DE2558385C3 - Income-enhancing funds - Google Patents

Description

R -CH-NH-CS-S

CH ₂ -NH-CS-S

Zn-X,

in softer

R represents hydrogen or methyl,
X stands for the NH ₃ group, and
π stands for numerical values from Obis 3,

and

15th

20th

25th

(2) a manganese salt selected from manganese sulfate, manganese carbonate, manganese (II) acetate, or a Manganese salt of ethylenediamine tetraacetic acid jo of the formula

CH, -COO

CH, -N

"Mn

CH, -COO

CH, -N

CH ₂ -COO (Z)

CH ₂ -COO (Z)

in which

Z stands for hydrogen, sodium, potassium or the ammonium group, or 2 symbols (Z) together stand for a positively divalent manganese ion,

contains

2. Yield-increasing agent according to claim 1, characterized in that the mixture in the The weight ratio of (1) to (2) is between 100: 0.1 and 100: 50

3. Use of agents according to claim 1 or 2 for increasing crop yields.

The present invention relates to new mixtures with a yield-increasing effect of known fungicides effective dithiocarbamidates and manganese salts.

It is well known that the alkylenebisdithiocarbamidates derived from primary diamines or use their complexes to fight fungal diseases. Here are in the Practice especially the zinc salts of ethylene bisdithiocarbamic acid and the 1,2-propylenebisdithiocarbamic acid, as well as their complexes with ammonia are used. Aim of treating the plants with these agents is to prevent the disease of the plants by fungal pests, thereby a full Maintain crop yield.

(Details on fungicidally active dithiocarbamidates can be found in numerous publications and Patent specifications, a general overview can be obtained e.g. B. from R. Wegler, »Chemistry of Plant Protection and Pest Control ”, Volume 2, pages 59 to 69, Springer-Verlag Heidelberg [1970}) Furthermore, is known that mixed precipitations consisting of zinc and manganese salts of dithiocarbamic acids increased have fungicidal activity (see, for example, German patent specification 11 67 586 and Swiss Patent specification 418 053) in relation to those dithiocarbamidates that have only one heavy metal atom exhibit.

Finally, two-part mixtures with a fungicidal effect are known, consisting of (1) alkali or alkaline earth salts of ethylene-bis-dithiocarbamic acid and (2) either water-soluble heavy metal salts or heavy metal salts the ethylene-bis-dithiocarbamic acid exist (Austrian patent 2 20 888).

Nevertheless, the yields achieved with the treated plants or cultures are not always complete satisfactory.

It has now been found that such active ingredient mixtures of a dithiocarbamidate and a Manganese salt that

(1) a dithiocarbamidate of the formula

50

55

bO

b5

R - CH - NH - CS - S

CH ₂ -NH-CS-S

Zn X _n

in which

R.
X

and

represents hydrogen or methyl,
stands for the NH ₃ group, and
stands for numerical values from 0 to 3,

(2) a manganese salt selected from manganese sulfate, manganese carbonate, manganese (II) acetate, or a Manganese salt of ethylenediamine tetraacetic acid

Hydrogen substances such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol

CH ₂ —COO and their ethers and esters, ketones, such as acetone,

^/ \ Methyl ethyl ketone, methyüsobutylkeion or cyclohe-

Mn 5 xanone, strongly polar solvents such as dimethylform-

_v / amide and dimethyl sulfoxide, as well as water; with liquefied

CH ₂ -COO required gaseous extenders or carriers

(II) liquids are meant which are normal

CH ₂ - COO (Z) temperature and under normal pressure are gaseous,

^/ ίο z. B. aerosol propellants such as dichlorodifluoromethane or

Trichlorofluoromethane; as solid carriers: natural

_v Rock flour, such as kaolins, clays, talc, chalk,

CH ₂ —COO (Z) quartz, attapulgite, montmorulonite, or diatomaceous earth

de, and synthetic minerals such as highly dispersed silica, aluminum oxide and silicates; as emulsifiers: non-ionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and alkyl sulfonates; as a dispersant: e.g. B. lignin sulfate and methyl cellulose.

The combinations according to the invention are preferably used in the form of wettable powders or dust powders. They are used for their production the usual wetting and dispersing aids, diluents or carriers. If necessary, they can colored with dyes or mixed with adhesives.

The combinations according to the invention can be present in the formulations as a mixture with other known active ingredients, such as fungicides, insecticides, Acaricides, nematicides, herbicides, bird repellants, growth substances, plant nutrients and soil texture improvers.

The formulations generally contain between 0.1 and 95% by weight of an active ingredient combination, preferably between 0.5 and 90%.

The active ingredients can be used as such, in the form of their formulations or those derived therefrom Diluting prepared application forms, such as ready-to-use solutions, emulsions, suspensions, Powders, pastes and granules can be used. It is used in the usual way, e.g. by Watering, spraying, spraying, dusting and scattering.

When used as foliar fungicides, the active compound concentrations in the use forms can be varied in a larger area. They are generally between 2 and 0.0005% by weight, preferably between 0.5 and 0.005%.

The following experiments explain the yield-increasing effect of the mixtures according to the invention:

Example A. Increase in yield in potato crops

Potatoes of the »Bintje« variety were grown during the growing season after the crop was closed Injected 7 to 10 times at intervals of 7 to 15 days. The application rate was the same for the individual test plots in a spray treatment,

However, to varies from 3 to 5 kg of preparation per hectare for the individual successive sprayings 6001 water each, e.g. B. first injection 3 kg preparation per ha, second and third spraying 4 kg / ha each, 4th to 10th spraying 5 kg / ha each.

When determining the harvest yield, only the bound tubers of 20 plants per plot 3 to 7 were identified Weeks after harvest taken into account The following results were achieved:

from the formula

CH ₂ -N

CH, -N

in which

(Z) stands for hydrogen, sodium, potassium or the ammonium group or two symbols (Z) together stand for a positive divalent manganese ion,

contain, have a yield-increasing effect.

Examples of compounds of the formula (I) are zinc-ethylene-bis-dithiocarbamidate (common abbreviation ZINEB) and zinc-propylene-l ^ -bis-dithiocarbamidate (common abbreviation PROPINEB) to be mentioned, as well as the ammonia adducts of the compounds mentioned. The connections and their Manufacturing are well known

The above-mentioned manganese salts of inorganic or organic acids to be used as the second component are also generally known Links.

The weight ratios of the active ingredient groups in the active ingredient combinations can be relatively large Areas fluctuate. In general, 0.1 to 50 parts by weight of active ingredient group (1) are allotted to 100 parts by weight Parts by weight of active ingredient of active ingredient group (2), preferably 0.5 to 20, in particular 1 to 10 Parts by weight.

As stated above, the combinations according to the invention are distinguished by a considerable yield-increasing effect.

The scope of the combinations according to the invention extends to different cultures, such as. B. fruit, vegetable and potato crops, which are attacked by plant diseases that can be combated by the dithiocarbamidate active ingredients contained in the combinations, such as z. B. Peronospora and Phytophthora species.

The combinations according to the invention can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, pastes and granulates. These are done in a well known manner manufactured, e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as a Extenders can be e.g. B. organic solvents can also be used as auxiliary solvents.

The following liquid solvents are essentially: aromatics, such as xylene, toluene, benzene or Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic carbon

Table A.

Increase in yield in potato crops

Try active ingredients floor Number of treatments Phytophthora Income lungs and time interval Infestation (a) untreated easier 10, 8-10 days each 37th, 50% 18.15 kg = 100% Marschboden distance Comparative preparation A *) 2.27% 21.53 kg = 118% Example 3 1.20% 24.83 kg = 137% according to the invention **) (b) untreated River clay 7, 8-14 days each 28.6 kg = 100% distance Comparative preparation A *) 30.4 kg = 106% Example 4 34.1 kg = 120%

according to the invention **)

untreated light sea clay

8, 8-15 days each
distance

29.6 kg = 100%

Comparative preparation A *) easier
Marschboden 10, 8-10 days each
distance 7, 8-14 days each
distance 31.8 kg = 107% Example 3
according to the invention **) 35.2 kg = 119% untreated 18.15 kg = 100% Comparative preparation A *) easier
Marschboden 10, each 8-10 days heavy infestation
distance 21.53 kg = 118% example 1
according to the invention **) 0.93% 23.70 kg = 131% untreated 1.33% 21.53 kg = 100% Comparison
preparation B ***) River clay 25.37 kg = 118% Example 2
according to the invention **) 27.90 kg = 130% untreated 28.9 kg = 100% Comparison
preparation B ***) 30.2 kg = 104% Example 2
according to the invention **) 32.3 kg = 112%

Explanations: *) Comparative preparation A:

Commercial product based on zinc propylene 1,2-bis-dithiocarbamidate with an active ingredient content of 70%.
**) Details of the mixtures according to the invention are given in the preparation examples.
***) Comparative preparation B:

Mixture of 66.5 kg techn. Zinc propylene-l ^ -bis-dithiocarbamidate, 11.0 kg zinc-propylene-l ^ -bis-dithiocarbamidai-ammonia complex, 1.5 kg wetting agent (alkylnaphthalene sulfonic acids 7.0 kg cell pitch and 14.0 kg silica, after Mix with a pin mill.

Example B:
Increase in yield in potato crops

Potatoes of the “Bintje” and “Bevelanden” varieties were each 3 kg of the active compound preparation in 6001

were applied 5 times per hectare in the water during the growing season, for the following Spriteun

Injected for 7 to 10 days

ge was in the 'individual test plots among each other- water per hectare.

the same for a spray treatment, but fluctuates. The following results were achieved in detail:
for the individual sprayings: at the first spraying

Table B.

Yield increase in potato crops Additional attempts in 1978

attempt

Active ingredients

Soil variety

Income

(a) Comparative preparation C *) Clay example 3 (according to the invention)

Example 1 (according to the invention)

(b) Comparative preparation D **) Clay comparative preparation C *)

Example 3 (according to the invention)

Bintje

Bevelands

18.7 kg (= 100%)

23.1 kg (= 124%)
23.3 kg (= 125%)

19.2 kg (= 100%)

19.3 kg (= 100.5%)
21.3 kg {= 111%)

Explanations:

*) Comparative preparation C:

88% by weight zinc-ethylene-bis-dithiocarbamate.

12% by weight of disodium-ethylene-bis-dithiocarbamal (corresponding to AT-PS 2 20 888, claim 1, second part, and 3). **) Comparative preparation D:

Mixture of disodium-ethylene-bis-dithiocarbamate and zinc sulfate with an excess of H)% by weight of the dithiocarhamate (Corresponds to AT-I'S 2 20 880, claim 1, first part, and 2).

Preparation examples Example 1

86.0 g of technical commercial product based on zinc-propylene-1,2-bis-dithiocarbamidate are mixed in a laboratory mixer, 10.0 g of dimanganese ethylenediamine tetraacetate and 4 g of silica and then grinds with a Jet mill and mix again briefly. The mixture obtained in this way contains 70% of the bisdithiocarbamidate active ingredient and 2.6% manganese.

Example 2

66.5 kg of technical zinc propylene U-bis-dithiocarbamidate, 11.0 kg of zinc

propylene-1 ^ -bis-dithiocarbamidate ammonia complex and 10 g manganese sulfate, 1.5 kg wetting agent based on alkylnaphthalenesulfonic acid, 7 kg cell pitch and 4 kg Silica about 30 minutes and then grind with a pin mill. The preparation thus obtained contains 70% Dithiocarbamidate active ingredient.

Example 3

In a pilot plant mixer, 77.5 kg of technical items are processed Zinc-propylene-l ^ -bis-dithiocarbamidate, 8 kg Manganese sulfate, 1.5 kg wetting agent based on alkyl naphtha sulfonic acid, 7 kg of ZeHpech and 6 kg of silica mixed for 30 minutes and then with a jet mill grounda After remixing, a wettable powder is obtained with the following analytical data:

36.4% removable carbon disulfide 15.8% zinc and
3.25% manganese

55

Example 4

172 g of technical commercial product based on zinc-propylene-1,2-bis-dithiocarbamidate, 20 g of disodium manganese ethylenediamine tetraacetate and 8 g of kaolin mixed and then with a Jet mill ground. This gives a preparation with 70% dithiocarbamidate active ingredient and 1.4% manganese.

Example 5

To 175.0 g of technical zinc-ethylene-bis-dithiocarbamidate 10.0 g of technical manganese carbonate and 3.0 g of wetting agent are mixed in a laboratory mixer Alkylnaphthalenesulfonic acid and 12.0 g of ZeHpech. After grinding the mixture with a laboratory jet mill a preparation is obtained with the following analysis data:

44.3% removable carbon disulfide
19.1% zinc and
2.1% manganese

Example 6

For 150 g of a commercial preparation based on zinc propylene 1,2-bis-dithiocarbamidate, Zinc propylene 1,2-bisdithiocarbamidate ammonia complex and polypropylene thiuram disulfide (weight ratios of zinc salts to thiuram like 3: 1 to 6: 1) with a total active content of 61% are in one Laboratory mixer given 10 g of manganese sulfate and mixed if minutes. After grinding with egg A laboratory mill is mixed for another 15 minutes and a preparation is obtained that contains 10% zinc, 135% manganese and Contains 2% bound ammonia

Claims (1)

Patent claims: 1. Yield-increasing agent with a content of an active ingredient mixture of a dithiocarbamidate and a manganese salt, characterized in that that it (1) a dithiocarbamidate of the formula