DE1928871B - 3 Phenylimino 4 chlorine 5 amino 1,2 dithiacyclopentene, process for their preparation and their use for fighting phytopathogenic fungi - Google Patents

Description

N - = N -

Cl

.— ei

Cl

s - s

where in the general formula IR ¹ and R ² each represent a methyl or ethyl radical or, together with the nitrogen atom to which they are bonded, the morpholino or piperidino ^{radical and R 3} denotes water-Itoff or chlorine.

2. A process for the preparation of the 3-phenylimino ~ 4-chloro-5-amino-l, 2-dithiacyclopentenes according to claim 1, characterized in that one 3,4,5-trichloro-1,2-dithiacyclopenteniumchIofid either

a) each with one equivalent of an amine of the general formula IH

R ¹

NH

HI

and the general formula IV

H, N

IV

or

b) with 2 equivalents of an amine of the formula V.

Cl

H ₂ N - <___ / V

converts, where R ¹ . R ² and R ^{J are} those given

Have meanings.

3. Use of 3-phenylimino-4-chloro-5-amino-1.l-dithiacyclopentenes of the formulas I and II given in claim I for combating phytopathogenic fungi.

60

The invention relates to new S-phenylimino- ^ chloro-S-amino-i ^ -dithiacyclopentenes. Procedure to their Production and their use for combating phytopalhogenic fungi.

In contrast to the 4,5-dichloro -1.2-diibi known from the German patent specification 1102 174.

c \ clopenten-3-on surprisingly became l -Iu: den that the new 3-phenylimino-4-chloro-5-ainine 1.2-dithiacyduper.tene and their acid additions; ii good fungicides in the case of low warm-blooded toxicity in: partly also have bactericidal properties.

The new 3-phenylimino.-4-chloro-5-amino-1.2 - .. :: thiacyclopentenes correspond to the formulas I and,;

15th

20th

35

40

45 where in the general formula IR ¹ and R ² each represent a methyl or ethyl radical or, together with the nitrogen atom to which they are bonded, the morpho lino or piperidino radical and R ^{3 represent} hydrogen or chlorine.

The new 3-phenylimino-4-chloro-5-amino-l, 2-dithiacyclopentenes are prepared by 3,4,5-trichloro-lj-dithiacyclopentenium chloride either

a) each with one equivalent of an amine of the general formula

R "

NH

and the formula

H ₂ N

Cl

R- ¹

or

b) with two equivalents of an amine of the general formula

H, N

converts, where R ¹ , R ² and R ^{3 have} the meaning given for the formula I.

The reaction is advantageously carried out in the presence of an acid-binding agent. As such both tertiary amines, such as trialkylamines, pyridine or Ν, Ν-dialkylaniline, but also weak ones inorganic bases, e.g. B. sodium hydrogen carbonate, sodium carbonate, magnesium or calcium carbonate can be used. In addition, the amines of the general formula III. in multiples of

The required amount is used in the reaction, and acid binding agents are used. It will be finer In accordance with the invention, it is useful in the presence of the document from across from the respective respondents inert solvents and / or diluents carried out. For example, the following are suitable for this: water, aromatic hydrocarbons, chlorinated ones jiliphatic and aromatic hydrocarbons. Alcohols, Ether, N.N-dialkylated carboxamides, Sulphoxides and mixtures of water with such solvents. The reaction temperatures are ■ preferably between -30 and + 80C.

The new compounds of general formula I and their acid addition salts have excellent properties Effect on numerous phytopathogenic fungi. The new active ingredients are against plant diseases producing fungi, for example against powdery mildew, such as cucumber powdery mildew (Erysiphe cichoracearum) and rose powdery mildew (Sphaerotheca pannosa); against downy mildew fungi, like the pathogens animal late blight of the potato (Phytophthora infestans); against leaf spot pathogens, such as Alternaria solani, against rust fungi, such as bean rust (Uromyces app.), Also against the particularly difficult controllable gray mold (Botrytis cinerea) etc. Since the l ^ -Dithiacyclopentene of the general Formula I also have systemic fungicidal properties; plants and their new growing parts 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 Spreading agents or granulates, dispersions (suspensions or emulsions) used in crop protection. The active ingredient concentrations required for crop protection are in the range of 0.01 up to 2%, the application rate is between 0.1 and 7 kg / ha, but depends largely on it protective plant material.

Some of the new active ingredients can also be used to combat it of fungi and bacteria that other organic materials, especially keratinous, cellulose-containing, synthetic materials and paints. In addition, the active ingredients can also be used to disinfect the floor. Their warm-blooded toxicity is low.

The fungicidal effectiveness of the active ingredients of the general formula I was determined on the basis of the following Experimental found.

Effect against Botrytis cinerea on Vicia faba (broad beans)

In Petri dishes, which are lined with moistened filter paper, three well-developed leaves of the same size of Vicia faba are placed, which are sprayed to runoff with a broth (0.1% active ingredient) made from an active ingredient formulated as a wettable powder. After the spray coating has dried off, they are infected with a freshly prepared spore suspension of the fungus. After the leaves have been kept in a humid atmosphere at 18 to 20 "C for 1 to 2 days, black, initially punctiform spots appear on the leaves in the event of an infection, which spreads quickly. The number and size of the infection sites serve as an assessment criterion r, \ ra \ p Effectiveness of the test substance.

evaluation
The effect is assessed on the following scale:

10 = ineffective, same infestation as untreated

dated control plan / s.
9 to 1 = infestation reduction.
0 = no infestation.

Prevention

3- (4'-chlorophenylimino) -4-chloi-5-di-

methyhmino-l ^ -dithiacyclopenten
3- (4'-chlorophenylimino) -4-chloro-

S-morpholino-lI-dithiacvclopenten
3- (3 ', 4'-dichlorophenylimino) -4-chloro-

5-morpholino-1 ^ -dithiacyclopenten
4,5-dichloro-1,2-dithiacyclopentene

3-on (known)

Effect / ahl

10

The following examples illustrate the manufacturing processes for the new compounds of the formula I. Parts mean parts by weight.

example 1

A mixture of 99 parts of 4-chloroaniline, 158 parts of triethylamine and 500 parts of ether is left in a suspension of 189 parts of 3,4,5-trichloro-1,2-dithiacyclopentenium chloride in 200 parts by volume of diethyl ether at -20 to -30 ° C. with stirring to drip. This mixture is then stirred at 25 ° C. for 12 hours. It is then filtered, the filter 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. Small amounts of a brau.ics oil precipitate here. from which is decanted. The solution is then shaken with activated charcoal, filtered and cooled to -60 ° C. Here, the 3- (4'-ChlorphenyliminoHl.S-dichloro-l ^ crystallized -dithiacyclopenten in yellow needles, mp 95-95 ⁰ C. Yield: 72Teile (31% of theory).

The following compounds were prepared in an analogous manner: To a solution of 15 parts of 3- (4'-chlorophenylimino) - 4,5 - dichloro -1,2 - dithiacyclopenten in 35 parts by volume of chlorobenzene are left with a solution of 6 parts of dimethylamine in 24 parts by volume of 1,2-dimethoxyethane Add dropwise while stirring and cooling with ice. The mixture obtained is left at 25 ° C. for 3 days stand. The precipitated dimethylamine hydrochloride is then filtered off. The filtrate is evaporated and the residue from evaporation from ethylene glycol monomethyl ether recrystallized. 5 parts of 3- (4'-chlorophenylimino) -4-chloro-5-dimethylamino-1,2-dithiacyclopentene are obtained in yellow needles from F. 119 to 120 C.

Example 2

24 parts of iAS-trichloro-l ^ -dithiacyclopenteniumchlorid are suspended in 50 parts by volume of ether and left without stirring; Cooling within one hour, a solution of 10 parts of triethylamine and 14 parts of 3-chloroaniline in ether are added dropwise. The mixture .vird 15 hours at 25 ⁰ C overnight, then filtered and the filtrate evaporated. The evaporation residue solidifies in the course of a few days. It is reprecipitated once from methylcellosolve / water and once off

Methanol incrystallized. The 3- | 3'-chlorophenylimino) - 4 - chloro - 5 - fV - chlorophenylaminol-1,2 - dithiacynpentene is obtained
I ·. 125 C (decomposition !.

in yellow fine needles.

Analysis:

Calculated:
C 46.5. H 2.3.

found:
C 46.9 H 2.3.

Cl 27.5. N 7.2. S 16.9 "

Cl 27.4. N 7.2. S 16.5 "

As described in the previous examples, the following additional compounds were also made manufactured:

3- | 4'-chlorophenyliniino) -4-chloro-5-morpholimt-

1.2-dithiacyclopentene: l · ". 133 to 134 <'.
3- | 3'.4'-dichlorophenylimino | -4-chloro-5-n) (ii-

pholino-1.2-ditniac \ ck> penten: F. 121 to 123 L '. 3- (4'-chlorophenylimino) -4-chloro-5-diethyl-

amino-1,2-dithiacyclopenien; F. 75 to 76 C. 3- {4'-chlorophenylimir, o | -4-ehlor-5-piperidino-

1,2-dithiacyclopentene, F. S4 to S5 C.
Fungal agents according to the invention are prepared in a manner known per se by intimately mixing and grinding active ingredients of the general formula I with customary carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients.

Claims (1)

Patent claims: 1. 3- Phen \ limino-4-chloro-5-amino-1.2-diihia-C \ clnpeiuene of the formulas I and II R- ¹ R ² Cl S-S