DE1793102A1 - New fungicides based on metal-ethylene-bis-dithiocarbamates and processes for their production - Google Patents

Description

DA-3016

B aa ohrelbun * «u of the patent application

of the company

PROGIL

77 »Rue de Miromesnil Paris / France

concerning

New fungicides based ron Metal"" Ethylene-bis-dithlooarbamates and processes for your production

Priority: August 3, 1967, Mr. 49 009, France

The present invention relates to new compounds based on hangan and zinc bsw. Qaduium-aTthylenbis-dithiocarbamaten and a process for their preparation. It also relates to the use of these compounds as active ingredients in fungicidal preparations.

109851/1877

It is known that a large number of metal xthylenebis-dithiocarbamates, especially those of copper ( ^B Kupreb ⁿ ), hangans ("Maneb") and zinc ("Zineb"), have excellent fungicidal properties (French patent specification No. 948 991). In order to improve the stability of these derivatives of dithiocarbamic acid and at the same time to increase their fungicidal effect, attempts were made to mix them or react with one another. For example, for Maneb and

Zineb simple physical mixtures (U.S. Patent No. 2,861,091), as well as zinc-manganese misohsalae (US patent No. 3,082,229j French patent specification Vr. 1 363 929) t zinc-containing complex salts dee Manebs (French Patent No. 1,326,689) or manganese-zinc-ethylene-bis-dithloearbamates obtained by joint reaction (French patent specification No. 1 352 11?) known.

All these known zinc-manganese compounds or complexes, whose structure is generally rather imprecisely defined, were determined by one of the methods described below obtain. By combining a water-soluble zinc salt with an aqueous maneb slurry or by reacting a mixture of water-soluble sinking and manganese salts with an aqueous solution of alkaline ethy-

109851/1877

SADORIGINAL

len-bis-dithiocärbaraat, wherein after generally carried out at room temperature mixing process, the thus obtained precipitate, of course, in a conventional manner filtered and washed _t were dried.

It has now been shown that by using a simple A process deviating from the methods described above contains a hangan and zinc (or cadmium) ion Ethylene-bis-dithiocarbamate is obtained, which differs in its structure and composition from those already known A distinction is made between mixtures, mixed salts and reaction products.

They according to the invention are in the form of manganese-ethylene-bis-dithiocarbamate before, its elementary particles with a PiIm made of zinc or cadmium-ethylene-bis-dithiocarbamate are coated. They are in the further description referred to as "coated maneb preparations".

The process for making these coated maneb preparations exists according to a very general execution " foriii in the fact that one an aqueous manebdispersi.on or egg v; ässrige.u .ManebteJ.g, masses previously in the usual way

10 9 8 51/18 7 7

BATH ORIGINAL

with an aqueous Ifttriua-athylenbiB-dithiocarbaaat solution ("fatriu & ditoan *) and a" water-soluble zinc * or cadmium flals combined "one A particularly advantageous way of working turns the aqueous latriuadithan solution into a reaction vessel at the same time and the watery maneb dough with the waeeorlöeliohen sink or cadmium as late. One can Jedooh you in modification diejea process the Ht.triumdithen directly in the watery i? it zinc (or oaduiuni-) eal «yereeteten and in Enter the dough placed in the reaction vessel or in Work in reverse order. Üt "Is also possible to mix Iatriuedilhan and Kaneb together and then the w & seri & e zinc (or cadeiue-jeal solution) ueufleteen.

In practice, the mixing of the manebe with the named reaction partners takes place under Rühnn with ordinary drvok and clearing tea repair, which is generally 10 to 50 ^(> 0.

The proportions between the sodium dithane and the zinc or Oadctium salts on the one hand and the quantity of maneb used on the other hand can vary widely

- 4 109851/1877

the water-soluble form, such as the chlorides or sulfates, in the approximately stoichiometric amount or in slight excess, voraugswelse bit to 5 # »based on the amount of sodium dithane added, should be used. In other words, 1 to 1.05 moles of SaIs are used (calculated as Zn or Cd ions) per mole of sodium ethylene bis-dithiocarbamate. Otherwise, the molar ratio between sodium dithane or - which comes to the same thing - between the zinc or cadmium ethylene-bis-dithiooarbamate formed in the reaction and maneb, between 0.01: 1 and 9: 1, preferably between 0.05: 1 and 1 t 1 lie

The practical implementation of the invention is based on the the following example.

example

In an aqueous suspension with a content of 10 wt. * Maneb (which was prepared by any known process) corresponding to 2.6 mol of manganese-ethylene-bisdlthiocarbamate, was stirred with continuous stirring at a temperature of ¹ of ^{10-25 0} O and a pH of 3 _f 5 - 7 an aqueous zinc carbonate solution with a content of 1.73 mol ZnClg together with an aqueous 1.70 mol sodium

- 5 -109851 / 1877 *

BATH ORIGINAL

ethylene-bis-dithiooarbam & t-containing solution entered, the reaction mixture was then filtered and then washed several times with water. As shown by eich, the wash water contained no significant traces of zinc and manganese ions or ethylene-bis-dithiocarbamic acid. After drying in the drum to a residual moisture yon O _V 5 i> water to obtain a product "Deesen analysis revealed it dad is a tjberfcogenee with Zineb Haneb ron completely different structure than that of simple physical mixtures or υοώ" compounds is, which contain manganese and zinc ions linked to one another via ethylene-bis-dithiocarbamino acids

The maneb coated according to the invention was very resistant and ignited even at temperatures above 100 ° G not (while the uncoated maneb with a water content of 0.5 5 * is already fatal at 60 ° C). It was also found that the fungicidal effect of this product, especially against Pfaytophtora infoctane, the one more stabilized, by simply whisking or co-precipitating maneb and zinc alaen obtained maneb preparations was superior. With this coated maneb under Zusata van Bisenferrocyanid (Prussian blue) a homogeneous product which is stable on the outside could be obtained.

- 6 «.

109851/1877

If one works under the same conditions, but uses only 0.22 Hol SnOl ₂ (instead of 1.73 mol) and 0.20 mol of sodium dithane, Ken obtains a product which has the same properties as the coated Maneb described above.

Comparable results achieved «finally with a product manufactured according to the same regulation, however using τοη oadmium chloride instead of Zinc chloride

Claims

109851/1877

BATH ORIGINAL

Claims (1)

Claims 1 · Process for the stabilization of manganese-ethylene-bisdithiocarbamate or "Maneb", thereby ge k e η η ζ e i c h η et that in an aqueous suspension or an aqueous dough of maneb in situ 2ink-ethylene-bis-dithiocarbamate ("Zineb") or Oadiaium-äthylenbls-dithiöearbaaat precipitates by adding sodium ethylene bis-dithlocarbamate (Sodium dithane) in a manner known per se with water-soluble zinc or cadmium derivatives implements. .; . · 2β Method according to claim 1, characterized in that it is calibrated nice that one in the aqueous maneb suspension at the same time aqueous solutions of sodium dithane and derivatives of zinc or cadmium are introduced »after mixing Stirring at room temperature, filtered off, washed several times with water and dried. 3. The method according to claim 1, characterized gekennzeioh net that one on an aqueous Natriuatdithanlösung one 109851/1877 aqueous previously rait a water-soluble zinc or Cadmium derivative added Manebsuspeneion by mixing allowed to act while stirring at room temperature. 4 »Process according to claims 1 to 3» characterized in that »0.01 - 9 mol of sodium dithane each Mol Maneb is used, the proportion of water-soluble 2ink or gadmiuraderivat 1 to 1.05 mol per mol of sodium dithane amounts to. 5ο method according to claim 1 bie 4 »characterized in that one is used as a zinc or oadmium derivative any water soluble compound, a, B. a chloride or a sulfate is used. O ₀ Stabilized manganese-ethylene-bis-dithiocarbamate, the particles of which are coated with a zinc or cadmium-ethylene bisdithiocarbamate. "9 - 109851/1877 OBlGlNAL