DD151040A5 - FUNGICIDAL AGENT - Google Patents

Abstract

The invention relates to fungicidal agents containing new Alkylenbisdithiocarbaminsaeuresalze as active ingredients. Compared with known agents, the compositions according to the invention have a more pronounced fungicidal activity with low phytotoxicity and pesticide toxicity.

Description

Areas of application of the invention

The invention relates to fungicidal compositions containing salts of N-substituted Alkylenbisdithiocarbaminsäuren, processes for the preparation of these salts and methods for controlling fungi.

21 9971 - ^v

Characteristics of the known technical solutions

Metal salts of alkylene bisdithiocarbamic acids such as maneb, zineb, mancozeb and propineb are known as fungicides.

Object of the invention

The aim of the invention is to provide new fungicidal compositions containing improved active ingredients, in particular with regard to the fungicidal. Efficacy, low level of phytotoxicity to plants that provide food, and reduced mammalian toxicity.

Explanation of the essence of the invention .

The novel salts used in the agents according to the invention, which are preferably salts of one or more metals, have a valence of more than 1, in particular 2 or 3. These are salts of an alkylenebisdithiocarbamic acid of the formula

ff & ν /

Υ _χ Y-

/ ^Ν - ^χ - ^κ χ (D.

HS-C S

in which

X is an alkylene group {straight-chain or branched) having up to 6 carbon atoms, preferably (Cp-C,) -alkylene, such as ethylene or 1,2-propylene,

Y and''Y ', which may be the same or different, respectively represent: ·

(1) hydrogen, except that both Y and Y ^{1 are} not hydrogen,

(2) (Cg-C ₂₀₎ alkyl, preferably (C _g -C _Q) alkyl,

ROH

Il

(3) a group of the formula --fCH- Y CHCH ₂ OR wherein

R is hydrogen or (C ₁ -C 6) -alkyl, preferably (C ₁ -C ₃ ) -alkyl, R _{1 is} hydrogen, (C-Go) -alkyl, preferably (C 1 -C 6) -alkyl, ( C ~ -C _ft) alkenyl, vorzugsv / ice (C -, - Cg) alkynyl, phenyl or phenyl substituted with up to three identical or different substituents selected from (C - C ^) - alkyl, preferably methyl , and halogen, preferably chlorine, and m is 0, 1 or 2, preferably 1;

(4) a group of the formula

wherein R _{2 is} hydrogen, halogen, preferably chlorine or (C.-C ₁ o) -alkyl, preferably methyl, η is 1 or 2 and ρ is 0, -1, 2 or 3,

• RR ₁

ι ι ->

(5) a group of the formula - (CH-I-CH-COOR ₄ , wherein R has the definition given above, R _{3 is} hydrogen, hydroxy or (C 1 -C 6) alkyl, preferably (C 1 -C 6) alkyl , is, and R. (C ₁ -C ₁ ) -alkyl, preferably

19971 -η-

(C ₁ -C ₁₂ ) -alkyl, (C ₁ -C ₆ ) -alkylamino (C ₁ -Cg) -alkyl, preferably (C ₁ -C ₃ ) -alkylamino (C ₁ -C ₃ ) -alkyl, di ( C ₁ -C 9 alkylamino (C -Cg) alkyl, preferably di (C ₁ -C ₃ ) alkylamino (C ₁ -C ₃ ) alkyl, (C ₂ -CG) alkenyl, preferably (C ₃ -Cg) - Alkenyl, (C ₃ -Cg) alkynyl, hydroxy (C ₁ -Cg) alkyl, preferably hydroxy (C ₃ -C ₃ ) alkyl or a salt-forming group or an atom such as ammonium, substituted ammonium, quaternary ammonium, alkali metal or a Is a group which contains, as a salt-forming element, a metal having a valency of more than 1, for example Zn, Cu, Fe, Ni, Co, Sn, Ca or Mg, while q is 0 or 1,

R R,

(6) a group of the formula - CH (CH ₂ ) - CH - CH ^S N, wherein R, R ₃

and q have the meanings given above,

(7) a group of the formula - (CHR 1 -CHR ₃ CONH ₂ ,

wherein R, R ₃ and q have the meanings given above,

(8) a salt, preferably a salt of a metal having a valency greater than 1, preferably 2 or 3, of a thioacid group of the formula - (CHR -) - CHR ₃ -OCSH _x

wherein R, R ₃ and m are as defined above,

(9) a group of the formula -CHR-CHR ₉ SH- or a metal salt thereof, wherein R and R _{2 have the} abovementioned definitions and is preferably a (C ₁ -Cg) -mercaptoalkyl group, in particular a C 1 -C 4 -functional group. -Mercaptoalkyl group or a salt, or a group ^ CH ^ yI ^ or -fCI ^ -) -, - NH - (- CH ^ -y-NH ^ with the proviso that only one of the substituents Y and Y ^{1 is} such an amino group while

19 37

- D -

the other is another organic substituent,

/ -V ²

(10) a group of formula -fCHRf ^ -CHOH \ '© / /

wherein R, R ₂ and m have the meanings given above or

(11) a group of formula - ^ ₃

wherein R and m have the meanings given above.

The new salts can be represented by the formula

^Y \ / ^Y "

-S-CC-S ~ / ^. -. ,

Il Ii < ^{I: r} )

s s

in which

(1) X, Y and Y 'have the meanings given in connection with the formula I and

(2) the two C-S groups with the salt-forming atoms or

Il

groups, which may be the same or different, are linked. -. ·

The new salts may alternatively be replaced by the simplified formula

^Y \. ^Y "

in which X, Y and Y 'have the meanings given in connection with the formula I, M and M ^{r are the} same or different salt-forming atoms or groups and r and r ^{1 represent} the valencies.

The preferred metal salts may also be defined as salts obtained by reacting an alkylene bisdithiocarbamic acid of formula I (or a water-soluble salt thereof) with a water-soluble salt of a metal having a valence greater than 1, preferably 2 or 3, in an aqueous medium at Temperature of 0 to 7O ⁰ C, preferably 2O ⁰ C, are obtained.

The N-substituted alkylene bisdithiocarbamic acids of the formula I can be prepared by a conventional method which provides for the reaction of a diamine with carbon disulfide. Examples of suitable diamine precursors are as follows:

N-octylethylenediamine, N-nonylethylenediamine, N- (2-ethylhexyl) ethylenediamine, N-decylethylenediamine, N-undecylethylenediamine, N-dodecylethylenediamine, N-tetradecylethylenediamine, N-cetylethylenediamine, N-octadecylethylenediamine, N, N'-dioctyldiethylenediamine, N-octyl-1,2-propylenediamine, N-dodecyl-1,2-propylenediamine, N-octylisopropylendiamine, N-dodecylisopropylendiamine, N-dodecyl, 1,1-dimethylethylenediamine, N, ¹ -dodecyl-1,1-dimethylethylenediamine, N -Dodecyl-1,2-dimethylethylenediamine, N-dodecyl-1,2-diethylethylenediamine, N- (2-mercaptoethyl) -ethylenediamine, N- (2-mercaptoethyl) -1,2-propylenediamine, N- (2- Mercapto-ethyl) -isopropylendiamine, N- (2-mercaptoethyl) -1,2-dimethyl-ethylenediamine, N- (2-mercaptoethyl) -1,1-dimethylethylenediamine, N ¹ - (2-mercaptoethyl) -1, 1-dimethylethylenediamine, (N- (2-mercaptopropyl) ethylenediamine, N- (2-mercaptopropyl) -1,2-propylenediamine, Nf (2-mercaptopropylisopropylendiamine, N- (2-mercaptopropyl) -1,1-dimethylethylenediamine , N ¹ - (2-mercaptopropyl) 1,1-dimethylethylenediamine, N- (3-mercaptopropyl) ethylenediamine, N- (2-mercaptobutyl) ethylenediamine, N- (3-mercaptopropyl) ethylenediamine, N- (3-mercaptopropyl) -isopropylendiamine, N- ( o-methylbenzyl) ethylenediamine, N- (m-methylbenzyl) ethylenediamine, N- (p-methylbenzyl) ethylenediamine, N- (2,3-dimethylbenzyl) ethylene

diamine, N- (2,4-dimethylbenzyl) ethylenediamine, N- (2,5-dimethylbenzyl) -äthy1endiamin, N- (3,4-dimethylbenzyl) ethylenediamine, N- (2,4,5-trimethylbenzyl) - ethylenediamine, N- (2,4,6-trimethylbenzyl) ethylenediamine, N- (2,3,4-trimethylbenzyl) ethylenediamine, N- (2,3,5-trimethylbenzyl) -1-ethylenediamine, N- (o Chlorobenzyl) ethylenediamine, N- (m-chlorobenzyl) ethylenediamine, N- (p-chlorobenzyl) ethylenediamine, N- (2,3-dichlorobenzyl) ethylenediamine, N- (2,4-dichlorobenzyl) ethylenediamine, N- (2,5-dichlorobenzyl) ethylenediamine, N- (3,4-dichlorobenzyl) ethylenediamine, N- (3,5-dichlorobenzyl) ethylenediamine, N- (2,4,6-trichlorobenzyl) ethylenediamine, N- (2,4,5-trichlorobenzyl) ethylenediamine, N- (o-bromobenzyl) ethylenediamine, N- (m-bromobenzyl) ethylenediamine, N- (p-bromobenzyl) ethylenediamine, N- (o-iodobenzyl ) ethylenediamine, N- (m-iodobenzyl) ethylenediamine, N- (p-iodobenzyl) ethylenediamine, N- (p-methylbenzyl) -isopropylendiamine, N ¹ - (p-methylbenzyl) -isopropylendiamine, N- (2, 4 Dimethy] phenethyl) ethylenediamine, N- ( 2, 4, 5-trimethylphenethyl) ethylenediamine, N- (methoxycarbonylmethyl) ethylenediamine, N- (ethoxycarbonylmethyl) ethylenediamine, N- (PrO-poxycarbonylmethyl) ethylenediamine, N- (isopropoxycarbonylmethyl) ethylenediamine, N- (butoxycarbonylmethyl ) ethylenediamine, N- (hexyloxycarbonylmethyl) ethylenediamine, N- (octyloxycarbonylmethyl) ethylenediamine, N- (dodecyloxycarbonylmethyl) ethylenediamine, N- (methoxycarbonylmethyl) -1,2-propylenediamine, N- (methoxycarbonylmethyl) -isopropylendiamine, N- (Ethoxycarbonylmethyl) -isopropylendiamine, N- (ethoxycarbonylmethyl) ethylenediamine, N- (isopropoxycarbonylmethyl) -isopropylendiamine, N- (propoxycarbonylmethyl) -isopropylendiamine, N- (butoxycarbonylmethyl) -isopropylendiamine, N- (isopropoxycarbonylmethyl) -1,2-dimethylathylenediamine, N- (isopropoxydicarbonylmethyl-1,1-dimethylethylenediamine, N ¹ - (isopropoxycarbonylmethyl) -1,1-dimethylethylenediamine, N- (2-methoxycarbonylethyl) -ethylenediamine, N- (2-

2TS97 1 _ ₈ _

Ethoxycarbonyläthy1) ethylenediamine, N- (2-isopropoxycarbonylethyl) ethylenediamine, N- (2-propoxycarbonylethyl) ethylenediamine, N- (2-butoxycarbonylethyl) ethylenediamine, N- (2-hexyloxycarbonylethyl) ethylenediamine, N- (2- 0ctyloxycarbonylethyl) ethylenediamine, N- (2-dodecyloxycarbonylethyl) ethylenediamine, N- (2-podecyloxycarbonylethyl) ethylenediamine, N- (2-tetradecyloxycarbonylethyl) ethylenediamine, N- (2-carbonylcarbonylethyl) ethylenediamine, N- (2- 0ctadecylcarbonylethyl) ethylenediamine, N- (2-methoxycarbonylethyl) -1,2-propylenediamine, N- (2-ethoxycarbonylethyl) -1, 2-propylene, diamine, N- (2-isopropoxycarbonylethyl) -1,2-propylenediamine, N - (2-isopropoxycarbonylethyl) -isopropylendiamine, N ¹ - (2-isopropoxycarbonylethyl) -isopropylendiamine, N- (2-propoxycarbonylethyl) -isopropylendiamine, N '- (2-propoxycarbonylethyl) -isopropylendiamine, N- (2-oxthoxycarbonylethyl) -isopropylendiamine , N- (2-methoxycarbonylethyl) -isopropylendiamine, N- (2-methoxycarbonylpropyl) ethylenediamine, N- (2-ethoxyca rbonylpropyl) ethylenediamine, N- (2-propoxycarbonylpropyl) ethylenediamine, N- (2-isopropoxycarbonylpropyl) ethylenediamine, N- (2-butoxycarbonylpropyl) ethylenediamine, N- (2-pentoxycarbonylpropyl) ethylenediamine, N- (2- Hexyloxycarbonylpropyl) ethylenediamine, N- (2-octyloxycarbonylpropyl) ethylenediamine, N- (2-decyloxycarbonylpropyl) ethylenediamine, N- (2-dodecyloxycarbonylpropyl) ethylenediamine, N- (2-tetradecyloxycarbonylpropyl) ethylenediamine, N- (2-cetyloxycarbonylpropyl ) ethylenediamine, N- (2-0ctadecyloxycarbonylpropyl) ethylenediamine, N- (2-methoxycarbonylpropyl) -propylenediamine, N- (2-ethoxycarbonylpropyl) -1,2-propylenediamine, N- (2-propoxycarbonylpropyl) -1,2- propylenediamine, N- (2-isopropoxycarbonylpropyl) -1,2-propylenediamine, N- (2-methoxycarbonylpropyl) -isopropylendiamine, N- (2-ethoxycarbonylpropyl) -isopropylendiamine, N- (2-propoxycarbonylpropyl) -isopropylendiamine, N- (2 -Isopropoxycarbonylpropyl) -isopropylendiamine, N- (2-butoxycarbonylpropyl) -isopropylendiamine, N- (2-isopropoxycarbonylpropyl) -1,2 dimethylethylenediamine, N- (2-isopropoxycarbonylpropyl) -1,1-dimethylethylene,

T - 9 -

N ¹ - (2-isopropoxycarbonylpropyl) -1,1-dimethylethylenediamine, N- (2,3-pihydroxypropyl) -ethylenediamine, N- (2,3-dihydroxypropyl) -1,2-propylenediamine, N ¹ - (2,3 -dihydroxypropyl) -isopropylendiamine, N- (2,3-dihydroxypiropyl) -1,2-dimethy1-ethylenediainine, N- (2-hydroxy-3-methoxypropyl) -ethylenediarnine, N- (2-hydroxy-3-methoxypropyl) - 1,2-propylenediamine, N- (2-hydroxy-3-methoxypropyl) -isopropylendiamine, N ¹ - ( 2- hydroxy-3-methoxypropyl) -isopropylendiamine, N- (2-hydroxy-3-xnethoxypropyl) -1, 2 dime thy la lendiamine, N- (2-hydroxy-3-ethoxypropyl) ethylenediamine, N- (2-hydroxy-3-ethoxypropyl) -propylenediamine, N- (2-hydroxy-3-ethoxypropyl) -isopropylendiamine, N - (2-hydroxy-3-ethoxypropyl) -1,2-dimethylethylenediamine, N- (2-hydroxy-3-propoxypropyl) ethylenediamine, N- (2-hydroxy-2-propoxypropyl) -1,2-propylenediamine, N - (2-hydroxy-3-propoxypropyl) isopropylendiamine, N- (2-hydroxy-3-isopropoxypropyl) ethylenediamine, N- (2-hydroxy-3-isopropoxypropyl) -1,2-propylenediamine, N- (2-hydroxy-3-isopropoxypropyl) Hydroxy-3-isopropoxypropyl 1 ) -isopropylendiamine, N- (2-hydroxy-3-isopropoxypropyl) -J, 2-dimethylethylenediamine, N '- (2-hydroxy-3-isopropoxypropyl) -1,1-dimethylethylenediamine, N- (2-hydroxy-3 -butoxypropyl) -ethylenediamine, N- (2-hydroxy-3-butoxypropyl) -1,2-propylenediamine, N- (2-hydroxy-3-butoxypropyl) -isopropylendiamine, N- (2-hydroxy-3-pentoxypropyl) -ethylenediamine, N- (2-hydroxy-3-pentoxypropyl) -1,2-propylenediamine, N- (2,3-dihydroxy-1-hexylpropyl) -ethylenediamine, N- (2-hydroxy-3-octyloxypropyl) -ethylenediamine, N- (2-hydroxy-3-decyloxypropyl) ethylenediamine, N- (2-hydroxy-3-dodecyloxypropyl) ethylenediamine, N - {2-hydroxy-3-dodecyloxypropyl) isoproylenediamine, N- (2-hydroxy-3-tetradecyloxypropyl ) ethylenediamine, N- (2-hydroxy-3-hexadecyloxypropyl) ethylenediamine, N- (2-HyROXy-S-OCtBdCCyIoXyPiOPyI) -ethylenediamine ,. N- (2-hydroxy-3-phenoxypropyl) ethylenediamine, N- (2-hydroxy-3-phenoxypropyl) -1,2-propylenediamine, N- (2-hydroxy-3-phenoxypropyl) -isopropylendiamine, N- (2 Hydroxy-3-phenoxypropyl) r1 / 2-dimethylethylenediamine, N- (2-hydroxy-3-parachlorophenoxypropyl) ethylenediamine, N- (2-hydroxy-3-para-

2 19,971

chlorophenoxypropyl) -1,2-dimethylethylenediamine, N- (2-hydroxy-2-phenylethyl) ethylenediamine, N- (2-hydroxy-2-phenylethyl) isopropylendiamine, N- (2-hydroxy-3-phenoxypropyl) ethylenediamine , N- (2-hydroxy-3-phenoxypropyl) isopropylendiamine, N- (1-methyl-2-hydroxy-2-ethoxycarbonylethyl) ethylenediamine, N- (1-methyl-hydroxy-ethoxycarbonylethyl) -isopropylendiarsine, N - (2-cyanoethyl) ethylenediamine, N- (2-cyanoethyl) propylenediamine, N- (2-cyanoethyl) isopropylendiamine, N- (2-cyanopropyl) ethylenediamine, N- (2-cyanopropyl) -1,2 -propylenediamine, N- (2-cyanoethyl) -isopropylendiamine, N- (2-aminocarbonylethyl) ethylenediamine, N- (2-aminocarbonylethyl) -1,2-propylenediamine, N- (2-aminocarbonylethyl) -isopropylendiamine, N-j \ 2- (2-hydroxyethoxy) carbonyl ethyl-ethylenediamine and N- (2- (2-dimethylaminoethoxy) carbonyl] ethylenediamine.

While it is preferable that the salts of the invention are based on alkylenediamines, it is also possible to use N-substituted polyethylenepolyamines if one of the substituents Y or Y ^{1 is} an organoamino radical. Examples of such polyamines are N-octyldiäthylentriamin, N ^ Decyldiäthylentriamin, N-Dodecyldiäthylentriamin, N-Dodecyltriäthylentetramin, N- (2-mercaptoethyl) diethylenetriamine, N- (2-mercaptoethyl) -Triäthylentetramin, N- (2-mercaptopropyl) -Diäthylentriamin , N- (2-methoxycarbonylethyl) diethylenetriamine, N- (2-ethoxycarbonylethyl) diethylenetriamine, N- (2-propoxycarbonylethyl) diethylenetriamine, N- (2-isopropoxycarbonylethyl) diethylenetriamine, N- (2-isopropoxycarbonylethyl) triethylenetetramine , N- (2-methoxycarbonylpropyl) -diethylenetriamine, N- (2-ethoxycarbonylpropyl) -diethylenetriamine, N- (2-propoxycarbonylpropyl) -diethylenetriamine, N- (2-isopropoxycarbonylpropyl) -diethylenetriamine, N- (2-isopropoxycarbonylpropyl) -triethylenetetramine, N- (2,3-dihydroxypropyl) -diethylenetriamine, N- (2,3-dihydroxypropyl) -triethylenetetramine, N- (2-hydroxy-3-ethoxypropyl) -diethylenetriamine, N- (2-hydroxy-3- ethoxy

propyl) -triethylenetetramine, N- (2-hydroxy-2-phenylethyl) -diethylenetriamine, N- (2-hydroxy-3-phenoxypropyl) -diäthy lentriamin, N- (1-methyl ^ -hydroxy ^ -äthoxycarbonyläthyl) -diathylentriamin, N- (2-cyanoethyldiethylenetriamine and N- (aminocarbonylethyl) diethylenetriamine.

Typical metal salts provided by the invention are salts of Zn, Mn, Cu, Fe, Fe, Ni, Sn, Co, Co, Ca and Mg (or metal salts in which two or more of the above metals are present to form salts) each of the N-substituted alkylenebisdithiocarbamic acids for which the above-mentioned N-substituted diamines and polyethylenepolyamines are precursors.

The above polyamines can be prepared by any method described in the literature, in particular, they can be prepared by subjecting polyamines, ie, alkylenediamines and polyethylenepolyamines, to addition reaction with acrylic acid derivatives, methacrylic acid derivatives, alkylene sulfides or alkylene oxides. This addition reaction is carried out by dropwise introducing one of the last-mentioned compounds into the polyamine or a solution of the polyamine in water or in an inert organic solvent at temperatures between 0 and 10O ⁰ C and preferably 20 to 60 ⁰ C. In general, the reaction is exothermic. The release of heat in this reaction is easily controlled by adjusting the rate of dropwise addition of the reactant or by cooling the reaction solution. The polyamine produced can be easily purified, for example by distillation under vacuum. If two or more polyamines are produced by the reaction, they can be separated by purification. Optionally, two or more polyamines produced may be used simultaneously in non-separated form as a raw material. The desired polyamines can also be readily prepared by

polyamines undergo a substitution reaction using halogenated benzyl derivatives and halogenated alkyl derivatives. This latter reaction can be easily carried out by dropwise introduction of the halogenated alkyl derivative in the given polyamine at temperatures between 0 and 100 ⁰ C and preferably between 20 and 60 ⁰ C. From the reaction solution, the desired polyamine is produced by treating the solution with an equivalent amount by weight of an alkali to neutralize the by-produced hydrogen halide and purifying the solution. This reaction is generally carried out in the presence of an excess of the polyamine. A polyamine having two or more identical introduced substituents can be generated by adjusting the amount of the polyamine used to carry out the reaction.

Then, the product obtained by the reaction of CS ₂ and the N-substituted polyamine in solution, preferably in water, and less preferably in another solvent such as alcohol or dimethylformamide, with a base to form the desired salt brought to implementation. The CS ^ reaction product is usually a free alkylene bisdithiocarbamic acid, but it may also be an amine salt if an excess is used as the polyamine. The above two reactions are usually carried out at temperatures between 0 and 80 ⁰ C.

The preferred metal salts, i. H. the salts of one or more metals valent higher than 1 can be prepared by subjecting a water-soluble salt of a corresponding N-substituted alkylene bisdithiocarbamate to double decomposition with a corresponding water-soluble metal salt. For example, the preparation can take place in that a solution

2 1 M ¹ I / I - 13 -

a water-soluble salt of an alkylsulfithiocarbamate of the formula I is prepared and a water-soluble metal salt is added, which is capable of inducing a double decomposition / wherein the reaction is allowed to proceed until its termination. In this way, formation of the desired precipitate is effected. Further, one can proceed in such a manner that the two compounds are introduced simultaneously into a reaction vessel, without even reversing the order of addition of the two compounds. As far as the solvent is concerned, the reactants can generally be used in the form of aqueous solutions, but any solvent can be effectively used as long as they guarantee the solubility of the materials to be dissolved therein. Examples of solvents used advantageously for the reaction are water, pyridine, methanol, ethanol, isopropyl alcohol, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, acetone and tetrahydrofuran. These solvents can be used in the form of mixtures. The reaction is carried out at temperatures between 0 and 70 ⁰ C or even higher, for example 8O ⁰ C. The metal salt produced by this reaction is generally isolated in the form of a solid. This also applies if the reaction solution contains crystallization water and / or a solvent. The by-products inorganic salts are easily removed by washing the precipitate with water. If the presence of such inorganic salts as by-products is not detrimental, then the washing treatment may be omitted Examples of soluble metal salts used for the double decomposition reaction are salts of zinc, manganese, iron, copper, nickel, tin, Cobalt, calcium and magnesium These metal salts are very effective when used in the form of a mixture of two or more compounds, especially zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, copper chloride, copper sulfate, Copper nitrate, copper acetate, ferric chloride, ferrous sulfate, iron nitrate,

Use nickelic acid, nickel sulfate, tin chloride, tin sulfate, tin nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, calcium chloride, calcium citrate, magnesium chloride, and magnesium nitrate. Other soluble metal salts can also be used. ,

The N-substituted alkylene bisdithiocarbamates of this invention are generally stable at room temperature. However, they tend to decompose gradually when exposed to high temperatures or stored for extended periods of time. The incorporation of a stabilizing agent contributes to increased stability of these products. The stabilizing agent may be added either during the preparation of the salts or during the formulation of the fungicidal agents. Examples of stabilizers are paraformaldehyde and hexamethylenetetramine.

The following Examples 1 to 3 illustrate the preparation of the metal salts according to the invention. According to these examples, Table I identifies the metal salts of Examples 1-3 and identifies many other additional metal salts falling within the scope of the invention.

embodiments Example 1_

In 200 ml of water, 47 g of an aqueous 40 wt .-% sodium N- (2-hydroxy-3-isopropoxypropyl) -äthylenbisdithiocarbamatlösung containing 0.05 mol. Sodium salt, stirred at room temperature. To the resulting aqueous solution, 13.6 g of an aqueous 50% stannous chloride solution containing 0.05 mol of ZnCl 4 is gradually added dropwise. After the dropwise addition, the reaction solution is continuously stirred for three hours at room temperature to form crystals, which are separated by filtration and washed with water to remove impurities. The washed crisis

Stalls are dried at 50 to 60 ⁰ C under vacuum. In this way, a zinc salt of N- (2-hydroxy-3-i.sopropoxypropyl) ethylenebisdithiocarbamic acid (Compound 6, Table I) is obtained. Compounds 1 to 5 and 7 to 60 in Table I are prepared in a similar manner using the appropriate starting materials.

Example 2

In 50 ml of water, 13 g of an aqueous 48 wt .-% sodium N- (2-mercaptoethyl) -äthylenbisdithiocarbamatlösung containing 0.02 mol of the sodium salt, stirred at 4. 5 to 50 ⁰ C. The remainder of the method is carried out under a stream of nitrogen gas. The sodium salt solution obtained are 9.5 g of an aqueous solution of 26.5% by weight of manganese (II), which contains 0.02 mol MnCl ^ gradually added dropwise at temperatures of 40 to 50 ⁰ C was added. After the dropwise introduction, the resulting mixture is stirred at 45 ° C for 1 hour. Crystals are formed which are separated by filtration and washed with water to remove impurities. The washed crystals are dried under vacuum. In this way, a manganese salt of N- (2-mercaptoethyl) ethylenebisdithiocarbamic acid (Compound 61, Table I) is formed. "

Example 3

It becomes an aqueous solution of the compound

CH ₀ CH ₀ -O- CS -Na / 22 II

Na-SC-NHCH ₂ CH ₂ NS

S C-S-Na

Il S

manufactured. This solution is formed by adding 24 g of an aqueous 50% by weight solution of the sodium salt (0.03 mol) to 300 ml of water with stirring at room temperature. To the solution thus prepared, 13 g of an aqueous 50% zinc chloride solution containing 0.045 mol of ZnCl _{2 is} gradually added dropwise at room temperature. After the dropwise addition, the resulting mixture is stirred at 45 ° C for 1 hour. Crystals are formed, which are separated by filtration and washed with water to remove impurities. The washed crystals are dried at 50 to 60 ⁰ C under vacuum. In this way, the zinc salt identified in Table I as Compound 63 is obtained. Compounds 62 and 64 to 67 in Table I are prepared in a similar manner using the appropriate starting materials.

Table I

Metal salts of N-substituted alkylene bisdithiocarbamic acids in which all -C-S - are linked to the indicated metal S

Connection no. N-substituted alkylenebisdithiocarbamic acid ' Appearance 'Metal 1 OH i H, CH ₀ CH-CH-OH / 22 HSCN-CH-CEL-NCSHIi ² * II; SS yellow powder-like solid Zn ⁺⁺ 2 9H '. H CH ₂ CH-CH ₂ -O-CH ₃ HSCN-CH-CH ₀ -NCSH Ii ^{2 2} II-: ss white powder-like solid material Zn ⁺⁺ 3 OH IH CH ₂ CH-CH ₂ -O-CH ₃ HSCN-CH ₀ CH ₀ -NCSH I! 2 2 HSS black powder artisan substance "++ • Cu

Table I (continued)

Connection no. N-substituted-alkenyl-bis-thiocarbamic acid Appearance metal 4 OH H .CH ₂ CH-CH ₂ -O ^ CH ₃ HSCN-CH ₀ CH ₀ -NCSH 11 2 2 ι, SS blackish brown powdery solid Fe ⁺⁺⁺ 5 'OH IH, CH ₀ CH-CH ₀ -OC ₀ H- / 2 2 2 5 HSCN-CH ₀ CH ₀ -NCSH Π 2 2, ι: ss slightly yellow powdery solid ; _Z n ⁺⁺ 6 OH _{/ C} H ₃ • H CH ₂ CK-CH ₂ -O-CH HSCN-CH ₀ CH ₀ -NCSH CH, II 2 2, 3 SS white powder-like solid Zn ⁺⁺ 7 OH IH CH ₂ CH-CH ₂ -OC ₄ H ₉ -Ji HSCN-CH-CH, -N-.CSH II 2 2 | i SS white powder like solid Zn ⁺⁺

Table I (continuation)

Connection no. N-Substituted allcene-bis-dithiocarbairic acid Appearance metal 8 i OH / C _o H _e I / 25 H .CH ₀ CH-CH ₀ -O-CH \ / 2- 2 \ HSCN-CH ₀ CH ₀ -NCSH'C ^ H, _o -n Il 2 2 ii β 13 SS , , white powdery solid 9 OH i H, CH ₂ CH-CH ₂ -O-CH ₂ Ch = CH ₂ HSCN-CH ₀ CH ₀ -NCSH 11. 2 2 κ •. SS ... white powder-like solid material : zn ⁺⁺ 10 • OH H CH ₀ CH _CH-0 -0- (O) \ / 2 ^{V 2} - ^y HSCN-CH ₀ CH ₀ 2 2 -NCSK Il "SS white powdery solid substance ": zn ⁺⁺ 11 OH IH * .CH _o CH-CH _o -O- <O-CH, \ / ΔΔ J -HS-CN-CH ₀ CH ₀ -NCSH O 2 2. , j. s-. s. white powdery solid Zn ⁺⁺ 12 OH, ^CH-1/3 of H · ₀ .CH CH-CH ₀ -O-CK \ / ² 2 \ HSCN-CH (CH ₀₎ CH ₀ CH ₀ Il -NCSH 3 2 .3 ii SS yellow powder type solid substance I Zn ⁺⁺

Table I (continued )

Connection no. N-substituted alkylenebisdithiocarbanic acid Appearance • lytetall 13 OH H CH ₀ CH _0-CH -O-CH- V- / 2 2 3 HSCN-CH (CH) CH ₂ -NCSH SS .... slightly yellow powdery solid Zn 14 H .CH ₂ COO-C ₂ H ₅ HSCN-CH ₂ CH ₂ -NCSH •. s. s. , ... yellow powder solid : Zn ⁺⁺ 15 : H .CH ₀ CH ₀ -COO-CH- / 22 3 HSCN-CH-CH ₀ -NCSH '. S. , S white powdery solid ^: . Zn ⁺⁺ . 16 H, CH ₀ CH ₀ -COO-CH- / 22 3 HSCN-CH ₀ CH ₀ -NCSH Il ^{2 2} I! S. S brown powder-like solid • Cu ⁺⁺ 17 H . CH ₂ CH ₂ COO-CH ₃ HSCN-CH ₀ CH ₀ -NCSH ·. 'Il ² 2 μ SS blackish-brown powdery solid   "+++. Fe 18 H CH ₂ CH ₂ COOC ₂ H ₅ HSCN-CH ₀ CH ₀ -NCSH II 2 2 11 SS .... white pulverar tiger solid Zn ++

'' ^ Oelle I (Will Continue t.ζ ung)

Connection number * N-substituted alkylene bisdithiocarboxylic acid Appearance metal 19 H CH ₂ CH ₂ CCOC ₂ H ₅ HSCN-CH-CH ₀ -NCSH Ii 2 2 1,. S. S .... brown powder-like solid Cu ⁺⁺ . 20 H, CH _n CH _n COOC _n H \ / 22 25 HSCN-CH ₀ CH ₀ -NCSH Il 2 2 j, p. S ... black powdery solid Fe ⁺⁺⁺ 21 H .CH ₂ CH ₂ COOC ₂ H ₅ • HSCN-CH _n CH _n -NCSH; I ²² I blackish-brown powdery solid 22 H CH ₂ CH ₂ COOC ₄ H ₉ -ISO HSCN-CH _n CH _n -NCSH • Ii 2 2 Ii SS white pulverar tiger solid 23 ^H \ * ^ CH ₀ CH ₀ COO-CH ₀ CH ₀ -Oh HSCN '' ^ N ^ I ^N CSH ^S I * = -CH (CH ₃ ) CH ₂ - or slightly yellow powdery solid 24 CH- 1 ³ H CH ₂ CH-COO-CH ₃ HSCN-CH ₀ CH ₀ -NCSH Il 2.2] | SS. slightly yellow powdery solid Ni ⁺⁺ Zn ⁺⁺ Zn ⁺⁺ , Zn ⁺⁺

Table I (continued)

Connection no . "N-substituted AlJcy'lenbisdithiocarbaininsäure Appearance metal 25 CH ₃ ♦ H .CH ₀ CHCOOC-H ,. 225 HSCN-CH ₀ CH ₀ -NCSH S slightly yellow powdery solid zn ⁺⁺ 26 : 'f ³ / ^CH ₃ H, ^CH ₂ CHCOCHC \ / \ _Γ π HSCN-CH ₀ CH ₀ -NCSH ^Crt 3 Il ^{2 2} II SS. , .... slightly yellow powdery · solid 27 ? ^H 3 / CH ₃ H .CH-CHCOOCHC • HSCN-CH ₀ CH ₀ -NCSH 2 ⁿ 5 ii ²² i; • ss white powdery solid material 28 CH- CH. , , I ³ I ³ H .CH ₀ CHCOO-C-CH. \ / ² I · 3. HSCN-CH ₀ CH ₀ -NCSH CH, I, 2 H 2 SS. , slightly yellow powdery solid _ ++ Zn 29 ^CH 3 .CH H ₀ H _oc CHCOOC _1o -n \ / ² 12 25 HSCN-CH ₀ CH ₀ -NCSH Il. ^{2 2} Il SS slightly yellow powdery solid Zn Zn ⁺⁺ Zn ⁺⁺

Table I (continued)

Connection no. N-substituted alkylenebisdithiocarbamic acid Appearance Itetall 30 .CH ₃ OH. H CH-CHCOOC ₂ H ₅ . HSCN-CH-CH - NCSH II 2 2 ρ SS slightly yellow powdery solid "++ Zn 31 ^ 3 CH H .... ^ CH, -CHCOOCKQ \. , , / * - ^ CK HSCN ^^ NCSH 3 Il Ii * = -CH (CH-) CH-- SS ό Ζ. or -CHir ^ (r-μη) - slightly yellow powdery solid 32 T ³ ^ ^CK 3 H .CH-CHCOOCHC \ / 2 \ HSCN-CH (CH-) CH (CH -) - NCSH 3 Ii 3 3 11 SS .. · ... 33 • .H, CH_CH - C = N \ / 2 2 H-S-C-N-CH-CH- N-C-S-H il 2 2 j, s s. , powdery solid Zn ⁺⁺ 34 CH-CH- I 3 ι 3 H JCH - CH-COOCH-CH-N \, * / ² I l \. HSCN'NNCSH CH ₃ IS * ⁼ "GH (CH ₃ ) CH ₂ - '* or -CH9CH (CH ₂ ) y- powdery solid Zn ⁺⁺ Zn ⁺⁺ Zn ⁺⁺

Table I (continued)

Connection no. N-substituted alkene salt mocarbairic acid Appearance metal 35 CH-H, CH ₂ -CHCOOCH ₂ -Ch = CH ₂ HSCN ^ - ^ NCSH. * ₌ -CH (CH ₃ ) CH ₂ -S. S or -CH ₂ CH (CH ₃ ) - yellow powdery solid "++ Zn 36 H CH ₂ CH ₂ SH HSCN-CH ₀ CH ₀ -NCSH Ii 2 2, S ·. , , S slightly yellow powdery solid 37 ^H \ / ^CH 2 ^CH 2 ^SH : HSCN-CH ₀ CH ₀ -NCSH Il 2 2 n • SS blackish-brown. powdery solid 38 H CH ₂ CH ₂ SH HSCN-CH ₀ CH ₀ -NCSH I! 2 2 j; , SS. , black pulp solid substance 39 fs; H .CH ₂ CH-SH HSCN-CH ₀ CH ₀ -NCSH Ii 2 2 η. SS • yellow powdery solid 40 H CH ₂ CH ₂ SH HSCN '^ NCSH ^Λ -CH (CH ₃ ) CH ₂ -S S' or- CH ₂ CH (CH ₃ J. yellow powder-like solid substance Zn ⁺⁺ Cu ⁺⁺ . Fe ⁺⁺⁺ Zn ⁺⁺ rr ++ Zn

Table I (continued )

Connection Nr, N-substituted alderibisdithiocarbamic acid Appearance metal   · 41 \ / ^C 8 ^H 17 ~ ⁿ HSCN-CH ₀ CH ₀ -NCSH Ii 2 2 j,: ss. , gelier powder-like solid substance 42 \ / ^α ιο ^Η 2Γ ^η HSCN-CH ₀ CH ₀ -NCSH Il 2 2 ι,. S. S yellow powder-like solid substance Zn ⁺⁺ 43 ^K _N / ^C 12 ^H 25 " ⁿ • HSCN-CH ₀ CH ₀ -NCSH Ii 2 2 j,.:. S. S. yellow powder-like Fe St- ⁴ substance : zn ⁺⁺ 44 HC, _O H _O γ · "'Π \ / 12 25 HSCN-CH ₀ CH ₀ -NCSH-J ²² I. , ,. .. black pul verhard fest. material :. ^{cu ++} 45 \ " / ^C 12 ^H 25" ⁿ HSCN-CK ₀ CH ₀ -NCSH Il 2 2 ii SS. yellow powdery solid ^: Ca ⁺⁺ 46 H C. _O H _O -η / 12 2 5 HSCN-CH ₀ CH ₀ -NCSH Il 2 2 j, · SS slightly yellow powdery solid J Mg ⁺⁺

Table I (continued)

Connection no. N-substituted alkylenebisitolmocarbamic acid   Appearance metal 47 H .C ,, Η, ς-η \ / 12 25. HSCN-CH ₀ CH ₀ -NCSH: N 2 2 υ S. S black powdery solid Fe ⁺⁺⁺ 48 \ / ^C 12 ^H 25- ⁿ : HSCN-CH ₀ CH ₀ -NCSH Il 2 2 I ₁ ; SS .... black powder-like solid Ni ⁺⁺ 49 : H, Ο., Η, .- η \ / 12 25 'HSCN-CH ₀ CH ₀ -NCSH Ii 2 2 ι, S. S ... black powder-like solid 50 • \ / l4 ^H 29- ⁿ HSCN-CH ₀ CH ₀ -NCSH. ü ^{2 2} 1. , , , . yellow powder-like solid 51 ^H \. / ^C l6 ^H 33 "HSCN ^n-CH ₀ CH ₀ ² 2 -NCSH Il Il SS.. yellowish-orange powdery solid 52 : \ / ^C 18 ^H 37 ~ ⁿ -HSCN-CH ₀ CH ₀ -NCSH Il 2 2 HSS slightly yellow powdery solid _ +++ Co Zn ⁺⁺ Zn ^{++ :} Zn ⁺⁺

Table e I (continued)

Compound No .: N-substituted AU-bis-dithiocarboxylic acid Appearance

metal

HSCN CH-CH _{n n} -NCSH

2-2 slightly yellow powdery solid

Zn

CH

H,

CH.

HSCN-CH ₀ CH ₀ -NCSH

Ii 2 2 Ii

yellow

powdery

solid fuel

Zn

CH

HSCN-CH ₀ CH ₀ -NCSH

Ii 2 2 Ii

slightly yellow powdery solid

Zn

CH ₉ - <O / -CH.

HSCN-CH ₀ CH ₀ -NCSH

S S

yellow powdery solid

Zn

HSCN-CH ₀ CH ₀ -NCSH

Il Δ Δ \ < yellow powdery solid

Zn

- 28 Table I (continued)

Connection no. N-substituted i-cylenebisdithiocarbandic acid Appearance metal 58 \ / ^CH 2 "<I> ^C 12 ^H 25 ⁿ HSCN-CH ₀ CH -NCSH Il 2 2 υ S. yellowish-orange powdery solid Zn ⁺⁺ 59 CH ₃ H ₀ NCH ₀ CH ₀ .CH ₀ - (SyCH-. 2 21 2/2 \ - / _c 3 HSCN-CH ₀ CH ₀ -NCSH 3 Il 2 2, ι SS '. yellow powdery solid Zn ⁺⁺ 60 OH H. CH ₂ CH- <o) HSCN-CH ₀ CH ₀ -NCSH: I 1 white powder-like solid material 61 : H CH ₂ CH ₂ SH HSCN-CH ₀ CH ₀ -NCSH il ^22; Il S β. , , but a powdery solid Mn ⁺⁺ 62 H _v 'CH ₀ CH ₀ -OCSH \ / ² 2 n HSCN-CH ₀ CH ₀ -NCSH S Il 2 2 κ SS yellowish-orange powdery solid Mn ⁺⁺ 63 H./CH ₂ CH ₂ -OCSH HSCN-CH ₀ CH ₀ -NCSH S Il 2 2 "SS. yellow perfume solid Zn ⁺⁺

Table I (Forte, ^ ung)

Connection no. N-substituted 'alkenylbisdithiocarbanic acid Appearance metal "64 \ / 2 2, ₁ HSCN-CH ₀ CH ₀ -NCSH S Ii 2 2 I,. SS black powder-like solid Fe ⁺⁺⁺ 65 H. CH-CH ₀ -OCSH \ * / ² * · Il HS- ¹ CN "" ^V NCSH S Il Il * = CH (CH-) CH ₀ - SS 3 Z or -CH ₂ CH (CH ₃₎ - yellow p'ulverartiger solid "zn ⁺⁺ 66 CK-I ^J H CH ₀ CH-OCSH \ / 2 I ₁ HSCN-CH ₀ CH ₀ -NCSH SI! 2 2, ι SS yellow pulverar tiger solid . "Zn ⁺⁺ 67 CH- I CH ³ ₀ K CH-OCSH. Λ * / 2H HSCN ^ "^ NCSH S * = -CH (CH-) CH ₀ - Ii""II ^{3 2} .SS or -CH ₂ CH (CH ₃ ) - yellowish-orange powdery solid ^: Zn ⁺⁺

CO CD "si

Emphasized are the compounds 1 to 67 in the. Table I in which the indicated metal is replaced by another metal consisting of Zn, Cu, Fe, Ni, Ca, Mg, Co and Mn, with Mn being the preferred replacement metal '. In this way, a total of 7 χ 67 = 469 other specific compounds falling within the scope of the invention are made available,

The compounds shown in Table I can also be represented by formulas corresponding to the formula III, so that, for example, the compound no. 1 can be represented as follows:

OH

H CH ₂ CHCH ₂ OH

Zn / ₂ SCN-CHCHZ

Compound 36 can be represented as follows:

-SCN-CH ₂ CH ₂ -NI

The connection 62 can be represented as follows:

H _v

-SCN-CH ₀ CH ₀ -NCS-MnZ ₀ "

1 ²² I ²

The same applies to the rest of the compounds in Table I.

The infrared absorption values of Compounds 1 to 31, 33 to 39, 41 to 44 and 47 to 67 of Table I are shown in the accompanying Figures 1 to 31, which respectively represent the infrared absorption spectra of Compounds 1 to 31. FIGS. 32 to 38 show the values for the connections 33 to 39, FIGS. 39 to 4 2 the values for the connections 41 to 44 and FIGS. 43 to 63 the respective

d, I Ό ο /. I. - 31 -

values of Compounds 4 7 to 67. Infrared values are obtained using the KBr disc method.

While it has been attempted to specify precise chemical formulas for the above-described metal salts of the present invention, i. However, these formulas do not always correspond to the actual circumstances, since these salts have a very complicated structure and may even be polymeric, as is the case with the compounds Maneb, Mancozeb and Zineb (see, for example, "The Pesticide Manual", The British Crop Protection Council, 6th edition, 1979). In general, these complex metal salts are not soluble in water.

Some or all compounds 1 to 67 are tested as fungicides after the following two tests.

Test 1:

From two cucumbers (species Tokiwa-hikari Sango), grown in a greenhouse to the trifoliate stage, aqueous suspensions are applied, each containing 1500 ppm of the active ingredient, namely the compounds 1 to 67 according to Table I, in the form of 75 wt .-% wetting wettable powders are used. The suspensions are applied by means of a small glass spray nozzle. On the second day after this spraying, a suspension of scurf pores (Cladosporium cucumerinurn) is sprayed onto the treated cucumber plants. The cucumber plants are kept in a warm greenhouse at a humidity of not less than 90% to promote the infection of the cucumber plants with the fungal spores. On the tenth day after infection with the spores, the two uppermost leaves which were open at the time of spraying are examined and evaluated for disease degree (on a scale ranging from 0 to 4) to determine the control index.

2 1 9 97.1

stuffs. In the scale ranging from O to 4 mean: O = no disease, 1 = 5% or less of the leaf area are affected by the disease, 2 = 5 to 20% of the leaf area are affected by the disease, 3 = 20 to 50% of the disease Leaf area are affected by the disease and '4 = more than 50% of the leaf area are affected by the disease. The results obtained are shown in the following Table II.

Ta belle II

Test for controlling the scab disease on cucumber plants

Connection No. Control index

1 74

2 72

3 70

4 76

5 68

6 89

7 65

8 81

9 73

10 80

11 72

12 88

13 '86

14 78

15 65

16 82

17 79

18 .70

19 61

20 76

21 78

22 64

23. 78

24 65

25 77

26. 82

27 66

28 82

29 · 78

30. 72

19 9 7 1 _ 34 _

Table II (continued)

Compound No. Control Index

31 83

32 79

33 70

34 74

35 68

36 82

37 72

38 80

39 75

40 86

41 70

42 69

43 75

44 64

45 77

46 78

47 79

48 73

49 "70

50 60

51 73

52 72

53 65

54 .81

55 75

56 58

57 75

58 71

59 66

60 82

71 -35-

Table II (continued)

Compound No. Control Index

61. 76

62 "73

63 70

64. 79

65 79

66 69

67 80

treatment

Test 2:

From two Toraatenpflanzen (species: · Sarashina-Fukuju) grown in a greenhouse up to the siebenblättrigen stage, aqueous suspensions are applied, each containing 1500 ppm of the active ingredients, of 9 of the compounds indicated in Table I. The compounds are used in the form of 75% by weight wettable powders. The suspensions are applied by means of a small spray nozzle. On the second day after this spraying a suspension of spores of Phytopthorainfestans is sprayed evenly on the treated tomato plants for their infection. On the 10th post-infection day, the five main leaves per plant and seven small leaves per main leaf are counted to determine the disease spots (on a 0, 1, and 2 scale) to calculate the "Control Index." Composed in the 0, 1, and 2 Scale means: G = no disease, 1 = less than 20% of the leaf area is affected by the disease and 2 τ 20%

or more of the leaf area are affected by the disease,

Table III

Test to determine the control of the disease on tomatoes

Connection no.

control Index

phytotoxicity

1 2

12 20 21 26 30 33 36 39

46 53 59 61 62 67

no treatment

74 81 86 73 69 75 84 77 79 80 68 77 76 83 79 75 85 86

none none none none none none none none none none none none none none none none none none none

So far, preferred salts have been highlighted, d. H. Salts of one or more metals with a valence of more than 1. Of importance, however, is also a subclass of salts of the formula

Y Υ ·

Ν-Χ-N _(τν)

M - SC CSM ¹ "

S S

wherein X, Y and Y 'have the meanings given in connection with the formula I and M "and M"'> which may be identical or different, for an alkali metal, in particular sodium, potassium or lithium, or a nitrogen-containing group such as ammonium , substituted ammonium or a nitrogen-containing heterocycle.

Are M "and / or M ^1" is a substituted ammonium, then the number of substituents can be up to 4 hours. The substituents may be selected from (C ₁ -C.) Alkyl, preferably methyl or ethyl, as well as phenyl (C ₁ -C ₂ ) alkyl. Examples of such substituted ammonium groups are methylammonium, dimethylammonium, benzyltrimethylammonium and dibenzyldiäthylammonium.

Typical salts of formula IV are the alkali metal, ammonium and substituted ammonium salts of each N-substituted alkylenebisdithiocarbamic acid, for which the N-substituted diamines and polyethylenepolyamines, as listed above, are precursors.

Salts of formula IV can be prepared by reacting an acid of formula I with a corresponding base or by double reaction using an acid of formula I. An example of such a double decomposition reaction occurs if CS ₂ ^m, is made to react it an excess of a diamine, for example, an N-substituted Ä'thylendiamins, wherein an amine salt own acid of formula I is produced. The amine salt is then reacted with an alkali metal hydroxide to form the corresponding alkali metal salt. These reactions are preferably in solution in a solvent such as water

2 19 3 71

or alcohol, dimethylformamide or other inert solvent. The respected Reaktionstem-. temperature can generally between 0 and 100 ⁰ C and preferably between 20 and 50, 70 or 80 and especially 30 to 40 ⁰ C. The acid of formula I can be prepared in situ by reacting carbon disulfide with a suitable diamine or other polyamine in the presence of a base, which then reacts with the acid formed to produce the desired salt of formula IV.

The reaction between CS and the diamine and other polyamine is to a certain extent exothermic and generally proceeds easily at temperatures of 30 to 40 ⁰ C. The 'reaction temperature, by controlling the speed of the dropwise addition of CS or external cooling of the reaction system. For example, the reaction may be carried out by dropwise adding CS to a solution containing the diamine or other polyamine and a base which causes the formation of the desired salt.

In the case of salts in which Y and / or Y ^{1 is} a group -4CHR ^ -CHR ₃ -OCM "(M ¹ "), a diamine or other polyamine reactant can be used which has one or more polyamine reactants

contains two N-substituents of the formula (-CHR-), the ebenin.

if they react with CS- to obtain the salt group mentioned above. Conveniently, this reaction is carried out in a solvent such as water, dimethylformamide, dimethyl sulfoxide, alcohols such as ethanol or N-methylpyrrolidone at a temperature of 35 to 45 ° C.

Examples of bases that can be used to advantage for the preparation of the water-soluble salts of formula IV are alkalis, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate,

2 19 37 y. - 39_-

Ammonia and aqueous ammonia, alkylamines, such as methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, monoethanolamine, diethanolamine, triethanolamine, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) hydrazine and hydrazine, arylamines and aralkylamines such as aniline, phenylenediamine, xylylenediamine and benzylamine, and heterocyclic amines such as morpholine, piperazine, pyridine and quinoline.

The following Examples 4 to 9 illustrate the preparation of salts of the formula IV. According to these examples, the identification of the metal salts of Examples 4 to 9 and the identification of many other further salts of the formula IV follow in Table IV.

Example 4

While 20 g (0.114 mol) of N- (3-isopropoxy-2-hydroxy-propyl) -ethylenediamine and 30 g of water at room temperature (20 ⁰ C) are stirred, 17g (0.228 mol) of carbon disulfide are gradually added dropwise. The reaction temperature is kept just below 38 ⁰ C. After the dropwise addition of CSp, the resulting mixture is stirred at 35 to 38 ° C for 1 hour. Then, 19 g of a 48% by weight aqueous sodium hydroxide solution (0.228 mol of NaOH) is gradually added dropwise to neutralize the solution. The reaction temperature is again kept directly below 38 ° C. After the dropwise addition of NaOH, the mixture is stirred again at 38 to 42 ^° C. for 2 hours. A light yellow transparent aqueous solution of sodium N- (3-isopropoxy-2-hydroxypropyl) ethylenebisdithiocarbamate (Compound 72, Table IV) is obtained. Compounds 68 to 71 and 73 to 79 in Table IV are similarly prepared using the appropriate polyamine precursor and sodium hydroxide, aqueous ammonia or dimethylamine.

O 1 QQ 7 1 - on -

amine produced. Each of compounds 68 to 79 is freed of water by evaporation of water from the solution, followed by drying under vacuum.

Ex iel 5

While .42 g (0.55 mol) of carbon disulfide and 50 g of water at room temperature (20 ⁰ C) are stirred, 44 g (0.275 mol) of N- (2-A'thoxycarbonyläthyl) -äthy.lendiamin are gradually added dropwise. The reaction is maintained directly below 38 ° C, the mixture being stirred for 1 hour. To the solution is added dropwise 46 grams of a 48% aqueous sodium hydroxide solution (0.55 moles NaOH) keeping the temperature below 38 ^° C. again. After the dropwise addition of the NaOH solution is stirred at 38 ° C for a further 3 hours. This results in a yellow transparent aqueous solution of sodium N- (2-A'thoxycarbonyläthyl) -äthylenbisdithiocarbamat (compound 81, Table IV). Compounds 80 and 82 to 99 of Table IV are prepared in a similar manner using the corresponding polyamine precursor as well as sodium hydroxide, potassium hydroxide or aqueous ammonia. Each of the compounds 80 to 99 is freed of water by evaporation of water from the solution, followed by drying under vacuum.

Example 6

While 30 g (0.156 mol) of N- (2,4,5-trimethylbenzyl) ethylenediamine, 40 g of water and 26 g of an aqueous 48% sodium hydroxide solution (0.132 mol of NaOH) are stirred at room temperature (20 ⁰ C), are 24 g (0.312 mol) of carbon disulfide added dropwise, keeping the temperature just below 35 ° C. After the dropwise addition of CS ", the mixture is stirred at 35 to 38 ° C for 3 hours. This is a uniform and clear aqueous

2 H η η "7 1 Λ ι

Solution of sodium N- (2,4,5-trimethylbenzyl) ethylenebisdithiocarbamate (Compound 104, Table IV). Compounds 100-103 and 105-110 in Table IV are prepared in a similar manner using the corresponding polyamine precursor and sodium hydroxide. Each of the compounds 100 to 110 is freed of water by evaporation of the same from the solution, followed by drying under vacuum.

Example 7

While 31.0 g (0.4 mol) of carbon disulfide and 40 g of water are stirred, 24 g (0.2 mol) of N- (2-mercaptoethyl) ethylenediamine are gradually added dropwise, keeping the temperature immediately below 38 ° C. becomes. After the dropwise addition of the diamine, the mixture is stirred at 35 to 38 ° C for 1 hour. Subsequently, 34 g of an aqueous 48% sodium hydroxide solution (0.4 mol of NaOH) is gradually added dropwise to effect neutralization. The reaction temperature is again kept below 38 ° C. After the dropwise addition of the sodium hydroxide solution, the mixture is stirred at 38 ° C for 2 hours and then cooled to room temperature. In this case, a uniform clear aqueous solution of sodium N- (2-mercaptoethyl) -äthylenbisdithiocarbamat (Verviridung 111, Table IV) is obtained. Compounds 112 to 116 are similarly prepared using the corresponding polyamine precursor as well as sodium hydroxide, aqueous ammonia or methylamine. Each of the compounds 112 to 116 is freed from it by evaporation of water, followed by drying under vacuum.

Ex iel 8

In 55 g of water, 60 g (0.25 mol) of N-dodecylethylenediamine and 85 ml of ethanol at room temperature (2O ⁰ C) are stirred until the dissolution of the diamine. To the solution thus obtained, 40 g (0.5 mol) of carbon disulfide are added dropwise, keeping the temperature just below 35 ° C. After the dropwise addition of CS2, the mixture is stirred at room temperature for 2 hours. Then, 42 g of an aqueous 48% sodium hydroxide solution (0.5 mol NaOH) is gradually added dropwise, again keeping the temperature just below 38 ° C. The mixture is then stirred at 42 ° C for 1 hour. This results in a uniform and clear aqueous solution of sodium N-dodecyläthylenbisdithiocarbamat (compound 119, Table IV). Compounds 117, 38, and 120 through 124 are similarly prepared using the appropriate polyamine precursor as well as sodium hydroxide; Made of potassium hydroxide or aqueous ammonia. Each of the compounds 117 to 124 is freed of the liquid by evaporation of the same from the solution, followed by drying under vacuum.

Example 9

While 55 g (0.72 mol) of carbon disulfide and 100 ml of dimethylformamide are stirred at room temperature, 25 g (0.24 mol) of N- (2-hydroxyethyl) ethylenediamine are gradually added dropwise, keeping the temperature below 35 ° C. , The mixture is stirred at 35 ° C for 1 hour. Subsequently, 31 g of a solid 93% sodium hydroxide (0.72 mol NaOH) are added, the temperature is kept below 4 5 ° C. After the addition of the sodium hydroxide, the mixture is stirred at a temperature of 42 to 45 ° C for 1 hour, while a uniform clear aqueous solution of a. Compound (Compound 125, Table IV)

which is the starting compound of Example 3 above in which the formula of the compound in question is given. Compounds 126-131 are prepared in a similar manner using the corresponding polyarene precursor as well as using sodium hydroxide or potassium hydroxide. Each of the compounds 125 to 131 is freed of the liquid by evaporation of the same from the solution, followed by drying under vacuum.

In connection with the heading of column 3 of the following Table IV it should be noted that, for example, compound III has the structural formula

CH ₀ CH ₀ SH

Na-SC-NHCH ₀ CH ₀ NCS-Na II ^{2 2} II

has, where Na. (A in column 3) replaces Zn in the compound (B in column 3), while similarly compound 125 gives the structural formula

CH ₂ CH ₂ OC-S-Na

Na-SC-CH NHCH _{0 0} NCS-Na Il HSS ² 2

where Na Mn in Compound 62 replaces.

Column 1 Table IV Column 3 B '1 Column 4 Connection no. Column 2 "" " salt-forming group (A) or Me tall '(A), which replaces the anoegebene metal in the compound no.' (E) in Table I. 2 Appearance 68th Structural formula, if not mentioned under column 3 A_ Na 5 orange solid - 69 N / A 6 pale yellow, 'gel-like solid' 70 N / A 6 light yellow .Feststoff 71 (CK ₃ J ₂ NH ₂ 7 yellow fet tiger solid fabric 72 N / A 8th yellow solid fabric 73 N / A 9 pale yellow solid 74 i • N / A pale yellow solid. 75 N / A solid matter

column

column

Table IIV. (Continuation)

Column 3

column

Connection no.

Structural formula, if no mention under column salt-forming group (A) or -Ms-. tall (A) which replaces the indicated metal in Compound No. (B) in Table I.

Appearance

Na-SC- ⁴ NHCH-CH-NCS-Na 2 2 ti

CH ₂ CH ₂ COOC ₄ H ₉ -ISO A Na

N / A

NH ₄

Na Na Na Na K

B 10

11 12

13 14 15 18 18

24

yellow solid

 white solid yellow greasy solid

yellow solid

yellow gelatinous solid

solid

! yellow solid

Yellow gelatinous solid

I light yellow

solid fuel

pale yellow solid

lawcJLie xv Column 2 \ Rurtbetzung; B. Column a Column 1 ' Structural formula, if not mentioned under column 3 column 25 Appearance Connection no. 26 ! 3 yellow solid 86 salt-forming group (A) or Me tall (A), which replaces the specified ifetall in the compound no. (B) · in Table I. 26 light yellow 87 A 27 solid fuel N / A 28th yellow gelar tiger solid   88 N / A 29 light yellow solid fabric 89 ^; , pale yellow solid: , 90 i I K - pale yellow solid 91 (CH ₂ J ₂ CONH ₂ , N / A yellow festival 92 Na-SC-NKCH (CH,) CH (CH-) NCS-Na Ii Δ ΔH N / A · 33 material H - * Il: ss N / A pale yellow solid 93   - N / A

Table IV Column 2 ι _t (Fortune.) B '. · Column 4 Column 1 Structural formula, if not mentioned under column 3 : ³¹ Appearance Connection no. Column 3. 31 Salt-forming group (Λ) or Fe tall (A), which replaces the metal specified in the compound no. (B) in Table I. 30 yellow gelarti ger solid 94 • A 34 yellow gelarti ger solid 95 N / A : 23 light yellow solid fabric 96 : NH ₄ 35 yellow gelarti ger solid 97 N / A 53 yellow gelarti ger solid 98 ; N / A : 54 yellow gelarti- crer solid 99 : N / A 55 "elb-orange solid 100 N / A light yellow solid fabric 101 N / A pale yellow solid 102, N / A N / A'

Table IV (continued )

column

• Column

column

column

Connection no.

Structural formula, if not mentioned under column salt-forming group (A) or metal (A), which replaces the indicated metal in compound No. (B) in Table (I)

Appearance

103 104

105

106 107

108

109

Na-SC-NHCH ₀ CH ₀ NCS-Na

Ii 2 2 ii

Na-SC-NHCH ₀ CH ₀ NCS-Na

ii 2 2 η Na Na

Well, na

N / A

56 58

57 59

60

yellow gelatinous solid

yellow solid

yellow-orange solid

slightly gelatinous solid

yellow solid

pale yellow solid

light yellow solid -

, , Table IV (continued) • Column 3. B Column 4 • Column 1 Column 2 salt-forming group (A) or Me tall (A), which replaces the specified metal in the compound no. (B) * in Table I. Appearance Connection no. Structural formula, if not mentioned under column 3 A - 61 110 , OH I - 61 pale yellow solid · CH ₂ CH-CCl ₃ Na-SC-NHCH ₃ CK ₂ NCS-Na N / A 61 yellow-brown solid 111 NH ₄ ' 39 pale yellow gelatinous solid. 112 CH ₃ NH ₃ . 39 yellow gelar tiger Feststo. 113 N / A 40 Solid material '114 ' Li yellow-orange solid ' 115 N / A yellow fat-like solid 116

Table IV (continued)

Column 1 Column 2. : Column 3 B · Column 4 Connection no. Structural formula, if not mentioned under column 3 salt-forming group (A) or Me tall (A), which replaces the indicated metal in the compound no. (B) in Table I. 41 Appearance A 42 117 : N / A 43 yellow solid 118 : N / A 43 yellow solid 119 : N / A 43 50 •; 51 yellow solid , 120 K 52 yellow-orange solid 121 122 123 • : NH ₄ ^: Na Na : 62 slightly gel-like solid. yellow solid yellow solid 124 ; N / A yellow solid 125 : N / A yellow-orange solid

Table IV (continued)

Column 1 Column .2 Column 3 : β Column 4 Connection no. Structural fonrel, if no mention under column 3 ' salt-forming group (A) or lef- metallic (A) replacing the indicated metal in the compound No. (B) in Table I. 62 Appearance A 66 - 126 K   - 65 aelb ^ orange solid 127 N / A 65 67 yellow-orange solid 128 N / A 67 orange solid fabric 129 130 K; N / A orange solid yellow-orange solid 131 K yellow-orange solid *

2 1 9 9 71

With the exception of compounds 84, 92, 103, 106 and 110, the compounds of Table IV are precursors, with a double reaction reaction being used for one or more of the compounds of Table I. However, compounds 84, 92, 103, 106 and 110 are also suitable precursors of the preferred metal salts of the present invention. Each of these five compounds is suitably subjected to a double conversion reaction with a metal salt, the metal being selected from the group consisting of

Zn, Cu, Fe, Ni, Ca, Mg, Co and Mn,

the last named metal being preferred.

From the foregoing, it can be seen that the salts of the acids of formula I can be prepared by a process which can be generally defined as a process which carries out an acid of formula I or a salt thereof in solution, preferably in aqueous solution Solution, a double reaction reaction with a suitable salt or a base or an addition reaction with ammonia or an amine including heterocyclic amines, such as pyridine, is subjected, wherein the above-mentioned reactions preferably at a temperature of 0 to 100 ⁰ C, preferably 20 to 50 ⁰ C, 70 or 80 ⁰ C or in particular 30 to 40 ⁰ C are performed.

Some or all compounds 68 to 131 are tested as fungicides following the following two tests:

Test 3:

On two cucumber plants (species: Tokiwa-hirari Sango) grown in a greenhouse to the trifoliate stage, an aqueous solution of each of the compounds 68 to 131 is applied by means of a small glass spray nozzle. On the second day after spraying, a scurf spore suspension (Cladosporium cucumerium) is added to the

sprayed treated cucumber plants. The cucumber plants are kept in a warm greenhouse with a humidity of not less than 90% in order to accelerate the infection of the plants with the fungal spores. On the 10th day after this infection with the spores, the top two leaves that were open at the time of spraying are examined and rated for disease degree (on a scale ranging from 0 to 4) to calculate the control index. The scale ranging from 0 to 4 is defined in the above Test 1. Each of compounds 68 to 131 is applied in the form of an aqueous 30% by weight solution which has been diluted 2000 times with water. The results are shown in Table V below.

Table V Test for control of scab disease on cucumber plants

Compound No. Control Index

68 77

69 79

70 74

71 81

72 "83

73 62

74 71

75. * 64

76 "68

77 73

78 87

79 83

80 71

81. 67

82 70

83 66

84 75

2 19 9 7 1 - 54 -

Table V (continued)

Compound No. Control Index

85 75

86 72

87 '84

88 83

89. 77

90 69

91 77

92 "· 72

93 63

94 80

95 81

96 73

97 73

98 72

99 68

100 72

101 '73

102 65

103 79

104 .63

105 - 71

106 .74

107 66

108 58

109 71

110 62

111 '86

112 83

113 82

114 85

115 -80

116 82

219 97 1

~ 55 - Table V (continued)

Compound No. Control Index

117 72

118 ₆₇

119 "65

120 p ₉

121 ₇₀

122 ₆₃

123 ₇ 4

124 *. · ₆₃ '

125 · .72

126 68

127 69

128 76

129 73

130 74

131 67

no treatment · . 0

Test 4:

On tomato plants (species: Sarashina fukujü) grown in a greenhouse up to the seven-petalled stage, an aqueous solution of each of the compounds listed in Table V is applied by means of a small spray nozzle. On the second day after this spraying, a suspension of spores of Phytophthoro infestans is evenly sprayed onto the treated tomato plants to infect them. On the 10th day after this inoculation, five leaves per plant and seven small leaves per main leaf are examined to:

219 9 7 1 _ ₅₆ _

Counting disease spots (on a scale of O, 1, and 2). In this way, the control index is calculated. The 0, 1 and 2 scale is defined in Test 2 above. Each of the 18 compounds is applied in the form of an aqueous 30% by weight solution which has been diluted 1000 times with water. The results are shown in Table VI.

Table VI Test for control of the disease on tomato plants

Compound No. Control Index

68 82

69 76 72 82 78 81 82 77 85 70 87. 84

93 74

94 80 97 73

'77

76 "83 72 75 72 69

 "76

no treatment 0

In general, the salts of the invention may be used in their use as fungicides for controlling fungi on plants, which are usually plants (including seeds) which are to be considered as crops. The use is generally similar to the use of analogous known alkylenebisdithiocarbamates which have no N-organo substituent. Such known analogous compounds are, for example, Nabam, Zineb, Maneb, Manoozeb and Propineb. The salts according to the invention can be used for controlling mildew, for example in paints, or microorganisms, such as algae, or for controlling microorganisms which produce a mucus.

By the term "combat" is meant any method by which the presence or growth of the living organisms in question is adversely affected.

Of course, the salts may be used in conjunction with other beneficial biologically active materials such as insecticides, acaricides, herbicides, plant growth regulators, as well as other fungicides such as carbendazim and benoaryl. In general, other biologically active materials may be those listed in the aforementioned "Pesticide Manual" provided, of course, that these other materials are compatible with the salts of the present invention.

The salts according to the invention are usually used as preparations which contain 1 to 99 and preferably 5 to 95% by weight. one or more of the salts as main constituents, while the remainder of the preparation consists of (1) a liquid or solid carrier or diluent, each acceptable for agricultural use, (2) surfactants, such as dispersing or emulsifying agents, (3) stabilizing agents, d. H. Agents containing the chemical

(4) thickeners and (5) tackifiers and propellants for aerosol applications or contains these components. ·

Typical liquid carriers or diluents are water, organic liquids, such as alcohols, such as ethanol, ethers, esters, ketones, such as acetone or methyl ethyl ketone or methyl isobutyl ketone, hydrocarbon liquids, such as mineral oils (for example paraffins or kerosene), benzyl, xylene, toluene or cyclohexane.

Typical solid diluents or carriers are by-produced inorganic salts such as sodium sulfate or chloride, which are due to the preparation of the alkylene bisdithiocarbamates, clays, talc, kaolin, bentonite, diatomaceous earth, potassium carbonate, silica or alumina.

Typical surfactants are soaps, salts of long chain alkyl sulfates or sulfonates such as sodium lauryl sulfonate, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, alkylphenoxy polyethoxyoxyethanols, quaternary ammonium salts such as lauryl trimethyl ammonium chloride, and lignosulfonates such as sodium and / or calcium lignosulfonate.

Typical stabilizing agents are paraformaldehyde, urea, hexamethylenetetramine, o-tolylbiguanidine, diphenylguanidine, diaminotoluene, 1,8-3,6-diendomethylene-1,3,6,8-tetraazacyclodecane, N, N ¹ -dimethylolurea, N-methylurea, N, N ¹ -Dimethylharnstof f and 1, 3, 5-tris / (cyanomethyl) hexahydrotriazine.

Typical thickening agents are methylcellulose, starch, polyvinyl alcohol, polyvinyl acetate, as well as gums, such as gum arabic.

2 19 971 -59-

By "agriculturally acceptable carrier or diluent" is meant a substance which can be used to dissolve, disperse, diffuse, or otherwise dilute the active ingredient without impairing the efficacy of the active ingredient no permanent damage occurs to the application sites, such as the soil, the plant used and the crops.

These fungicidal preparations can be prepared in the form of ready-to-use dusts, aerosols, solutions, emulsions, or suspensions. Optionally, they may be formulated in the form of concentrated solutions, wettable powders, emulsifiable concentrates, flowable emulsion concentrates, dust concentrates, pastes or flowable liquid pesticides suitable for dilution with another liquid, usually water, or finely divided solids to obtain dilute Solutions, suspensions, emulsions or dusts are suitable, which are then used directly as a pesticidal agent. Further details about such formulations can be found in the following statements.

dust concentrates

Such concentrates usually contain 10 to 9 5 wt .-% and in particular 60 to 95 wt .-% of one or more of the salts according to the invention. They may be prepared by grinding at least one purified and dried salt of the invention with the addition of a stabilizing agent to obtain dust particles which typically have an average particle size below 4 microns. The drying can be carried out using a vacuum dryer. The grinding can be carried out using any conventional dry grinding apparatus, for example a ball mill or a

19 9 7 1

direction, like a sand mill, sometimes referred to as a bead mill. A typical dust concentrate formulation is as follows:

Wt .-%

Compound 6, Table I 93

Hexamethylenetetramine 3

Precipitated silica 3

The average particle size of the above formulation is 2.0 to 3.5 microns, with 95 wt% of the particles having a size of 1 to 10 microns.

Directly usable dusts

These formulations can be prepared in the manner described above and usually have an active ingredient concentration of 1 to 20 wt .-% on. A typical formulation is a dry blend of:

Wt .-%

Compound 5, Table I 5.5 containing 5 wt .-% hexamethylenetetramine

Kaolin 80

Talc '· 14.5

The average particle size of the preparation is 2 to 5 microns.

solutions

A typical concentrated solution is an aqueous solution containing from 5 to 20% by weight of the active ingredient and usually also a surfactant. Typical 5 to 20% solutions are as follows:

Wt .-%

water IV 94 7 79 0 Compound 72, Table 5 20 sodium lauryl sulfate O, 3 1,

Directly usable solutions are prepared by diluting the above two indicated solutions with water to establish a drug concentration of 1500 ppm.

Emulsifiable concentrates

These usually contain from 10 to 60% by weight of at least one water-insoluble compound according to the invention in an organic solvent which also contains an emulsifier. A typical formulation is the following:

Wt .-%

Xylene 69

Compound 54, Table IV, containing 25-5% by weight of hexamethylenetetramine

Octylphenoxypoly (ethyleneoxy) ethanol, containing 6 ethyleneoxy groups

emulsions

The emulsifiable concentrate described above is diluted with water to obtain an emulsion containing 1500 ppm of compound 54.

Wt .-% 40 4 90 2 6 4 6 5 ο, 1 51

2 19 9 7 1 - 62 -

Wettable powders

These formulations usually contain a dispersing agent and about 40 to 90% by weight of the active ingredient. Typical formulations are as follows:

Compound 12, Table I Hexamethylenetetramine Calcium lignosulfonate Sodium octyl sulfosuccinate Clay

The average particle size of the above formulations is between 2.0 and 3.5 microns, with 90 wt% of the particles having a size of 1 to 10 microns.

Diluted suspensions ready for use

The above-described wettable powder is formed into a paste and then dispersed in water to obtain a suspension containing 1500 ppm of Compound 12.

Water-dispersible pastes

These pastes usually contain water, a dispersant and 35 to 40 wt .-! of the active ingredient. A typical formulation is the following:

2 19 3 7 1

Wt .-%

Water 38

Compound 12, Table I 42

Sodium lignosulfonate 12

Sodium nonylnaphthalenesulfonate · 1

Sodium chloride 5

Hexamethylenetetramine 2

The ingredients in the above formulation are wet ground in a sand mill until the average particle size is about 3 microns, with 95 wt% of the particles having a size below 15 microns. The paste may be dispersed with water to adjust a ready-to-use suspension containing 1500 ppm of Compound 12.

Water-dispersible granules

These contain a dispersing agent and usually 50 to 85% by weight of the active ingredient. A typical granular formulation is prepared by molding the above-described composition into tablets having a thickness of 0.5 to 1 mm and a diameter of 5 mm. The granules are then dried in an oven until the water content is below 3% by weight. The granules prepared in this way are readily dispersible in water to give a suspension containing 1500 ppm of compound 12.

2 19 971 - 64 -

Flowable concentrated liquid suspensions

These are liquid, usually aqueous, suspensions containing, for example, from 30 to 40% by weight of the active ingredient. A typical formulation is the following:

Wt .-%

Water 47 Compound 12, Table I 35 Propylene glycol 10 Calcitonum sulfonate 3 Sodium chloride 3 xanthan gum (long chain polysaccharide obtained by fermentation of molasses) 0.5 Hexamethylenetetramine 1.5

A slurry of the above ingredients is sand-milled until the average particle size is between. 1.5 and 2.5 microns and not less than 99 wt .-% of the particles have a size below 10 microns. The concentrated suspension obtained can be diluted with water to obtain a dilute aqueous suspension containing 1500 ppm of Compound 12.

Dry mixtures

These are mixtures of water-soluble salts according to the present invention with metal salts, which undergo a double reaction in aqueous solution to form the preferred water-insoluble metal salts according to the present invention. A typical dry mix is prepared by mixing (a) 100 g of a mixture containing 93 g of Compound 72, Table IV, 4 g of hexamethylenetetramine and 3 g of sodium lignosulfonate with (b) such an amount of zinc sulfate in a dry mixer prepared in.

a 10 wt .-% excess to the stoichiometric amount required to form the compound 6 according to Table I in aqueous solution. A similar dry blend is made by using an equivalent amount of manganese (II) sulfate instead of the zinc sulfate.

The above-mentioned dry mixes can be used by the end user in such a way that they are filled with stirring in a tank containing water, wherein a dilute suspension of the zinc or. Manganese-N-substituted Äthylenbisdithiocarbamats having an active ingredient content of, for example 1500 ppm is obtained.

Concentrated mineral oil suspensions

These are suspensions in a mineral oil, usually containing 30 to 40 wt .-% of the active ingredient. A typical formulation is the following:

Wt .-%

White Oil 57

Compound 12, Table I Octylphenoxypoly (ethyleneoxy) ethanol, containing 5 Xthy- 8 lenoxygruppen

The above oil suspension may be mixed with water to form a ready-to-use emulsion containing 1500 ppm of the active ingredient.

Fungicidal mixtures

The above described, ·. 90% wettable powder formulation of compound 12 is mixed with an equal weight

2 19 971 - 66 -

amount of the fungicide known under the name benomyl. Another mixture is by replacing the benomyl. produced by an equal amount of the fungicide carbendazim.

Claims (10)

Inventive sprue h 1. A fungicidal composition, characterized in that it contains one or more Alkylenbisdithiocarbaminsäuresälze of the formula S S together with an agriculturally acceptable diluent or carrier, wherein in the formula the substituents have the following meanings: X is an alkylene group having 2 to 6 carbon atoms, Y and Y ¹ , which may be the same or different, respectively (1) a hydrogen atom, except that both Y and Y ¹ are not hydrogen, 19 971 - (2) (C ₆ -C ₂₀ ) -alkyl, ROH (3) a group of the formula (CH 1 -C wherein R is hydrogen or (C - Cg) alkyl, R ₁ is hydrogen, (C ₁ -C _g.) alkyl, (C ₂ -CG) alkenyl, (C ^ -CG) -alkynyl, phenyl or phenyl is substituted by up to three identical or different substituents selected from (C 1 -C ₄ ) -alkyl and halogen and m is O, 1 or 2, (4) a group of the formula wherein R _{2 is} hydrogen, halogen or (C 1 -C 8) -alkyl, η is 1 or 2 and ρ represents 0, 1, 2 or 3, (5) a group of formula - (CH-J-CH-COOR ₄ / wherein R is as defined above, R ₃ is hydrogen, hydroxy or (C "Cg) alkyl, while R ₄ (C ₁ -C _ß.) alkyl, (Cj-Cg) alkylamino, (C ₁ - C 9) alkyl, di (C ₁ -C 9) alkylamino (C -Cg) alkyl, (C ₂ -C 9) alkenyl, (C ₃ -Cg) alkynyl, hydroxy (C ₁ -Cg) alkyl or a salt-forming group or a salt-forming atom and q is 0 or 1, (6) a group of the formula wherein R, R ^ and q have the meanings given above,. / 7) a group of formula ^ wherein R, R ₃ and q have the meanings given above, 2 1997 1 (8) a salt of a thioacid group of the formula - (CHR) -CHR_-O-C-S-H, wherein R, R and m are the have the meanings given above, (9) a group of the formula -CHR-CHR ₂ SH- or a metal salt thereof, wherein R and R _{2 have} the meanings given above, or a group -CHF-> - ^ - NH »or a group 2 '2 2 - (CH ₅ - ^ w -NH-fCH ₉ 4 NH_, with the proviso that only one of the substituents Y and Y ¹ may be such an amino group while the other is another organic substituent, (10) a group of formula (-CHRf _1n Cl i \ ^ / _/ wherein R, R ₂ and m have the meanings given above, or (11) a group of the formula ^ -fCHRi ^ -CH (OH) CCl ₃ / in which R and m have the meanings given above. 2. Composition according to item 1, characterized in that in the formula X is (C ₂ -C 4) -alkylene, preferably ethylene or 1,2-propylene,
Y is hydrogen,
Y ^{1 has the} following meanings: (D (C ₈ -C ₁₈ ) alkyl, (2) -JCH) _1n -CHCH ₂ OR ₁ , in which R is hydrogen or (C ₁ -C ₃ ) -alkyl, R _{1 is} hydrogen, (C ₁ -C _g ) -alkyl, (C ₃ -Cg) - Alkenyl, phenyl or phenyl substituted with up to three identical or different substituents consisting of methyl and chlorine, 2 1997 1 -70- (3) - (- CH) -r (0 / / ^{vol:) ei R} _{2 is} hydrogen, chlorine or methyl, I ? 3 (4) -fCH-) CH'COOR. ', where R is the above-mentioned R 1 is hydrogen, hydroxy or (C ₁ -C ₃ ) -alkyl, and R _{4 is} (C ₁ -C ₂ ) -alkyl, di (C ₁ -C ₃ ) -alkylamino (C ₁ -C ₃ ) -alkyl, (C ₃ -Cg) -alkenyl, hydroxy (C ₁ -C ₃ ) -alkyl or a salt-forming group or a salt-forming atom, (5) - £ cH-j_-CH-c = N / where R and R _{3 have} the meanings given above, (6) a (C ₁ -Co) mercaptoalkyl group, (7) a salt of a thioacid group or (8) the group -CHR ^ HOH "" 3. Composition according to item 1 or 2, characterized in that the active ingredient is a salt of a metal having a valence of more than 1. 4. Composition according to item 3, characterized in that the active ingredient is a salt of Zn, Mn, Cu, Fe, Ni, Sn, Co, Ca or Mg. 5. Composition according to items 1 to 4, characterized in that- the active ingredient is selected from a compound of formula γ yi N X N ^ M "-S-C C-S l Il 2 19 9 7 1 - 71 - wherein X, Y and Y ^{1 have} the meanings given in claim 1 or 2 and M "and M ¹ " are an alkali metal, an ammonium mono- or di- (C ₁ -C ₄ ) ammonium group. ·. 6. Composition according to one of the items 1 to 4, characterized in that in the formula Y is a hydrogen atom and Y ^{1 is} -CH ₂ CH (OH) CH ₂ OR ₁ , where R is hydrogen, CH ", ^C 2 ^H 5 ' ^C 3 ^H 7' ^C 9 ^H 19 ' ^Pr ° P ^en yl / phenyl or tolyl. 7. Composition according to one of the items 1 to 4, characterized in that in the formula Y is hydrogen and Y '. f. , P - (CH) CH-COOR ₄ wherein R is hydrogen or methyl, R is hydrogen, methyl or hydroxy, and R _{4 is} ^CH 2, ^C 2 ^H 5, C 1 H ₇ , C ₄ H, C, H, _C , dimethylaminoethyl, hydroxyethyl or Represents propyl. 8. Composition according to one of the items 1 to 4, characterized gekenn ~ characterized in that in the formula Y is hydrogen and Y ¹ C ₂ H ₄ SH, C ₃ H ₆ SH, C ₂ H ₄ CN, C ₈ H ₁₇ , C ₁₀ H ₂₁ , C ₁₂ H ₂₅ , ^e 14 ^H 29 ' ^C 16 ^H 33' ^C 18 ^H 37 ^{or benz} yl, where the phenyl group is substituted by chlorine, C., H ₅₁ - or up to three methyl groups. 9. Composition according to one of the items 1 to 4, characterized in that Y is hydrogen and Y ¹ phenyl + + hydroxyethyl, or the active ingredient is a Mn, Zn or Fe salt of a thioacid group of the formula -CH ₅ CHR ^ OC-SH, where R, is hydrogen or methyl. S 2 19,971 10. A method for controlling fungal attack on plants using a chemical fungicide, characterized in that .. the fungicide used consists of at least one salt according to one of claims 1 to 9. Here are some drawings