DE1917458A1 - Fungicides based on manganese ethylene bisdithiocarbamate - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL.-ING. GERHARD COLDEWEY

PATENT LAWYERS

β MÖNCHEN 23 ■ 8IEQE88TRASSE26 · TELEPHONE 3480 87 · TELEGRAM ADDRESS: INVENT / MONCHEN

TELEX 5 29 686

UoZ. t E 213 (Vo / kä) Oaee P-97

Α0ΕΪΟ CHEMICAL CO., INC.,
Flushing, New York, V ₀ St.A.

"Fungicides based on manganese ethylene bisdithiocarbamate ⁿ

Priority; April 10, 1968, VoSt.A., Hrc 720 357

July 2, 1968, VoSt.Ao, Hr _e 741 $ 40

It is already known that Fhytotoxizität the fungicides maneb, d _o h. Manganese ethylene bisdithiocarbamate, to be reduced by adding small amounts of water-soluble zinc or cadmium salts «. Bs is also known for this purpose AuCu water-soluble copper, cobalt and iron salts to use ₀ In this connection, it was considered essential that manganese äthylenbisdithiocarbamat with the water-soluble zinc, cadmium, copper, cobalt, or iron salt in the presence of Bringing water together _o Due to the water solubility of these salts, a large amount of the corresponding metal ions is present in an aqueous solution with which the manganese ethylene bisdithiocarbamate is brought into contact.

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The attempts to reduce the phytotoxic & ty of maneb, were therefore carried out _p because this connection, the diluted alone or old inert Trägeretoffen, an eyelet valuable Fungiold is plants, especially young and growing £ f Lausten different genera harms Furthermore, maneb decomposes slowly on standing especially in the warmth and in the presence of moisture, so that its activity gradually decreases. Sometimes Kaneb can also spontaneously decompose under fire sunshine _a This is of course a major disadvantage that affects the usability of Haneb

The object of the invention is to fungioide means avf the grundlag · of manganese äthylect & Bdithiooarbamat sur to make available "the aforementioned laughs hurry Mefet

This task is solved by the invention _o

The subject of the invention are thus fungicidal agents, each containing 100 ropes of manganese-ethylene bisdithiooarbamate 0.5 to 5 parts metallic zinc, iron or copper or a water-insoluble sdos ¹ in the general sparingly soluble Sehwermetallverhlndung the general • an Itorael

M- ϊ

in the M a zinc, lead, iron, copper, cobalt, tin or Kiokelkation and Y means an inorganic or organic anion, and where H has a lower affinity for Y than for sulfur »or a mixture of metals or Heavy metal compounds as a stabilizer »

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ÖAÖ ORIGINAL

Surprisingly, it was found that the addition of metallic zinc _p iron or copper in finely divided form or one of the heavy metal compounds mentioned, the phytotoxicity and the tendency to self-decomposition of maneb is considerably reduced, regardless of whether maneb in the usual concentration of about 80 wt _o - # or in another concentration, ZcBo between about 50 and 95 Gew _e ~ # _p based on the fungicidal agent _{r o}

The expression "water-insoluble or sparingly soluble in water" means a solubility of the heavy metal compound in water at room temperature of less than 0 _f 1 mol- # and preferably less than 0.05

The heavy metal compound used in the present invention is intended to be a have a higher solubility product in water at room temperature than the corresponding metal sulfide

The zinc content of the fungicidal agent of the invention is preferably at least about 1 pounds based on the weight of maneb and 2 to 4 wt% _p based on maneb when all metals are iron or copper or lead, iron, copper, cobalt - _r tin or nickel compound is used.

Preferably, the fungicidal compositions of the invention contain about 50 to 95 Gewo- # _p particular about 75 to 85 wt _o - # Manebo The fungicidal compositions of the invention may contain inert excipients, stabilizers "wetting agents and other excipients Be contained ferred inert carriers are clay and clay marl" Furthermore, aluminum oxide and carbon, such as activated carbon, can be used as carriers. These carriers can be used in amounts of about

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5 to 30% »based on Maneb, to be present»

Very good results are obtained with zinc oxide or Zinkoarbonat ale stabilizer One can verhältniemäseig impure compounds Ketall use .B 2 ₀ the oven from the ZinJc-Muf fei obtained dust-like zinc oxide _{Eieenerzpulver%} or copper compounds from the flue dust from copper smelters.

As the iron compounds are preferably the divalent tin compounds used _p cobalt and nickel compounds are indeed effective "but verhältnismäeeig expensive and therefore less preferred for economic reasons.

When using lead compounds, it must be taken into account that they are poisonous to mammals and therefore common are undesirable.

For the above reasons, the erfindungegemäss guide preferably used heavy metal compounds of zinc, ferrous iron, monovalent and divalent copper from _p old hatred provided that the affinity of the zinc, iron or copper low to the corresponding anion 1st · than the affinity of these metal Ie against Sulfur.

Metallic zinc, iron or copper in finely divided form, or alloys which contain substantial amounts of one or more of these elements, especially under such conditions can be used in which the metal is oxidized in the presence of air and moisture.

The addition of the stabilizers to the fungicidal agents can after usual procedures. So you can ζ »B. the metals or Mix, stir or stir heavy metal compounds with Maneb

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■ lonely wed »The mixtures obtained by either Dry-mixing or Haas-mixing can be obtained on the plants are applied by conventional methods, e.g. B. breathed or sprayed in the form of an aqueous dispersion will.

The solubility products of the heavy metal compounds used according to the invention are known and can be found in the literature; see ZoB ₀ Lange's Handbook of Chemistry (1956).

ZoBo iron (III) hydroxide cannot be used for the purposes of the invention, since its solubility product is about 1 × 10 ~ ', while the solubility product of egg (III) sulfide is much higher, namely about 10 ". that iron · * ion not from the EisendIi) hydroxide for the hypothetical reaction with hydrogen sulfide available to ₀ according to the invention sohwtr soluble or water-insoluble heavy metal compounds used müesen a higher Lösliohkeitsprodukt possess than the corresponding metal sulfides So let example EisendI) hydroxide whose Lösliohkeitsprodukt about 2x10 * is excellently suited, since the solubility product of the corresponding iron (II) sulfide is only 4x10 ^.

Excellent results are obtained with the compounds listed below, the solubility product of which is greater ala the solubility product of the corresponding metal sulfides, The use of these compounds is preferred, but the invention is not limited to these compounds

Specific examples of suitable zinc compounds are

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Zinc valerate, formate, gallate, hydroxide, lactate, laurate ', -oleate, -oxalate, -oxide, -orthophosphate, -pyrophosphate, -salicylate, ~ stearate, -tartrate, -benzoate, -butyrate, -caproate, -chromate, undecylenate, nitrate and carbonate.

Specific examples of suitable cobalt compounds are cobalt (II) carbonate, - (II) hydroxide, - (II) formate, - (II) oxalate and - (II) phosphate.

For the purposes of the invention, both copper (I) and Copper (II) compounds are used. Copper (II) compounds are preferred because of their stability and costs.Special examples of suitable copper compounds are copper (II) carbonate, - (II) -for »iate (hydrated), - (II) -hydroxyd, - (]: i) -benzoate, - (II) -lauxate, - (I) -chloride and - (i) -oarbonate.

Special examples of suitable bison compounds are iron Biien (II) hydroxide, - (II) oxide, - (II) carbonate (siderite), - (II) fluoride, - (II) oxalate, Fe ₃ O ₄ ( Magnetite), iron (III) -acet £ t and - (III) -evenato

Specific examples of suitable Miekel connections are LickeKlD formate, - (II) hydroxide, - (II) carbonate, - (II) fluoride, - (II) -oxalate and - (II) -laurate.

Specific examples of tin compounds are tin (II) oxalate, - (II) fluoride, - (II) hydroxide and - (IV) hydroxide _{or the like}

Specific examples of suitable lead compounds are lead (II) acetate (basic), - (II) benzoate, - (II) chloride, - (II) -formate, - (II) -carbonate, - (II) -hydroxyd, - (II) -laurate, - (II) oxide and - (II) sulfate.

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It has use of the substantially water-insoluble heavy metal compounds numerous advantages "compounds having a solubility of less ale 0.1 or 0.05 MoI-Jt ₅ z.Bo can be considered as practically insoluble _f and therefore they do not react in the presence of water with other additives in the fungicidal agents ο If necessary, additives can be used that are incompatible with more soluble heavy metal compounds ο Furthermore, some of the relatively cheap soluble salts of the aforementioned heavy metals have a corrosive effect "which can lead to difficulties and malfunctions during storage and mixing o Another advantage the use of water-insoluble or sparingly water-soluble heavy metal compounds as well as metallic zinc, copper and iron can be seen in the fact that the fungicidal agent; containing these elements or compounds can be used as dusts. This would be less possible if the fungicidal agents contain hygroscopic compounds, as is the case with some of the soluble salts of the aforementioned heavy metals «

The zinc, iron or copper or the heavy metal compound are preferably in finely divided form in the fungicidal agents _o Their particle size should be such that they pass a sieve with a mesh size of 0.074 mm and preferably 0.044 mm. However, the invention is not restricted to the aforementioned particle size range. The examples explain the invention. In Examples 2 to 7, technical maneb is mixed with various amounts of soluble and insoluble zinc compounds.

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gicidal agents are used that contain 80 # maneb «maneb, which are inert additives and fiie hacking agents

thoroughly mixed together, ηιιύ. Subsequently, an aqueous slurry is prepared from the mixture "The slurries are set to _f to 2, 4 or 8 wt _o -% maneb given These slurries are then applied to three different types of plants, namely, tomatoes, pickles and flax» sprayed The The results obtained are compiled in a table according to Example 7. The numerical evaluation of the results is carried out as follows: the plants are examined 7 days after spraying and rated according to the extent of their damage Plants ο The values obtained with the 3 concentrations of maneb are added, so that a value of 30 in the 3 experiments does not mean any phytotoxicity. Each test was carried out in duplicate. The average of two identical tests carried out at the same time is given in the table. The entire test series was repeated three times during an autumn season Experiments marked B, E and H on November 7th and experiments marked C, F and I on November 14th. November started «

Maneb contain £ - The compositions listed below are processed to aqueous slurries containing 2, 4 and 8 wt _o <

example 1

This example serves to control ₀ Dae fungicidal agent contains 80 36 Maneb 20 and inert additives _o

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_ Q -

Example 2

Dae fungicide contains 80 $ 6 active ingredients, namely maneb and soluble zinc sulfate. The zinc content corresponds to 2 %, based on the weight of Maneb ₀

Example 3

DaB fungioide agent has the same composition as the Mi1-tel of Example 1, jedooh be 1.3 wt _o -} 6 of inert additives replaced by zinc oxide "

Example 4

The base fungioid agent of this example corresponds to the agent of example 1, but 2 # inert additives are replaced by 2 » zinc carbonate.

Example 5

Bas fungicidal agents such · example corresponds to the agent of Example 1, except that 2.6 i "of inert additives rsetst by zinc oxide."

Example 6

The fungioid agent in this example corresponds to the agent dee Example 1, however, 4 3 * of the inert additives are through Replaces zinc carbonate.

Example 7

Bas fungioid agent of this example corresponds to the agent of Example 1, however, 9.7 # of the inert additives are replaced by zinc benzoate

When the treated plants were examined, no significant differences with regard to the fungicidal activity were found

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between the control sample of Example 1 and the "preparations of Example 2 to 7 can be determined, despite the different Phytotoxizi.tät the preparations.

Tabel

1 Fungicides 2 middle from example 6th 1 1 4th 1 tomatoes 23 30th - - Attempt a 26th 30th 27.2 29 - 30th 29 Varsuch B 27 30th 28.5 29.5 27.5 29 27 Attempt C , 5 29 30th 26.2 Pickles 20th 30th - - Attempt D 30th 30th 24.5 28.3 - 30th 29 Try 22nd 26th 30th 30th 28.3 27.5 24 Vera F 25.5 27.5 25th area 19th 21 - - Attempt G 15th , 5 19th 22nd 19.5 - 17.5 17th Vexauoh B 18th 13th 17th 16.5 17th 20.5 22nd Vtrsuch I 22nd , 5 25.4 19th 20th 22.5 25.8 24.7 Durchechnittiveri;
of all attempts , 4 24.8 25.5 24.4

The table shows that the phytotoxicity of maneb can be reduced when practically water-insoluble zinc compounds are used. The same results are obtained when metallic zinc in finely divided form is used

Example 8

A mixture of 80 g of maneb, 3 g of iron (II) oxide and 17 g is used Tonnergel made ingredients are so fine separately marry that they have a sieve with a mesh size of 0.044 mm

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happen., Then they are in water at a concentration of 2 %. Given solids and sprinkled on young tomato plants. The phytotoxicity of this spray is considerably lower than that of a similar spray, which contains the same concentration of maneb and instead of iron (II) oxide the same amount of clay marl.

Example 9

A mixture of 80 g of Maneb _c, 5 g of cobalt (II) oxalate _p, 2 g of activated charcoal and 13 g of dried sulphite liquor is prepared. The mixture is sprayed onto young tomato plants as a 2 # slurry. The phytotoxicity of this spray is lower than that of a comparable spray. , which was produced from a mixture of 80 g of maneb and 20 g of dried sulphite waste liquor ₀

Example 10

30 g of maneb are mixed with 2 g of iron potato pulper and 18 g of clay marl mixed The ingredients are ground so finely beforehand, that there is a sieve with a mesh size of 0.044 mm. The mixture is slurried in water to form a 2 # dispersion and sprayed on young tomato plants. Compared to a similar mixture of maneb without scrap iron powder observed a strong reduction in the phytotoxicity of the mixture.

Example 11

75 g maneb, 3 g copper carbonate, 3 g scrap iron powder and 19 g Clay marls are thoroughly mixed together

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clear maeohe width 0.044 mm paired. The mixture becomes too a 2 56 concentration in water on ge and on young tomato plants sprayed la. Compared to a similar mixture of maneb without iron achyott powder, a strong reduction in the phytotoxicity of the mixture can be observed

Example 12

80 g of maneb, 3 g of magnetite and 17 g of clay marl are thoroughly mixed with one another. The ingredients were individually so finely ground such that it _is a CIEB of mesh size 0.044 mm paseierten "Thereafter, the mixture in water to a concentration of 2 i» slurried in ge and lances on young Tomatenpf sprayed · Compared to a similar spray which was made from 80 g of Manet and 20 g of clay marl, the phytotoxicity of this magnetite-containing spray is considerably lower

Example 1?

80 g of Manebp, 5 g of cobalt carbonate and 13 g of charcoal are intimately mixed with one another. “The components were previously separated and ground so finely that they passed a sieve with a mesh size of 0.044 mm. The mixture is then suspended in water at a concentration of 2 liters and sprayed onto young tomato plants. The phytotoxicity of this spray is considerably lower than that of a similar spray that contained the same amount of clay marl instead of cobalt carbonate "

Example 14

20 g nickel carbonate, 20 g basic lead carbonate and 80 g maneb are mixed together. The mixture becomes one in water

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Suspended 2% slurry and apply it to young tomato plants splashed. The spray shows a significant reduction in phytotoxicity compared to a 2 # spray, which was made from 80 g maneb and 40 g clay marl.

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Claims (2)

- 14 sponsorship awards I ₀ Fungicides containing per 100 parts of manganese ethylene bisdithiocarbamate 0.5 to 5 parts of metallic zinc, iron or copper or a water-insoluble or poorly soluble heavy metal compound of the general formula M-Y in the M a zinc, lead, iron, copper, cobalt, tin or Nickel cation and Y is an inorganic or organic anion, and where M has a lower affinity for Y than compared to sulfur, or a mixture of metals or heavy metal compounds as stabilizers 2. Fungioid agents according to claim 1 containing 50 to 95 Gewo-? 6 Mangan-Ethylenbisdithiosaxbaotat 909842/171 1