DE1929130C - 1,2 Dithia 3 phenyhmino 4 chlorocyclopentene - Google Patents

Description

It has been found that l, 2-dithia-3-phenylimino- -1-chloro-cyelopentene compared to the Belgian Patent specification 698 869 known 1,2-dithiol-3-on-5-ylsulfiden a superior fungicidal activity, in particular on the basis of systemic fungicides.

The new I ^ -DithiaO-phenylimino ^ -chlor-cyclopentene correspond to the formula

S-S

R ¹ - S

J = NR ²

Cl

in which R ^{1 is} a methyl, ethyl or / »- chloroethyl radical, R ^{2 is} a phenyl, 4-chlorophenyl or 3 ', 4'-dichlorophenyl radical and t is the number 0 or 2. The new l ^ -dithia-S-phenylimino ^ -chlorocyclopenlenes are prepared by adding a 1,2-dithia-4-chloro-cyclopentene-3-one of the general formula (which has become known from Belgian patent specification 698 569)

R ¹ -S-

Cl

in tier R ¹ and f have the meaning given, with an inorganic or organic sulfur chloride to form a 3,4-dichloro-1,2-dithiolium chloride of the formula

R ¹

S-- S

Jf +: L
, γ Cl

Cl

Cl

35

transferred and this with an amine of the general formula R ² - NH ₂

in which R ^{2 has} the meaning given.

The reactions are inert towards the respective reactants in the presence of l. solvents or thinners. The following are, for example, suitable as such: hydrocarbons, such as benzene, halogenated hydrocarbons, such as chloroform, trichloroethane. Chlorobenzene, M.N-disubstiluicrte carboxamides, nitriles, ethers lind; ithor-like compounds. so

For the implementation of the Dithioliumchlorid.s with an amine is the addition of a base, in particular tines' critical amine, advisable.

The new ancestors are painted to a different ancestor 1,2-1) ithia-3-phcnylimino-4-chloro-cyclopentenc her- ss ordered by making a 3-plicnylimino-4,5-dii: lilor-1,2-dithiol the general formula

S S

Cl with a compound of the general formula ⁶ J

[OJ,

reacted, in which R ¹ and / have the meaning given and R 'represents a hydrogen or an alkali metal atom, in particular sodium or potassium. This reaction is also carried out in the presence of solvents or diluents; as such, for example, those mentioned above can be used.
As compounds of the general formula

R ¹ —S — R '
[O],

come for the preparation of the invention! ^ - Dithia ^ -phenylimino ^ chloro-cyclopentene, where f O means thiols or thiones convertible into thiols in question. These can be both as such and can also be used as alkali metal salts for these processes. In some cases it is beneficial to ao the reaction in the presence of an acid-binding agent, such as. B. weaker in the presence of salts Acids, metal oxides, tertiary amines, etc. For the production of the invention U-DithiaO-phenylimino ^ -chlorocyclopentene, in which / the number 2 means are used as starting materials of the general formula

R ¹ S R- [O],

Salts of sulfinic acids (R ¹ SO ₂ H), in particular the sodium and potassium salts of corresponding sulfinic acids, are used.

The new 1,2 - [) ithia-3-phenylimino-4-chlorocyclopentene have an excellent effect against numerous phytopathogenic fungi. The new active ingredients are against plant diseases Effective against fungi, for example against powdery mildew, such as cucumber powdery mildew (Frysiphc cicharaccarumlund Rose dew (Sphaerotheca pannosa): against false powdery mildew fungi, such as the pathogens of the knee and potato bulbs (Phytophtora) mfestans): against leaf spot pathogens, such as Alternaria solani: against rust fungi, such as bean rust (Uromvces appl), also against the particularly difficult to fight Gray mold (Botiytis cincrca).

Since the new 1,2-dithiols also have systemic properties, their use can protect plants and their newly to be warmed parts from further fungal infections even after treatment. The new active ingredients can also be used to treat seeds without affecting their germination. The active ingredients are used in the form of solid or liquid work-up forms, such as dusts or grit or granules, dispersions (suspensions or emulsions) in crop protection. The active compound concentrations required for crop protection are in the range from (M) 1 to 2 "n, the application rate is between 0.1 and 7 kg / ha, but depends largely on the plant matter to be protected.

Some of the new active ingredients can also be used to fight fungi and bacteria organic materials, especially kerutinic, Carry out cellulose-containing,?} nthelical materials and paints. The active ingredients can also be used to disinfect the soil Find. Their warm-bloodedness is low.

The fungicidal activity of the 1,2-dithia-3-phenylimino-4-chloro-cyclopcnienes which can be used according to the invention was found by the following experiment and with two from the Belgian patent specification 698 869 known dithiolones compared in terms of effectiveness:

Action against Botrylis cinerea on Vicia faba (broad beans)

In Peiri dishes, which are lined with moistened filter paper, three gul unfolded, equal large leaves of Vicia faba and made with an active ingredient formulated as a wettable powder Broth (0.1% active ingredient), sprayed to runoff. After the spray coating has dried they are infected with a freshly prepared spore suspension of the fungus. After the leaves 1 to 2 days have been kept in a humid atmosphere at 18 to 20 C, show up on the leaves in the case of a Infection black, initially punctiform spots (which spread rapidly. Number and size of the infection sites serve as an evaluation standard for the effectiveness of the test substance.

Assessment The effect is assessed on the following scale:

IO = ineffective, same infestation as untreated control plants, 9 to 1 = infestation reduction,

0 = no infestation,
f f- I- combustion. Leaves destroyed.

Bolrytis cinerea

connection

1.2-1) iihia-3-phcnylimino-4-chloro-5-ethylmcrcaplo-cyclopentene ....

1,2-Dithia-3- (4'-chlorophenylimino) -4-chloro-5- (2'-chloroethyl mercaptocyclopentene

l, 2-I) ithia-4-chl (ir-5-ethylmercapti> cyclopentcn-3-one *)

1,2-1) ithia-4-chloro-5- (2'-chlorithylmercapto-cyclopcnlen-3-one *) ....

IO

sunHlasl ^ -Difbia-J-phenylimino- ^ chloro-S-iiihylmercapto-cyclopenten off, yellow plates F. 3K to 39 C.

In the route described in Example I, the following compounds were prepared using the appropriate Get raw materials:

connection

IO l ^ -Dithia-S-phenylimino ^ -chlor-5-methylmercaplo-cyclopenlene

1,2-Dithia-3- (4'-chlorophenylimino) -4-chloro-5-methylmercapto-cyclopemes - · ■

1,2-dithia- (3 ', 4'-dichlorophenylimino) -4-chloro-5-methylmercapto-cyclopentene

1,2-Dithia-3- (4'-chlorophenyl-imino) -4-chloro-5-ethylmercapto-cyclopentene

1,2-Dithia-3- (4'-chlorophenylimino) -4-chloro-5- (2'-chloroethylmercapto) -cyclopentene ...

Example 2

F.

94 to 96 C

102 to 103 C

109 to 112 C

76 to 78 C.

99 to 101 C

*) Hck.iinil; uii ilcr heluiuhcn Ι'.ιΙιίιΙμππΓι ft ') H Χή'λ

The following examples illustrate the manufacturing process.

Example I.

26.S file 3,4-Diehlor-5-ethylthio-1,2-dilhiolium chloride are suspended in 100% volume of chloroform. To this end, a mixture of 9.1 parts of aniline, 10.1 parts of triethylamine and 100 parts by volume of benzene is added dropwise with stirring and while cooling with ice. The mixture is stirred for a further 2 hours at 25 ° C. and evaporated. The evaporation residue is dissolved in a mixture of 100 parts by volume of chloroform and 400 parts of water. The Chloroformschkhi is separated, dried and evaporated with magnesium sulfate, The EirtdampfrUckstand is taken in hot isopropanol to ^'6 S and cooled. Here, long-crystallized A mixture of 20 parts of l, 2-dithia-3- (4'-chlorophenylimino) -4,5-dichloro-cyclopcnten, 1 5 parts of Naja triutnsalz Äthansulfinsäurc and 50 [rush of dimethylformamide for 6 hours at 20 to Stirred at 25 ° C. The reaction product is then precipitated with ice water and recrystallized twice from benzene-cyclohexane. This gives 11 parts of l, 2-Dith; a-3- (4'-chlorophenyl-VS imino) -4-chloro-5-älhylsulfonyl-cyclopentcn j _n orange platelets, melting at 117 to 120 C.

The 3,4-dichloro-1,2-dithiolium chloride used as the starting material is produced on the the following way: 100 parts l, 20Hhia-4-chloro-5-eth> lmercapto-cyclopenten-3-one are mixed with 2 (K) parts by volume of chloroform and 100 parts by volume of oxalyl chloride Heated under reflux for 50 hours. The solvents are then distilled off under reduced pressure and extracted the crystalline evaporation residue three times with 200 parts by volume of hot benzene each time. Unsolved 91.5 parts (76%) of 3,4-dichloroethylmercapto-1,2-dithiolium chloride remain in orange needles. F ". 140" C (decomposition).

Claims (1)

Patent claims: I. 1,2-I) ithia-3-phenylimino-4-chloro-cyclopenu-iic the general formula R ¹ KH S S Cl in which R 'denotes methyl, ethyl or (- chloroethyl res ", R ¹ denotes a phenyl, 4'" carbonphenyl or 3 ', 4'-dichlorophenyl residue and t denotes the number 0 or 2. ciiplo-cyclopcntcn. .1. 1,2 - Oithia · 3 - (4 '- chlorophenyl) - 4 · chloro-5- (2' * chloroethylmercaptoK ^< yclopenten.