DE1928889B - 3 Phenyhmino 4,5 dichloro 1,2 dithia cyclopentene - Google Patents

Description

It has been found that 3-phenylimino-4,5-dichloro-1,2-dithiacyclopentenes of the general formulas A and B.

S —S

S-S

in which R is a hydrogen or chlorine atom or a methoxy radical and R ^{1 is} a hydrogen atom or a chlorine atom in the 2'- or 3-position, have a good fungicidal effect with low warm-blooded toxicity, in contrast to the 4 known from German patent 1 102174, 5-dichloro-1,2-dfmi «d <-3-one.

The preparation of 3-phenyhinino-4,5-dichloro-1,2-dithiacyclopentenes the general formula given is carried out by adding 3,4,5-Trichlorl ^ -dithiacyclopentadieniumchlorid with one equivalent of a primary amine of the general formulas

H ₂ N-

H ₇ N

R ¹

CI

35

40

in which R and R ^{1 have} the meaning already given.

The reaction is advantageously carried out in the presence of an acid-binding agent. As such, both tertiary amines, e.g. B. trialkylamines, pyridine, N ^ dialkylaniline, as well as weak inorganic bases, e.g. B, sodium hydrogen carbonate, sodium carbonate, magnesium or calcium carbonal can be used. In addition, the amine, used in a multiple of the amount required, can serve as an acid-binding agent. Furthermore, the process according to the invention is expediently carried out in the presence of solvents and / or diluents which are inert towards the respective reactants. For example, water, aromatic hydrocarbons, chlorinated aliphatic and aromatic hydrocarbons, alcohols, ethers, Ν, Ν-dialkylated carboxamides, sulfoxides and mixtures of water and such solvents are suitable. The reaction temperatures are preferably between -30 and + 8O ⁰ C.

The 3 - phenylimino - 4,5 - dichloro -1,2 - dithiacyclopentenes have an excellent effect on numerous phytopathogenic fungi. The new Active ingredients are effective against plant disease-causing fungi, for example against real powdery mildew fungi, such as cucumber powdery mildew (Erysiphc cichoracearum) and rose powdery mildew (Spaerothcca pannosa); against false powdery mildew, such as the causative agents of leaf rot and tuber rot of the potato (Phytophthora infestans); against leaf spot pathogens such as Alternaria solani; against rust fungi, such as bean rust (Uromycec app.); further against the gray mold (Botrytis cinerea), which is particularly difficult to control. Since the 1,2-dithiacyclopentene Plants and their plants can also have systemic fungicidal properties through their use newly growing parts are protected from further fungal infections even after the treatment. the new active ingredients can also be used to treat seeds without affecting their germination. The active ingredients are in the form of solid or liquid work-up forms, such as dusts or Scatter, granules, dispersions (suspensions or emulsions) used in crop protection.

Some of the new active ingredients can also be used to fight fungi and bacteria other organic materials, in particular keratin, cellulose-containing, synthetic materials and paints. The active ingredients can also be used to disinfect the soil Find. Their warm-blooded toxicity is low.

The fungicidal effectiveness of 3-phenylimino-4,5-dichloro-1,2-dithiacyclopentenes was determined on the basis of the following tests and that which became known from the German Auslegeschrift 1 102 174 4,5-dichloro-1,2-dithiacyclopenten- (3) -one compared in terms of effectiveness.

The active ingredients used in each case were as 25% wettable powders with the following composition formulated:

25 parts by weight each used as the active ingredient

Connection,
25 parts by weight of kieselguhr,

2 parts by weight of hexadecyl glycol ether sulfate,

1 part by weight of sodium lauryl sulfate,

7 parts by weight of sodium lignin sulfate,
40 parts by weight of kaolin.

These wettable powder formulations were then mixed with water to give spray mixtures which had a concentration of 1.1% of active ingredient.

Effect against Alternaria solani on tomatoes
(Solanum lycopersicum)

Tomatoes of the "Lukullus" variety are grown in the greenhouse for 3 to 4 weeks with the test substance in the form of a spray liquor (conc, 0.1% active ingredient) sprayed to runoff and after infected with a standardized spore suspension of the fungus after the spray coating had dried on. After about 5 days in a humid atmosphere, small ones develop in the case of an infection black spots of infection on the leaves. As an evaluation basis for the evaluation of the experiment serves the number of spots.

Effect on Erysiphe cichoracearum
(Cucumber mildew) on cucumber (Cucumis sativus)

Leaves of young cucumber plants are formulated as a wettable powder with an oil percent suspension Active ingredients sprayed dripping wet. After the spray coating has dried, the plants are with sprayed a spore suspension of powdery mildew of cucumber, then placed in a greenhouse at 23 ° C. After 8 days, the degree of infestation (proportion

the leaf surface covered by the mycelium coating) on the infected, treated leaves in comparison determined for untreated, infected controls.

Effect on Uromyces appcndiculates

(Bean rust) on beans (Phaseolus vulgaris)

Bean plants in the two-leaf stage are formulated with a suspension of the wettable powder Substances sprayed to runoff point (conc, 0.1% active ingredient). After the spray coating has dried the plants are infected with a fresh spore suspension of the bean rust (five plants per active ingredient) and then 1 day in a moist

connection

3- Phenyllimino-'U-dichloro-1,2-dithiacyclopentene

3- (3 ', 4'-dichlorophenylimino) -4,5-dichloro-

1,2-dithiacyclopentene

4,5-dichloro-1,2-dithiacyclopenten- (3) -one
(known from the German exposition
1 102174)

th chamber, then kept in the greenhouse at 20 to 22 ° C. The test evaluation is based on the Number of rust pustules present after about 8 to 12 days.

evaluation
The effect is assessed on the following scale.

10 = ineffective, same infestation as untreated

Delte control plants,

9-1 = infestation reduction according to linear estimation,
0 = no infestation.

Uromyces appcndiculates

10

Alternaria
solani Botrytis
cinerea Erysiphe
cichora-
ccarum 1
10 1
10 0
10

The example] explains the manufacturing process; Parts mean parts by weight.

example

In a suspension of 189 parts of 3,4,5-trichloro-1,2-dithiacyclopentadieniumchlorid in 200 parts by volume of diethyl ether is allowed to at -20 to -30 ^c C under stirring a mixture of 99 parts of 4-Chloranilih, 158 parts of triethylamine and 500 parts of Add ether in drops. This device is then ^{stirred at 25 °} C. for 12 hours. It is then filtered, the residue is washed three times with 300 parts by volume of ether each time and the combined filtrates are concentrated to about 400 parts by volume. Here, small amounts of a brown oil precipitate, which is then decanted off. The solution is now shaken with activated charcoal, filtered and cooled to ⁰ C -6O It crystallizes 3 - (4 '- chlorophenylimino) - 4,5 - dichloro -1,2 - dithiacyclopenten in yellow needles, mp 94-95 ° C The following compounds were obtained analogously:

3-phenylimino-4,5-dichloro-1,2-dithiacyclopentcn,

M.p. 78 to 79 ⁰ C;
3- (2 ', 4'-dichlorophenylimino) -4,5-dichJor-

1,2-dithiacyclopentene, mp 81-82 ° C;
3- (3 ', 4'-dichlorophenylimino) -4,5-dichloro-

1,2-dithiacyclopentene, m.p. 86 to 88 ⁰ C;
3- (4'-methoxyphynylimino) -4,5-dichloro-

1,2-dithiacyclopentene, F. 82 to 83 "C.

Claims (2)

Claims: 1. S-phenylimino- ^ S-dichloro-l ^ -dithiacyclopentenes of the general formulas A and B. S-S R ¹ in which R represents a hydrogen atom or a chlorine atom or a methoxy group and R ^{1 represents} a hydrogen atom or a chlorine atom in the 2- or 3-position. 2. A process for the preparation of 3-phenylimino ^ .S-dichloro-l ^ -dithiacyclopentenes of the general formulas defined in claim 1, characterized in that 3,4,5-trichloro-1,2-dithiaoyclopentadieiitumchlorid with one equivalent of a primary Amines of the general formulas
or H ₂ N H, N J V R ¹ Cl in which R and R ^{1 have} the meaning given, converts.