ ' O O ^C 2 ^H 5 O O CH ₂ CH ₂ CH ₃ O O CH (CH ₃ ) 2 O O CH ₂ CH (CH ₃ ) ₂ O O C (CH ₃ J ₃ S. O CH ₂ CH ₂ CH ₃ O O CH ₂ CH ₂ CH ₃ O S. CH ₂ CH ₂ CH ₃ GDM = powdery mildew of the vine TLB = tomato rot

GDM TLB 42 (100 ppm) 79 (100 ppm) - 23 100 99 0 23 96 0 - 0 99 35 82 (100 ppm) 91 (100 ppm) 100 96

(Plasmopara viticola) (Phytophthora infestans)

Example 6

In this example follow-up tests regarding the preventive Powdery mildew activity and preventive tomato rot activity using the inventive method

2 bonds carried out in which Y stands for -O- and R H is / while η is 1, and the corresponding substi-

1 2

tuent R stands for ethyl and R for n-pentyl homologues.

The same methods are used as explained in connection with the tests described above are used, with the exception that the specified doses are observed. There will also be tests using dosages of 250 and 100 ppm to various Time points compared to tests performed using doses of 40, 16 and 6.4 ppm. The results of these tests are shown in Table II below.

As can be seen from Table II, show the invention Compounds have a much better preventive powdery mildew activity in these tests and clearly over-

II · · 4

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10

15th

20th

25th

30th

35

lower (lower) ED ₅₀ / "" values. The tomato rot activity is also better in the case of the compounds according to the invention, but not as outstanding as the powdery mildew activity.

Table II Preventive Fungal Activity

CH

- ^C 2 ^H 5

^ED 50/90 -CH ₂ CH ₂ C

^ED 50/90

^ED 50/90

^ED 50/90

* N.T "= * N.C. =

dosage percent GDM Combat ppm 100 TLB 250 96 80 100 80 54 40 44 0 16 20th 0 6.4 18/72 ppm N.T. * 100 105/380 ppm, 250 100 94 100 96 76 40 82 48 16 43 0 6.4 7/25 ppm N.T. 100 46/190 ppm 250 100 96 100 60 35 40 54 28 16 N.T. 8th 6.4 3.7 / 6.8 ppm N.T. 100 N.C * 250 37 91 100 27 37 40 16 3 16 N.T. / 6.4 38/100 ppm N.T.

not tested
not calculated

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Example 7

This example compares the fungi toxicity of different ones Aniline derivatives including the compounds according to the invention with N-methoxyacetyl-N- (1-methoxycarbonylethy1) 2,6-dimethylaniline, hereinafter referred to as "comparison substance" in this example, the opposite to mutants of Pythium ultimum and / or Pythium vexans as well as against the sensitive naturally occurring species of these Is fungus resistant. The opposite of the comparison bar punch resistant mutants are obtained from the laboratory of the L.V. Edgington of the University of Guelph.

This investigation is carried out in such a way that Including ethanol solutions of the compounds to be tested in each case the reference substance can be produced. 1 ml of the ethanol solutions is melted with 100 ml of a V-8 juice agars mixed. The medium is poured onto plates and allowed to cool. Use a cork drill bit (No. 2) to be Parts of the agar mycelium cultures of the respective fungi are removed from the edge and placed in the center of the treated agar plates placed upside down. Surface growth measurements (diameter in mm) are in carried out two directions. The average values and the 8 mm diameter of the inoculated material are determined subtracted. The values are plotted on dose response curves on a log probability paper plotted / from which in turn the ED. values are determined. Each treatment comes in three editions performed, being tested one or more times V-urd. The dose response curves encompass four doses of compound.

The results of this study are shown in Table III below. The ratio of ED ^ -resistant to ED ₅ Q-sensitive is an indication of the extent to which the fungi toxicity of the compounds is caused by the

'Jf -ι

Fungi developed comparative ^ hardiness being affected. The smaller the ratio, the more likely it is that the connection the blocking by the resistance to the comparison connection breaks through (a change in the Ratio between the two mutant species indicates that the resistance developed between the two Mutants varied).

From this table it can be seen that although the relative EO _g "ratios for the compound in which R stands for ethyl is very good, the actual ED _gQ values are over twice the ED ₅ values of the compound , in which R is propyl, in the case of P. ultimum (resistant), and ten times higher in the case of

p. ultimum (sensitive). The ED _gn value of the compound in which R is ethyl is more than three times higher than the value of the compound _; in which R is propyl _; namely with regard to P. vexans (resistant) and is more than two times higher than in the case of P. vexans (susceptible). In the case of the compound in which R is butyl,

the ED _g - _n value of the compound in which R stands for ethyl is more than three times above the value of the compound in which R stands for butyl, with respect to P. vexans - (resistant) and is more than ten times with respect to

P. vexans (sensitive). The compound in which R is pentyl shows an excellent EDj.-R / S P. vexans ratio and an excellent ED _gQ P. vexans (resistant) value. The fungitoxicity of these compounds appears to be significantly less affected respect vine mildew be generated by the acquired resistance to the comparison compound as each of the compounds in Table III and the actual base-ED_ _n value fungi according to Table II of Example 6, but is (of course) already 4 to 10 times higher than in the case of the compounds according to the invention in which R is propyl or butyl.

The compounds according to the invention show a very good action in combating powdery mildew of the vine which is produced by non-mutant fungi (see Table II, Example 6). As can also be seen from Table III, these compounds are influenced less by the mutants resistant to a comparative compound than by the comparative compound or two of the leading newer powdery mildew aniline fungicides in which -CH ₂ OCH ₃ or R is -CH ₂ Cl.

,1

comparison
-CH ₂ OCH ₃
-CH ₂ Cl
-CH ₂ CH ₃
- (CH ₂ J ₂ CH ₃
- (CH ₂ J ₃ CH ₃
- (CH ₂ J ₄ CH ₃

Pythium ultimate sensitive resistant

(naturally occurring)
ED ™, ppm

ED ₅₀ ppm

0.036

0.005

0.005

0.216

0.02

N _f T. *

N. T.

940 800 120 210 95

N.T. N.T.

* N.T. = not tested

Table III

CH

ED ₅₀

Ratio ,, R / S

26,000

160,000

24,000

808

4,750

Pythium vexans sensitive resistant

(naturally occurring)
ED ₅ ppm 'ED _{! 50} ppm

0.075

0.15

0.19

0.43
0.10
0.56

635

400

145

140

43

40

16

S0

Ratio, R / S

8,467

8,000

763

<140

100

400

29

cn *

I »a a

CO

cn

CD

Claims (1)

ί ■ > ■ tftl ft · ·· «
* · * Me ** · · · »
• a * · * · · ¹ """* ·· 3147156
- 1 - Claims ι 5 M. X compound of the formula
■ 7: A i
a
Ar-N R
\ e - «U 10 Y 15th wherein Ar is phenyl or phenyl substituted with 1 to 3 alkyl groups with 1 to 4 carbon atom (s), R has the same or different meanings and Hydrogen or alkyl with 1 to 6 carbon atom (s) represents 20th 2
R hydrogen or alkyl with 1 to 6 carbon atom (s) vers imaged, m is 1 or 2, η is 1 or 2 and Y and Z are acidic 25th are substance or sulfur. 2. A compound according to claim 1, characterized in that Y and Z represent oxygen. 3. A compound according to claim 2, characterized in that 30th η = 1 and R and R are hydrogen. 4. A compound according to claim 3, characterized in that ax cue α, o-üiaxKyipnenyi represents :. 35 5. A compound according to claim 4, characterized in that Ar is 2,6-dimethylphenyl. 6. A compound according to claim 5, characterized in that m means 1. ■ S w β ■ » 9 # η *« f ν ·· * «* · r * "" '' '** 3U7156 7. A compound according to claim 5, characterized in that m is 2. 8. A compound according to claim 1, characterized in that Y means oxygen, Z is sulfur, Ar 2,6-Dimethy1- phenyl b <. denotes phenyl, η is 1 and R and R represent hydrogen 3. Connection to. Claim. 3, thereby kersTizeigns, because ° generally stands for 1 10. A compound according to claim 9, characterized in that m means 2. 11. Fungicidal agent, characterized by a fungicidally effective amount of a compound according to claim 1 and an inert carrier. 12. A method for combating powdery mildew of the vine, characterized in that that the powdery mildew or its growth point is contacted with a fungicidally effective amount of a compound according to claim 1.