DE1542710B - Fungicides - Google Patents

Description

The invention relates to fungicidal agents which, as an active ingredient, are a polyhaloethylthio compound the general formula

Ac

NSC-CX ₃
RY

contain. In this formula, Y and at least two of the symbols X are chlorine or bromine, where the remaining X symbols are hydrogen, chlorine or bromine, Ac is a phenylsulfonyl, parachlorophenylsulfonyl, lower alkanesulfonyl or di (lower alkyl) aminosulfonyl radical, R is a lower alkyl, Allyl, phenyl or parachlorophenyl radical, or Ac and R together with the N atom denote Succinimide maleimide, or those optionally in the 5-position by alkyl groups having 1 to 7 carbon atoms substituted hydantoin residue.

Biologically active compounds with the functional N-trichloromethylthio group are already known for a long time. Despite the long period during which the N-trichloromethylthio compounds are known are, and the excellent effect that the N-trichloromethylthio derivatives as fungicides and Parasiticides have shown no successful attempt, homologues or analogues of these Bringing compounds into trade. The fact that you can rely on the N-trichloromethylthio group shows the great sensitivity of the biological effectiveness to structural changes. It was therefore considered very unlikely that the N-trichloromethylthio compounds could be improved are.

However, it has been found that the biological effectiveness is with an N-polyhaloethyl compound with at least three halogen atoms, which are either chlorine or bromine, and of which at least one is bonded in α-position to the sulfur atom, can be significantly improved. These derivatives have a remarkable potency, often well above that of the N-trichloromethylthio compounds goes out. On the other hand, variations in the ethyl group give rise to derivatives derived from differentiate the compounds according to the invention, to a considerable reduction in the effectiveness, if not to almost complete inactivity.

The compounds according to the invention can generally be prepared by reacting the corresponding polyhaloethylsulfenyl chloride or bromides with the corresponding amide or imide or the metal salt this connection.

Usually the alkali metal salt is suspended or dissolved in a suitable inert medium, such as B. in benzene, toluene and in some cases in water, alcohol, etc., the mixture violently stirred and the desired sulfenyl halide is added. The sulfenyl halide can be used as a solution added using an inert medium as a solvent or without a solvent will. Suitable solvents are, for example, hydrocarbons, such as. B. petroleum ether or hexane mixtures. After an appropriate reaction time, the product is filtered off or by removal of the solvent and isolating the solid product. The product can then if desired, be recrystallized. For representative compounds of the succinimide-maleimide group the analytical results are given in Table I.

Table I.

Melting point
( ⁰ C) element analysis found connection Cl (%) 47.1 85 to 87 Cl theory 40.0 N- (l, l, 2,2-tetrachloroethylthio) succinimide 124 to 125 Cl 47.5 40.0 N- (1 ^^ - trichloroethylthio ^ succinimide 113 to 115 Cl 40.6 47.3 N- (1,1,2-trichloroethylthio) succinimide 131 to 132 Cl 40.6 51.5 N- (1,2,2,2-tetrachloroethylthio) succinimide 123 to 125 S. 47.5 11.3 N-ipentachloroethylthioJ-succinimide 65 to 68 N 53.6 ' 4.9 N- (l, l, 2,2-tetrachloroethylthio) maleimide 10.9 4.8

Analysis results for products of the hydantoin group are given in Table II:

Table II

connection Melting point
( ⁰ C) element analysis
(%) found Cl calculated 43.4 3- (l, 2,2,2-tetrachloroethylthio) - 161 to 164 43.5 5,5-dimethylhydantoin Cl 39.0 3- (l, l, 2-trichloroethylthio) hydantoin 145 to 148 S. 40.4 11.7 Cl 12.1 43.0 3- (1,1,2,2-tetrachloroethylthio) - 196 to 199 43.5 5,5-dimethylhydantoin

continuation

connection Melting point
CC) element analysis
(%) found Cl calculated 8.1 3- (2-chloro-1,2,2-tribromoethylthio) - 187 to 189 Br 7.7 52.1 5,5-dimethylhydantoin Cl 52.2 47.8 3- (1,1,2,2-tetrachloroethylthio) hydantoin 158 to 160 S. 47.7 11.6 Cl 10.8 33.2 3- (2-Bromo-1,1,2-trichloroethylthio) hydantoin 157 to 158 Cl 31.1 49.3 3- (pentachloroethylthio) - 183 to 187 49.2 5,5-dimethylhydantoin Cl 32.7 3- (l, l, 2,2-tetrachloroethylthio) - 112 to 114 S. 35.9 7.5 5- (1-ethylamyl) hydantoin Milliequi- 8.1 0.0111 3- (2-bromo-l, l, 2-trichloroethylthio) - 190 valente 0.0108 5,5-dimethylhydantoin Halogen, all in all*)

*) No individual analysis was obtained for each halogen. Only the total number of milliequivalents of halogen added was established.

Table III gives the analytical results for sulfonamides.

Table III

Melting point
( ⁰ C) element > Cl analysis found connection S. (%) 15.3 ._ 126 to 128 Cl calculated N-4-chlorophenyl-N- (1,1,2,2-tetrachloro- Cl 15.3 37.0 ethylthio) ethane sulfonamide 72 to 75 Cl N-ethyl-N- (1,2,2,2-tetrachloroethylthio) - Cl Br 37.0 42.3 benzenesulfonamide 103 to 105 Cl N-methyl-N- (1,2,2,2-tetrachloroethylthio) - Br 44.1 35.0 4-chloro-benzenesulfonamide 92 to 96 Cl N-phenyl-N- (1,2,2,2-tetrachloroethylthio) - S. 35.6 42.7 dimethylaminosulfonamide 120 to 122 S. N-methyl-N- (l, l, 2,2-tetrachloroethylthio) - 44.1 31.9 4-chloro-benzenesulfonamide 118 to 122 17.5 N- (2-bromo-1,1,2-trichloroethylthio) - 31.7 25.0 N-methyl-4-chloro-benzenesulfonamide 119 to 121 17.8 30.1 N- (1,2-dibromo-1,2-dichloroethylthio) - 27.1 47.8 N-methyl-4-chloro-benzenesulfonamide 71 to 75 32.4 14.8 N-methyl-N-pentachloroethylthio- 47.5 16.3 4-chloro-benzenesulfonamide 60 to 61 14.3 N-allyl-N- (l, l, 2,2-tetrachloroethylthio) - 16.2 benzenesulfonamide

connection R. Ac element Analysis (%)
calculated found N-methyl-N- (1,1,2,2-tetrachlorethylene thio) -
dipropylaminosulfonamide CH ₃ / C ₃ H ₇
SO ₂ N _x Cl
N 36.2
7.15 37.58
6.13 C ₃ H ₇ S. 16.35 17.16, N-butyl-N- (l, l, 2,2-tetrachloroethylthio) -
butanesulfonamide C ₄ H ₉ SO ₂ C ₄ H ₉ Cl
N 36.38
3.58 36.80
3.20 S. 16.38 16.80 N-methyl-N- (1,1,2,2-tetrachloroethylthio) -
diethylaminosulfonamide CH ₃ C ₂ H ₅
SO ₂ N CI
N 39.10
7.68 39.12
7.54 ^N CzH _s S. 17.60 17.70

The following tables not only show the superiority of the agents according to the invention the previously known analogous active ingredients, but also the sensitivity of the biological effectiveness against structural changes.

Each compound tested for fungi toxicity was dissolved in acetone at the level of dilution expressed in parts per million in the table. Sheets of paper previously inoculated by impregnation with equal amounts of a fungus culture broth were placed on a potato-dextrose agar medium and an exactly equal amount of each fungicidal solution was centered on them. After treatment with the respective compound, the leaves were incubated together with inoculated, but not treated, control leaves at ambient temperature until the non-treated leaves were filled with mycelial growth. The leaves were placed on an agar medium and the fungitoxic activity of the chemical compound was determined by comparing the radii of mycelial growth on the agar medium, measured from the edge of the leaf, in treated and untreated samples. The ratio of these radii gives a percentage of infection. After subtracting 100%, the percentage inhibition of fungus growth is obtained, which expresses the biological effectiveness of the toxic agent investigated.
In Table IV, various derivatives according to the invention with the N-lJ ^^ - tetrachloroethylthio group are compared with known derivatives of the N-trichloromethylthio group.

Table IV

Organism*)

N-polyhaloalkyl group

1,1,2,2-tetrachloroethyl | Trichloromethyl

(Concentration, parts / million;
percentage inhibition)

HRVHR

Acyl-N

Succinimide

5,5-dimethylhydantoin

N-methyl-p-chloro-benzenesulfonamide

125 /

/ 100
500 /
/1
1000 /

100

¹²⁵ no. ₁

250 /

100

/ 96

° /
/ 100

1000 /
/ 99

/ lOO
125 /

/ 100
1000 /
/ 63

¹²⁵ I:

500

27
'/ 78

125 /
/ 13

125

250 /
1000 /

/ 35
'/ 21

125 _/;
1000

724

770

*) H = Helminthosporium; R = Rhizoctonia; V = Verticilium.

These results clearly show that Table V shows the improved fungicidal effectiveness fungicidal activity of the acyl derivatives according to the invention with various polyhalogen compounds Compounds to the hitherto begenäthylgruppen, which are within the scope of the present

knew analog connections. 40 invention fall. Test procedure as in Table IV.

Table V

Organism*) Concentration, connection Parts / million, H percentage inhibition N-1,1 ^ -trichloroethylthio-S ^ -dimethylhydantoin F. 1000 /
/ 100 3- (1, l, 2,2-tetrachloroethylthio) -5- (1-ethylamyl) hydantoin R. 1000 /
/ 100 N-1,1,2,2-tetrachloroethylthio-N-methyl-benzenesulfonamide R. 1000 /
/ 99 N-M ^^ - Tetrachloroethylthio-N-phenyl-benzenesulfonamide H 1000 /
/ 100 S-pentachloroethylthio-S ^ -dimethylhydantoin R. 500 / H / 98 3- (2-bromo-l, l, 2-trichloroethylthio) -5,5-dimethylhydantoin R.
F. 500 / F. / 100
looo /
/ 100 3- (1,1,2,2-tetrachloroethylthio) hydantoin H 1000 /
/ 100 N-Methyl-N-il.l ^^ - tetrachloräthylthio ^ dipropylamino- F. 500 /
""^'10 ° sulfonamide R. ⁵⁰ %! H
R. 500 /
/ 100 N-butyl-N- (l, l, 2,2-tetrachloroethylthio) -butanesulfonamide IN.
H 500 /
/ 61
500 / N-methyl-N-il.l ^^ - tetrachloräthylthioJ-diethylamino- F. / 97
500 /
/ 100 sulfonamide R. 500 /
/ 69 500 /
/ 100

*) H = Helminthosporium; F = Fusarium; R = Rhizoctonia.

Various active ingredients according to the invention, a compound prepared by the previous process with the functional N-trichloromethylthio group and one of its derivatives, which by incorporation a methylene group between the sulfur atom and the trichloromethyl group were obtained on their fungicidal effectiveness according to the method entitled “The Standard Spore Slide Germination Method for Determining Fungicidal Activity "in American Phytopathological Society Journal, Vol. 33, P. 627 to 632, volume 1943, compared methods described. This procedure is used to measure the fungitoxic effectiveness of fungicidal chemical compounds. The effectiveness is expressed as a percentage Expressed inhibition of the germination of fungus spores.

Each compound that was tested was diluted at 10 parts / million and 3 parts / million dissolved in acetone. These solutions were then placed into welled microscope slides pipetted and dried. The wells were filled with a spore suspension of the test organism, Monilinia fructicola, filled and incubated overnight in a humid chamber. A group of 100 spores were examined, and the numbers of germinated and non-germinated spores were counted and applied to show the biological effectiveness as a percentage of germ inhibition.

The results of these experiments are given in Table VI.

Table VI

connection

M. Fructicola
Percent inhibition; concentration

10 parts / million 3 parts / million 100 98 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 45; 100 100 99 2 37 ■ - 100 100

N-l ^ -Trichloroethylthio-N-ethyl-benzenesulfonamide

N- ^ l ^^ - Tetrachloroethylthiosuccinimide

N-l ^^^ - Tetrachloroethylthiomaleimide

N-1,1 ^^ - Tetrachloroethylthio-N-phenyl-dimethylamino-

sulfonamide

N-lJ ^^ - Tetrachloroethylthio-N-methyl-p-chloro-benzene-

sulfonamide

N- ^ l ^^ - tetrachloroethylthio-N-p-chlorophenyl-ethane-

sulfonamide

N-l ^^ - Tetrachloroethylthio-N-methyl-p-chloro-benzene-

sulfonamide

S-M ^^ - Tetrachloroethylthio-S.S-dimethylhydantoin

S-1.l ^ -Trichloroethylthio-S ^ -dimethylhydantoin

N- (l, 2-dibromo-l, 2-dichloroethylthio) -N-methyl-p-chloro-benzene-

sulfonamide,

N-trichloromethylthio-N-methyl-p-chloro-benzenesulfonamide

(Comparison substance)

N - ^^ - trichloroethylthio-N-methyl-p-chloro-benzenesulfon-

amide (comparison agent)

N-1,1,2,2-tetrachloroethylthio-N-allyl-benzenesulfonamide

(according to the invention)

It has been found that the group of the invention Active ingredients the best analog known active ingredients to combat many diseases caused by a fungus is equivalent or, in most cases, far superior. It was completely unexpected that when compared with the analogous active ingredients known to date, the Group of the compounds according to the invention would have this clear superiority.

Except in the compositions and application forms, which are in the preceding examples have been described, the compounds according to the invention can be in or on inert liquids and solids Carriers like. z. B. inert clay, xylenes, etc., be dispersed. The solid supports can be as dust or in Compound with a suitable wetting agent can be used to produce a wettable powder. The fungitoxic compounds according to the invention can also be used with other solvents, Dispersing agents or emulsifying agents are mixed. Furthermore, these compounds not only used on its own or in a mixture with other compounds of the group according to the invention but they can also be mixed with other active toxic substances Compilation of agriculturally valuable agents for combating infecting plants Epidemics or diseases are used.

The connections can also point to a surrounding area that hosts the fungus or where there is a risk of a fungus infestation consists. For example, the fungicidal compositions can be applied directly to a plant or a other host, the plant seed, the soil or other plant environment or sprayed otherwise applied or used in a similar manner to the fungus and those carried by it fight diseases caused.

109 517/381

9 10

Tables VIII to X below contain the results of further comparative tests.

Table VIII

Mycelium-inhibiting effect of succinimide derivatives according to the invention compared with Helminthosporium to N-thiotrichloromethylsuccinimide (according to German patent specification 887 506)

Serial No. O connection Cl Cl
Il Inhibition (%)
Helminthosporium,
500 parts / million 1 H ₂ -CC N — S — C — C — H
/ ■ Il Cl H Cl N-S-C-Cl
/ I 59 H ₂ CC Cl O Cl Cl
j I (Comparison substance) ^V N-S-C-C-Cl
/ ι ι 2 O Cl Cl H ₂ -CC ^ 100 H ₂ CC 3 Il
O O
Il Il 100 H ₂ C- (Z Il
O

Table LX

Mycelium-inhibiting effect of polyhalogenethylthiosulfonamides according to the invention against Rhizoctonia im Compared to N-trichloromethylthio-N-butyl-p-chlorobenzenesulphonamide (according to US Pat. No. 2,553,775)

Serial No. connection Inhibition (%)
Rhizoctonia
1000 parts / million 1 OC ₄ H ₉ Cl
Il II y ~ v Ii I I ¹⁶ O Cl (Comparison substance)

11th

continuation

12th

Serial No.

connection

Inhibition (%)

Rhizoctonia parts / million

O CH ₃ Cl Cl \ _ _S _ _N _ _S _ _C _ _CH

O Cl Cl

99

SO ₂ -N (CH ₃ ), N Cl Cl

\ I I

S-C-CH Cl Cl

100

0 CH ₃ Cl Cl Cl ^^ ^^ S-N-S-C-CH O Br Br

C ₂ H _5- S-N
Il ^N \
Q Cl Cl 0 O / - < -CH Cl Cl

100

O CH ₃ Cl Cl

-N-S-C-C-Cl O Cl Cl

O CH ₃ Cl Cl / VSN-S-C-CH

II ο egg egg

0 C ₆ H ₅ Cl Cl

Il I I I

S-N-S-C-CH O Cl Cl

100

13th

Table X

14th

Mycelium inhibitors
comparison C. / ηττ \ / Il \ I (CH ₃ ), ( Il NSC-CH ₂ Cl Inhibition (%) Rhizoctonia Fusarium C. N-S-C-Cl
/ 1 NH-C Cl
Il 250 parts / million 1000 parts / million Serial No. NH-C Cl Il
O Effect of hydantoin derivatives according to the invention against various organisms in the
to N-thiotrichloromethyl-SS-dimethylhydantoin (according to US patent specification 2553 775) O O 1 (Comparison substance) CH ₂ -C Cl Cl 35 connection O
Il 40 \ II ·
N — S — C — C — H
/ ι ι O
Il / 1 1
NH-C Cl Cl
Μ Il ■
O oH ₅ O
\ " CH- (
/
₄ H ₉
1 80 2 : h — c ei ei
N — S — C — C — H
sfH - C Cl Cl 55 O - 3 100 . 100 4th

Table XI a

Mycelium-inhibiting effect of fungicidal active ingredients according to the invention against Rhizoctonia in various Concentrations compared to N-trichloromethylthio-tetrahydrophthalimide (according to German patent specification

921290)

Serial No.

connection

Inhibition (%)
Rhizoctonia

125 ppm

250 ppm

Inhibition (%) M. Fructicola

0.25 ppm

N-trichloromethylthiotetrahydrophthalimide (reference substance)

69

53

continuation

Serial No. connection C. :—( :H ;—( :H Inhibition (%)
Rhizoclonia 250 ppm Inhibition (%)
M. Fructicola : h — c ei ei
Il / Ii JL
CH ₃ O _r / \ ₎ Cl Cl 125 ppm 0.25 ppm 2. ( C. Il
O : h-c CH ₃ O Cl Cl
\ Il 83 D. \ Il
N — S — N — S— (
/ Il I V - 75 : egg egg N — S— ( 3 - 85 -.

Table XIb

Mycelium-inhibiting effect of fungicidal active ingredients according to the invention compared with Alternaria Solani to N-trichloromethylthio-tetrahydrophthalimide (according to German patent 921290)

Serial No. connection Inhibition (%)
Alternaria Solani
3 ppm 1 N-trichloromethylthiotetrahydrophthalimide (reference substance) 52 ■ 2 O CH ₃ Cl Cl
_C1 __ ^^ y_ _s -ν-S-C-CH
\ = / ι] ι ι
O Cl Cl 92 3 O Cl Cl
C ₂ H ₅ -SNSC-CH
Il I Il
O J \ Cl Cl
Cl 98 4th O Cl Cl
<\ ~ \ - S - N - S - C - CH
O CH ₂ Cl Cl
CH
Il
CH ₂ 75

Claims (1)

17 18 contains, in which Y and at least two of the Sym-Fatentansprucn: _{bole χ chlorine or ßrom), the rest of which are} Fungicidal agent, marked by the X symbols are hydrogen, chlorine or bromine atoms draws that the active ingredient is a poly, Ac a phenylsulfonyl, parachlorophenyl halogenethylthio compound of the general form- 5 sulfonyl-, low-alkanesulfonyl- or di- (low- mel alkyl) -aminosulfonyl radical, R is a lower alkyl, Ac X is allyl, phenyl or parachlorophenyl, or \ I Ac and R together with the N atom form the suc- N - S - C - CX ₃ cinimide, maleimide, or the in / I io 5-position by alkyl groups with 1 to 7 carbon atoms R Y men mean substituted hydantoin radical.