DE3222010A1 - Fungicides - Google Patents

Abstract

Fungicides containing a compound of the formula I <IMAGE> in which R is -CH2ZR1 in which Z is -O-, -SO-, -SO2-, R1 is alkyl, alkenyl, -CH2Hal (Hal is chlorine, bromine or fluorine), or R is a heterocycle having 1 or 2 hetero atoms and X is <IMAGE> where Y is O or S, in combination with one or more compounds selected from the group comprising fentin-acetate, folpet, captan, maneb, zineb and mancozeb, have advantageous synergistic activity.

Description

HOECHST AKTIENGESELLSCHAFT HOE 82 / F 126 Dr. AU / Rt

Fungicides

The present application relates to fungicidal agents which are characterized by the content of a compound of the general formula I _f

vorm
R = -CH ₃ ZR ₁ , -CH Hai or a saturated or

unsaturated heterocycle with 1 or 2 heteroatoms with

Z = -0-, -S-, -SO-, -SO--, R ₁ = (C.-CoJ-alkyl, (C ₁ -CJ-AIkCnYl,

15 ^ö

Hai = chlorine, bromine or fluorine and

CII.
X = -CH-COYCII ₃ and Λ. A ^with Y = 0, S

mean

in combination with one or more compounds from the group of compounds of the formulas II to VI,

Il ♦. · · ■

322201C

- ¥ -

XSCCl -

NHCSS

CIL

"^ NlIC S S

CIL

CJi ₂

, Νίί-CSS

(V ₁ )

v. where in formula V Me stands for a manganese, zinc or iron cation and in formula VI M stands for an equimolar amount a mixture of zinc and manganese cations.

The compounds of the formulas I are fungicides that are described in German Offenlegungsschriften 26 43 403, 26 43 404, 29 48 568, 29 48 734 and 29 10 920, in the Belgian patent specification 871 - 668 and in the European patent application 34,205 are disclosed. Since the compounds of formula I have at least 1 asymmetry center, they can be used as mixtures of enantiomers or in the form of pure optical isomers in the agents according to the invention can be used.

The compounds of the formulas II - VI are d.io literature known Fi.mgiz.ide fentin acetate (formula II) , Folpe.t (formula III), captan (formula IV), Maneb,

Zineb (Formula V) and Mancozeb (Formula VI).

It is known that the above compounds are a z. T. excellent fungicidal effect especially against the Oomycetes belonging to the class of Phycomycetes, such as Pythium, Phytophthora, Peronospora, Pseudoperonospora and Plasmopara.

This allows fungi to grow on a wide variety of crops, TO such as maize, rice, grain, sugar beet, vegetables, cucumber plants, Potatoes, tomatoes, vines, hops, tobacco, citrus and paprika varieties, ornamental plants, cocoa, bananas and rubber can be combated or inhibited or their occurrence on these plants completely prevented. You let can also be used as a dressing agent for combating seed-borne fungi on seeds or for combating those occurring in the soil use phytopathogenic fungi.

When combining the claimed compounds of the formula I with the abovementioned compounds known from the literature Fungicides of the formulas II - VI have surprisingly been found that the claimed combinations in certain Concentration ranges with a ratio of the compounds of the formula I to the compounds of formulas II to VI in the range from 4: 1 to 1: 4, in particular 1: 1 to 1: 4, produce a synergistic effect. As is well known, synergism exists when the fungicidal effect (degree of effectiveness) of the combination of two or more active ingredients is greater than that theoretically expected sum of the effects of the individual components separate application (method of S.R. Colby: Calculating Synergistic and Antagonistic Responses of Herbicide Combinations in Weeds 1_5 p. 20-22, 1967).

5 The cyncrgistic effect of the claimed combinations of active ingredients is special for agriculture

α> * «* ft · φ ft« 4

322201C

valuable because on the one hand they lead to a noticeable reduction in in "some cases it even leads to a halving of the application rates and thus a reduction the ecological burden. 5

Agents preferred for use are those which contain the compounds 1/1 to 1/8 of the formula I from below Table in which the symbols R and X relate to formula I, table

Ve Γ-
Ιι intimate ig χ R. I / l -CII (CH-) CO ₂ CH ₃ -CH ₀ OCH ^ 1/2 ' -CH (CH-) CO ₂ CH ₃ ■ Ö ' 1/3 -CII (CH ₇ ) CO ₀ ClI- -SOjCH ₃ I / ': t - ^
► C - <ii »- J ' CU ₂ CII ₃ CH- 1/5 *
Co ₉ CJi- -CH ₂ OCH ₃ - ¹ A

-JB-

Ver
binding, X 6th R. 1/7 -CH ₂ Cl 1/8 -CII ₀ OCH ₅

a) in combination with the compound of formula III or

b) in combination with the compound of formula VI or

c) in combination with a mixture of the compounds of Formula II and the formula V, which in turn varies in particular in the ratio range II: V from 4: 1 to 2: 1 can be, or

d) in combination with a mixture of the compounds of Formula IV and the formula VI which in turn varies in particular in the ratio range IV: VI from 1: 2 to 2: 1 can be included.

Particularly preferred are agents that contain the compounds 1/1 and Ϊ / 4 in combination with Folpet (formula

III), Captan + Mancozeb (formulas IV and VI) as well as Contain fentir acetate + maneb (formula II and V).

The combinations according to the invention can use the active substance of the formula I in a mixture with one or more compounds of the formulas II - VI in one Total concentration of 10-90% by weight, preferably 40-80% by weight in addition to the usual formulation auxiliaries

contain.

The combinations can be used as wettable powders, emulsifiable Concentrates, sprayable solutions, dusts, mordants, dispersions or microgranulates in the

• J ·

usual preparations are used.

It.

Wettable powders are evenly dispersible in haters Preparations which, in addition to the active ingredient, optionally contain a diluent or inert substance, wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenyl sulfonates and dispersants, e.g. sodium lignosulfonic acid, 2,2'-dinaphthylmethane-6,6'-disulfonic acid Sodium, sodium dibutylnaphthalenesulfonic acid or oleoylisethylauric acid Contain sodium. They are produced in the usual way, e.g. by grinding and mixing of the components.

Emulsifiable concentrates can be prepared, for example, by dissolving the active ingredient in an inert organic solvent, for example butanol, cyclohexane, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. In the case of liquid active ingredients, the solvent content can also be wholly or partially omitted. Examples of emulsifiers that can be used are: alkylarylsulphonic acid calcium salts such as calcium dodecylbenzenesulphonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide, condensate cation products, alkyl diorbitol fatty acid sorbitol or ethylene oxyester polyglycol ethers, sorbitol ethersorbitol ethersorbitol ethersorbitol ethersorbitol ethersorbitol ethersorbitol oxyester, polyglycol fatty esters, sorbitol oxyesters, polyglycol ethers, sorbitol oxyesters, polyglycol ethers, sorbitol oxyesters, polyglycol ethers, sorbitol ethers.

Dust can be obtained by grinding the active ingredient with finely divided, solid substances, e.g. talc, natural Clays such as kaolin, bentonite, pyrophillite or dieitomc earth obtained.

-fain wettable powders, the active ingredient concentration is e.g. about 10 to 90% by weight, the remainder being 100% by weight from common formulation components. In the case of emulsifiable concentrates, the active ingredient concentration can be approximately 10 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight of active ingredient, sprayable Solutions about 2 to 20% by weight. In addition, contain the active ingredient formulations mentioned optionally the adhesive, wetting, dispersing, emulsifying, penetration, solvent, filling or Carriers.

For use, the concentrates present in commercially available form are optionally used in the customary manner diluted, e.g. with wettable powders, emulsifiable concentrates, dispersions and sometimes also with microgranulates by means of water.

Dust-like and sprayable solutions are usually no longer inert with more pus before use Diluted substances. Mixtures or mixed formulations with other pesticidal active ingredients, such as insecticides, Acaricides, herbicides or growth regulators are possible given fillers.

To obtain the agents according to the invention, both the Ready-to-use single active ingredients are nibbled together are or we}: substances first mixed and then be formulated.

The Aufwanrfcengen the crfindungsgemäßen means vary between 0.4 to 1.8 hg / ha of active ingredient JEM sch and 0.1 - 0.25% Viirkstoffga bsi 5 "0 -? 2 ^r 0 1 / ha Svritzbrühe / preferably in the range of 0 , 4 - 0.6 kg / ha or with 0.1% active ingredient mixture.

The following are some to explain the invention biological examples listed.

ft 9

- ' SC · -

Example I.

Plasmopara viticola vines grown in pots susceptible variety Müller-Thurgau were treated with combination preparations containing either 20 parts of the compound 1/4, 40 parts of N- (Trichlcromethylthio) -phthalimide (Folpet) and 40 parts of formulation auxiliaries (wetting agent + dispersant) or 20 parts of de Compound 1/1 (metaxylyl), 40 parts of N- (trichloromethylthio) -phthalimide (Folpet) and 40 parts of formulation auxiliaries, treated. The tests were four times repeated.

Likewise, the active ingredient components were found on grapevines individually applied to grapevines.

The amounts of active ingredient used per liter Spray liquors can be seen from Table I below

After the spray coating had dried on, the plants were then sprinkled with a sporangia suspension

inoculated by Plasmopara viticola. After an incubation period of approx. 7 days, it was placed in the humidity chamber the infestation broke out, the intensity of the infestation with Plasmopcira viticola percentage values based on untreated infected control plants and the efficacy

degree determined.

The results are shown in Table I. They show that the fungicidal effect in both examples of the mixture the combination of two specific active ingredients is considerably greater than the sum of the effects of the individual components with the same amount of active ingredient and separate application.

While the amount of active ingredient is e.g. 0.125 ppm each of the Connection 1/4 or 1/1 used alone only

provide an efficiency of 65 or 75%, show

the same amounts of active ingredient in combination with each 0.125 ppm Folpet practically still completely free from infestation of the plants.

Bei p iel II

In Example II, the procedure was as in Example I, but the mixing partner for the compounds 1/4, or 1/1 a captan / mancozeb mixture ratio of 1.2: 1

used.
10

The combination preparations are made up of 12 parts of the compound 1/4 or 1/1, 48 parts Captan / Mancozeb (1.2: 1) and 40 parts formulation aid (wetting agent + dispersant)

composed. The results (see Table II below) show 15th

that with a combination of 0.25 or 0.125 ppm of the compound 1/4 or 1/1 with 1.0 or 0.5 ppm captan / mancozeb a synergistic effect occurs.
Example III

In the greenhouse, young potato plants were made from eye cuttings used and with a vegetable oil of 10 cm with various combinations of active ingredients as follows Composition treated:

1. 30 parts of the compound 1/4 and 30 parts of fentin acetate / Maneb (ratio 3: 1) plus 40 parts formulation aid .

2. 30 parts of the compound 1/4 and 30 parts of Mancozeb and 40 parts formulation aid.

3. 30 parts of fentin acetate / maneb (3: 1) plus 30 parts of compound 1/1 plus 40 parts of formulation aid

COPY]

Likewise, eye cuttings were made with the individual Active ingredient components in those given in Table III Treated drug concentrations.

The treatment was carried out in 4-fold manner. After the spray coating has dried, the plants were a temperature of 25 ⁰ C exposed for 24 hours in a humidity chamber at 95% relative humidity bis'100. The plants were then ^{further cultivated at 18 to 20 °} C. in the greenhouse. 8 days after the treatment, the degree of damage was assessed visually and the degree of effectiveness of the combinations and the individual active ingredients was determined.

The results of Table III show in accordance with that at 0.25 ppm of the compound 1/4 i ⁿ combination with 0.25 ppm fentin acetate / maneb or mancozeb, and in the combination of 0.25 ppm fentin acetate / Maneb with 0:25 ppm of compound 1 / 1 Synergism is demonstrable: the fungicidal effect of the combination of the active ingredients combined in each case is greater than the sum of the effects of the individual components when used separately.

9 m # I

-M-

Table I.

Efficiency in% at Plasraopara viticola (wine) at ppm active ingredient

A: Connection 1/4 0.125 0.06 ppm B: Connection 1/1 0.125 0.06 ppm C: Folpet 0.25 0.125 ppm A: Connection 1/4
% Efficiency 65 40 % B: Connection 1/1
% Efficiency 75 65 % C: Folpet
% Efficiency 0 0 % Connection 1/4
A + C: + folpet
% Efficiency 95 65 %

Compound 1/1 B + C: + Folpet

% Efficiency

Font roll

100

Total infestation 0

90-85%

Table II

Efficiency in % for Plasmopara viticola (wine) with ppm active ingredient

A: link 1/4 D. 0 / 25 0 , 125 ppm B: link 1/1 0 , 25 0 , 125 ppm D: Captan;
Mancozeb (1 , 2 : 1 , 0 C. , 5 ppm

Connection I / 4 A: % efficiency

Connection 1/1 B: % efficiency

Captan:

D: Mancozeb {1,2:% efficiency

75

95

65

75

■ s a «a *

β ft * O

222010

- ta -

continuation
Table TI

Efficiency in % with Piasmopara viticola (wine) with ppra Wirksv.ofj

Connection 1/4 A + D: Captan:

Mancozeb (1.2:% efficiency

Connection 1/1 B + D: + Captan
Mancozeb
% Efficiency

control

97

80

lOO

100-97

Total infestation

Table III

Efficiency in% with Phytophthora infestans (potatoes)

Connection 1/4 at ppm active ingredient 0.125 ppm A: Fentin acetate / maneb
(3: 1) 0.25 0.125 ppm E: Mancozeb 0.25 0.125 ppm Q: Connection 1/1 0.25 0.125 ppm B: Connection 1/4
% Efficiency 0.25 40 % A: Fentin acetate / maneb (3:
% Efficiency 65 0 % E Mancozeb
% Efficiency D.
0 0 n. Q: Ve rb i ηduηg 1/1
% Efficiency 0 85 % B: Connection 1/4
: Fentin acetate / maneb
% V? i rk un gsgra: 1 90 50 C. A + E 95-90

- 4-3 -

Fortsei- - ¹ -'τ efficiency in - "with Phytophthora

—.—! R - "': _; ^. L ^. infestans (potatoes) at ppm

Table III Active Ingredient

A + F: connection 1/4 +

Kancozeb,% efficiency 90-85 4 0

Fen ti r. acetate / marieb
E + B: + pre-tying 1/1

% Efficiency 100

Control of total infestation

Claims (7)

• «· 1 HOE 82 / F 126 patent claims: 1. Fungicidal agents, characterized by a content on a compound of the formula I, (D wherein R \ ^ = "-CH ^ ZR ₁ , -CH ₂ HaI or a saturated or unsaturated heterocycle with 1 or 2 Iiete.ro atoms with R ₁ = (C ₁ -Cg) -alkYl, Hai = chlorine, bromine orier fluorine and ²⁰ mean X = -CH-COYCH ₃ and -C J with Y = O, S in combination with one or more compounds from the group of compounds of the formulas II to VI, ²⁵ I ( ^f VlSnOCOCH (IH) 3 0 W \ NSCCl. (IV) I ί / 1 NHCSS CH ₂ MI-CSS ^CH 2 - ,. ^Cn / 'NIICSS ^3o ! M (VI) ^CH 2 - ^ / - NiI-CSS « Λ V w> w HOE82 / F 126 where in formula V Me stands for a manganese, zinc or iron cation and in formula VI M stands for an equivalent amount of a mixture of zinc and manganese cations.
5 2. Fungicidal agents according to claim 1, characterized in that the mixing ratio of the components the formula I to the components of the formulas II bis VI is 1: 4 to 4: 1.
10 3. Fungicidal agents according to claim 1, characterized in that that the mixing ratio of the components of the formula I to the components of the formulas II to VI is 1: 1 to 1: 4.
15th 4. Fungicidal agents according to Claims 1 to 3, characterized in that they contain, as component I, the compound of the formula I with X = -CH (CH ₃ ) CO ₂ CH ₃ and R = -CHpOCH- or the compound of formula I with 20th CH-, X = B ** C - <jf H ^CO 2 ^CH 3 and R = -SO ₂ -CH ₃ as well as as components of formulas II to VI a) the G compound of the formula III or b) the compound of formula VI or c) a mixture of the compound of the formula II with the compound of the formula VI or d) a mixture of the compound of the formula TV with the compound of formula V included. 32220U HOE 82 / F 5. Fungicidal agents, characterized by a content from 10 to 90 wt .-% of an active ingredient combination according to claims 1 to 4, the remainder being 100 wt consists of common formulation auxiliaries. 5 6- Use of the agents according to claims 1 to 5 to combat harmful fungi. 7. A method of combating harmful fungi, characterized in that one is infected by them Cultivated soils, plants or substrates with an agent according to Claims 1 to 5 in a fungicide effective amount treated or brought into contact.