FI56304C - fungicide - Google Patents

Description

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Patent- och regl »ter« tyrel «en '' Antökan utitgd och utl.ikrifun published 20.Uy. fy (32) (33) (31) Privilege requested — Begird prloritet 27 · 06.73

France-France (FR) 732U301 (71) RhSne-Progil, 25, Quai Paul Doumer, 92 * + 08 - Courbevoie, France

France (FR) (72) Bernard Buathier, I <yon, Jose Moyne, Caluire, France-France (FR) (7 * +) Berggren Oy Ab (5 * +) Fungicides - Fungicides

The present invention relates to a fungicide for controlling parasitic fungi.

U.S. Patent No. 3,109,772 discloses compounds having the general formula: r = \

\ / O

/ 5 =, \

S1 5C = S

and have a significant antifungal effect. Other patents, in particular French Patent No. 1,526,768 and English Patent No. 1,183,6 * J5, also describe the antifungal activity of compounds which contain a dithiol-thione ring but in which position 4 and / or 5 is substituted by heteroatoms. such as nitrogen and sulfur.

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The Applicant has now surprisingly discovered that compounds having the general formula:

R1 \ X R2

C = C

/ \ S c = s s ^ where R1 and R2, which may be the same or different, represent hydrogen or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, have a considerable fungicidal effect · *

The invention therefore relates to a fungicide which can be used to control parasitic fungi and which is characterized in that it contains at least one of the compounds described above as active ingredient.

The synthesis of these known products can be performed in a number of known ways. French Patent No. 1,472,699 describes a process for reacting substituted olefins with vapor in the vapor state at a temperature of 450-475 ° C. It is also possible to obtain dithiol thiones substituted in positions 4 and 5 by sulfurization of bis- (methylthio) dialkylalkenones or β-carbonyl esters.

As mentioned above, positions 4 and 5 of the ring may have aliphatic hydrocarbon groups containing 1 to 4 carbon atoms as a substituent. However, it has been found that the simplest compounds have the most potent fungicidal activity, i. with those compounds whose substituents have a lower molecular weight. Thus, dithiol-1,2-thione-3 and methyl-4-dithiol-1,2-thione-3, methyl-5-dithiol-1,2-thione-3 and dimethyl-4,5-dithiol-1,2 -thion-3 are the most effective of the compounds of the invention in the fight against parasitic fungi.

The synthesis of some effective products will be described in detail below, for the sake of illustration only.

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Example 1

Synthesis of dithiol-1,2-thione-3 by sulfurization of propylene.

Propylene and sulfur are reacted in a ratio of 1 mole of propylene per 5 gram atoms of sulfur at 500 ° C in the vapor phase in a stainless steel reactor. The crude reaction product is condensed in several successive receiving vessels, then distilled. At 1 mm Hg, dithiol-1,2-thione-3 distills at about 110 ° C. The hall is 50%. The product obtained is brown crystals melting at 82 ° C.

Example 2

Synthesis of methyl 5-dithiol-1,2-thione-3 by sulfurization of trans-2-butene.

The procedure is the same as in Example 1 to give the desired product as yellow crystals, melting at 33 ° C.

Example 3

Synthesis of dimethyl-4,5-dithiol-1,2-thione-3 by sulfurization of bis- (methylthio) -dimethylalkenone.

For half an hour, a solution which contains, dissolved in 100 g of xylene dimethylthio-l, l-dimethyl-2,3-one-3-propylene-I, three liters of boiling xylene containing 300 g of phosphorus pentasulfide-suspend-Tua. Decant and dissolve the crude reaction product in ether, then filter and wash with soda solution. The dimethyl-1,5-dithiol-1,2-thione-3 mercury complex is then isolated according to the Classical Method. Recrystallize from cyclohexane to give 32 g of dithiolthione (yield: 35%), which are yellow scales melting at 95 ° C.

Starting from dimethylthio-1,1-ethyl-2-methyl-3-one-3-propen-1 and dimethylthio-1,1-methyl-2-ethyl-3-one-3-propene 1, the same under conditions other than those mentioned above for ethyl M-methyl-5-dithiol-1,2-thione-3 melting at 40 ° C and methyl-H-ethyl-5 'dithiol-1,2-thione-3 melting at 28 ° C.

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Example 4

Synthesis of methyl 1-dithiol-1,2-thione-3 by sulfurization of ethylpholylpropionate.

13 g (0.1 mol) of ethyl formyl propionate are dissolved in 100 vagins of dry xylene. 22 g of powdered phosphorus pentasulfide are added to the resulting solution, which is distilled with a vertical condenser for 1 hour. 50 cm3 of ethanol, 150 cm3 of benzene and 50 cm3 of water are then added to the mixture; is mixed and then poured into a vessel containing 300 cm @ 3 of water. The organic layer is collected, washed and dried. Methyl-dithiol-1,2-thione-3 is precipitated as a complex mercury salt. Distill and recrystallize from ethanol to give the dithiol thione as yellow crystals, melting at 13 ° C.

Of the fungi that are very sensitive to the effects of dithiol thiones, mention should be made of some species whose development is particularly destructive in various materials such as wood, leather, paper, textiles, vines, paintings, as well as fruit, especially during storage. Of these fungi, mention should be made in particular of Coriolus Versicolor, Sterigmatocystis nigra, Cladosposium Herbarum and Botrytis Cinerea.

The amount of active substance used depends on the materials to be treated. Illustratively, for example, doses of 2-10 kg of active ingredient per m3 of wood provide complete protection and that the same result has been obtained using 0.25-5 kg of active ingredient per hectare in the vineyard in the fight to eradicate Botrytis Ciner.ea.

The active ingredient is usually made into aqueous emulsions or organic solutions containing 1 to 5% by weight of dithiol thiones. These formulations may also contain any of the classical excipients which aid in fixing, penetrating and wetting the substance, etc.

The following example demonstrates the efficacy of the products of the invention on some particularly widespread fungal species.

r

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Finely ground active ingredients are placed in the center of the si Iivi, 5 S6304 with malt and agar. The results are recorded 5 days after contact between the active substance and the fungus as follows: 0: no effect 2: moderate effect 4: complete effect.

In this way, the following products have been studied:

Product No. 1: dithiol-1,2-thione-3

Product No. 2: methyl-4-dithiol-1,2-thione-3

Product No. 3: methyl-5-dithiol-1,2-thione-3

Product No. 4: dimethyl-4,5-dithiol-1,2-thione-3

Product No. 5: Ethyl 4-dithiol-1,2-thione-3 and for comparison:

Product No. 6: phenyl-4-dithiol-1,2-thione-3

Product No. 7: mercapto-5-phenyl-4-dithiol-1,2-thione-3

Dose g / 11 2 3 4 5 6 7

Coriolus

Versicol 0.1 4000000 1 4444400 10 4 4 4 4 4 0 4

Sterigmato- 0,1 2 0 0 0 0 0 0 cystis] _ 4444 4 02 nigra 10 4444404

Cladospo- 0.1 4444200 siium ^ ± 4444400 herbarium 10 4 4 4 4 4 0 4

Botrytis 0,1 4 2 2 2 4 0 2 cinerea ^ 4444402 10 4 4 4 4 4 0 4

The above table, which shows the results obtained, clearly shows the superior superiority of the products used according to the invention over those products for which the fungicidal efficacy has been described so far.