DE1928889C - 3 phenylimino 4,5 dichloro 1,2 dithia cyclopentene - Google Patents

Description

It has been found that 3-phenyl imino-4,5-dichloro-I ^ -dithiacyclopentenes of the general formulas A and B

S-S

s — s

R ¹

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 good fungicidal action with low warm-blooded toxicity, in contrast to the 4 known from German patent 1102 174 , 5-dichloro, 2-dithiol-3-one.

The preparation of the S-phenylimino ^ S-dichloro-1,2-dithiacyclopentenes the general formula given is carried out by adding 3,4,5-trichloro-1,2-dithiacyclopentadienium chloride with one equivalent of a primary amine of the general formulas

H ₇ N

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, Ν, Ν-dialkylaniline, as well as weak inorganic bases, z. B. sodium hydrogen carbonate, sodium carbonate, magnesium or calcium carbonate can be used. In addition, the amine, used in a multiple of the amount required, can serve as a 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. Examples of this are water, aromatic hydrocarbons, chlorinated aliphatic and aromatic hydrocarbons, alcohols, ethers, NN-dialkylated carboxamides. Sulphoxides and mixtures of water and such solvents are suitable. The reaction temperatures are preferably between -30 and +80 ° C.

The 3 · phenylimino. 4,3 · dichlor · 1,2 - dithiacyclopentenes have an excellent effect against * numerous phytopathogenic fungi. The new active ingredients are effective against plants which cause plant disease, for example against powdery mildew, such as cucumber powdery mildew (Brysiphe eichoracearum) and rose powdery mildew (Spattathcca pannosa); against false flour mushrooms, such as the causative agents of the leaf rot and tuber rot of the potato (Phytophthora infestans); against Biait stain pathogens such as Alternaria solani; against rust fungi, such as bean roses (Uromycec app.); also against the gray mold (Botrytis cinerea), which is particularly difficult to control. Since the 1,2-dithiacyclopeittene also have system fungicidal properties, plants and their newly growing parts can also be used after the treatment

ίο be protected from further fungal infections. 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

ίο other organic materials, especially keratinic, cellulosic ^ synthetic materials and paints, infested. In addition, the Active ingredients can also be used to disinfect the floor. 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 variety »Lukulh: -.« Become after 3- to 4-week cultivation in the greenhouse with the test substance in the form of a spray mixture (conc. 0.1% Aktiväubsunz) sprayed to dripping wet and after the spray coating has dried with a standardized Spore suspension of the fungus infected. After staying in a humid atmosphere for about days In the event of infection, small black spots of infection develop on the leaves. When The number of spots serves as the basis for the evaluation of the test

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

Leaves of young cucumber plants are sprayed to runoff with an oil, 1% suspension of the active ingredients formulated as wettable powder. After the spray coating has dried, the plants are with sprayed with 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 BluituhcrfHichc) covered by the Myeel lining on infected, treated blisters compared to untreated, infected controls.

Effect on Uromyces appendiculates

Bean rust) on beans (Phaseolus vulgaris)

Bean plants in the two-leaf stage are mixed with a suspension of the substances formulated as wettable powder sprayed to runoff point (conc. 0.1% Active ingredient). After the spray coating has dried off, the plants are sprinkled with a fresh spore suspension of the bean rust infected (five plants per active ingredient) and then 1 day in a moist Chamber, then in the greenhouse at 20 to 22 C held. The evaluation of the experiment is based on the number of occurrences after about 8 to 12 days Rust pustules,

evaluation
The effect is assessed on the following scale:

10 = ineffective, same infestation as untreated

German control plants,

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

connection Uromycei
appendi
culates Alterna ria
solani Botryiis
cinerea Erysiphe
cichora-
cearum J-Pheny ^ mino ^ S-dichloro-l ^ -dithiacyclopenten
S-P '^' - dichlorophenyliminoHU-dichlor-
1 2-dithiacyclopentene 1
10 1
10 1
10 0
10 AS-dichloro-l ^ -dithiacydopenten-PJ-one
(known from the German exposition
1 102 174)

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

example

A mixture of 99 parts of 4 chloroaniline, 158 parts of triethylamine and 500 parts of ether is added dropwise to a suspension of 189 parts of 3,4,5-trichloro- '1 ^ -dithiacyclopentadiene chloride in 200 parts by volume of diethyl ether at -20 to -30 C with stirring . This mixture 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 40 parts by volume. Small amounts of a brown oil precipitate, which is then decanted. The solution is then shaken with activated charcoal, filtered and cooled to -60 ° C. The 3 - (4 '- chlorophenylimino) - 4,5 - dichloro -1,2 - dithiacyclopentene crystallizes in yellow needles with a melting point of 94 to 95 ° C The following compounds were obtained analogously.

3- Phenylimino ^ S-dichloro-1,2-dithiacyclopentene. F. 7 "to 79 C;

^ en, m.p. 81 to 82 C;
S-p '^' - dichlorophenyliminoHU-dichlor-

1 ^ -dithiacyclopenten, F. 86 to 88 C,
3- (4'-methoxyphenylimino) -4,5-dichloro-

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

Claims (2)

Claims: 1. 3-Phenylimino-4,5-dtchlor-1,2-dithiacyclopentenc of the general formulas A and B S - S S S 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 ^' position. 2. Process for the preparation of 3-phenylimino-4,5-diGhlor "1,2-dithiacyclopemene im Claim I defined general formulas that · 6 $ characterized in that one 3,4,5-Trichlorl ^ -dithiacyclopentadieniumchtorid with a Equivalent of a primary amine to the general one Formulas or H ₁ N H ₂ N in.which R and R ^{1 have} the meaning given.