SU743561A3 - Microbicidic and plant-growth regulating agent - Google Patents

Abstract

1498199 Heterocyclic amides CIBA-GEIGY AG 1 April 1975 [2 April 1974 10 Feb 1975] 13349/75 Heading C2C Novel compounds of Formula (I) wherein R 1 represents a halogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms, R 2 represents a hydrogen or halogen atom, an alkyl group of 1 to 3 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, R 5 represents a hydrogen or halogen atom or an alkyl group of 1 to 3 carbon atoms, and R 6 represents a hydrogen atom or a methyl group and the total number of carbon atoms in the substituent groups R 1 , R 2 , R 5 and R 6 on the phenyl ring does not exceed 8; X represents the group R 3 represents the group (wherein each of R<SP>1</SP>, R<SP>11</SP> and R<SP>111</SP> represents a hydrogen atom or a methyl or ethyl group); and R 4 represents an unsubstituted or halosubstituted furyl, tetrahydrofuryl, pyridyl, or pyrimidyl group; but excluding the compounds N - (1<SP>1</SP> - methoxycarbonylethyl) - N - (furan- (2<SP>11</SP>) - carbonyl) - 2,6 - dimethylaniline and N - (1<SP>1</SP> - methoxycarbonylethyl) - N - (furan- (2<SP>11</SP>) - carbonyl) - 2,3,6 - trimethylaniline) are used in fungicidal compositions. They may be prepared either by (a) acylating a compound of Formula (II) with a compound of formula or an acid halide, or anhydride thereof or by (b) reacting a compound of Formula IV with butyl lithium or sodium hydride to give the corresponding alkali metal salt and then reacting this salt with a compound of formula where Hal is a halogen atom. The enantiomeric D-form of the compounds of Formula (I) in which X = -CH(CH 3 )- may be prepared by reacting the racemic compound of Formula (VI) with a nitrogen-containing, optically active base to give the corresponding salt, followed by fractional crystallization and liberation of the acid of Formula VI which is enriched with the optical D-antipode. The D-form of the ester of Formula II may then be prepared in conventional manner from the D-form of the acid of Formula VI. The D-form of the amide of Formula II may be prepared by reacting the D-form of the acid with the amine of formula HN(R<SP>11</SP>)(R<SP>111</SP>). The D-form of the compound of Formula (I) may then be prepared as in step (a) above. The D-form of the compound of Formula VI may also be prepared by replacing the hydroxy group in the naturally occurring L(+) lactic acid by halogen and reacting this product further with the aniline of Formula VII with reversal of the configuration.

Description

the ash ring contains other substituents, when it is in the 2,6 or. 2,3,6 position it contains methyls as substitutes and when it is simultaneously a 2-furanyl residue and XR is the residue of L-propionic acid methyl ester, in an amount of 0,0120 weight .%.

On plants and parts of plants (fruits, flowers, foliage, stems, tubers, roots) of these and similar useful crops with the help of biologically active substances of formula (I) can be destroyed or development can be inhibited.

fungi, and later grown plant parts also remain unaffected by fungi of this type. Biologically active substances exhibit activity against phytopathogenic fungi belonging to the following classes: (for example, Erysiphaceae); Basidiomycetes primarily rust fungus; Fungiimperfecti, but especially against such Oomycetec, belonging to the class Phycomycetes, as Phytopthora, Peronospora, Psendoperonospora, Pythum or .PPasmopara.

In addition, the compounds of formula (I) act systemically. They can be used as disinfectants for treating seed materials (fruits, tubers, grains) and cuttings of plants for the purpose of protection before infection with fungi, as well as against phytopathogenic fungi that are

0 in the soil.

In tab. 1 shows compounds of formula (I)

Table 1

n (cN СН СНз СНз СНз Н-СН- € ООСН 13 СН, CHj СН-СН СООСН15 product ГТ.ПЛ. 132-139 С. ilJ т. кип. 171-176 с / / 0,2 mm Hg Mp 126-132s

Table 2 shows the compounds that contain one or two substituents in the phenyl core, among them are the compounds of formula (II)

6-UK

CH,

5-ce

se

Continuation of table 1,

X-r.

-N

WITH

Xox

table 2

Mp. 128-130 s

m.p. iio-iia c

Continuation of table 2

6-CH.

50

CH

J.

As r "icrobicidal agents, it is preferable to use compounds of formula (I) in which R is a methyl radical, Rg is in the o-position to the amino group and is a methyl radical, ethyl radical, or a chlorine atom, X-Кз has the group:

; sn,

-CH-COOR

At the same time, R, Rg 6 R and 1 take the meanings indicated for these symbols. These compounds must be assigned to the group of compounds (II).

Among these compounds (I), such compounds are isolated in which is a methyl radical substituted, but preferably an unsubstituted 2-furanyl residue.

In this last group, compounds of particular importance as microbicides are those in which X-Кз is a residue of l-propionic acid methyl ester and in which the total number of carbon atoms in the substituents R, .R, Rj and R le exceeds 4, - - for example, production 2,3,5,6-n. tetramethylaniline, 2, b-dimethyl-3-ethylaniline or 2,6-dimethylamiline, as well as such derivatives of 2,6-dimethylaniline, which still contain the third substituent Rj or Rg in the phenol core.

Among the group of compounds (I1), it is of interest

as other microbicides, a group of such compounds in which the ID of PR6D consists of a 3-furanyl tablet containing one or two methyl radicals as substitutes.

Another group of compounds that are preferably used to regulate plant growth includes compounds of formula (I), in which

RI is a methyl or ethyl radical, Rg is in the o-position with respect to the amino group and is a methyl radical, an ethyl radical or a chlorine atom, X-R is a group

.ONCR) (R-) while R, Rj. RS R and I exceed the values specified for these characters.

Plant growth regulation, in the first place, should be understood as inhibiting control of the natural development of plants, mainly the desired reduction in the size of plants, in particular their height. A similar reduction in growth is observed in the case of monocotyledonous and dicotyledonous plants, especially in grasses, crops and ornamental plants.

The compounds of the formula () with a view to expanding the spectrum of action can be applied with other suitable pesticidal or biologically active substances promoting plant growth.

The compounds of formula (I) may be used alone or together.

with suitable carrier materials and / or other additives. Suitable carrier materials and additives may be solid or liquid substances and correspond to substances commonly used in the preparation of compositions, such as, for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesion enhancers, thickeners fertilizers or fertilizers.

The content of biologically active substances in commercial products 0.1-90 wt.%.

For use, the compounds of formula (I) can be in the following working forms (the preferred amounts of the active compound are shown in parentheses, wt.%):

solid working forms: powdered preparations and chemicals for soil application (up to 10), granulated preparations, granulated preparations with a shell, impregnated granulated preparations and homogeneous granulated preparations (1-80)

liquid working forms: dispersed in water concentrates of biologically active substances, wettable powders and pastes (25-90 in commercial packaging, from 0.01-15 in ready-to-use solution); emulsion and soluble concentrates (10-50, 0.01-15), solutions (0.01-20)

Biologically active substances of the formula () can be transferred to the drug, for example, in the following ways.

Dust preparation. To obtain a 5% or 2% powdered drug, the following substances are used, respectively: 5 hours of biologically active substance and 95 hours of talcum powder or 2 hours of biologically active substance, 1 hour of highly dispersed silicic acid and 97 hours of talcum powder.

The biologically active substance is mixed with a carrier substance, grind. The preparation in the form obtained can be applied by a pollination method.

Granular product. To obtain a granular preparation, the following substances (parts) are used:

biologically active substance5 etylchlorohydrin 0.25 methyl polyglycol ether 0.25

Polyethylene glycol 3.5 kaolin (grain size 0.3-0.8 mm) 91 The active substance is mixed with ethylahydrin and the mixture is dissolved in acetone, after which Polyethylene glycol and methyl polyglycol ether are added. The kaolin is sprayed with the solution obtained in this way and the acetone is immediately evaporated under vacuum. A microgranular preparation of this type is used primarily to combat soil fungi.

Wettable powder. To obtain 70% (a), 40% (b), 25% (c, d) and 10% (d) wettable powders, the following components (parts) are used, respectively:

a) biologically active substance 7Q sodium dibutylnaphthylsulfonate 5

condensation products of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde (3: 2: 1) 3 kaolin 10

chalk from Champagne 1

b) the biologically active substance 40 sodium salt ligninsulfonic acid 5 sodium salt dibu,. tylnaphthalene sulfonic acid1

silicic acid 54

c) biologically active substance25 ligninsulfonate 4, 4

mixture consisting of

chalk from Champagne and

hyroxingtilcellulose (1: 1) 1.9

sodium dibutylnaphthalene sulfonate 1.5

silicic acid. 19.5 chalk from Champagne 19.5 kaolin 28.1

d) a biologically active substance 25 isooctylphenoxypolyoxyethylene ethanol 2.5 mixture consisting of

chalk from Champagne and hydroxyethyl cellulose

(1: 1) .1,7

Sodium aluminum silicate8, 3

Kieselguhr16,5

kaolin46

e) the biologically active substance 10 a mixture of sodium salts of sulfates of saturated fatty alcohols 3 naphthalene sulfonic acid condensation product

and formaldehyde 5 kaolin82

The biologically active substance is thoroughly mixed in a suitable mixer with additives and ground in a suitable mill and roller, ah. As a result, a wettable powder is obtained, having excellent wettability and ability to be suspended, which can be diluted with water to obtain a suspension of any desired concentration and be used, in particular, for treating the leaves.

Able to emulsify concentrate. To obtain a 25% emulsifiable concentrate, the following substances (parts) are used:

biologically active substance25

poxidated vegetable oil 2.5 mixture of alkylarylsulfonates and polyglycolic ester of fatty alcohols 10 dimethylformamide 5 xylene 57.5 By diluting with water from the resulting concentrate, it is possible to obtain emulsions of any desired concentration that are suitable especially for leaf treatment,

 Below are examples of testing the proposed remedy.

Example 1. Action against Phytopthora intestans on tomatoes.

Residual Preventive Effects Tomatoes, after growing for three weeks and after spraying with a liquid containing 0.05% of the active substance (obtained from the biologically active substance, processed into a wettable powder), followed by drying the applied liquid, were infected with a suspension of zoospitophytosis. The plants are kept for six days in a climatic chamber at a temperature of 18–20 ° C and under conditions of artificial fog that occurs when splashing liquid. After the specified time has elapsed, typical phytophtoras appear on the leaves. Their number and size is the scale for evaluating the test substance.

Therapeutic effect.

Tomatoes, after being harvested for three weeks, are sprayed with a suspension of zoospores of the fungus and incubated in a chamber at 18-20 ° C in an atmosphere saturated with moisture. Moistening is stopped after 24 hours. After the plants have dried, they are sprayed with a liquid that contains a biologically active substance, processed into a wetted powder, at a concentration of 0.05%. After the applied liquid has dried, the plants are again kept in a moist chamber for four days. The number and magnitude of typical spots on the leaves, which appeared after this time, serve as a scale for assessing the activity of the test substance. Protection of system action. A biologically active substance prepared in the form of a wettable powder in a concentration of 0.05% (based on the volume of the soil) applied three not to plant tomato plants on pots on the soil surface on tomato plants by age. After three days

0 extracts the underside of the leaves of plants is sprayed with phytophthora suspension of zoospores. Then the plants were kept for five days in a spray booth at a temperature of 18-20 ° C.

to in the atmosphere natiatenogo moisture. After the specified time has elapsed, typical spots are formed on the leaves, the number and size of which serve to evaluate the activity of the test substance.

Q

Of the 48 compounds tested, when using 11 compounds, the damage by fungi was only O-5%, 35 compounds - less than 20%, and only with the use of two compounds, the damage

5 mushrooms accounted for 20-40%.

Example 2. Action against PBasmopara vitico8a on the vine.

30 Residual safety action.

In the greenhouse planted grapes. In the 10 leaf stage, three plants are sprayed with liquid.

the resulting igr processed in

after wetting the applied liquid, the plants are infected evenly from the underside of the leaves with a suspension of spores of the fungus. Immediately after this, the plants are kept for 8 days in the moisture chamber. After the indicated time, clear symptoms of the disease appeared on the control plants. The number and size of the affected areas serve as the scale for evaluating the effectiveness of the study.

Therapeutic effect.

Winery saplings planted in

in the greenhouse and in the 10 leaf stage, the spores of PP are infected with a suspension of spores from the underside of the leaves. viticopa. After 24 hours in the humid chamber of the plant sprayed with a liquid containing a biologically active substance that was prepared from a wettable powder containing a biologically active

substance. Immediately after

this plant has been kept in a humid chamber for seven days. After the indicated time, clear signs of disease appeared on the control plants. The number and size of the affected areas serve as a scale for evaluating the effectiveness of the test compound.

In these two experiments, the compounds of formula (I) predominantly showed a good fungicidal effect on the leaves. Compounds in all cases reduced the lesion with fungi - up to 20%, almost no lesion was observed (0-5%) ..

Example 3. Action against Erysiphe gramtnis on barley.

Residual protective action.

Barley plants about 8 cm high are sprayed with a liquid obtained from a biologically active substance wettable powder (0.05%) of the active substance in a liquid. After 48 hours, the treated plants were dusted with fungal conidia. Infected plants are placed in a greenhouse and kept for 10 days at a temperature of about 22s, after which the extent of fungal infection is assessed.

Some compounds of the formula (.1) showed a decrease in fungal infection by up to 20%.

Example 4. Action against Phythium debaryanum on sugar beet.

Action after tillage.

Fungi are cultivated on sterile oat grains and mixed into a mixture of earth and sand. The land infected by this method is placed in flower pots and sugar beet seeds are sown. Immediately after sowing, the earth is poured over with an aqueous suspension prepared from an experimental preparation, prepared in the form of a wettable powder (2.0 ppm, of a biologically active substance in the calculation of

on the volume of soil). After that, the pots are incubated for two to three weeks in a greenhouse at 20-24 ° C. At the same time, the soil is kept in a uniformly wet state by lightly spraying with water. In evaluating the test, the germination of sugar beet plants as well as the number of cured and diseased plants are determined.

Action after treatment with the composition.

Fungi are cultivated on sterile oat grains and mixed into a mixture of earth and sand. The soil contaminated by this method is placed in flower pots and sugar beet seeds are sown, which are pickled by an experienced preparation prepared as a pickled fox grass

(loco ppm, biologically achenogo

substances based on grain weight). Pots with sown soil. Hold for two to three weeks in

greenhouse at a temperature of 20-24 ° C. At the same time, the soil is kept in a uniformly wet state by lightly spraying with water.

In the assessment, the germination of plants is determined, as well as the number of recovered and sick plants.

After treatment with biologically active substances corresponding to formula (i), both under the conditions of experiment a) and under the conditions of experiment c), more than 85% of the sugar beet plants germinated, they had a healthy type. In the case of untreated control plants, about 20% of the plants were partly diseased.

Example 5. Inhibition of growth of herbs.

On an open-air lawn, covered with herbs Lo6iurn perenne, Poaprafensis, Festica rubr, 3 M cases were sprayed two days after springing with water preparations containing biologically active substances of formula (I). The use of biologically active substances - 5 kg of active substance per 1 ha. Untreated plots were control. Six weeks after the treatment, the average height of the grasses on the treated and untreated cuttings was determined. The plots treated with biologically active substances had a healthy appearance. The biologically active substances of formula (I), in which —X — R means the residue defined for formula (I) —CO — N (R) (R), have shown strong and almost complete growth inhibition.

Claims (1)

Invention Formula Microbicidal and plant growth regulating agent based on active ingredient - chloroacetanilide and one or more solid or liquid fillers or solvents, characterized in that, in order to increase the activity of the agent, as an active start taking compound of general formula X-r. -N with II Oh R r C-C-alkyl or halogen, hydrogen, Cj-Ci-alkyl or halogen; RC hydrogen, Cj-C-alkyl or halogen, hydrogen or methyl, with the most carbon atoms in R exceeding eight; CH / CHj /; r2 rnnOtTGGGT / PM, or CON -. (i COOR where R, R and R are hydrogen, methyl or ethyl, R is unsubstituted or substituted by halogen 2-furanyl, pyrimidine or 2-tetrag1-schrofuranyl, provided that the benzene ring contains other substituents when it is 15 in position 2, b or 2,3,6 contains methyls as substituents and when one 743561 with R R5 in s or tat moms with Germany it is temp 18 - 2-furanyl and X-Rj-methyl ester residue -propionic acid, in an amount of 0.01-20 wt.%. Priority on the grounds: 02/04/74 with R, R, R, X, R. and R have the specified value, and Rg, is hydrogen, replaced by a beam Methyl 56-membered heterocyclic sedge with one or two heteroatoms, February 10, 75, for all other terms Sources of information that are taken into account during the examination 1. Inventory Description of Invention No. 2006471, class 45 g 9/24, spec. 27.08 , 70 (prototype).