DE1274573B - Process for the preparation of dithiocarbamic acid esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4507IW PATENT OFFICE

EDITORIAL

Int. Cl .:

German class:

Number:
File number:
Registration date:
Display day:

C07c

AOIn

12 ο -17/02
451-9 / 12

P 12 74 573.2-42 (F 47991)

December 23, 1965

August 8, 1968

The present invention relates to a process for the preparation of new dithiocarbamic acid esters, which are fungitoxic.

It has already become known that isocyanide dichlorides are used can react with the salts of dithiocarbamic acids, with splitting off the corresponding thiuram monosulfides are the isothiocyanates corresponding to the isocyanide dichlorides form (cf. Angewandte Chemie, 74, pp. 861 to 866 [1962]).

It has now been found that dithiocarbamic acid esters the general formula

IO

Process for the production of
Dithiocarbamic acid esters

Applicant:

Paint factories Bayer Aktiengesellschaft,

5090 Leverkusen

C-N = C

—C — N

Il ^s

(I)

/ 2

in which R and R 'stand for hydrogen, alkyl, alkenyl and cycloalkyl is obtained when trichloromethyl isocyanide dichloride the formula

Cl ₃ CN = CCl ₂ (II)

with dithiocarbamic acids of the general formula Named inventor:

Dr. Engelbert Kühle, 5070 Bergisch Gladbach;
Dr. Hans Holtschmidt, 5090 Leverkusen;
Dr. Ferdinand Grewe, 5673 Burscheid;
Dr. Helmut Kaspers, 5090 Leverkusen

MeSC - N

in which R and R 'have the meaning given above and Me for an alkali metal, ammonium or the ammonium residue

H ₂ N

stands, where R and R 'have the meaning given above.

Cl ₃ C -N = CCl ₂ + 5 NaSC-N (CH ₃ ) ₂

(III) The dithiocarbamic acid esters of the formula (I)

have strong fungitoxic properties.

It can be described as extremely surprising that in the implementation according to the invention Isothiocyanates are not formed in accordance with the state of the art, but, under Elimination of sulfur, dithiocarbamic acid esters containing thiourea groups.

Furthermore, it is to be described as extremely surprising * that the inventively obtainable Dithiocarbamic acid esters have a stronger fungicidal effect than that from the prior art known tetramethylthiuram disulfide.

The reaction according to the invention can be represented by the following equation:

"(CH ₃ J ₂ NCS-" CN =

CN (CH ₃ ),

+ 2 S + 5 NaCl

809 589/475

3. 4th

The trichloromethyl pastes and granules required for the implementation. These are known in

isocyanide dichloride is already prepared from the literature loading manner, z. B. by mixing the active

knows (e.g. from the German Auslegeschrift substances with extenders, i.e. liquid solvents

1 222 917). agents and / or solid carriers, optionally

The dithiocarbamic acid salts required are 5 using surface-active agents, precisely characterized by the general formula (III), ie emulsifiers and / or dispersants. I'm well-known and well-known. In this formula, if water is used as an extender, R and R 'are preferably hydrogen; B. organic solvents as with 1 to 4 carbon atoms, alkenyl with 2 to auxiliary solvents can be used.
4 carbon atoms and cycloalkyl with 5 to ₁₀ The active ingredients according to the invention can be in the 6 carbon atoms. Me preferably stands for application forms in a mixture with other sodium, potassium, ammonium and the above-known active ingredients,
given amine radical, where R and R 'the preferred The use forms generally contain wise meaning. between 0.1 and 95 percent by weight active ingredient,

Examples include: the potassium salt and _15, preferably between 0.5 and 90.

the sodium salt of N-methyl, Ν, Ν-dimethyl, The active ingredients can be used as such, in the form of their

N, N-dibutyl, Ν, Ν-diallyl and N-methyl application forms, such as ready-to-use solutions,

N-cyclohexyl-dithiocarbamic acids. Emulsions, suspensions, powders, pastes and grades

As solvents come nulate for the implementation, are used. The application all inert organic solvents into consideration, 20 takes place in the usual way by spraying, spraying

z. B. hydrocarbons such as benzene, chlorinated carbon spray, atomizing, dusting, pouring or spraying

sprinkle hydrogen, such as chlorobenzene, ether, such as dioxane.

and tetrahydrofuran, ketones such as acetone. The active ingredient content of the active ingredient to be used can be determined However, even in one of two layers, substance preparations can vary widely, depending on existing solvents work, one being 25 depending on the purpose pursued. In general used a layer of water. if it is between 0.001 and 5.0 percent by weight,

The reaction temperatures can be preferably between 0.01 and 0.5.
can be varied over a wide temperature range. In general, the reaction is preferably carried out between 0 and 100 ⁰ C, between 20 and 6O ⁰ C. ₃₀ Comparative Experiment A

When carrying out the implementation, one sets

expediently equimolar amounts of Aus Fusicladium test (apple scab) / curative
raw materials. Preferably 1 mole is used

Trichloromethyl isocyanide dichloride to 5 to 5.5 moles of solvent: 4.7 parts by weight of acetone

of the dithiocarbamic acid salt. The work-up 35 emulsifier: 0.3 part by weight of alkyl aryl

the reaction mixture is carried out in the usual way. polyglycol ether

An embodiment of the invention

The method consists in that you first of all from the water: 95.0 parts by weight
corresponding amine, carbon disulfide and the

Lye produces the dithiocarbamate solution and in the 40 one mixes the for the desired active ingredient

reaction mixture obtained in this way then immediately concentrate the necessary active substances in the spray liquid

Trichloromethyl isocyanide dichloride is added dropwise. The amount of iso-

lation of the dithiocarbamic acid salt is not a solvent and dilutes the concentrate with the

necessary. specified amount of water, which the said

The dithiocarbamic acid esters have a strong 45 additives content.

fungitoxic effect. Due to their small young apple seedlings, which grow in the 4- to 6-leaf

Warm-blooded toxicity they are located to combat with an aqueous stage

suitable for unwanted fungal growth. Your good conidia suspension of the apple scab pathogen (Fusi-

Tolerance for higher plants allows ins- cladium dendriticum Fuck.) Inoculated and 18 hours

especially their use as pesticides 50 den long in a humid chamber at 18 to 20 ⁰ C

against fungal plant diseases. and 100% relative humidity. the

So the active ingredients for combating plants can then come into the greenhouse,

parasitic fungi on above-ground parts of plants They dry off.

be used, such as scab agents, e.g. B. After a reasonable dwell time, the Fusicladium species, and powdery mildew, ζ. B. the Podo- 55 plants with the spray liquid, which in the above sphaera, Sphaerotheca and Microsphaera species. The "indicated way" was prepared up to the drip active ingredients have not only splashed a protective fungicidal wet. Then come the plants Effect, but also a curative one. again in the greenhouse.

In comparison to known fungicidal salts, the infestation of the

Dithiocarbamic acids and known fungicidal apple seedlings in percent of the untreated, however

Thiurams have the active ingredients according to the invention also determined inoculated control plants,

when combating scab pathogens, a significant 0% means no infestation, 100% means that

borrowed a stronger effect on powdery mildew fungi and the infestation is just as high as in the control

also show a stronger curative effect plants,

against infestation with non-powdery mildew fungi. 65 active ingredients, active ingredient concentrations, the

The active ingredients according to the invention can be used in the waiting time between inoculation and spraying as well

customary application forms are converted, the results are from Table I below

like solutions. Emulsions, suspensions. Powder. emerge:

Table I.
Fusicladium test / curative

Active ingredient

Dwell time
in hours

Infection in% of the infestation of the untreated

Control at one
Active ingredient concentration (in%) ^of

0.1

CH
^ n ₃

/ CH,

N — C — S — S — C — N

48

90

(known from US Pat. No. 1 972 961)

- (CH ₃ J ₂ NC-Sl

CN = CT-C-N (CH ₃ J ₂ "48

19th

Tris-idimethyldithiocarbanioylI-methylimido-mesoxalic acid-bis-dimethylthioamide

Comparative experiment B
Fusicladium test (apple scab) / Protective

Solvent: 4.7 parts by weight acetone
Emulsifier: 0.3 part by weight of alkyl aryl

polyglycol ether
Water: 95.0 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dilute the concentrate with the specified amount of water, which contains the additives mentioned.

Young apple seedlings, which are in the 4 to 6 leaf stage, are sprayed with the spray liquid until they are dripping wet. The plants remain for 24 hours at 20 ⁰ C and a relative atmospheric humidity of 70% in the greenhouse. Subsequently, they are (Fusicladium dendriticum Fuck.) With an aqueous conidia suspension of the apple scab, and incubated in a humid chamber at 18 to 2O ⁰ C and 100% relative humidity for 18 hours. The plants are then returned to the greenhouse for 14 days.

15 days after the inoculation, the infection of the seedlings is determined as a percentage of the untreated, but also inoculated control plants . 0% means no infestation, 100% means that the infestation is just as high as in the case of the control plants.

Active ingredients, active ingredient concentrations and results are shown in Table II below:

Table II
Fusicladium test / protective

Active ingredient C-N = C 3 r-CN (C ₂ Hs) ₂ I.
Il __ __ f— \ -WT S — i
v_- IN v_- 3 "CN (CH ₃ J ₂ ^ 2 Infection in% of the infestation of the untreated
Control at one
Active ingredient concentration (in%) of _ s J ₂ S. 0.025 CH ₃ S ^ / CH ₃ Tris-idiäthyldithiocarbamoylJ-methylimido-mesoxal-
acid-bis-diethylthioamide Tris-idimethyldithiocarbamoylJ-methylimido-mesoxal-
acid-bis-dimethylthioamide Ν —C —S —S —C —N 21 (known from US Pat. No. 1 972 961) 0 (CH ₃ J ₂ N-C-S "(C ₂ Hs) ₂ NCSI Il
S. Il
S. 0

Comparative experiment C Podosphaera test (apple powdery mildew) / Protective

Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkyl-aryl

polyglycol ether water: 95.0 parts by weight

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dilute the concentrate with the specified amount of water, which contains the additives mentioned.

Young apple seedlings that are in the 4- to 6-leaf stage are sprayed with the spray liquid are up to dripping wet. The plants remain at 20 ° C. and relative atmospheric humidity for 24 hours of 70% in the greenhouse. They are then dusted with conidia of the apple powdery mildew (Podosphaera leucotricha Salm.) Inoculated and placed in a greenhouse with a temperature from 21 to 23 ° C and a relative humidity of about 70%. 10 days after the inoculation, the Seedlings determined as a percentage of the untreated, but also inoculated control plants.

0% means no infestation, 100% means that the infestation is just as high as in the case of the control plants.

Active ingredients, active ingredient concentrations and results are shown in Table III below:

Table III Podosphaera Test / Protective

Active ingredient infestation in% of the infestation of the untreated

Control at an active ingredient concentration (in%) of

0.1 0.05

CH ₃

N — C — S — S — C —N

(known from US patent specification 1 972 961) "(CH ₃ ) ₂ N - C - S- ¹ IC- N = C p - C - N (CHj) ₂ "

Tris-f-dimethyldithiocarbamoy ^ -methylimido-mesoxalic acid-bis-dimethylthioamide

56

Rqh ^ n-c-s-

C-N = C

Tris-idiethyldithiocarbamoyrj-methylimido-mesoxalic acid-bis-diethylthioamide

B e i s ρ i e 1 1 tris-idimethyldithiocarbamoylJ-methylimido-mesoxalic acid-bis-dimethylthioamide:

N = C -CN (CH ₃ );

a) 45 g of dry sodium salt of dimethyldithiocarbamic acid are dissolved in 250 ml of acetone and 13.5 g of trichloromethyl isocyanide dichloride are added dropwise at room temperature. The temperature rises to 54 ^° C. during this process. The mixture is stirred for a while, the precipitated common salt is filtered off with suction and the filtrate is concentrated. The residue obtained is 30 g of crystals with a melting point of 60 ° to 67 ° C.

Analysis:

Calculated ... C 35.5, H 5.23, N 14.63, S 44.6%; Found ... C 34.29, H 5.4, N 14.36 ', S 43.9%.

b) In 400 ml of a 42% aqueous solution of technical sodium dimethyl dithiocarbamatlösung is added dropwise at 2O ⁰ C the solution of 43 g Trichlormethylisocyaniddichlorid in 150 ml of benzene and the temperature is allowed to rise to 40 ° C. The layers are separated, the benzene solution is concentrated after filtering off and 73 g of the abovementioned compound are obtained.

Example 2

Tris- (diethyldithiocarbamoyl) -methylimidomesoxalic acid-bis-diethylthioamide:

CN = C - CN (C ₂ H ₅ ) ₂ ~

73 g of diethylamine are dissolved in 500 ml of benzene and added dropwise at 10 to 40 ° C. while cooling mixed with 38 g carbon disulfide. After brief stirring, 20 g are added dropwise at 20 to 40 ° C Add trichloromethyl isocyanide dichloride, stir for a while and shake out with water. After this Drying and concentration of the filtered off benzene solution 57 g of a viscous oil remain.

Analysis:

Calculated C 45.3. H 7.0. N 11.8. S 35.8 ",,:

found C 45.7, H 7.5. N 12.3. S 35.2 »,,.

Claims (1)

Claim: Process for the preparation of dithiocarbamic acid esters of the general formula N — C — S— R " C-N = C / 3 -C-N "R ' (D ZO in which R and R 'stand for hydrogen, alkyl, alkenyl and cycloalkyl, thereby characterized in that 1 mole of tri- 10 chloromethyl isocyanide dichloride of the form! CLiC-N = CCl ₂ (II) with 5 to 5.5 mol of dithiocarbamic acid salts the general formula MeSC - N (III) in which R and R 'are as defined above and Me is an alkali metal. Ammonium or the ammonium residue H, N R ' is, at temperatures between 0 and 100 ° C., preferably between 20 and 60 ° C., is reacted. Considered publications:
Houben - We y 1, Methods of Organic Chemistry, Vol. 9. 1955, p. 838;
Angewandte Chemie, Vol. 74, 1962. pp. 861 to 866. S09 589/475 7.62 © Bundesdruckerei Berlin