DE1186458B - Process for the preparation of fungicidally active manganese-ethylene-bis-dithiocarbaminates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 07 c

German class: 12 ο -17/02

Number: 1186458

File number: C19519IV b / 12 ο

Filing date: July 31, 1959

Opening day: February 4, 1965

The well-known manganese salt of ethylene-bis-dithiocarbamic acid is made by double reaction of a water-soluble alkali or ammonium salt Ethylene-bis-dithiocarbamic acid made with manganese sulfate or another soluble manganese salt. The yellow salt obtained in this way, which is sparingly soluble in water, contains about 20% manganese.

It has been now found a process for the preparation of fungicidally active manganese -Äthylen-bis-dithiocarbaminaten found, which is characterized in that 1 mole of ammonium salt of ethylene-bis-dithiocarbamic acid at 10 to 50 ° C, preferably 20 to 4O ⁰ C, in Reacts aqueous solution with 1.0 to 2.5 mol, preferably 2 mol, of an oxide of manganese, after which the reaction mixture is neutralized with an acid, filtered off with suction or centrifuged and dried. In general, 2 moles of manganese oxide react, so that there is 1 mole of manganese oxide per dithiocarbamic acid residue and only 2 gram atoms of sulfur per gram atom of manganese. In contrast, in the previously known manganese salt, which is prepared as described above, two dithiocarbamic acid groups are bound by only 1 manganese atom, so that the ratio of manganese to sulfur corresponds to a value of 1: 4.

Another difference is that the new compounds contain oxygen, while the previous ones known to be free of oxygen.

The manganese compounds produced according to the invention also differ in their chemical properties Behavior significantly different from the well-known salt. This is because they already show themselves during the suction process or centrifuging after most of the water has been removed, being susceptible to oxidation by they change into a stable form with self-heating, but only when oxygen is present. These The reaction does not occur if the work is carried out in the absence of oxygen or air. By adding Self-heating can be dampened by vacuuming small amounts of water. After subsiding the evolution of heat a stable product is obtained which normally dries to constant weight can be and is then shelf-stable.

The causes of self-warming have not yet been fully clarified. It was only observed that ammonia is released and that self-heating, as already mentioned, only occurs in the presence of oxygen takes place, with part of the manganese being converted into a more valuable form. The dried one Product still has a low ammonia content.

A stable product is also achieved if after the conversion between manganese oxide and Process for the preparation of fungicidally active manganese-ethylene-bis-dithiocarbaminates

Applicant:

Chemical works Albert,

Wiesbaden-Biebrich, Albertstr. 10-14

Named as inventor:

Dr. Johannes Reese, Wiesbaden-Biebrich;

Dr. Ernst August Bartels, Wiesbaden

the ethylene-bis-dithiocarbamonic acid ammonium, which can be determined by iodine titration, either dehydrated in a vacuum or with acids such as sulfuric acid, nitric acid, hydrochloric acid or acetic acid is neutralized.

According to the invention, 1.0 to 2.5 mol z. B. Manganese (II) oxide with 1 mole of ammonium ethylene bisdithiocarbaminate around. The yield is most favorable with 2.0 moles of manganese (II) oxide. Get less than If 2 moles of manganese (II) oxide are used, the yield drops because the amount of ammonium ethylene bis-dithiocarbamate provided is not exploited. This is evident from the following list in which the amount of ammonium dithiocarbamic acid still present, which is determined iodometrically in the filtrate can be recorded when using different amounts of manganese (II) oxide. It was the reaction carried out until the final value practically no longer changed.

Manganese (II) oxide used
to 1 mole of carbamate

Mole

1.0

1.5
2.0
2.5

Still dissolved in the filtrate

Ethylene-bis-dithiocarba-

minat

Mole

0.45
0.17
0.04
0.027

The duration of the reaction depends on the stirring speed and the particle size of the manganese oxide and the temperature. In general, a constant end value is reached after about 2 hours. the Implementation is associated with a slight heat release, which is, however, easily reduced by external cooling in Limits can be kept. Generally has

509 507/367

I 186 458

3 4

a reaction temperature of 10 to 50 ⁰ C, at a vacuum of 25 mm in a boiling water is preferably 20 to 40 ^'0 C, proven. ■ heated bath, whereby the mass as well as possible.

From the German Auslegeschrift 1 041 031 it is mixed. After 3 hours the vacuum is known away that zinc oxide is taken with the ammonium salt and the drying at 45 ° C in the air reacts with the ethylene-bis-dithiocarbamic acid, with 5 continuing. 379 parts of a green powder were obtained, the normal zinc ethylfen-bis-dithiocarbaminate. The analysis gives 28.0% manganese and in crystalline form it was not to be expected that 32.9% sulfur, corresponding to a ratio of that manganese oxides behave differently than zinc oxide, Mn: S like 1: 2.0, as well as 13, 6% oxygen and 11.1% by forming oxygenated salts that are replaced by nitrogen. The fungicidal effectiveness is the same as drying in the air, in a vacuum or by neoplasm as that of the product according to Example 1.
can be stabilized with acids and. .
which for each dithiocarbamic acid group a manganese e ι s ρ ι el
contain. In the same way as in Example 1, Man-

Compared to the previously known manganese salt gan (II) oxide with the ethylene-bis-dithiocarbamine-

have brought the process products according to the invention to the 15 acidic ammonium to implement. Of the

Vprteil that they precipitate with the same fungiz ^ the effectiveness is sucked off and on the suction filter

have a higher mangati content and are therefore left with air sucked through. Warmed up in the process

at the same time a better supply of the micro-nutsch contents within 20 minutes up to

nutrient manganese enable, which is particularly good for 61 ° C. After cooling, the product that

Manganese deficient soil is important. For the production of 20 then still contains about 25% water, finely ground

Fungicidal preparations can be dried according to the invention and at 45 ° C. to constant weight

Manganese compounds produced with wetting agents Yield: 381 parts. ; ■,. ·. i

or emulsifiers, fillers, carriers and 80 parts of the product, 12 parts of cellular pitch powderj

Solvent are provided. You can put together 3 parts of wetting agent and 5 parts of kaolin in dusts

Agents, spray powder, emulsions and mixed together give something that can float in water

Ren known application forms' of fungicidal spray powder, which in an amount of 400 to

come into use. In addition, there are also 600 l / ha as a 0.3 to 0.45% aqueous suspension

Combinations with other fungicidal agents possible against Phytophtora infestans in potatoes or as

borrowed. ^: 'τ .. ·.! · 0.2% strength suspension against ^e Plasmopora vitioola at

In the following examples, unless otherwise specified, 30 vines are excellently effective.

indicated is parts by weight. The examples are supposed to. . : ... ·.

merely explain the invention without illustrating it 4

limitq. . . · ■: · .- ·· .. ·. ■;! ■ _i; . The solution or suspension of the as in Example 1

B e i s b i e 1 I of the reaction product made from manganese (II) -

-.; ,, · ι 35 oxide and ammonium-ethylene-bis-dithiocarbaminate

·. By stirring 60.5 parts of 99% strength for 2 hours, 1130 parts of 10% strength HCl are added before suction

Ethylenediamine, 148 parts ammonia (23 volume offset; no self-heating occurs when suction is filtered

percent) and 152 parts carbon disulfide in one. It is dried as above; Yield: 345 parts *

4QO parts of water at 30 to 4O ⁰ C; becomes the Ammo The oxygen content is 15.8%.

nium-ethylene-bis-dithiöcarbaminat formed, whereby 40 is worked with 840 parts of 40% nitric acid,

the carbon disulfide goes into solution without a trace. In the so, the yield is 375 g.

Solution, 173 parts of finely powdered technical 6 parts of the product with 94 parts of talc are good

Manganese (II) oxide with a content of 82% MnO mixed and ground provide a dusting agent that

given, and the mixture is stirred further, with an application of 20 to 25 kg / ha the occurrence

the temperature between 30 and 40 ⁰ C is kept. 45 downy mildew prevented in vineyards.

After 2 hours, the proportion of dissolved _R. -, - - ■

Ethylen-bis-dithiocarbaminats only 5% of the urispi

initial amount, as the titration with iodine shows. When sucking off the reaction product

The precipitate is filtered off with suction. Mother liquor obtained after a short example 1 is used instead of

Time it begins to heat up from the suction filter, where 50 400 parts of water according to Example 1 are used and in the

when ammonia is also released. rest of the time the same approach is used. After leaving

It is spread out in the air, and after 40 microns, self-heating subsides and drying, 44 ° C is reached. After cooling to 45 ⁰ C, a yield of 400 parts of room temperature uöil comminution in environmental an equally effective product,
running a drying oven at 45 ⁰ C to constant weight 55 ". . ,,
dried. The yield is 391 parts. The Anaceispieio
lysis results in a manganese content of 28%, the sulfur 60.5 parts of 99% ethylenediamine are dissolved in 400 dough content is 30.4% corresponding to a ratio of water and 148 parts by volume of Mn: S as 1: 1.9. The substance also contains ammonia (23 percent by volume) and 152 parts sulfur-9.2% nitrogen, of which 2.0% is added as ammonia initially. After stirring for 2 hours at the are. The oxygen content is 16; 4%. In the test 40 ° C a clear, orange-colored solution is obtained, to the fungus Alternaria tenuis is already at a technical in the 129.7 parts of manganese (II) -oxyd (Pro-application rate of Syßcm * the germination of the domestic product with a fungal Content of 82% MnO) given werspor suppressed. the. After 75 minutes, a sample is sucked off and the content of soluble ethylene-bis-dithio-

carbaminate to 20% of the original content

A product produced according to Example 1 is just right. This changes after another 15 minutes

Sucked off and still wet in a still do not stir any more. After vacuuming it heats up

10

the precipitate reaches 58 ^° C. within 40 minutes. Then it is dried ^{at 45 ° C.}

The product contains 27.3% manganese and 30.7% sulfur, corresponding to a ratio of Mn: S like 1: 1.94. The oxygen content is 15.7%.

The effectiveness of this product against Alternaria tenuis is very good. 5y / cm ² prevent complete germination.

Example 7

60.5 parts of ethylenediamine (99%) are reacted with 152 parts of carbon disulfide and 74 parts by volume of ammonia (23 percent by volume) in the presence of 400 parts of water and 173 parts of manganese (II) oxide containing 82% of MnO are stirred in. The precipitate formed within 5 hours at 30 ^° C. is filtered off, suspended in water and again filtered off with suction. After the product has warmed itself by lying in the air, it is dried to constant weight at 45 ° C., after which a yield of 350 parts is obtained. It has a manganese content of 27.0% and a sulfur content of 29.5%, corresponding to an Mn: S ratio of 1: 1.9. The nitrogen content is 10.0%, of which 2.2% is present as ammonia. The fungicidal activity against Alternaria tenuis is excellent.

Example 8

174 parts of manganese dioxide with 47, Act with 7% Mn content while stirring vigorously. With gentle heating, the temperature being kept at 30 to 40 ^° C., a greenish reaction product is formed. This is spread out in the air after suctioning off, with self-heating up to 54 ° C. After further drying in a circulating drying cabinet at 45 ° C., 352 parts of an olive-green powder with very good fungicidal action are obtained with a manganese content of 24.11% ^{and a} sulfur content of 30.4%, corresponding to an Mn: S ratio of 1 : 2.16. The content of oxygen is 16.7% and that of nitrogen 10.7 ° / _0th The fungicidal effectiveness of the product is the same as that of the product according to Example 1.

Example9

400 parts of water are mixed with 132 parts of concentrated ammonia (2 mol) and 60.5 parts of ethylenediamine (99%). After addition of 152 parts of carbon disulfide (2 mol) is stirred 2 hours at up to 4O ⁰ C until a clear solution is formed. 204 parts of 85% manganese dioxide (2 moles) are then added and stirring is continued at the same temperature for an additional 2 hours. After suctioning off, maturing and drying, 385 parts of the new fungicide are obtained.

Example 10

To the like obtained in the preceding example, aqueous solution of ethylene-bis-ammonium dithiocarbaminsauren are (/ 85 ° _o solution) was added 255 parts of manganese dioxide. The yield after drying at 45 ^° C. is 444 parts.

Example 11

To a mixture of 400 parts of water, 132 parts of concentrated ammonia, 60.5 parts of ethylene diamine (99%) and 204 parts of manganese dioxide (85 ⁰ / "strength) with good stirring at 30 to 40 ⁰ C 152 parts of carbon disulfide over 2 hours added dropwise. After stirring for a further hour at the same temperature, it is filtered off. Yield: 326Teile after drying at 40 ⁰ C.

Claims (3)

Patent claims: 1. Process for the production of fungicidally active manganese-ethylene-bis-dithiocarbaminates, characterized in that 1 mol of the ammonium salt of ethylene-bis-dithiocarbamic acid Reacts at 10 to 50 ° C in aqueous solution with 1.0 to 2.5 mol of an oxide of manganese, after which the reaction mixture is neutralized with an acid, filtered off with suction or centrifuged and is dried. 2. The method according to claim 1, characterized in that the from the ammonium salt Ethylene-bis-dithiocarbamic acid and an oxide of manganese obtained during the reaction mixture or after suctioning or spinning off while still moist due to the admission of oxygen, expediently atmospheric oxygen, stabilized and then dried. 3. The method according to claim 1, characterized in that the from the ammonium salt Ethylene-bis-dithiocarbamic acid and an oxide of manganese obtained reaction mixture in vacuo is drained. Considered publications:
U.S. Patent No. 2492 314. 509 507/367 1.65 © Bundesdruckerei Berlin