DE2458658A1 - ORGANOSULFUR DERIVATIVES OF TETRACHLORDICYANOBENZENE, METHOD FOR THEIR PRODUCTION AND USE - Google Patents

Description

Diamond Shamrock Corporation, 1100 Superior Avenue, Cleveland, Ohio 44114 / USA

Organosulfur derivatives of tetrachlorodicyanobenzenes, Process for their manufacture and their use

The invention relates to organic compounds useful as pesticides, and in particular to certain ones Organosulfur derivatives of tetrachlorodicyanobenzenes with fungicidal and bactericidal properties.

The compound 2,4,5-trichloro-6- (methylthio) benzene-1,3-dicarbonitrile is already in J.C.S., Perkin Trans. II, 2104 (1972). The crystal structure

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this compound, also called 4-methylthio-2,5,6-trichloroisophthalonitrile can be designated is in Acta. Cryst., Section B, 28 (Pt. 11), 3430 to 3434 (1972). However, there is no evidence of biological activities in these references or · other uses of this connection.

The present invention now relates to organosulfur derivatives of tetrachlorodicyanobenzenes of the general formula:

GN ■

S (O) _n R (X) _n ,

wherein η is 0, 1 or 2, R is a C ^^ - alkylene, ^C 2-12 alkenylene ~, C ₂ _-j2 "" ^A - ^l - y ^{l kin} - ^en "means" arylene or aralkylene , X represents a hydrogen atom, a halogen atom, or an alkoxy, acyl, acyloxy, alkylthio, alkylsulfonyl, cyano, thiocyanato, alkylsulfonyloxy or amino group and m is 1 to 3, with the proviso that - when η is 0 - the -CN groups are in the 1- and 3-positions and that - when X is hydrogen, R is not a methylene radical.

Compounds according to the invention in which η is 0 in the above formula are biologically active and they are also as intermediates for the preparation of organosulfinyl and organosulfonyl trichlorodicyanobenzene compounds suitable according to the invention. The known compound 4-methylthio-

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2,5,6-trichloroisophthalonitrile has been found to be active as a pesticide proven.

The dicyanobenzene compounds according to the invention can also more specific than alkylthio, alkylsulfinyl or Alkylsulfonyl derivatives either of tetrachlorophthalonitrile, Tetrachloroisophthalonitrile or tetrachloroterephthalonitrile are referred to, which in individual cases thereof depends on whether the cyano (CN) substituents of the benzene ring are ortho, meta or para to one another are located. Accordingly, this more specific terminology is intended to be used generally hereinafter to refer to To designate individual compounds according to the invention. However Naturally, these compounds can still broadly be used as organosulfur derivatives of tetrachlorodicyanobenzenes are designated.

Because of their valuable properties and the fact that they are relatively easy to manufacture, certain compounds currently preferred according to the invention. These compounds correspond to the formula:

CN

S (O) _n R

where η is 0, 1 or 2 and R is a methyl or ethyl radical means, with the proviso that when η is 0, and the -CN groups are in the 1- "and 3-positions, R is not methyl.

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As special organosulfonyltrichlorodicyanobenzenes, i.e. compounds of the structure:

SO ₂ R

where R is a methyl or ethyl group, the following compounds can be mentioned:

4-methylsulfonyl-2,5, β-trichloroisophthalonitrile ^ 3- (and / or 4-) methylsulfonyltrichlorophthalonitrile, 2-Ä.thylsulfonyl-3,5,6-trichloroterephthalonitrile, 4-ethylsulfonyl-2,5,6-trichloroisophthalonitrile, 3- (and / or 4-) ethylsulfonyltrichlorophthalonitrile, 2-methylsulfonyl-3,5,6-trichloroterephthalonitrile.

Special organosulfinyltrichlorodicyanobenzenes with the structure:

SOR

in which R denotes a methyl or ethyl group are, for example, the following compounds:

4-methylsulfinyl-2,5,6-trichloroisophthalonitrile, 3- (and / or 4-) methylsulfinyltrichlorophthalonitrile,

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2-ethyl sulfynyl-3,5,6 - trichloro-ephthalonitril, 4-ethylsulfinyl-2,5,6-trichloroisophthalonitrile, 3- (and / or 4-) ethylsulfinyltrichlorophthalonitrile, 2-methylsulfynyl-3,5, δ-trichloroterephthalonitrile.

As special new organothiotrichlorodicyanobenzenes, i.e. compounds of the structure: ■ ".

"SR

wherein R is methyl or ethyl, with the exception that when the -CN groups are in the 1- and 3-positions, R is not Is methyl, the following compounds can be named, for example:

4-ethylthio-2,5,6-trichloroisophthalonitrile, 3- (and / or 4-) ethylthiotrichlorophthalonitrile, 2-methylthio-3,5,6-trichloroterephthalonitrile, 2-ethylthio-3,5,6-trichloroterephthalonitrile, 3- (and / or 4-) methylthiotrichlorophthalonitrile.

The organothiotrichlorodicyanobenzene intermediates, in turn, are prepared by adding approximately equimolar Proportions of a corresponding mercaptotrichlorodicyanobenzene with an alkylating agent, e.g. a dialkyl sulfate, in an aqueous alkaline Medium with one another. The dialkyl sulfate is transferred to the dicyanobenzene starting material in small amounts given a period of several minutes, as this change

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Settlement is highly exothermic in nature and difficult to control is. After the addition of the alkylating agent, the reaction is completed by bringing the reaction mixture to an elevated temperature, e.g. on a steam bath, is heated over a period of 1 to 4 hours. The reaction mixture is then cooled and filtered. The crude isolated solids are washed with water. The product is made through selective extraction of the crude solids and recrystallization from suitable solvents.

The organothiotrichlorodicyanobenzene compounds are all colored solid materials. They are normally less than 5% soluble in water, but more than 5% soluble in common organic solvents.

The organosulfinyl and organosulfonyltrichlorodicyanobenzene compounds of the invention are suitably prepared from the corresponding aforementioned organothiotrichlorodicyanobenzenes, prepared in the manner described above, by reacting the intermediate with a peroxy compound in an acidic medium, such as a peracid, e.g. peracetic acid, or with hydroperoxide in an acidic medium , such as acetic acid. In general, about 0.1 to 10 moles of the peroxy compound can be reacted with each mole of the sulfide compound. Within this range, the peroxy compound and the corresponding organothiotrichlorodicyanobenzene are preferably reacted in approximately equimolar proportions so that optimum yields of the organosulfinyl derivative are ensured. A molar ratio of about 2.0 to 3.5 peroxy compound per mole of organothiotrichlorodicyanobenzene is used to fully

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To ensure proper oxidation of the sulfide to the corresponding organosulfonyl derivative. The reaction is typically carried out at temperatures up to about 50 ⁰ C, preferably from about 30 to 50 ⁰ C, extend generally from about 5, when producing a Organosulfinylderivat. Temperatures of 50 to 110 ⁰ C, optimally from 80 to 105 ° C are applied when manufacturing a Organosulfonylderivat. Under these conditions, the reaction times are generally 2 to 5 hours.

After the reaction has ended, the solid product is obtained by first placing the reaction mixture in an ice-water bath and then adding the solid that precipitates. isolated. The crude product is typically washed well with hot alkanol, e.g., isopropanol, and then finished dried.

The new compounds according to the invention and the known 4-methylthio-2,5,6-trichloroisophthalonitrile are effective pesticidal compounds. Although they are undiluted Form can be applied to the plant or other material to be protected, it is common expedient to use these compounds in admixture with a solid or liquid inert pesticidal auxiliary. For example, the compounds can be applied to plants for pesticidal purposes by using the Plants sprayed with aqueous dispersions or with dispersions in organic solvents of the compounds. The selection of the appropriate solvent is determined by factors such as concentration the active ingredient, the volatility required in the solvent, the cost of the solvent and the nature of the material being treated.

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Solvents used as carriers for these compounds can be used are e.g. hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, heating oil, Hydrocarbons and naphtha compounds, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, are chlorinated Hydrocarbons such as trichlorethylene, perchlorethylene, Esters such as ethyl acetate, amyl acetate and butyl acetate, monoalkyl ethers of ethylene and diethylene glycols, e.g. monomethyl and monoalkyl ethers, the monoethyl ether of propylene glycol, and alcohols such as ethanol, isopropanol, Pentanols and the like.

These compounds can be applied to the plants and other materials along with inert solid auxiliaries or carriers, e.g., talc, attapulgite, chalk, diatomaceous earth, kaolinite, montmorillonite, pyrophyllite and other silicates, silica, lime, calcium carbonate, certain organic carriers such as walnut shell flour, wood flour, ground corn cubes and the like.

It is often useful to use a wetting agent (a surface-active Agent) to be used in pesticidal agents. When formulating solid or liquid agents anionic, non-ionic or cationic wetting agents can be used. Typical wetting agents are e.g. alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, Alkylamide sulfonates, alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols, ethylene oxide addition products of these esters, and ethylene oxide addition products of long chain mercaptans and the like.

Formulations are preferably used for dusting, in which the active ingredient in amounts of 5 to 50%,

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based on the total weight. However, concentrations outside this range are suitable and are contemplated herein means into consideration that 1 to 99 wt -.% Contain the active ingredient and the balance being carriers and / or any desired additives or auxiliaries.

For spraying, the active ingredient can be dissolved in liquid carriers such as water or other suitable liquids or disperse. The active ingredient can be in the form of a solution, suspension, dispersion or emulsion in be added to aqueous or non-aqueous medium. Appropriately, 0.5 to 1.0% by weight of wetting agents are in the liquid funds available.

Any desired amount of the wetting agent can be used as an aid can be used, e.g. up to 250% by weight of the active ingredient, If the wetting agent is only used to To impart wetting properties to a spray solution, as little as 0.05% by weight or less of the wetting agent is sufficient. Larger amounts of the wetting agent are more likely due to the biological behavior of the wetting agent used instead of its wetting properties. These considerations are particularly important when dealing with Plants important. The active ingredient in liquid formulations can often not be more than 30% by weight of the total mixture and it can be 10 wt% or even as little as 0.01 wt%.

The terms "pesticide" and "pesticide" used herein are intended to refer to the killing and / or the Relate control of fungi, bacteria and other microorganisms. Thus, through these expressions

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bactericidal and fungicidal uses.

The invention is illustrated in the examples. With everyone product described herein, the IR spectrum is consistent with the assigned structure. In the Examples are all details relating to the percentages, proportions and amounts, unless otherwise is given, based on weight.

Examples 1 to 6

Preparation of 4-methylthio-2,5,6-trichloroisophthalonitrile:

To a stirred slurry of 25.8 g (0.098 mol) 4-mercapto-2,5,6-trichloroisophthalonitrile in 50 ml water containing 4.4 g (0.11 mol) sodium hydroxide are slowly added 12.6 g 0.1 mol) dimethyl sulfate was added. The temperature of the reaction mixture rises to about 7O ⁰ C. The mixture is then ^{heated to 90 to 100 °} C. for 1 hour, cooled and filtered. The crude product is isolated as a slightly tan solid. The crude product is washed with water, dried and recrystallized from a benzene / petroleum ether mixture, whereby 13.6 g (yield 50%) of a yellow solid are obtained. This product, which ^{melts at 157 to 159 °} C., is identified as 4-methylthio-2,5,6-trichloroisophthalonitrile.

Table I gives the characteristics of this known compound as well as the new one produced by this procedure Alkylthiotrichlordicyanobenzenes again, whereby as alkylating agent either dimethyl sulfate or diethyl sulfate was used. The reaction temperature extends

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typically from 50 to 80 ^° C. The table shows the reaction time, the yield in percent and the melting point of the product ( ⁰ C) and the values of the elemental analysis as% C, H and N '. ·

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Table I.

example

Compound reaction, efficacy, melting time, te, % point, std " ⁰ C

Analysis Calculated, % Found, %

4-methylthio-2,5,6-trichloroisophthalonitrile

4-ethylthio-2,5,6-trichloroisophthalonitrile

2-methylthio-3,5,6-trichloroterephthalonitrile

3- (and / or 4-) methylthiotrichlorophthalonitrile

3- (and / or 4-) ethylthiotrichlorophthalonitrile

2-ethylthio-3,5,6-trichloroterephthalonitrile

50

47

51

66

6J>

90

157-9

151-2

153-5

116-8

9β-8

165-8

a = yield of the crude product

C.
H
N 38.9
1.1
10.1 C.
H
N 39.35
1.2
9.95 ro C.
H
N 41.2
1.7
9.6 C.
H
N 41.4
1.8
9.6 cn
QO C.
Ή
N 38.9
1.1
10.1 C.
H
N 39.7
1.3
10.2 ^ j
cn
OO C.
H
N 38.9
1.1
10.1 C.
K
N 39.1
1.2
10.0 C.
H
N 41.4
1.7
9.6 C.
H
N .41.2
1.8
10.1 C.
H
N 41.2
1.7
9.6 C.
H
N 41.3
1.9
9.5

Examples 7 to 12

Production of 4-ethylsulfonyl-2,5,6-trichloroisophthalonitrile:

A slurry is prepared from 15.5 g (0.053 mol) of 4-ethylthio-2,5,6-trichloroisophthalonitrile (product of Example 2) in 100 ml of glacial acetic acid. 22.7 g (0.2 mol) are added 30% aqueous hydroperoxide to this slurry and the resulting mixture is heated for 2.5 hours at 105 to 108 ⁰ C. After cooling, the reaction mixture is poured onto ice and water. The precipitate formed is filtered off. It is then slurried in methanol, filtered again, and air dried to give 13.8 g of a light yellow solid (80% yield). This material melts at 237 to 238 ⁰ C and is identified-ethylsulfonyl-2,5,6-trichlorisophthalonitril 4 by elemental analysis as.

Table II shows the characteristic data for this compound and for other organosulfonyltrichlorodicyanobenzenes according to the invention, which were obtained by the same procedure using the corresponding organothiotrichlorodicyanobenzene intermediates (products of Examples 1 and 3 to 6). The table also contains the reaction temperature and time for each reaction, the percent yield and melting point (C) for each product, and the values of the elemental analysis as % C, H and N.

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Table II

Example connection game

Reaction Reaction Melting Analysis Temperature, time, te, % point, calculated,% found, % ⁰ C std ° C

O CO OO

10

4-ethylsulfonyl-2,5,6-105 -8

trichloroisophthalo-

nitrile

4-methylsulfonyl-2,5,6-

trichloroisophthalo-

nitrile

2-methylsulfonyl-3,5-6-105-8

trichloroterephthalo-

nitrile

2-ethylsulfonyl-3,5,6-

trichloroterephthalo-

nitrile

100

11-3 (and / or 4-) methyl-105-8 sulfonyl trichlorophthalonitrile

3- (and / or 4-) ethyl- I ₁₀₀ sulfonyltrichlorophthalonitrile

80 91 76 64

62

237-8 269-70 253-5 221-2 159-61 166-8

a = yield of the crude product

C.
H
N • 37.1
1.6 -
8.7 C.
H
N 37.4
1.6
9.0 cn C.
H
N 34.9.
1.0
9.1 C.
H
N 35.3
1.1
9.5 CD
cn
OO C.
H
N 34.9
1.0
9.1 C.
H
N 35.2
1.1
9.7 C.
H
N 37.1
1.6
8.7 C.
H
N 37.7 «
9-Ό " C.
H
N 34.9
1.0
9.1 C.
H
N 35.1
1.1
9.2 C.
H
N J ι · -L
1.6
8.7 " C.
H
N 37.2
1.5
9.0

Examples 13 to 16

Production of 3- (and / or 4-) ethylsulfinyltrichlorophthalonitrile:

A stirred mixture of 19.2 g (0.066 mol) 3- (and / or 4-) ethylthiotrichlorophthalonitrile (product of Example 5), 12.5 g (0.066 mol) 40% peracetic acid and 110 ml acetic acid is heated to 40 for 3 hours heated to 47 ° C. The cooled reaction mixture is treated with 125 ml of water. The resulting solids are filtered off and dried, yielding 20.4 g of a product (yield 100%) can be obtained, or the by IR and NMR spectra and by elemental analysis% C, H and N as a reference 3- (and / 4-) ethylsulfinyltrichlorophthalonitrile is identified.

In Table III are the characteristics for this compound and for other representative organosulfinyltrichlorodicyanobenzene compounds compiled according to the invention, which by the same procedure using corresponding organothiotrichlorodicyanobenzene intermediates (Products of Examples 1, 3 and 6) have been produced.

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Table III

Example connection

Yield, %

Melting

analysis

point, C Calculated,% Found, %

13 3- (and / or 4-) ethylsulfinyltrichlorophthalonitrile

14 4-Mettiylsulfinyl-2,5,6-trichloroisophthalonitrile

15 2-methylsulfinyl-3,5,6-trichloroterephthalonitrile

16 2-Ethylsulfinyl-3,5,6-trichloroterephthalonitrile

100

165-6

226-31

223-4

167-70

H
N

H
N

H
N

H
N

39.0 1.6 9.4

36.8 1.0 9.5

36.8 1.0 9.5

39.0 1.6 9.1

39.7 1.9 8.9

37.8 1.5 9.5

36.7

1.2

10.1

39-8 1.6 9.1

Example 17

Early fire test (FB) and late fire test (SB):

In the early fire test (FB) the ability of the test compound to detect the early fire Alternaria solani (Eil. And Mart.) Jones and Grant, the leaf-staining symptoms Leaflets of Lycopersicon esculentum, Tomato var., Bonny Best to control, and in the late fire test (SB) the ability to detect the late fire Phytophthora infestans (Mont.) de Bary, with the leaf-staining symptoms Lycopersicon esculentum, Tomato var. Bonny Best, intended to control leaflets.

A base formulation is prepared containing 0.125 g of the test compound (or 0.125 ml if it is a liquid is), 4.0 ml emulsifier solution (0.25% Triton X-155, Rohm and Haas Co., Philadelphia, Pa.,% By volume in acetone) and contains 96.0 ml of deionized water. The concentration of the test compound in this formulation is 1250 ppm. Lower concentrations of the test compound are obtained by diluting the basic formulation with the emulsifier solution containing 4 ml of emulsifier in 96.0 ml of deionized water. The lower ones Concentrations differ only based on the content of the test compound.

Test compound formulations made according to the above Procedure are established on individual tomato plantings with 3 to 5 extended leaves sprayed on. When the spray application dries (about 1 hour after spraying), the tomato plants are inoculated en masse in the early burn test by with a conidial suspension (about 2.0 χ 10 / ml)

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Sprayed by A. solani in deionized water which is fortified with 1% frozen commercial orange juice ' has been. In the late fire test, a spore suspension (about 1.5 x 10 / ml) of P. infestans sprayed in deionized water. Uniform suspension addition is standardized to 20 ml / 0.5 min.

The inoculated plants are immediately placed in a water-saturated steam atmosphere of 21.1 ⁰ C and at the breakfast fire test of 15.6 ⁰ C at the late burn test. The plants are then incubated under these conditions for 24 hours. At the end of the incubation period, the test plants are transferred to a greenhouse culture. In the early burn test, the total number of injuries on the three youngest fully expanded leaves of each plant is determined 48 hours after removal from the incubator. In the late fire test, the total number of injuries to the three youngest completely expanded leaves is determined 72 hours after removal from the incubator. The percentage infestation control is then calculated using the number of total injuries to the treated plants and the untreated control plants. The results obtained are rated on the following scale:

Evaluation = 90% control at the stated concentration in ppm _. . _

3 32 to 64

4 16 to 32

5 8 to 16

Using this procedure, the test compounds get the following results:

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- 19 -. Table IV

Test connection
Product of the example valuation
FB infestation control
SB 1 4th 4th 2 4th 2 3 2 3 • 4 3 2 2 2 ^v 6 2 2 7th 4th 2 . . 8th- 2 2 9 3 4th 10 5 5 11 4th 3 12th 3 2

Example 18 '
Braunfleekentest (BF):

This test determines the potential chemical activity of the test compound, the brown spots (BF), i.e. the Staining symptoms of with Helminthosporium oryzae van Breda-infected leaves on leaflets of Oryza sativa L., rice var. Nato, to be checked.

Test compound formulations are prepared according to Example 17 and 10-14 days after sowing

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sprayed on rice plants. The plants become en masse inoculated by being deionized with a conidial suspension (about 4.0 χ 10 / ml) of the organism Water containing a wetting agent can be sprayed. The suspension is dispensed at a rate of 20 ml / 0.5 min fed.

The inoculated plants are immediately placed in a water vapor saturated atmosphere of 21.1 ⁰ C and incubated for 24 hrs. The plants are then transferred to a greenhouse and one day after the incubation, the appearance of brown spots on the leaves is determined visually. The percentage control of the infestation is calculated by comparison with the infestation of brown spots in untreated control plants based on these visual observations. The results obtained are compiled in the following table according to the evaluation as in Example -17:

Table V

Test compound Infestation control assessment Product of the example of brown spots (BF)

1 5

3 2

J ₁ . ■ 2

5 2

8 4

10 · "5

11 5

12 2

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Example 19
Bean rust protection (BR -) test:

The Bean Rust Protection (BR) test determines the ability of the test compound to protect beans from being produced by Uromyces phaseo-Ii (Pers.) Wint. uredospore-caused disease symptoms, namely, pustules, to protect.

Formulations of the test compounds prepared according to Example 17 are applied as foliar sprays three seedlings of bean plants var. Pinto with unifoliated leaves which are 75% expanded and which extend

are in a pot with a soil surface of 58.06 cm, upset.

After applying the test substance as a foliar spray the plants are dried and then with a ureodosporen suspension (about 4.0 χ 10 / ml) from U. phaseoli inoculated en masse in deionized water containing 5 ppm Tween-20 wetting agent. The uniform Uredospore suspension addition is standardized at 20 ml / 0.5 min .

The inoculated test plants are incubated for 24 hours in a water saturated atmosphere from 15.6 to 21.1 C ^0. After the incubation, the test plants are transferred to a greenhouse culture. A visual determination of the appearance of the rust pustules is carried out 10 to 14 days after the incubation. The percentage infestation control is then calculated using the values determined for the occurrence of rust pustules in treated and untreated test plants; the results are rated according to the following scale:

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Evaluation = 90% control in the case of the specified Concentration in ppm

A. > 300

B 150-300

C x 75-150

D 57.5-75

E 18.8-57.5

P 9-18.8

G * .Ί-9Λ

Using this procedure the following results are obtained:

Table VI

Test compound Assessment of infestation control

Product of the example

1 ρ

2 ρ

3 D * D

.5. ■ B

"δ B

8 E.

9 D

10 E.

11 B

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Example 20
Corn rust protection (MR) test:

This test determines the ability of the test compound to To protect corn var. Golden X Bantam from corn rust caused by the fungus Puccinia sorghi Schw will.

Formulations of the Testyerbindings are as in the example 17 manufactured; Each test formulation is used as a foliar spray on three corn plant seedlings each three plants placed in a pot with a soil surface of 58.06 cm.

After application of the test formulation, the plants are dried and as mass inoculated in Example 19, wherein a Ureodosporsuspension the test fungi is used .. The inoculated plants are stored in a water vapor saturated atmosphere for 24 hours at 21.1 ⁰ C. They are then transferred to a greenhouse and 10 to 1.4 days after storage in the greenhouse, a visual determination of the appearance of the rust pustules on the leaves is made. The percentage infestation control is calculated using the values determined for the occurrence of rust pustules on treated and untreated test plants. These results are rated according to the scale given in Example 19. The following ratings are received:

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- 24 Table VII

Test compound Evaluation of the infestation control product of the example

21 5 8th 9 example

^B G

Test of bactericidal activity:

This test determines the potential chemical activity of the test compounds to cause bacterial infestation from animal diseases control at different concentrations.

As in Example 17, formulations of the test compounds are prepared. With each test there is a single Petri dish made of polystyrene with the dimensions 100 χ 15 mm with a mixture of 8 ml of 2% agar (Difco Bacto) plus 0.8% nutrient broth, 0.2% tryptic broth (Difco) and 2.0 ml of the test formulation overlaid.

The agar surface is simultaneously exposed to cell suspensions of cultures of the following four pathogens inoculated:

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(Eds.) Haemophilus gallinarum Delaplane, Erwin and Stuart, (Sa) Styphyolococcus aureus Rosenbach, (Sf) Streptococcus faecalis Andrews and Horder, and (Sg) Salmonella gallinarum (Klein) Bergey.

After the inoculation, the plate 48 .If std incubated at 28 ί 2 ⁰ C. The inhibition of the growth of the organisms is determined visually by comparison with the growth of the organisms on untreated control agar. Each compound is rated for bacterial control on the following scale:

Evaluation 1OO? 6ige control at the indicated Concentration in ppm

1 "32-64

2 16-52

3 ... ".8-16

4th 4-8

5. . 2-4

The control test results obtained with the test compounds are summarized in Table VIII:

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Table VIII

Tests on bactericidal effectiveness

Test compound evaluation of the control of the Bak product of the example serial growth

Hg Sa Sf Sg

1 5

.7 1

8 2 2

9 "2

10 1 1

11. 1

12 3

509825/1089

Claims (19)

Claims 1-. Organosulfur derivatives of tetrachlorodicyanobenzenes the general formula: wherein η is 0, 1 or 2, R is a C ^^ - alkylene, ^C 2-12 "alkenylene, C ₂ _ 2 ₁ ~ ^len ~ y ^alkyne" arylene or aralkylene radical is, X is a hydrogen atom, a halogen atom or an alkoxy, acyl, acyloxy, alkylthio, alkylsulfonyl, cyano, thiocyanato, alkylsulfonyloxy or amino group and m is 1 to 3, with the proviso that - when η is 0 - the -CN- Groups are present in ^- 1- and sub-positions and that - when X is hydrogen, R. is not a methylene radical. 2. Organosulfur derivatives of tetrachlorodicyanobenzenes the general formula: S (O) _n R wherein ηΌ, 1 or 2 and R is a methyl or ethyl radical .Means, with the proviso that when η is 0 and the -CN groups are in the 1- and 3-positions, R is not methyl. -28 -50 9 8 25/1089 3. Compounds according to claim 1, characterized in that they are organothiotrichlorodicyanobenzenes acts. 4. Compounds according to claim 2, characterized in that they are organothiotrichlordicyanobenzenes acts. 5. Compounds according to claim 4, namely 4-ethylthio-2,5,6-trichloroisophthalonitrile, 2-methylthio-3,5,6-trichloroterephthalonitrile, 3- (and / or 4-) methylthiotrichlorophthalonitrile, 2-ethylthio-3 , 5 , 6-trichloroterephthalonitrile or 3- (and /. Or 4-) ethylthio-3,5,6-trichlorophthalonitrile «, 6. Compounds according to claim 1, characterized in that they are organosulfinyltrichlorodicyanobenzenes acts. 7. Compounds according to claim 2, characterized in that that it is organosulfinyltrichlorodicyanobenzenes. 8. Compounds according to claim 7, namely 4-methylsulfinyl-2,5 , 6-trichloroisophthalonitrxl, 3- (and / or 4-) methylsulfinyltrichloroterephthalonitrile, 2-ethylsulfinyl-3,5,6-trichloroterephthalonitrile, 4-ethylsulfinyl-2,5 , 6-trichloroisophthalonitrile, 3- (and / or 4-) ethylsulfinyltrichlorophthalonitrile or 2-methylsulfinyl-3,5,6-trichloroterephthalonitrile. 9. Compounds according to claim 1, characterized in that they are organosulfonyltrichlorodicyanobenzenes acts. 50982S / 1089 10. Compounds according to claim 2, characterized in that. that they are organosulfonyltrichlorodicyanobenzenes acts. 11. Compounds according to claim 10, namely 4-methylsulfonyl-2,5,6-triohlorisophthalonitrile, 3- (and / or 4-) methylsulfonyltrichlorophthalonitrile, 2-ethylsulfonyl-3 , 5, 6-trichloroterephthalonitrile, 4-ethylsulfonyl-2,5,6-trichloroisophthalonitrile, 3- (and / or 4-) ethylsulfonyltrichlorophthalonitrile or 2-methylsulfonyl-3,5,6-trichloroterephthalonitrile. 12. Process for the preparation of organothiotrichlorodicyanobenzene compounds according to claim 2, characterized in that a mercaptotrichlorodicyanobenzene is used and a dialkyl sulfate in approximately equimolar proportions 1 to 4 hours in an aqueous alkaline medium converts at elevated temperature. 13. Process for the preparation of organosulfinyltrichlorodicyanobenzenes according to claim 2, characterized in that one temperature from 5 to 50 ° C an organothiotrichlorodicyanobenzene is reacted with a peroxy compound in an acidic medium, 0.1 to 10 moles of peroxy compound being used per mole of the organothiotrichlorodicyanobenzene. 14. The method according to claim 13 »thereby g e k e η η ζ e i ch η e t that the implementation 2 to 5 hours performs in approximately equimolar proportions at a temperature of 30 to 5O ⁰ C and using the peroxy compound and of the Organothiotrichlordicyanobenzols. -30- 509825/1089 15. The method according to claim -14, characterized in that the reaction with peracetic acid in an acetic acid medium. 16. Process for the preparation of organosulfonyltrichlorobenzenes according to claim 2, characterized in that g ek e η η, that one at a temperature of 50-105 ⁰ C, a Organothiotrichlordicyanobenzol reacted with a peroxy compound in.einem acid medium to yield 0.1 to 10 moles per mole of the peroxy compound Organothiotrichlordicyanobenzol applied. 17 · The method of claim 16, characterized geke η η zei seframe that one carries out the reaction at 80 to 105 ⁰ C and under .Use of 2.0 to 3.5 mole of the peroxy compound per mole Organothiotrichlordicyanobenzol. 18. The method according to claim 16, characterized in that there is hydroperoxide in the acetic acid medium used. 19. Pesticide, characterized in that it contains at least one compound in addition to the usual auxiliaries according to any one of claims 1 to 11. 509 825/108 9