SK7196A3 - Acaricidal-fungicidal agents and process for producing them - Google Patents

Abstract

There are disclosed polysulfide-based acaricidal-fungicidal agents which contains at least one of polysulfides of the formula MemSn wherein Me is potassium, sodium, copper or zinc, whilst coefficients m and n acquire the following values: m = 1 - 2 and n <= 6. These agents are prepared by reacting elementary sulfur present in an aqueous medium and hydroxid or alk. metal sulfide, whilst from 0.3 to 6.5 moles of elementary sulfur, preferably from 2 to 4 moles of elementary sulfur are admixtured into a reaction mixture. The reaction can be carried out in or without the presence of a catalyst. Temperature of the reaction mixture is higher than 25 DEG C and lower or equal to a boiling temperature of the reaction mixture. The reaction is carried out at atmospheric pressure or higher to enhance reaction. The aqueous solution thus obtained contains at least one of alk. metal polysulfides and can be further subjected to reaction with urea to improve a phase stability of the preparation and stimulate sulfur penetration into fungi spores. Polysulfides of copper and/or zinc are prepared by precipitating reactions of aqueous solutions of alk. metal polysulfides and materials which contain copper and/or zinc.

Description

BACKGROUND OF THE INVENTION

In addition to copper and mercury, sulfur is another element which, in its elemental form and in the form of several compounds, has significant fungicidal activity.

The fungicidal properties of sulfur have been known for almost two centuries, although Homer has been known to mention the use of sulfur dioxide in relation to the control of plant diseases and insect repellents. Already in 1803 ROYAL GARDENER FORSYTH recommended spraying fruit trees with sulfur. In the 19th century, the use of sulfur also spread in connection with the cultivation of vines.

The mechanism of fungicidal effect of sulfur was. long unclear and has not been satisfactorily explained yet. According to one of the first theories, it considered the carrier of the fungicidal effect of hydrogen sulphide (H2S) because it was experimentally confirmed that the spores of most fungi easily reduce elemental sulfur to hydrogen sulphide, which is toxic to them. This theory was challenged in the 1950s when it was shown that colloidal elemental sulfur had a significantly higher fungicidal activity than an equivalent amount of hydrogen sulfide. Other hypotheses ascribed to i

Jungitoxicity of sulfur by a variety of oxidation products, such as e.g. sulfur dioxide and sulfuric, sulfuric, thiosulphuric and pentationic acids. Since no sulfur derivative satisfactorily explains the fungicidal properties of sulfur, it is now widely accepted that the classical SEMPIA theory is nowadays that sulfur as an Ss molecule is toxic to fungi. There is also some evidence that sulfur penetrates into fungal spores, and its toxicity is most likely to act as a hydrogen acceptor, thereby interfering with vital hydrogenation and dehydrogenation reactions in fungal cells.

It is also difficult to explain the specific toxicity of sulfur to fungi and the fact that sulfur, unlike heavy metals (such as copper, silver, mercury ...), is not practically toxic to mammals. A possible explanation is the different availability of the site of action in the fungus.

In addition to the use of elemental sulfur, which is produced for fungicidal use by colloidal milling, usually in wet conditions, the use of a liquid sulfur product - sulfur trioxide - has also been extended. It is prepared by boiling elemental sulfur with slaked lime in an aqueous suspension. An orange-colored solution is obtained, which mainly contains calcium polysulphides, which are slowly decomposed in the air, releasing elemental sulfur. The content of polysulfides in sulfuric acid is therefore a major indicator of its quality.

IJ is currently produced and distributed under the commercial designation SULKA by Sulfur, which contains 14 masses. X of polysulfide sulfur.

The production of the preparation in question is considerably inefficient and operationally demanding, while the operation also produces solid waste - filter sludge (about 10 7 of the weight of the reaction mixture). The presence of a calcium cation in the molecule of the active substance, although suitable from an agronomic point of view, makes it virtually impossible to mix with liquid fertilizers and other plant protection products.

The relatively low solubility of calcium polysulfides in water does not allow the preparation of more concentrated formulations and is the reason for their low phase stability at. near freezing temperatures.

SUMMARY OF THE INVENTION

It has now been found that the polysulfide-based formulations according to the invention better meet the sulfuricidal requirements for acaricidal fungicidal effects and the possibility of producing them.

The new acaricidal fungicidal preparations based on polysulfides are characterized by: polysulfides of the general formula:

M n Sn wherein Me is potassium and / or sodium wherein for the coefficients m and n pla1, they contain at least one of and / or copper and / or zinc, with m = 1 to 2 and n < 6.

to 2

From the point of view of production, but in particular of use, it has proven to be particularly advantageous to consider the preparation of formulations in which potassium and / or copper are used as the cation. In the case of preparations containing copper polysulphides, the fungicidal activity of sulfur is expediently combined with the long-term contact action of the slowly soluble forms. A study of copper in its distribution of 1 y su 1 fid and 1 sludge, other metals contained in the preparation revealed the presence of MeaSa, MeaSs, lleaS4, with the largest extent of potassium modification being present in products

Ks Sa e Ka Se.

The process for the production of acaric bottom-pharmaceutical compositions according to this solution is characterized in that elemental sulfur in the aqueous medium undergoes a chemical reaction with at least one of the alkali metal hydroxides and / or sulfides, such that per mole of hydroxide and and / or an alkali metal sulfide is introduced into the reaction medium from 0.3 to 6.5 moles of elemental sulfur, preferably from 2 to 4 moles of elemental sulfur.

The reaction may be carried out without, or in the presence of a catalyst, at a temperature above 25 ° C and below or equal to the boiling point of the reaction mixture, at normal or elevated pressure. It has been experimentally confirmed that by adding some organic bases to the reaction mixture, as their catalyst, the reaction rate can be significantly increased in the desired direction, even when the reaction temperature is substantially reduced. Compounds of the polyalkylpolyamines group (e.g.

d i e t y é th e m a n, th e t y e y th e t e a m e, d e o y y th e t y a m e,

N-dimethylpropylenediamine and the like). Conducting the reaction at elevated pressure without the use of a catalyst allows the reaction time to be shortened and promotes the formation of higher polysulfides.

In order to increase the phase stability of the reaction products and also to increase the penetration of the sulfur contained in the preparation into fungal spores, it has been found expedient to react the prepared aqueous polysulfide solution with urea (CO (NHa) 2).

In order? For the preparation of copper and / or zinc polysulphides, it is also possible to prepare the aqueous solution containing at least one of the alkali metal polysulphides optionally further to precipitate with a copper and / or sinc source. Sulfates, chlorides, chloroamocomplexes, amocomplexes and the like have proven to be suitable sources of copper and zinc for this purpose.

The reaction products according to this solution can be made into concentrates suitable for the preparation of so-called concentrates by the addition of oily substances in the presence of active additives. washing, especially spring sprays against perenospore, leaf lice eggs and also against various mite pests. For this purpose, it is particularly suitable from an ecological point of view to use vegetable oils which are degraded in nature considerably more rapidly in comparison with the mineral oils used today. Particularly suitable for this purpose is rapeseed oil or its methyl ester, the so-called green diesel.

Execution examples in

The following examples illustrate and document, but do not limit the subject matter of the invention.

Example 1

A sulphonation flask equipped with a stirrer, reflux condenser and thermometer, placed in a water tempering bath, was weighed with 226.6 g of water of 651.2 potassium sulphate (K ₂ S x

H 2 O) containing

XK ₂ S and elemental sulfur.

After closing the flask and opening the cooling water supply to the reflux condenser, the reaction mixture was tempered to 92-96 ° C with stirring.

Mixing of the contents of the flask continued until virtually complete dissolution of the sulfur (ca.

4-5 hours)

The product was a practically clear orange solution. It contained 24.5 wt. 7. Sulfur.

Example 2

A sodium analogue of a solution-type acaricidal fungicidal preparation was prepared in a similar laboratory procedure to that described in Example 1, wherein the reaction mixture at the start of the experiment consisted of:

758 g (ml) of water

121 g technical asii 60% sodium sulphide in the form of flakes according to STN 65 3113, type A

121 g powdered elementary

The product as a solution reaction and contained about 15 Z

Example 3

Using laboratory examples 1 and 2, potassium sulphide (KsS x Hs (sulfur.

orange with sulfur. color had alkaline apparatus how in previous lžilo 376 g (ml) water, 524.9 g

)) containing min. 65 7. Pcs S a

99.1 g of elemental sulfur powder. The reaction mixture was refluxed for several hours to obtain an aqueous solution of potassium polysulphide according to a solution in which the disulfide predominated. Prepared clear orange solution

he was c ha rak terized as follows; specific weight, d2 &gt; = 1.5064 g. cm ^-3 sulfur content 19.8% N potassium content 29.1% K ₂ 0 pH, i.e. solution in i water distribution 10.7 for to prepare the goods polysulfide copper in the sense of the solution

further proceeded by dissolving 77.3 g of CuSO4SH5O in 211 g (ml) of distilled water, and 100.3 g of the potassium polysulfide solution specified above was gradually added to the solution thus prepared.

The precipitation reaction gave a slurry of a brown-green color, a slightly acidic chemical reaction (pH 4.85). The reaction product was subjected to free sedimentation in a graduated cylinder, after 20 hours of free sedimentation the volume of the sedimented layer was 42 vol. 7. The pasty product after removal of the clear layer was made into a DKV formulation after addition of the finalizing ingredients using a laboratory dispersing device.

Example 4

In order to prepare a solution-type acaricidal fungicidal composition according to the invention, 529 masses, parts of a 44.1% aqueous solution of KOH, were introduced into a heated stirred reactor, which was aerated via a reflux condenser.

Q

267 parts by weight of elemental sulfur.

The reaction mixture was heated to the boiling point with stirring, maintaining it at this temperature (112-115 ° C) until virtually complete disappearance of solid sulfur (about 5 hours). The aqueous potassium polysulfide aqueous solution prepared by this procedure was a basic reaction (pH: 11.4) and its density at 40 ° C was 1506 kg.m ⁵ . The product contained 33.5 7th sulfur, 14.7 KsO and predominantly contained polysulfide type Ks S4

Example 5

116.8 ml of scaled sulfur-type water was introduced into the glass apparatus according to Example 1

SULPHUR R0T0F0RM and 716.6 g 44.17. KOH

With stirring, diethylenetriamine diets were added to the reaction mixture. By addition of the amine, the reaction mixture started to brown immediately. The reaction mixture was heated to 60 ° C with stirring (water was heated in a temperature bath at the indicated temperature)

As a result of the exothermic reaction heat, the temperature of the reaction mixture reached 78 ° C after about 14 minutes, during which time about

X sulfur sulfur

F’oi 140 minutes after the catalyst was added, the reaction mixture no longer contained sulfur in insoluble form

Example 6

In order to assess the efficacy of diethylenetriamine as a catalyst for the course of the reaction of interest, a laboratory experiment was performed under the same conditions as described in the previous Example 5, but without supplying heat to the reaction mixture from outside (in an autothermal configuration).

The temperature of the reaction mixture was 21 ° C prior to addition of the weighed (2.44 wt.%) Diethylenetriamine. By adding the verified catalyst, the reaction mixture began to turn brown gradually, and the gradual heating of the mixture was noted. The maximum temperature of 63.8 ° C was reached by the reaction mixture, which was stirred continuously, minutes after the catalyst had been introduced.

After stirring for 50 minutes, the temperature of the reaction mixture was 0 ° C and the stirred suspension contained only about 10 7 of the original amount of elemental sulfur. Stirring of the reaction mixture was complete after four hours, when the orange to brown product contained only slight traces (1-2 g) of insoluble sulfur which immediately sedimented. The specific gravity of the product at room temperature was 1.414 9.0 (11-3 ⁾ and the pH of its 17th solution in distilled water was 10.3.

Example 7-9

In these three experiments, under similar laboratory conditions as described in Example 5, they were verified as catalysts for the reaction in question:

th e th e th e th e th e th e th e th e th e th e th e n th e N - th e th e th e th e th e n th e th e.

All the catalysts tested here proved to be effective in the reaction environment under consideration - they greatly reduced the heating and stirring time of the reaction mixture. Their effect on the reaction rate was more pronounced already at 0.5X of the catalyst content in the reaction mixture, showing a 2-3% addition of the corresponding polyamine as completely satisfactory.

Examples 10 and 11

The heated stirred reactor as in Example 4 was charged with: 205.16 parts by weight of water,

702.65 parts by weight, parts by weight of sulfur-dioxide and 1392.19 parts by weight of parts 44, IX of potassium hydroxide

The reaction mixture is boiled for several hours. 1 solution of potassium polysulphide solution, density at.

which contained 30.55 masses. 7. Sulfur, its ° C being 1445 kg.m- ³

The sulfur concentrate prepared by the above process was further modified according to the following recipes:

Mixed ingredient Mixed component weight / X / ' Example ! 10 Example 11 J aqueous solution of potassium phosphate (30.55 X S) 65.57 65, 57 í Water 24.43 ... í Concentrated suction vapors (55 X dry matter) - 24.43 [G ran u and p u uran ((46.2 X N) 10.0 10.0 í Final product specification! sulfur content (mass X S) 20.0 20, 0 1 - amide nitrogen content 1 (mass X N) 4.6 4.6 i - specific weight - density, I d2 <> ° C (g. cm ³ ) 1,328 1,388 1 ~ ρΗκ onz. 11.9 11.2

10.7

9.4 pH (IX solution)

Example 12

Potassium polysulphide solution concentrate containing.

30.55 wt

X of sulfur was adjusted according to the recipe of Example 10 by adding urea and water to the intermediate containing 20 X

S and 4.6 X N-NHa

In order to prepare an emulsion sulfur-oil concentrate intended for the preparation of washing sprays intended for spring application, it was efficiently mixed into an emulsion of masses, parts of the sulfur intermediate (20 XS and 4.6 X ΙΜ-)2) masses, parts of SL.OVASDI._u SF respectively. 255 parts by weight of crude (unrefined) peanut oil.

The obtained concentrate had the character of a reduced orange-red mayonnaise and was applied in the form of 2-5X aqueous emulsion at the onset of budding (until the red buds) as a spring washing spray against perenospore, with 1 lenticular lice against mites. fruit growing (apple, pear, peach, plum) and vine growing

Λ. -J

Example 13

An emulsion sulfur-oil concentrate for solution was obtained by emulsifying these components

30.0 masses. parts of sulfur intermediate (20 X S? 4.6%

N-NHa) prepared according to Example 11,

56,0 materials. parts lester's plate 7.0 materials. parts SLOVÁCID 06 1.4 materials. parts SLOVÁCID R 2 5.6 materials. parts SLOVAFOL 906 Ready i emulsion a horse

D rapeseed oil (RD Salgovce) centrate was applied at 4Z concentration as a spring washing spray

Claims (4)

Patent claims A polysulfide-based acaricidal fungicidal composition comprising at least one of the polysulfides of the general formula; Me _m Sn where Me is potassium and / or sodium and / or copper and / or zinc, where m = 1 and 2 and 6. 2. A process for the preparation of an acaricidal fungicidal composition according to claim 1, characterized in that the elemental sulfur in the aqueous medium is subjected to a chemical reaction with at least one of the alkali metal hydroxides and / or sulphides by per mole of alkali metal hydroxide and / or sulphide. 0.3 to 6.5 moles of elemental sulfur, preferably 2 to 4 moles of elemental sulfur, are introduced into the reaction medium, the reaction being carried out without or in the presence of a catalyst at a temperature above 25 ° C and below or equal to the boiling point of the reaction mixture; of normal or elevated pressure, the aqueous solution containing the alkali metal polysulphides thus prepared is reacted with urea and / or at least one of optionally further precipitates with a copper and / or zinc source, optionally adjusting the duty by adding an oily substance forms of concentrate suitable for the preparation of so-called. washing spray. 3. A process according to claim 2, characterized in that one of the organic bases, preferably one of the polyalkylpolyamines, is used as a catalyst to accelerate and deepen the reaction. 4. A process for the preparation of an acaricidal fungicidal composition according to claim 2, characterized in that, as an oily substance for processing into a concentrate suitable for the preparation of a so-called concentrate. For example, one of the vegetable oils, preferably rapeseed oil or methyl ester thereof, is used in the washing spray.