DD222770A1 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to novel fungicidal compositions containing as active ingredient a 1,2,4-thiadiazole of the general formula in addition to extenders and / or surface-active agents in which XBr, Cl; n0,1,2 and RChloralkyl having 1-4 carbon atoms, optionally substituted by further halogen atoms, ester, cyano or keto groups; Chloro or oxocycloalkyl; aralkyl; Aryl (optionally substituted); hetaryl; 3-chloro-1,2,4-thiadiazol-5-yl substituted thiomethyl or when n0 cyano. Surprisingly, the 1,2,4-thiadiazoles used in accordance with the invention show a considerably higher, selective fungicidal action with good cultivar compatibility than the compounds of analogous constitution and the same direction of action known from the prior art. formula

Description

VEB CHBMIEE01 £ BI! I'AT -BITTERZSLD. 2316

Q- ,

"Fungicides,

Field of application of the invention <^;

The invention "relates to new fungicidal agents which are suitable for controlling plant parasitic fungi. In particular, it relates to fungicidally active compounds _: and their preparations for combating Oomycetes, for example Phytophthora infestans.

Characteristic of the known technical solutions

It is known that 3-halo-1,2,4-thiadiazole pesticides ζ. As insecticidal, herbicidal, fungicidal and growth-stimulatory, have gululatory properties (US-PS 3,736,328, US-PS 3,691,183). However, the compounds described in these patents share the significant disadvantage that they have no effect against currently difficult to control harmful fungi, such as Phytophthora infestans.

ο ο β ο "" · '"·

-2 -. 2316

WP A 01 Ν / 260 883/5

It is also known that the practical use of these compounds for controlling harmful fungi on crops is opposed by a relatively high phytotoxicity. . '' _{

Phytophthora active fungicides of agricultural practice, such. B. Preparations based on substituted acetanilides, machen.schon after several years of use, the 'application' increased »application rates required. - '- Preparations based on dithiocarbamates, however, are not fully operational because of toxicological concerns.

Object of the invention . ;. , .. · '

 ', ·. - ":." .. \. - "" '

The aim of the invention is to develop new fungicidal agents, which have a good fungicidal activity especially at low application rates, especially against Oomycetes such as Phytophthora infestans and thereby have a good plant tolerance.

Explanation of the essence of the invention

This object is achieved in that compounds of the general formula as active ingredients in addition to conventional excipients and Srägerstoffen

-Έ

- 3 -. , 2316

in which η is 0.1 or 2 and X is bromine or chlorine, and R is an optionally substituted by further halogen atoms, by ester, cyano or keto groups substituted chloroalkyl having one to four carbon atoms; "a chloro or oxo-cycloalkyl with five or six carbon atoms; an aralkyl radical; an optionally substituted aryl radical, a five-membered hetaryl radical, a 3-chloro-1,2,4-thiadiazol-5-yl substituted thiomethyl radical or, in the case of η = 0, CE

The compounds of the general formula can be prepared by methods known from the literature. They are, for example, by halogenation of dipotassium cyanimido-dithiocarbonate and subsequent addition of the obtained 3-halo-l, 2,4-thiadiazol-5-sulfenyl chloride to olefins and olefinic double bonds compounds or by. Its reaction with ketones, aromatics, heteroaromatics or cyanide accessible. Other representatives of the active compounds according to the invention can be obtained by halogenation of honoester salts of; Cyanimidodithiokohlensäure and subsequent oxidation or chlorinating cleavage of bis (3-chloro-1> 2,4-thiadiazOl-5-thio) methane can be obtained.

Embodiments .

The fungicidal activity of the active compounds according to the invention is to be explained in more detail in the following examples. , "

- 4 - - 2316

: Mean:. , -

Connection-Hr. 1: 3-Chloro-5-benzylsulx "inyl-1,2,4-thiadiazole Compound-Ur. 2: 3-chloro-5-benzylsulfonyl-1,2,4-

  - thiadiazole

Connection LTR. 3: 3-chloro-5 (2 ', 3 ^r -dichloropropylthio) - ,'

1,2j4-thiadiazole '. -

Yerbindtmg-ilr. '.4: 3-chloro-5-chloromethyltioio-1,2,4-

tMadiazole '

Connection-Hr. 3 * 3-chloro-5 (2- ^f -chloro-o-cyclohexylthio) -

1,2,4-thiadiazole. _

: Compound iiTr. 6: 3-chloro-5 (2'-chloro-2-ethyl-2'- ''.

iae tliosycarbonyl) -1,2,4-thiadiaz oil • Compound-Ur .. .. Tf '3-Chloro-5 (3 ^f -bromo-2'-chloro-propyl ·

thio) -1,2,4-thiadiazole '.

Verbindtnig-h'R. '8th; 3-chloro-5 (2'-chloroethylthio ⁾ -: -

, .. - cyano) -1,2,4-thiadiazole. Connection-lr. 9: 3,3-Chloro-5 (2,3-dichloro-prop-1-enylthio) -

1,2,4-thiadiazole Compound Ir., 10: 3-Chloro-5 (T-methylcarbonyl-ethylthio) -

/ 1,2,4-thiadiazole compound -Ur. : 11. 3-chloro-5 (2'-oso-cyclohesylthio) -

    - 1,2,4-thiadiazole Compound-Ir. 12: 3-bromo-5 (2'-chloro-2'-methyl-propylthio) -

  1,2,4-thiadiazole, ·

Connection LTR. 13 s. 3-chloro-5 (2 ', 3'-dichloro-2' -methj ^ l-

_; , propylsulfonyl) -1,2,4-thiadiazole Compound ITr. 14: 3-bromo-5 (2 ^! -Chloro-cyclothylthio) -

1,2,4-thiadiazole Compound Jr. 1: 3-bromo-5 (2 ·, 3'-dichloro-propylthio) -

1,2,4-thiadiazole,

Connection-Hr. 16: 3-Chloro-5 / (3 ^f -chloro-1,2,4-thiadiazol-.5-yl) -thiomethylsulfonyl / -1,2,4-thiadiazole '. Compound ¥ r. 17: · 3-chloro-5 (thienyl-2-thio) -1,2,4-thiadiazole -. ^v

- 5 - 2316

Connection LTR. 18: 3-chloro-5 (furyl-2-thio) -1,2,4-

- thiadiazole Compound Sr. 19: 3-chloro-5-rhodano-1,2,4-thiadiazole

Example 1 In vitro test

The TesVpilze Alternaria tennis, Botrytis cinerea and Fusarium culmorum were inoculated on agar plates, "on ge, the active compound concentrations of 0.1 wt .-%, 0.01 wt., And contained 0.001 part by weight fo.

The evaluation took place on the 10th day according to the following scheme:

1 β no growth inhibition. ,

2 β weak growth inhibition

3 = strong growth inhibition

4 = complete growth inhibition. ;

The fungicidal action of the invention Yerbindüngen against o.g. Mushrooms are shown in Table 1.

Table 1

Inhibition of fungal growth by the erfindungsgemäSen

Medium , ..· -,

Compound Conc. {%) AS A. tenuis 3. cinerea F. culmorum

1 0.1, 0.01

  0.001. ·. 4 4 4

2 ' 0,1 4' ^l 4. 4

0.01 4 4 4

0.001 1 1 .1

4 4 4 4 4 4 4 4 4 4 1 1

2316

,connection 6 Conc. '' ^: 3. "',; 0.1 0.01 7 0.001 \ 0.1 0.01 8th 0.001 0.1 ν 0.01 Q 0.001 0.1 0.01. 10 0.001 "· 0.1 0.01 11 0.001 0.1 0.01 12 0.001 0.1 0.01 13 0.001 0.1 0.01 " 15 0.001 0.1 0.01 16 0.001 0.1., 0.01 0.001 0.1 0.01   0.001 0.1. 0.01 0.001

Κοηζ. (%) AS AV-tenuis B. cinerea Ί ?. culmorum.

4 , 4 ' 4 4 -4-; 4 4 4 4 4 '4 4 , 4 4 '4 1 Ί 1 4 4 '. 4 4th 4 4 1 1 'Ί 4 ' 4. 4 4 4 '  '4 1 1 1 4 4 4 4 .4   ; ' 4 4 4 4 4 · 4 4 4 ^{> 4} 4 4 • 4 - '4 4 .4   · 4 4 4 1 1 4 4 4 - 4 4  4  4 4. , 3 ·. 4 4 4 4 4 ' 4 4 1 \ 1 4 4 4 4 4 ..: 4 2 ·. 1 ·. . ' , '4 4 4 4 4  4 4 4 '4 -4 4 4 4 4   4 , 4 4 4 4

2316

connection - 19 Conc. 17 - 0.1 0.01 Metal asylum 0.001 18 (known) 0.1 0.01 maneb 0.001 (known) 0.1 0.01 0.001 0.1 0.01 0.001 0.1 0.01 0.001

Conc. {%) AS A. tenuis B. cinerea P. culmorum

4 4 4 4 4 " 4 3 1 1 4 4 4 4 4 4 3 1 4 4 4, 4 4 4 4 2 4 4 4 4 4 3 4 4 1 3 1 4 4 4 4 4 ¹ 4 1 3 3

Example 2

In vivo test

The fungicidal action of the compounds of the invention proved to be particularly good in vivo test with the test fungus Phytophthora infestans. ''

Tomato plants were treated with spray mixture containing 0.1% of active ingredient and, after the spray coating had dried on, were infected with the test fungus.

The incubation was carried out at 20 ⁰ G and 96 - 100 % , relative humidity. The percentage of leaf infection by the harmful fungus was evaluated on 5 days and recorded in Bonitümoten -

The results are summarized in Table 2.

Boniturschema: '

1 * no control success.

2 = low control success,

3 = average control success

4 = good control success

Table . 2 '

Inhibition of fungal growth by the erf in to the invention

Compound Phytophthora infestans'

... '. - ,. ' , '0.1 % AS 0.01 % AS

1, ^:::; 4.0 ^; 3.7

2 4.0 - - 3.0

5 '; , ^: . :; 4,0 '-. · 2,3

·. 7 ^: ./ .. '. ^; 4.0. . ' 1.3

9 4.0 ·. 1.0

10 4.0. 1.0

12. 3.7 Λ, 3

14 · - 4.0-. , , _v. 1 * 7.

15. 4.0 .. 1.3

17. ';>. 4.0 1.0

18 ^; 4.0; 4.0 19 ¹ ; , · 4., Θ '. ; 2.3

Hetalasyl (known) .4,0 1,0

Maneb (known) 4.0. , '·. 1.3

- 9 - 2316

Example 3

The good fungicidal activity of the agents according to the invention is due to the penetration of the fungiζiden active ingredient in the plant system. The drug absorption is possible by leaf and root. - Sheet recording

latency plants are sprayed on the top of the leaves with 0.1 % and \ • 0.2 % active ingredient containing drug suspension. After 48 h of recording leaves are taken and "leaf underside infected with a spore suspension of Phytophthora infestans. '

The evaluation took place on 5 days by detecting the percentage of leaf infestation by the harmful fungus (Table 3).

: - root reception

Tomato plants are placed in. 0.1 % and 0.2 % active ingredient containing drug suspension and thus the acropetale (transport of the active ingredient in the plant system allows.

Hach 48 h recording time were taken and leaves with a spore suspension of the pathogen of late blight of potato (Phytophthors ^infesfäns): infected.

The percentage of leaf infection by the harmful fungus was evaluated on 5 days and recorded in Boniturnoten. The results are shown in Table 3.

rating scale:

= no control success

= low control success

= average control success

= good control success: '.-.'

- 10 -

- 10 - 2316

In iQammern, the credit score for phytotosicity is given; , , _; '. ,

1 - Plant severely damaged, \

2 - Plant damaged medium,

3 = plant slightly damaged

4 = plant healthy

Table 3

Inhibition of the Pilζwachsturns by the inclusion of the active ingredient in the Pflanzensyst _v em ·

connection Blat Inhibition of 0.2 (4) ' Pils growth % 0.2 % 0.1 taufnähme 2.0 (4) Würz e1aufnahme (45 2.7 (4) 1.4 % 2.2 (4) 0.1. (4) 2.6 (4): ¹ '··' - '', ' 1.6 (4) 2.2 (4) 2.0 (4) 2.0 (4) -. 2 ·. '.. "-.' . ^: 1.4 (4) 1.4 (4) 2.6 (4) 2.0 (4) 1.0 (4) 2.2 (4) 2.0 (4) 2.6 (4) 4th 1.4 (4) 2.0 (4) 1.6 _t (4) 2.0 (4) '' 5 - . i, 4 (4) 2.2 (D 2.0 ^l (4) · 2, τ (4) 1.4 (4) - 1.6 (D: '-' (D 18 ' 1.0 (4) 2.6 Metalaxyl-, - (3) - (known) Example 4

Clay of the tested compounds was field tested to confirm the effect against Phytophthora infestans compound no. Determines the degree of infestation (BG) to be examined.

-. 11-2316

connection Conc. {%) AS 0.5 BG (55) 2 0.2 66.66 0.4 46.66 unbenandelt - 100.00 Metalaxyl (known) 0.25 49.99 Cupral (known) 89.99

Claims (1)

- 12 - 2316 'WP A 01 H / 260' 883/5 Claim for invention · ' Fungicidal agent for controlling Oomycetes, in particular Phytophthora infestans. in that, in addition to customary excipient excipients, it contains as active ingredient a 1,2,4-hiadiazole derivative of the general formula ¹ V s - 'Wte. in which η is 0.1 or 2 and X is bromine or chlorine, and R is an optionally substituted by, further salogen atoms, by esters, cyano or keto groups, substituted chloroalkyl having one to four carbon atoms j a chlorine or Cxocycloalkylrest with five or six carbon atoms, an aralkyl radical; an optionally substituted aryl radical, a five-membered hetaryl radical, a 3-chloro-1,2,4-thiadiazol-5-yl substituted thiomethyl radical or in the case of η = 0 is a cyano radical.