DE2242185A1 - HETEROCYCLIC COMPOUNDS - Google Patents

Description

CLBA-GElGY AG, CH-4002 Basel V ^ li-Λί * ^ "" ³ "

Dr. F. Ziimstein Sr. - Dr. E. Assmann Dr.R.Koenigoborger - Tue ;; l. Phys. U. Holzhauer

Dr. F. Zurnjtcin j: in.

P α I β η I α n w ä I I β

8 Munich 2, Bröuhausslraße 4 / III

Case 5-7710 / 1 + 2 /?

Heterocyclic compounds

The present invention relates to new Thiadiazolderi.vace, Process for their production, means containing the new substances, as well as their veneering.

The new thiadiazole derivatives correspond to formula I.

Ι ί

R ₂ - S (O) _n JJ ^ H

^ι α)

s ■ *.

in V7CIcher

R-j ^ hydrogen, an unsubstituted or 1-3-fold by Halogen, alkoxy or alkylamino-substituted alkyl radical with 1-4 carbon atoms, alkenyl radical with 2-4 carbon atoms or cycloalkyl or. Gycloalkenyl radical with 5-7 carbon atoms,

R-2 is a straight chain or branched alkyl radical with 1-4 K fj h1e 11 ü tο f fa L omcη _{f un} d

η means 1 or 2.

309811/1196

New thiadiazole derivatives of the formula I, in which H 2 is, are prepared according to the invention by a 5-chloro-thiadiazole of the formula II

(H)

in which R has the meaning given under formula I with a compound of formula III

R ₂ - S (O) _n - Me (III)

in which R2 has the meaning given under formula I, η 2 and Me means an alkali metal cation.

The reaction is preferably carried out in an inert solvent. As such, for example, are suitable: Alcohols such as methanol, ethanol, ethers such as tetrahydrofuran or dioxane, also Ν, Ν-dimethylformamide and dimethyl sulfoxide. Particularly Polyhydric, partially etherified alcohols such as methyl cellosolve or glycol monomethyl ether are suitable. The reaction temperatures lie between 0 ° and the reflux temperature of the reaction medium, preferably between 80 ° and 100 ° C.

Thiadiazole derivatives of the formula I in which η denotes 1 or 2, are prepared according to the invention by a thiadia

zole derivative of the formula IV, oxidized.

N

(IV)

In Formula IV, R, and R _? the meaning given above.

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This oxidation can be carried out in the usual way with inorganic and organic oxidizing agents. Suitable Oxidizing agents are, for example, halogens, e.g. moist chlorine, Salts of oxidizing oxygen acids of the halogens, e.g. sodium periodate, Metal oxides or salts, e.g. chromium trioxide or potassium permanganate and preferably peroxides, e.g., hydrogen peroxide and percarboxylic acids such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid or monoperphthalic acid. For the production of sulfoxides (n = l)

equivalent amounts of oxidizing agent are used. The reaction takes place in a solvent. As such come preferred chlorinated hydrocarbons, e.g. methylene chloride, chloroform, carbon tetrachloride or chlorobenzene.

The 5-chloro-thiadiazoles required as starting materials of the formula II can by reacting amidines of the formula .V

R ₁ -C (V)

^m 2

in which R has the meaning given under formula I with Perchloromethyl mercaptan (trichloromethanesulfenic acid chloride) in Presence of an acid-binding agent, for example alkali hydroxide, in an inert solvent, such as methylene chloride, Chloroform, benzene or toluene can be obtained. (See J. Goerdeler et al. Chem. Ber. "90, 182 [1957], ibid. 90, 892, [1957]). .

Compounds of the formula V are obtained, for example, by reacting nitriles with ammonia in the presence of hydrogen chloride. (See Pinner, Die Iminoether, Verlag Oppenheim, Berlin [1892]).

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The reaction of compounds of the formula V with perchloromethyl mercaptan is expediently carried out in such a way that a compound of the formula V is in one of the abovementioned Submit solvent, add the perchloromethyl mercaptan and then at 0 ° to bind the resulting hydrogen chloride add necessary amount of aqueous alkali hydroxide. The amount of alkali hydroxide added depends on whether the compound of formula V was used in free form or in the form of its hydrochloride, 3 or 4 moles per mole of compound V. The reaction mixture can be worked up by separating off the organic phase, evaporating off the solvent and recrystallizing or distilling the residue.

The compounds of the formula I are colorless substances, some of which are obtained in crystalline form and some as oily liquids. Their production is explained in more detail by the following examples:
example 1

3-methyl-5-methylsulfonyl-1,2,4-thiadiazole

The mixture of 70 g (0.5 mol) of 3-methyl-5-chloro-l, 2,4-thiadiazole, 300 ml of methyl cellosolve and 51 g (0.5 mol ) of sodium methylsulfinate 1 hour at 100 ⁰ C. Then the mixture is poured into 1 1 of water and stir the solution three times with 200 ml of methylene chloride. The separated, combined fractions of methylene chloride are over Na ₂ SO, anhydr. dried and evaporated. The residue is recrystallized from ethanol and gives 62 g (69% of theory) of colorless crystals of S-methylsulfonyl-l ^. ^ - thiadiazole, melting point 90-92 ° C.

Analysis for C ^ H ^ O ^

Calculated: C. 27 , 0 H 3 , 36 N 15, 7th 0 17, 9 S. 36 , 0 Found 26th , 80 3 , 47 15, 87 17th 99 36 , 0

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Example 2
3-methyl-5-methylsulfinyl-1,2,4-thiadiazole

96 g of the 3-methyl-5-methylmercapto-1,2,4-thiadiazole obtained above are placed in a mixture of 300 ml of glacial acetic acid and 300 ml of methylene chloride and added dropwise at room temperature and at vigorous stirring 90 g of 52% peracetic acid in 100 ml of glacial acetic acid. The batch is stirred until a drop is no longer present Coloration of Potassium Iodide Starch Paper produced more. Then stir 1 l of water are added and the mixture is extracted four times with 100 ml of methylene chloride in a separating funnel. The separated organic phases, dried and evaporated to give a product which, after recrystallization from cyclohexane, 64 g of colorless crystals with a melting point 72-74 ° C delivers (56% of theory).

Analysis for 0. H ₆ N ₂ OS ₂ (MW 162.2): Calculated C 29.61 H 3.73 N 17.26 S 39.53 Found 29.52 3.73 17.52 39.35

Example 5

3-trichloromethyl-5-ethylsulfonyl-1,2,4-thiadiazole

26.5 g of 3-trichloromethyl-5-ethylmercapto-1,2,4-thiadiazole (0.1 mol in 100 ml of glacial acetic acid are dissolved in a 350 ml three-necked flask with a stirrer, dropping funnel, internal thermometer and heat bath, and at 6O ⁰ C dropwise and 29.3 g of peracetic acid (52%, Elfa-Chemie, 0.2 mol) in 50 ml of glacial acetic acid are added with stirring. The reaction is then carried out at 80 ° C. until the potassium iodide starch paper no longer stains Mixed with 500 ml of water, the product can be extracted in a separating funnel containing 4 × 70 ml of methylene chloride. The organic phase is dried over MgSO, anhydr. And evaporated in a rotary evaporator. The residue is rubbed and the colorless crystals formed are purified by recrystallization in cyclohexane Yield 13 g of 3-trichloromethyl-5-ethylsulfony1-1,2,4-thiadiazole with a melting point of 50 ° -51 ° C. (45% of theory).

Analysis for ^C 5 20th I ₃ K 2 ⁽ CM 1 2 1 » 7th 9 Cl 36, 1 N 9 , 5 Calculated C. 20th A. Il 1 7th 36, 1 9 , 5 Found 3 A. / 1 1 6th 09 8th 1

SAD

Example 4 Z242 1 85

5-methylsulfonyl-1,2,4-thiadiazole

22.4 g (0.2 hol) of methylsulfinate sodium salt are suspended in 100 ml of methyl cellosolve and, after addition of 24 g of 5-chloro-1,2,4-thiadiazole (obtained analogously to Goerdeler, Ber. 90, 182 [1957)] ) 1 hour at 100 ^° C. in a 350 ml sulphonation flask with internal thermometer and stirrer. The batch is then poured into 500 ml of water and extracted four times with 100 ml of methylene chloride. The combined, dried organic phases are evaporated and, after recrystallization from methanol, 17 g of colorless crystals with a melting point of 60 ° -61 ° C. (52% of theory) are obtained.

Analysis for C-II ^ N ₂ S ₂ O ₂ (MW 164) Calculated C 22.0 H 2.4 N 17.0 0 19.5 Found 21.8 2.5 16.8 19.6

Example 5

3-Tr i fluorine thy 1-5-methylsulfony 1-1,2,4-thiadiazole

In a 350 ml three-necked flask equipped with a stirrer and internal thermometer, 19 g of 3-trifluoromethyl-5-chloro-1,2,4-thiadiazole (0.1 mol) are dissolved in 100 ml of methyl cellosolve and mixed with 10.5 g of sodium methyl sulfinate (0 1 mole ausgertihrt) 1 hour at 100 ⁰ C. Then 100 ml of chloroform and 100 ml of water are added and everything is transferred to a 500 ml separating funnel. The chloroform phase is separated off and the aqueous phase is washed twice with 50 ml of chloroform. The combined organic fractions are _{anhydrated over Na 2} SO ^. dried, evaporated to dryness and the remaining oil stimulated to crystallize. Recrystallized from ether / petroleum ether 1: 1, 14 g of colorless crystals of 3-trifluoromethyl-5-methylsulfonyl-1,2,4-thiadiazole with a melting point of 40-5O ⁰ C (60% of theory) are obtained.

Analysis for ^C 4 ^H 3 ^F 3 ^N 2 ° 2 ^S 2

Calculated C 20.6 H 1.3 F 24.6 N 12.0 Found 20.6 1.5 24.4 12.0

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The S-trifluoromethyl-S-methylsulfonyl-1,2,4-thiadiazole used as starting material is obtained as follows:

3-trifluoromethyl-5-chloro-1,2,4-thiadiazole

39Og SbF ₃ (2.2 mol) and 58.5 g of SbCl ₃ (0.175 mol) are stirrer, internal thermometer, dropping funnel · heated gas inlet tube at 150 ⁰ C in a 1.5 1 flask equipped with a multi-neck. 39 g of Cl ~ (0.55 mol) are passed in with stirring, the mixture becoming a colored solution. The inlet tube is then exchanged for a distillation attachment with a descending condenser and receiver, and 234 g (1 mol) of 3-trichloromethyl-5-chloro-1,2,4-thiadiazole are added dropwise. The resulting product is distilled off directly. After another distillation, 131 g of 3-trifluoromethyl-5-chloro- _1,2,4 -thiadiazole, boiling point 124 ~ 126 ° C / 76O ^ 69 ° at 90 mm are collected. n ² ^ = 1.4348. Yield 70% of theory.

Example 6

In 240 ml of a 0.06 molar solution of monoperphthalic acid in diethyl ether was in the course of 5 minutes at -10 ° C Solution of 7.7 g of S-ethyl-S-methylmercapto-l ^^ - thiadiazole in 100 ml of diethyl ether are added. The mixture was warmed to room temperature overnight with stirring. The reaction mixture is then filtered, twice with saturated sodium bicarbonate solution washed, filtered again and evaporated. The remaining oil is distilled in vacuo. You get that 3-Ethyl-5-methylsulfonyl-1,2,4-thiadiazole with a boiling point of 110 ° C.

u, 1

3-Aethyl-5-ethylsulfonyl-1,2,4-thiadiazole, boiling point _n , 136 ° C. is obtained in an analogous manner.

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Example 7

A fermented solution of 7 .g Sn-butyl-S-methylmercapto-1,2,4-thiadiazole in 235 ml of chloroform at temperatures between 0 ° and -5 ° C was 18.2 g of 87% m-chloroperbenzoic acid during a added half an hour. The mixture was then stirred overnight, the reaction mixture warming to room temperature. After the same process as in Example 7 _{n nr} 129-134 ⁰ Cj was the 3-n-butyl-5-methylsulfonyl-l, 2,4-thiadiazole, bp. Obtained.

In an analogous manner, 3-n-butyl-5-ethylsulfonyl-1,2,4-thiadiazole was obtained Kp. _{Q Q5} 152-156 ⁰ C.

Example_8

3.7 g of S-trichloromethyl-S-methylmercapto-l ^^ - thiadiazole and 9.1 g of 85% m-chloroperbenzoic acid were carried out analogously to Example 7 implemented and processed. The solid residue obtained after evaporation of the solvent was recrystallized from isopropanol. It became S-trichloromethyl-S-methylsulfonyl-1,2,4-thiadiazole obtained from melting point 111-113 ° C.

3-Trichloromethyl-5-ethylsulfonyl-1,2,4-thiadiazole was obtained in an analogous manner with a melting point of 48-5O ° C.

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The methods described in Examples 1 - A are used to produce:

Link: · . Phys. data

2o

3-Isopropyl-5-methylsulfonyl-1,2,4 _{-thiadiazole n ß 1,5124}

Of)

S-propyl-S-methylsulfonyl-1,2,4-thiadiazole n ^ 1,518

3-methyl-5-isopropylsulfonyl-1,2,4-thiadiazol mp. 30 C ⁰

3-methyl-5-isopropylsulfinyl-1,2,4-thiadiazole m.p. 130-132 ° C

3-propyl-5-methylsulfinyl-1,2,4-thiadiazole m.p. 52-54 ° C

S-trichloromethyl-S-methylsulfonyl-1,2,4-

thiadiazole m.p.

thiadiazole OeI

3-trichloromethy1-5-isopropylsulfinyl-1,2,4-

thiadiazole. ^κ Ρ 2 68-7O ° C

S-trichloromethyl-S-isopropylsulfonyl-1,2,4-

thiadiazole "m.p. 77-78 ° C

3-trifluoromethyl-5-methylsulfinyl-1,2,4-thiadiazole OeI

3-trifluoromethyl-5-ethylsulfinyl-1,2,4-

thiacliazole OeI

3-trifluoromethyl 1-5-isopropylsulfinyl-1,2,4-thiadiazole _: OeI.

3-trifluoromethyl-5-methylsulfonyl-1,2,4-

thiadiazole m.p. 40 ^° C

3-trifluoromethyl-5-ethylsulfonyl-1,2,4-thiadiazole OeI

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α-Chloromethyl-S-methylsulfonyl-I.Z.A-thiadiazole

thiadiazole a-methyl-S-n-butylsulfonyl-l ^ .A-thiadiazole 3-tert-butyl-5-methylsulfonyl-1,2,4-thiadiazole 3-n-Butyl-5-n-butylsulfonyl-1,2,4-thiadiazole

3- (4'-Chlorobutyl) -5-methylsulfooyl-1,2,4-thiadiazole

S-Cyclopropylmethyl-S-methylsulfonyl-l ^^ - thiadiazole

3- (3-chloropropyl) -5-methylsulfonyl-1,2,4-thiadiazol 3-n-hexyl-5-methylsulfonyl-l, 2 _J 4-thiadiazol 3-n-undecyl-5-methylsulfonyl-1,2, 4-thiadiazole

3-Trichloromethyl-5-methylsulfinyl-1,2,4-thiadiazole

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The compounds of the formula I have an excellent bactericidal and fungicidal action, as demonstrated in the following tests became:

A. Soil test

500 ppm of active substance are incorporated into dry, sterilized soil by intensive mixing.

In plastic containers with a content of 250 ecm, 100 ecm this earth filled.

Approx. 10 sterilized oat kernels are placed in each of these containers placed below the surface of the earth, each of which is mixed with mycelium of one type of the following fungi:

Fusarium oxysporum , P ythium debaryanum , Rhizoctonia s olani, Verbicillium albo atrum.

Subsequently, with 34 ml dist. Water-moistened and the vessels are incubated at 20-24 ⁰ C.

After 5 days an assessment is carried out, whereby it is determined whether fungal mycelia grow from the grains into the surrounding soil.

Of the substances of the formula I tested, for example the following compounds have excellent effects:

3-Trichloromethyl-5-ethylsulfinyl-l, 2,4-thiadiazole 3-trifluoromethyl-5-methylsulfinyl-l, 2,4-thiadiazole 3-trifluoromethyl-S-ethylsulfinyl-l ^, 4-thiadiazole S-trifluoromethyl-S -isopropylsulfinyl-l ^^ - thiadiazole 3-trifluoromethyl-5-ethylsulfonyl-1,2,4-thiadiazole 5-methylsulfonyl-1,2,4-thiadiazole
S-Isopropyl-S-methylsulfonyl-1 ^^ - thiadiazole 3-Propyl-5-methylsulfonyl-1,2,4-thiadiazole

3-methyl-5-methylsulfonyl-l, 2,4-thiadiazol-3-5-Methyl. isopropyls.uir onyl-1, 2, 4-thiadiazol-3-propyl-5 mcthylsulfinyl-1,2, 4-thiadiaaol

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B. Pickling test

Wheat is artificially infected with the fungus Fusarium nivale. The wheat is then pickled with 200 ppm active substance and laid out on moist filter paper in Petri dishes.

After 10 days of incubation at 20-24 ° C, the development rated by mushroom mycelium.

Of the tested compounds of formula I showed to Example of the following excellent effect: · '■

S-trifluoromethyl-S-methylsulfinyl-1,2,4-thiadiazole 3-Tr i fluorine thy 1-5-ethylsulfiny 1-1,2,4-thiadiazole 3-isopropyl-5-methylsulfonyl-1,2,4-thiadiazole 3-propyl-5-mene thyisulfiny 1-1,2,4-thiadiazole 3-methyl-5-methylsulfiny1-1,2,4-thiadiazole 3-methyl-5-n-propylsulfonyl-1,2,4-thiadiazole 3-methyl-5-tert-butylsulfonyl-1,2,4-thiadiazole 3-methyl-5-sec-butylsulfonyl-1,2,4-thiadiazole 3-methyl-5-ethylsulfonyl-1,2,4-thiadiazole 5-methylsulfonyl-1.2.4-thiadiazole 3-Isopropyl-5-methysulfonyl-1.2.4-thiadiazole S-propyl-S-methylsulfonyl-1.2.4-thiadiazole S-methyl-S-methylsulfinyl-1.2.4-thiadiazole S-methyl-S-methylsulfonyl-1.2.4-thiadiazole S-methyl-1-isopropylsulfonyl-1.2.4-thiadiazole 3-propyl-5-methylsulfinyl-1.2.4-thiadiaa3l

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Cup test

The solution of the active ingredient is mixed with the still hot nutrient agar and poured into bowls. After solidification the test germs are spread on and incubated at 37 ° C. for 48 hours. By varying the amount of In this way, the minimum inhibitory concentration of the active ingredient can be determined.

I. Bacteria

The following bacterial strains were examined:

Staphylococcus aureus

Escherichia coli

Staphylococcus faecalis

Brevibacterium ammoniagenes

Sareina ureae

Proteus vulgaris'

Bacillus subtilis

Salmonella pullorum

Mycobacterium phtei

Corynebacterium diphteroides

The compounds of formula I showed very good effect, for Example the 3-isopropyl-5-methylsulfonyl-l, 2,4-thiadiazole, the S-propyl-S-methylsulfonyl-l ^^ - thiadiazole, the 3-methyl-5-methylsulfonyl-l, 2,4-thiadiazole, 3-trichloromethyl-5-ethylsulfinyl-1,2,4-thiadiazole and 3-trifluoromethyl-5-ethylsulfinyl-1,2,4-thiadiazole.

II. Fung i

The following strains were examined: Kpiderwophyton floccosuin
Tricliopliyton gypscura
Candida albicans

Saccharomycps ccrcverijine

BATH ORIGINAL

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Fusarium oxysporum Torula utilis Aspergillus flavus Penicillium expansum Aspergillus niger Pullularia pullulans Coniophora cerebella Poria vapararia

Lenzites abietina \

Polystictus versicolor Fomes annosus Alternaria tenuis

The compounds of the formula I showed a very good effect, for example:

3-methyl-5-methylsulfiny1-1,2,4-thiadiazole 3-propyl-5-methylsulfinyl-1,2,4-thiadiazole ' S-trifluoromethyl-S-methylsulfinyl-1,2,4-thiadiazole 3-trifluoromethyl 1-5-isopropylsulfiny1-1,2,4-thiadiazole 3-trifluoromethyl-5-ethylsulfonyl-1,2,4-thiadiazole 5-methylsulfonyl-1,2,4-thiadiazole.

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D., Henrazone Test

Method e

In the exhaust or padding process, the active ingredients are made from solutions with different active ingredient contents on textile or applied paper rondelles. Ethylene glycol monosethyl ether was used as the solvent here. As nutrient agar so-called two-layer agar plates are used. These consist of one layer of Bacto agar and one layer Layer of agar suitable for the respective test organisms. This second layer is beforehand with the test germs inoculates. The discs provided with active ingredient are then placed on these plates and incubated at 37 ° for 24 hours. The growth of the test organisms on and under the discs is then assessed.

The test organisms used were: ". #

Bacteria n: Staphylococcus aureus SG 511 (Rutrient agar +

Potassium tellurite)

Escherichia coli (nutrient agar)

Fungi : Aspergillus nige'r (word agar) ".

Candida albicans (word agar)

• For example: 3-Trichloromethyl-5-ethylsulfinyl-1,2,4-thiadiazole showed a very good effect 3-methyl-5-methylsulfinyl-1,2,4-thiadiazole S-methyl-S-methylsulfonyl-1,2,4-thiadiazole

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E. Disinfection test

The active ingredients are extracted in the exhaust process (padding). Solutions with different active ingredient content on textile or Applied paper rondelles. These candidates are then inoculated with suspensions (physiological saline solution with 107 »broth content) of the various test organisms. Then the discs are heated in a humid chamber for 24 hours at 37 ° and then in 20 cm physiological Saline solution (contains to block the active ingredient.

Polyoxyethylene sorbitol mono-oleate) washed out. Of this Solution, aliquots are taken and placed on appropriate Breeding grounds flattened out. The culture media are then incubated at 37 ° for 24 hours. The test organisms listed under 2. mentioned used. The number of living germs in comparison to the control is then determined.

The test organisms used were:

Staphylococcus aureus

Escherichia coli ...

Aspergillus niger ATCC

Candida albicans

For example: S-trichloromethyl-S-ethylsulfinyl-l ^^ - thiadiazole showed a very good effect 3-methyl-5-m-methylsulfinyl-1,2,4-thiadiazole 3-methyl-5-methylsulfonyl-1,2,4-thiadiazole

BATH ORIGINAL

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F. Mold stain test

Paper discs are placed on a sterile Wort Agar plate, the active ingredient solutions are applied to die.im foulard process vjurden, applied and inoculated with a germ suspension of the test organisms. Then the rondelles will be 3 days incubated at 28 ° and 75-85% humidity. Then the growth on and under the specimens is assessed.

The following test organisms are used:

Penicillium expansum '

Aspergillus niger '. . · · '.

Alternaria tenuis ^:

For example: 3-Triehlomethyl-5-ethylsulfinyl-1,2,4-thiadiazole showed very good effects 3-methyl-5-methylsulfinyl-1,2,4-thiadiazole 3-methyl-5-methylsulfony1-1,2,4-thiadiazole

3 0 9 811/119 6

t # ♦ · * I

G. Microbicidal Effectiveness in Paints

method

χ parts of active ingredient four dissolved first in 5 parts of a 1: 1 mixture of diniethylformamide and ethylene glycol non-methyl ether and (90%) parts of a commercially available emulsion paint based on polyvinyl acetate-ethyl acrylate copolymer and 5 parts of water a ready-to-paint color mixed homogeneously. Filter paper, for example Whatmann 3 MM, is provided with a paint which is dried at room temperature for 3 days. The test specimens are then ventilated for 8 days in the children's channel at 65 ° and 80-907 °, relative humidity. The test specimens are then cut up and placed on inoculated agar plates.
(Fungi coating upwards, bacteria coating downwards)

The following were used as test organisms: '

Fungi

Pullularia pullulans Paecilomyces varioti PeniciIlium cyclopium Aspergillus oryzae Chaetomium globosum Aspergillus niger Candida albicans

Sabouraud Maltose Agar

Bact

Staphylococcus Escherichia coli

aureus Ί i. J

Nutrient agar

Then the plates are incubated:

Fungi: 7 days at 28 ° and 7O-SO74 relative humidity Bacteria: 24 hours at 37 ° and 60X relative humidity

Of the substances of the formula I tested, for example 3-isopropyl-5-methylsuJ Conyl-1,2,4-thiadia :: ol and the 3-propyl-5-methylethyl i; ul finyl-1,2,4-thiadiazole excellent Effectiveness.

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■ · "BATH

H, house lazy . '

Samples of different types of wood are used to determine the Dry weight 16 to 20 hours at 105 ° dried. Then the samples are using vacuum using Acetone solutions of various concentrations soaked. By back weighing the amount of the absorbed Active ingredient determined.

^ i

Furthermore, powder bottles are half made with quartz sand

3
and 15 cm of a nutrient solution, glucose, peptone dissolved in phosphate buffer, malt extract, filled. A piece of wood of a kind suitable for the growth of the fungus is inserted into the quartz sand (feederbloc) with the fungus culture and pre-incubated for 3 weeks.

Place the Pieces of wood soaked with active ingredient. The arrangement will then kept at 24 ° C for 2 months. Then the mushroom growth and the quality of the wood are assessed. The samples are then ventilated with fresh air for 4 weeks in the wind tunnel at 65 ° and one more time Subjected to assessment of fungal growth.

The following test organisms and types of wood were used:

Coniophora cerebella on pine (Pinus silvestris) Coriulus versicolor on beech (Fagus silvatica) Poria incarnata on linden (Tilia spec.)

Of the substances of the formula I tested, for example the following excellent effectiveness:

3-methyl-5-methylsulfonyl-1,2,4-thiadiazole S-methyl-S-methyls-ilfinyl-l ^^ - thiadiazole 3-isopropyl-5-n-ethylsulfonyl-1,2,4-thiadiazole 3-trichloroiethyl -5-ethylsulfinyl-1 _} 2,4-thiadiazole

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SAD ORIGINAL

22-21-5

I. Plastic

PVC foils with a preserving and sterilizing effect are prepared by adding 0.5 g of the active ingredient in 5 g Dissolve Methylccllosolve and then with 55.0 g PVC-Pasto (Ln 5 g Petrol) mixes, homogenizes and heats to a lfiO ° C Presses the plate into foils. The PVC paste has the following Composition:

73 parts by weight PVC GEON 120 χ 203 * ^l

2 "" dibutyltin millilurate 15 "" dibutyl sebacate 10 "" dioctyl phthalate 10 "" gasoline boiling range 80-110 ° C

makes 100 "" PVC paste

These foils are now on their mikrobizi.de and, fungistatic Effect tested in 3 ways;

Test 1

For this purpose, a complete agar medium with 10 microorganisms

3
men per cm agar prepared in a dish, Ronde] lon from the FoIi.enmatcrial 'are placed on the soil and bebrtitet the cup at 37 "C for 24 hours. When a substance is rated effective if no growth of organisms under the roundel occurs more.

Test 2

The cidc effect is confirmed by the fact that a .. suspension with approx. 10 microorganisms on a Triigci :, κ. Β. Paper, made with a piece of art; to be kept in contact for 6 hours at 37 ° C. Everything is then washed green in physiological saline solution and an equivalent of this solution is inoculated with a lUuii 11 tm-ilrllho. If the substance to be tested was active, no germ is able to multiply.

309811/1196 bad original

Tost 3

The plastic-preserving effect of the products is demonstrated by offering approx. 10 of the microorganisms to be tested an agar without a carbon source and adding samples of the PVC film. After 14 days at 26-28 ° C, the weight loss of dibutyl sebacate and the changed physical constants of the PVC film due to the loss of the plasticizer are determined. In the case of positive active substances, the weight loss remains less than 10% of the original dibutylbazate amount. ■ ^Λ "

Tested organisms . .

Test 1 ^ Staphylococcus aureus SG 511

Test 2 J Escherichia coli 8196
Candida albicans 2-2
Aspergillus niger ATCC 6275 Salmonella pullorum VBIZ 23

Test 3: Aspergillus niger ATCC 6275

Penicillium funiculosum
"Paec. Varioli
Trich. viride
Chaet. phobosum

Of the substances of formula I tested, showed 3-methyl-5-methylsulfinyl-1,2,4-thiadiazole 3-methyl-5-methylsulfonyl-1,2,4-thiadiazole 3-n-propyl-5-methylsulfonyl-1,2,4-thiadiazole 3-isopropyl-5-methylsulfonyl-1,2,4-thiadiazole particularly good effectiveness.

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The thiadiazole derivatives of the formula I can generally be used as fungicides. In particular, connections of the formula I as soil fungicides, i.e. used to combat fungi that affect parts of plants in the ground (roots, Stalk base, seeds, tubers and seedlings, seedlings and other parts of the plant used for reproduction), such as:

Plasmodiophora species Aphanomyces species Pythium species

Phytophthora species

Myoosphaerella species Ophlobolus species

Cochliobolus (= Helminthosporium) species

Pellicularia species

Thielavlospsls species VerticiIlium species P hialophora species Fusarium species

Fhoma species Sclerotium species Septoria species Ustilapo species

Tilletia species

Urocystis and Tuburcinia species

e.g. Plasmodiophora brassicae e.g. Aphanomyces laevis e.g. Pythium ultimum

Pythium debaryanum

e.g. Phytophthora infestans Phytophthora cactorum Phytophthora cinnamoni

e.g. Mycosphaerella fragariae e.g. Ophiobolus graminis

e.g. Helminthosporium sativum Helminthosporium oryzae Helminthosporium teres

e.g. Pellicularia filamentora (= Rhizoctonia solani) Pellicularia sasakii

e.g. Thielaviospsis basicola e.g. Verticillium albo-atrum e.g. Phialophora cineresceua

e.g. Fusarium oxysporum Fusarium nivale

e.g. Phoma betae

e.g. Sclerotium rolfsii e.g. Septoria nodorum e.g. Ustilago zeae Ustilago avenae Ustilago nuda

e.g. Tilletia caries

e.g. Urocystis cepulae Tuburcinia occulta

In addition, compounds of the formula I, in which η denotes 1 or 2, can be used to protect organic materials, such as wood, paper, textiles, paints and plastics, against attack by harmful microorganisms, in particular for decorating and preserving Serving materials.

309811/1196

SAD ORIGINAL

The applicability of the thiadiazole derivatives of the formula I for combating microorganisms; "in particular of bacteria and fungi, and for protecting organic materials and objects from attack by microorganisms is very vielseitigSo they can be incorporated directly into the to-slit material, for example in material based on synthetic resins, such as polyamides and polyvinyl chloride, in paper treatment liquors, in printing thickeners made from starch or cellulose derivatives, in varnishes and paints containing, for example, casein, in cellulose, in viscose spinning pulp, in paper, in animal slimes or oils, in permanent sizes based on from polyvinyl alcohol, in cosmetic articles, in ointments or powders, they can also be added to preparations of inorganic or organic pigments for the painting trade, plasticizers, etc.

By combining the compounds of the invention with Surface-active, in particular washing-active substances, one arrives at detergents and cleaning agents with excellent antibacterial properties or antifungal effect. Aqueous preparations of such detergents and cleaning agents. Which inventive • contain bonds, are suitable as antimicrobial cleaning agents especially in the food and beverage industry, e.g. in breweries, dairies and slaughterhouses.

Then you can the thiadiazole derivatives of the formula I in the form of their organic solutions, for example as so-called Use "sprays" or as dry cleaners or for impregnating wood, preferably using as organic solvents Water-immiscible solvents, in particular petroleum fractions, but also water-miscible solvents, such as lower ones Alcohols, for example methanol or ethanol or ethylene glycol monomethyl ether or monoethyl ether come into question. Some of the new compounds can also be used in aqueous solution will.

3 0981 1/1196

-M -

Do connections can be used for disinfection and preservation purposes of formula I can also be used in combination with known antimicrobial agents. These include, for example:

Halogens and halogen compounds with active halogen, e.g. sodium hypochlorite, calcium hypochlorite, chlorinated lime, sodium p-toluenesulfochloramide, p-toluenesulfodichloramide, N-chlorosuccinimide, 1,3-DiChIOr-S, 5-dimethyl-hydantoin, trichloroisocyanuric acid, potassium dichloroisocyanurate, iodine, iodine complex compounds and iodine trichloride with surfactants such as polyvinylpyrrolidone, alkylphenoxypolyglycbles, polyoxypropylene glycols, alkylaminoethanesulfonic acids and sulfonates, alkylarylsulfonates, quaternary ammonium compounds.

Boron compounds ■.

e.g. boric acid, borax.
Organometallic compounds

2.B bis-tributyltin oxide, triphenyltin hydroxide, tributyltin salycylate, Tributyl tin chloride, phenyl mercury borate, plienyl mercury acetate.

Alcohols

e.g. hexyl alcohol, trichloroisobutyl alcohol, 1,2-pi'opylene glycol, Triethylene glycol, benzyl alcohol, '-I-chlorobenzyl alcohol,?, 4- and 3,4-dichlorobenzyl alcohol, 2-phenylethyl alcohol, S-f ^ l-chlorophciiyl) ethyl alcohol, Ethyl glycol monophenyl ether, menthol, linalool, 2-bromo-2-nitro-propanediol-1,3

Aldehydes

e.g. formaldehyde, paraformaldehyde, glutcraldehyde, benzaldehyde, ^ -Chlorobenzaldehyde, 2,4- and 3,4-dichlorobenzaldehyde, cinnamaldehyde, Salicylaldehyde, 3> L5-dibromosalicylaldehyde, 4-hydroxybenzaldehyde, Anisaldehyde, viinillin.

3098HZ ₁₁₉₆

Carboxylic acids and derivatives

e.g. trichloroacetic acid, glycol monobromesslgate, sodium and calcium propionate, caprylic acid, undecylenic acid, zinc undecylenate, sorbic acid, potassium and calcium sorbate, lactic acid, malonic acid, aconitic acid, citric acid, benzoic acid, 4-chlorobenzoic acid, benzoic acid benzyl ester -Chlorosalicylic acid n-butylamide, salieylanilide, 2,4 ', 5-tribromosalicylanilide, 3.3 ^I »4', 5-tetrachlorosalicylanilide, 4-hydroxybenzoic acid, 4-hydroxybenzoic acid ethyl ester, gallic acid, mandelic acid, phenylpropiolacetic acid, Variillic acid propyl ester

Phenols

for example phenol, mono- and polychlorophenols, cresols, 4-chloro-3-methylphenol, 4-chloro-3,5-dimethylphenol, thymol, 4-chloro-thymol, 4-t-amylphenol, saligenin, 4-n-hexylresorcinol , Carvacrol, 2-phenylphenol, 2-benzyl-4-chlorophenol, 2.2 ^t -dihydroxy-5.5 ^l -dichlorodiphenylmethane, 2.2'-dihydroxy-3.3 ^f »5» 5 * »6.6 ' -hexachlorodiphenylmethane, 2,2 ^f -dihydroxy-5,5'-dichlorodiphenyl sulfide, 2,2'-dihydroxy-3i 3 '»5,5'-tetrachlorodiphenyl sulfide, 2-hydroxy-2', 4,4 ' -trichlorodiphenyl ether, dibromosalicyl.

Quinones,

e.g. 2,5-dimethylquinone, 2,3,5,6-tetrachloro-benzoquinone, 2,3-dichloro-1,4-naphthoquinone. · '

Carbon ens äure derivatives

e.g. pyrocarbonic acid diethyl ester, tetramethylthiuram disulfide, 3,4,4'-trichloro-N, W ^! -diphenylurea, 3 ~ trifluoromethyl-4,4 ^! - dichloro-N, N'-diphenylurea f, N-3-trifluoromethylphenyl-N '-2-ethylhexylurea, 1,6-bis- (4'-chlorophenyl-di-guanidino) -hexane, dodccylmethyl-guanidine acetate, ammonium rhodanide , 4,4 ^f -Di amidi no -et, CJ -diphenoxy-hexane.

3 0 9 8 1 1 /. 1 1 9 6 ^0Rli ? WAl.

e.g. dodecylpropylenediamine, dodecyldiethylenetriamine, diaminobenzene dihydroiodide

Quaternary ammonium compounds

ζ.ß. Alkyl-dimethyl-benzyl-ammonium chloride, alkyldimethyl-ethylbenzyl-ammonium chloride, Dodecyl-dimethyl-3i ^ -dichlorobenzylammonium chloride, Dodecyl-di- (2-hydroxyethyl) -benzyl-ammonium chloride, Dodecyl di (2-hydroxyethyl) benzyl ammonium pentachlorophenolate, Dodecyl-di- (2-hydroxyethyl) -benzyl-ammonium-4-raethylbenzoate, Dodecyl-dimethyl-phenoxyethyl-ammonium bromide, 4-diisobutyl-phenoxyethoxyethyl-dimethyl-benzyl-ammonium chloride, 4-Diisobutyl-cresoxyethoxyethyl-dimethyl-benzyl-ammonium chloride Dimethyl didecyl ammonium chloride, cetyl trimethyl ammonium bromide, Dodecyl pyridinium chloride, cetyl pyridinium chloride, dodecyl isoehinolinium chloride, Decamethylene-bis-4-aminochinaldinium dichloride, a-fp-TolylJ-dodecyl-trimethyl-ammonium methosulfate, (Dodecanoyl-N-methyl-aminoethylJ-iphenylcarbamoyl-riH thyl) -dimethylammonium chloride.

Quaternary phosphonium compounds

e.g. dodecyl triphenyl phosphonium bromide

Amphoteric compounds

e.g. dodecyl di (aminoethyl) glycine.

Heterocyclic compounds

e.g. 2-mercaptopyridine-N-oxide, Na and Zn salt of 2-mercaptopyridine-N-oxide, 2,2 * -dithiopyridine-1,1'-di-N-oxide, 8-hydroxyquinoline, ^ -Chlor- e-hydroxyquinoline, 5-chloro-7-iodo-8-hydroxyquinoline, 'S ^ -dichloro-B-hydroxychinoline, 5,7-0ichlor-8-hydroxyquinoline, bis-2-methyl-'f-amino-quino3yl-c 'arbamid-hydroch] orid, 2-kercaptobenzothiazole, 2- (2'-hydroxy-3', 5 ¹ -dichlorophenyl) -5-chlorobon ? A: al <]: ■. zo?. 2-Aniin oa c ri d in -hyriroch lori d, 5 »6-T> i oh lor hen zoxn zol cn,

rj el, üiKJ:

11/119 6 BAD original

Furthermore, the compounds of the formula I, together with wetting or dispersing agents, can be used in the form of their aqueous dispersions, for example for protecting substances that tend to rot, such as protecting leather, paper, etc.

Active ingredient solutions or dispersions that protect them Materials can be used which advantageously have an active ingredient content from at least 0.005 g / liter to, for example 0.01 to 5, preferably 0.1 to 3 g / liter.

The new thiaiazole derivatives can also be special Use advantage for the production of antimicrobial plastic films, for example made of polyvinyl chloride. Such films are valuable packaging materials for goods, which are to be protected against attack by harmful microorganisms.

The compounds of the formula I are also suitable for combating of such phytopathogenic fungi that damage seeds · !! and their spores, as well as to protect the seeds from such Mushrooms. The compounds according to the invention can therefore be used successfully as seed dressings.

According to the invention, all types of seeds can be treated up.J effectively protected against fungal attack, e.g. wheat seeds, Rye, barley, oats, corn, rice, cotton, beet, vegetables, Tubers, such as potatoes, etc. The dressing agents according to the invention allow the control of practically all phytopathogens Fungi and their spores, which damage seeds in the ground and cause serious parasitic plant diseases, in particular lead to the well-known fire and visual diseases. Among other things, the following can be used with the pickling agent according to the invention phytopathogenic fungi are combated: smut fungi (e.g. Tilletia tritici, Ustilago tritici, Ustilago '

undae, Ustilago avenea, Ustilago ceae) Schnoeschirnmel (Fusariitrn nivale)
Root ^ l mushrooms (T \ 'rii: -: oQtorii'a solanl) ■

Halrn overturning diseases (Pythlum species)

30981 1/1196: 'f

The treatment with the seed dressing compounds proposed according to the invention, comprising compounds of formula I, can be carried out in a manner known per se according to the wet pickling method or the dry method a reading or slurry containing the dressing agent is wetted or dipped therein . The concentration of the active ingredient in such a liquid dressing agent preparation is 0.01-4% by weight, preferably 0.1-1% by weight Dry dressing, the seed is powdered on the surface with the dressing agent, which is available in finely divided form.The amount of dressing agent used should be such that, after treatment, 0.01-10 g, preferably 0.1-3.0 g, of the active substance present per 1 kg of seed. the erf indungsgem'Jss worshipful en mordant kör.r.er. addition to liquid or solid carrier coffer. emulsifying, dispersing, auxiliary and Verteilungsrr.ittel as well as means for increasing adhesive cer strength and surface-active i-üncel contain. As liquid Tra'gerstoffe aqueous Systc-rc can also orgcniscr.c-solvent or diluent into consideration; ko-roicn. As solid triggers, the invention contains gi'-Jass verv-encoten Micuel f one-part or powder: ': t ^; Pure, preferably inert, materials, in particular mineral materials, see bze. inorganic products Self-understandable kb'nncn the erfinciungsgo; rii; ssc-n verv; c-ndeten Beizmittelzubc-rc'itungc ·; *. still \ .cxi: ere for ömp. Vi j. ^ Nzenschu: ■ suitable-

Active ingredients such as insecticides, nematocides, rodenticides and Remedies against Vo ;; e] i .. ;; -; s, to be kept in place in sweet concentrations.

11/119 6 ^BAD original

A preferred field of application of the Thiä4lräl; 6 \ Le * ^ . ·. of formula I consists in disinfecting laundry items and slitting laundry items against attack by microorganisms. Man uses rinsing liquors for this purpose which contain the thiadiazoles mentioned

with advantage in concentrations of approx. 5-200 parts per Million, based on the fleet.

In addition, the liquor can also contain the usual auxiliaries, such as optical brighteners, plasticizers, acidic salts, such as Ammonium or zinc silicofluoride or certain organic acids, such as oxalic acid, and finishing agents, for example such Resin base or starch. \

As laundry items which are made with compounds according to the invention containing rinsing liquors can be sterilized, comes above all Organic fiber material into consideration, namely those of natural origin, such as cellulosic, for example cotton, or polypeptide-containing, for example wool or silk, or fiber material of synthetic origin, such as those based on polyamide, polyacrylonitrile or polyester or mixtures of the above Fibers.

The thiadiazole derivatives according to the invention give in the above-mentioned concentrations of both the liquor and the laundry treated with it have an extensive and remanence Freedom from Staphylococcus and Coliforms, which even after Exposing the active ingredient or the goods treated with it exist remain. They are characterized by their lightfastness on the laundry treated with them as well as by their high activity and Broadly effective against gram-positive and gram-negative organisms.

Particularly valuable is the use of the novel thiadiazole derivatives of the formula I as active ingredients for the healing of conditions of the skin, the intestinal system and the horns of warm-blooded animals, which i; .i cn from the excellent effectiveness against pathogenic bacteria and fungi., The relative ger-tnr '; n Tox.i // Λ 1; ^:; Λ üow.i. <- Φτ wm l; r ^r . ·; K -: rifl in unv ^ r-ihdovlev, w1.rk; - :: ior I ¹ V.γ..ι -'ji-fo " Lgf.-rifl ^ n Au:;.; '- hvi'! Imp; Mir;>; · '"· ϊπ -K" Jrpor orf / Jbt.

The: ort'incliiti {', fjgeriiii £ if5t ⁱ n .'UltimiiM'oblollon means contain

rriiri'ir -; :). frif ·, oiti Th i ίΊ i ■: ·.: (> ! <\ <ν I v.-it -Or Fnnil · "! I al: ·; Wj rk.'otoTi ' ΐ, υ-

1098 11/1196

SAD ORIGINAL

together with common pharmaceutical carriers. The type of carrier depends largely on the area of application. For external use, for example for disinfecting healthy skin, for disinfecting wounds and for treating Dermatoses and mucosal affections caused by bacteria or fungi! come, in particular, ointments, powders, tinctures into consideration. Bases for ointments can be anhydrous, for example, they consist of mixtures of wool fat and vaseline, or they can be aqueous emulsions in which the active ingredient is suspended. Suitable as a carrier for powder For example, starches, such as rice starch, if desired for example by adding highly dispersed silica specifically can be made lighter or more difficult by adding talc.

Tinctures contain at least one thiadiazole derivative of the formula Γ in aqueous, in particular 45-757 <, - strength ethanol, the optionally 10-207 * glycerine are added. In particular for disinfecting healthy skin, solutions are also suitable that with the help of customary solubilizers, such as polyethylene glycol, and, if appropriate, are prepared by emulsifiers. The active ingredient content of the aforementioned external application forms is preferably between 0.1 and 5%.

In all forms of application, be they technical, agricultural, cosmetic, hygienic or medical Determined areas of application, the new thiadiazole derivatives of the formula I can be present as the sole active ingredients or but with other known bactericidal, and especially fungi:; iden Combine active ingredients, for example for widening d-js Effective area. The following substances, for example, come into consideration as a mixture or combination partner:

309811/1196

Elemental sulfur arcnonium polysulphide Nairium polysulphide Barium polysulphide

Calcium polysulphide and calcium thiosulphate calcium hypochlorite
Boric acid

Sodium Tetraborate Decahydrate (BORAX) Zinc Chloride Magnesium: borate nickel sulfate Ka1iunichro! R.at Lead Senate

Cadsnum chloride "

Cadmium carbonate Copper (l) oxide (COPPER OXIDE) Bordesux-Bröhe

Copper sulfate pentahydrate (COPPER SULFATE) Basic copper (II) chloride (COPPER OXIC CHLORIDE) CopperdDphosphai

Tribasic copper sulphate (THREE BASIC COPPER SULPHATE) Basic copper (lJ) carbonate (KUPFERCARBOf) AT) Copper (11) dihydrazine sulfate Copper amine coupling complexes

Copper (11 Jsuifai-Anuoniuiiicarbonat-Mixture Copper DO chloride-basic copper (l!) Sulphate-Mixture Basic copper-carbonate-zinc salt-mixture CopperdD-zinc-chroraai-KompIex (KUPFER ZINK CHROMAT) KupferdD-Z'nk-cadiuDi-calcium-chromate-Koniplex copper (II) Saiz of oleic acid (copper oleate) copper (II) salts of fatty acids KupferdDsalz the Naphthenslure KupferdDsalz of the 8-hydroxyquinoline copper (II) salt of l, 2-fJaphthochinonoxinis- (2) of copper a ^r 'II) salt of 3-Phenylsai icylats Bis- ("i" in-butyltin) oxide
Triphf-yhinnhydroxyd (HEHTIBh ¹ YDROXID) Tripl, / 1tinnacetat (FENTINACETATE) bis- (i-ibutyltinnjsuccinat
Cadtii '-' succinate

Cadmii - di ~ n-propyl xanthate

CadKit -'- B-hydroxyquinolate ■

PhenylaninocadTiiuiüacetat Rienylc "inocadniundi-lactate MethylarsiJisulfid Zinke" iat
Zinc eggeate
Formally in
Paraformaldehyde acrolfine
Kcthy ^ -rcnid RelJi>: ■ ir'ilhiocyanat letra .odalhylen

1,3-chloropropene and veniand ^ e chlorinated C -hydrocarbons i)

3 0 9 811/119 BAD ORIGINAL

trans-1,4-dibromobutene (2) 1,3-dichloropropene (O) l-chloro-2-nitro-propane 2-chloro-1-nitropropane

Trichloronitrone ethane Oichloretrafluoroacetone Sodium salt of propionic acid Calcium salt of propionic acid Chiorfumaric acid bis-p-chloroethyl ester Sorbic acid and its potassium salt

2-propene-l-diol acetate '

2-aminobuian

Dodecyclguanidine acetate (dodine) Dodecylguanidine phthalate

«-Chloracety1-1,3-arainopropionitri1

a-bropiacetylvalinamide

1,2-dichloro-l-imethylsulfonyl) ethylene 1,2-dichloro-l- (butylsulfonyl) ethylene trans- 1,2-bis (n-propyisulfonyl) ethylene

p-Oichlorbenzo!

llexachOrbenzoi l, 2,4,5-tetrachloro-4-n-urobenzene CTECHAZEN) Pcntachloronitrobenzo! _ (QU! ΠΤΟΖΕΝ) l, 3,4-trichloro-2,4, B-trinitrobenzene Isomeric mixture of 1,3,4-trichloro-2,6-dinitrobenzene and 1,2,3-trichloro-<, 6-dinitrobenzene ^ iS.ß-Tetrachloroisophthalic acid nitrile 2,4-D'nitrophenyl thiacyanate Diphenyl

O-nitrodiphenyl

l-chloro-2, a-dinitronaphthalene

Acenaphthene

2,4,6-trichlorophenol 2,4,5-trichlorophenol 2, < _f 5-trichlorophenyl acetal 2, ^, 5-trichlorophenyl chloroacetate

Trichlorophenol, zinc salt

■ -Kresylace did

2,3,4,6-tetrachlorophenol

Pentachlorophenol (PCP) O-dihydroxybenzene

2, A-oxy-n-hexylbenzene 2-phenylphenol

3,5-Oibromsalicylaldehyd 2-benzyl-4-chIorphenol 2,2'-0ihydroxy-5,5i-dichloro-d! PhcnylinethaR (dichlorophen) of _{2,2'-dihydroxy-3>} 3 ', 5,5', 6, 6 ^l -hexachlorodiphenylrcethane 2,2'-0ihydroxy-5.5 ^l -dichlorodiphenyl sulfide 2,2'-dihydroxy-3,3 ', 5,5'-1 eI rat hIor-di pheny1s υ H id 2,2'-Dihydroxy-3,3 ', 5,5'-tetrachlorodip (icnylsilfid-di-N3tr1u (nsalz 4-Ch 1 or-Op ¹ ery 1 pheno 1 l, 4-DicMor-2, ^r j -dkelhGxybeM2o] (CHLCRNTB) salicylanilide

llismuth salicylate Trifluon halved with chlorine or Rrom pM.yhal i. yhnil \ Λ

309811/1196

Broraated Salicylamide '

(3,5-Dimethy1-4-chlorophenoxy) ethanol 2- {l- «ethy1-n-propyl) -4,6-diniirophenyl-2-methykrffltoat (BIfJAPACRYL) 2- (T-methyl-n-propyl) -4,6-dinHropheny1isopropylcar33iBnat (DUiOBUTON) 2- (l-methyl-n-heptyl) -4,6-dinitrophenylcrotonai (OSCaP) Ethyl-2,6-dinitro-4- (l-ethyl-hexyl) pfienylcarboijat -3 · iasttiy] -2,6-dinitro-4- (l-propyl-pentyl-phenylcarbonatfDIMOCTON) 4-nonyl-2,6-dinitro-phenylbutyrate S-Me "thy] -2- (1-! R.ethyI-n-hepiyl) -4,6-dinitrophenyltS3foEari3onat

2,6-dichloro-4-nitroanil.in (DICHLORANE) 2-cyanoethyl-N-pfienylcarbamai Propyny1-N-pheny1carbamate tt- (2-bromoacei: oxy) acetanilide

2,3,5 _f 6-Te {raGhlor-benzoquinone (1,4) '(CHLORAfJIL) 2,3-dichloro-naphthoquinone {1,4) (DICHLON) 2-alino-3-chloro-naphthoquinone (1,4 ) 2-Ch] or-3-acetaluino-naphthoquinone (], 4) 4-Kethyl-2,3,5,10-tetrahydro-3,5,10-trioxo-4H4-H _r ! Jap! Iitto O, 3 , -b) -l, 4-iriazine 2,3, ßjV-Tetrachioro- ^ ajSa-epoxy-l, 2,3,4,4a, Ba-liexa% iärjä-1,4-niethanonaphihaline-5,8-dlon

Quinone oxime benzoyl hydrazone (BENQUINOX) ■. . . -

N4richlormeihylihio) phthalkid (FOlPET) N- (Trich] ormethylthio) cyclohex-4-en-1,2-dicarboxlsiiisl (CAPTAN) N- (1,1,2,2-teirachloräthy1thlo) cyclohex-4-en-l, 2- ^ lcarbox1nid (CAPTAFOL) N-Meihansul f onyl-N-trichloromethylthio-p-chloranilisa N'-dichlorofluoromethylthio-NN-disieihyl-N'-phenylsulfaiay (OICHLORFLUAMID) S- {2-pyndyl-1-oxide) -S'-trichloroethyl disulfide;

0,0,0-trimethyl thiophosphate 0,0-diathyi-phihalinidophosphonoihioate 5-ara1no-bis (diiiiethylamido) phosphinyl-3-ph8nyl-1,2,4-ynazo1 (TRIAMIPHOS) 5-methylamino-bis (dimeihylamido) phosphine] -3-pheiiyI-1,2j4-tr1azo1 0,0-diethyl-0-2-pyrazinyl-phosphorothioate O-Ae thy 1-S, S-d ΐ pheny1-d i th i 01phos phat O-ethyl-S-benzyl-phenyldithiophosphonate 0,0 diethyl S-benzyl thiol phosphate Zinc salt of dithiocarbazic acid sodium-N-methyl-dithiocarbamate (METHAM) Sodium N-methoxyethyl-thiocarbainate Sodium-N ^ I-dir.ethyl-dithiocarbaiiate (DDC) Ammonium-NjH-diir.ethyl-dithiocarbaraat Zinc-N, N-diethyl dithiocarbamate (ZIRAM) Eisen-N, H-dimethy] -dith1ocarba! R.at (FERBA) Copper-N, N-dk.ethyl-di thiocarbamate disodium-ethylene-l ^ -bis-dithiocarbasiat (ΝΆΒΑΗ) Zinc-ethylene-l ^ -bis-dithiocarbarnate (ZINEB) E i sen-ä thy 1en-1,2-b is-d i th i ocarbana t HangandD-äUiylen-l ^ -bis-dithiocarbamate (MANEH) CaIc! 'Jii-alhylei.-l, 2-b is-öHhlccar-Ln-at A-nsoniuiii-äthyle, ·: -], 2-bk- ■; i üiir.o-ir Larat Zir! K-pro {./ leri-l, 2-bis-dilliicf.ari; a - :. at (MEZfflFB) (FESPWEB) To. (dimethylthiocarbany]) - äthylεπ-1,2-bis-diüiiccarfcaciat Complex consisting of (MAfIES) and zinc salt (IMCOZEi) Tetraethyl tbiuran inonosuliid

BIs- (N, N-dir.ethyldithiocarbarayln.erkapto) -iiielhylarsine 3 0 9 8 1 1/1

Tetramethylthlurav jisulfide (THIRAM) ßß?

DlpyrrolldylthiuraB disulfide

N.fJ'-Bis-fdiRethylaBiinoHhlurandUulfid Polyethylene thiurase sulfide Complex consisting of (ZINEB) and polyethylene thlurane disulphide (KETIRAU) Bis (3,4-dichloro-2 {5) -furanoyl) ether (mucochloric anhydrte)

2-methoxymethyl 1-5-nitrofuran 5-nitro-furturaldoxlsi- {2) 5-nitro-furfuryl-a »1doxiin- {2) l-Oxy-3-acetyJ-6-nethy 1-cyclohexen- (5) dicn- (2, A) (dehydracetic acid)

(cycloheximide) phthalimide

Pyridine-2-thiol-1-oxide-bz ·. l-Hydroxypyr1din-2-thione zinc salt of pyridine-2-thiol-1-oxide manganese salt of pyridine-2-thiol-1-oxide S1 (l-0 (ido-2-pyridyl) isothiuronyl chloride «, e-b1s (4- Chloropheny]) - 3-pyrldiMethanol (PARINOL) 8-hydroxyquinoline (8-QUIfJOLINOL) 8-hydroxyquinoline sulfate (CHINOSOL) benioyl-8-hydroxyquinoline salicylate 3- {2-methylp1peridino) propyl-3, ^ - dichlorobenzoate 6-alkoxy - | _v 2-d1hydro-2 _f 2 _t 4-triBethyTchlnolin. (ETHOXYQUIN) -.

N-Lauryl-isochlnoltniunbroiid 9- (pn-Hexyioxypher> yl J-10-methyl-acrtdiniumchlorid 9- (pn-Hexyloxyphenyl) -10-methyl-acridiniiii! Ip - tQluolsulfonat 2-n-heptadecylinihaiondinacetatyl- (GLYOOIN) l-Hydroxydinacetatyl- (GLYOOIN) l-Hydroxydinacetatyl- 2-heptadecylinidazoHdin l-Pheny1-3,5-d1methy! - * ~ nHrosopyra7ol lp-chlorophenyl-3 _t 5-d1methyl-A-ni trosopyrazole 1-p-sulfa ^ y ipfienyl-SjS-dimetbyl-i-ni trosopyrazole H- (1-Phenyl-2-nitropropyl) plperazln 2-Dimethyl aino-6-diethyl-5-n-butyl-4-hydroxypyriBldin M-Dodey1-1,4,5,6-tetrahydropyr1 with 1 π N-Dodecyl-2 -eethyI-l, ^, 5,6 - tetrahydropyrimidine 2-n-heptadecyltetrahydropyrimidine 1- (4-Amino - + - propyl-5-pyri-tdy1-meihy1) -2-methylpyrldiniumchloride-hydroxychloride 2- (2'-furyl) -benzimidazQl (FURIDAZOL) S-dodecyl-1-ynethyl ^ -phenylbenziaidazolium-ferricyanide methyl -H-benziraidazol-Z-yl-N-butylcarbamoyDcarbajiat (BENOMYL) 2- (0-chloroanilino) -4 _l 6-dichloro-syiii.-triazine 2-ethylamino-6-iiiethy1-5-n-butyM-hydroxy pyrJaJdin

2,3-0icyano -), 4-dithia-anthraquinone (DIIHIANON) 2- (Mh1azolyl) -benzimldazole 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone (ORAZOLONE)

ThlaioHdlnen-4-thlon- (2) (RHODANINE)

3- (p-Chlorphenyl ) -5-aethylrhodanine 3,5-dimethyl] tetrahydro-1 _f 3,5-thiadiazine-2-thlone (DAZOMEI) 3,3'-ethylene-bis (tetrahydro-4,6-dinethyl ) -2H-1,3 _t 5-thiadazin-2-th1on) (? IlLNEB) 3-0enzylideriaaino-4-phcnyl lhij; til in-2-thione 6-chlorotenzthiazo] -2-thiol, zinc.) Iζ 6- P-Diatliy 1 amino-ethoxy-2-diethylar, ino-beriithlazol dihydrochlcrid hfonoä lhano) ammonium-b

30981 1/1196

BATH

Zinc and Natirunsalze of 2-Kerikaptobenztüiilazols IMD Diiseühyldithiocarbamats 6- (ß-Diäthy} arnino3tr _£ oxy) -2-dirr, eihylamincfcenziliiiazol dihydrDchlorid-3-TrichloriiiethyHhiobenzothiazolon 3-Trichlorniethyl {h5efceiiizoxazo] one 3- (Trichlonr, ethyl) -5-ethoxy -1,2,4-thiadiazole 6-methyl-2-oxo-1,3-dithiolo [4,5-b] -quinoxaline (QBIHBEIHIOHAT) 2-thio-1,3-dithiclo [4,5-b] - quinoxaline ΠΗΙΟ0ΙΙΙΗΚ).

2,3-Dihydro-5-carbsx3nilido-6-r -ihyl-l _f 4-oxathin 3,3,4, ^ - TetrachlorideirahydrothiGphen-ljI-diioxyd 2,3-dihydro-5-carbex3iiilido-6-irctfiy] - l, 4-03Hiii5iii! -4 _J 4-dij> xyd Aeihyl-trimethy] a -: caiuEbroniid n-Alkyl ^ .-, C ₁ C.) dmeihylbenzylaainioniiniicblorid Alkenyl-dinetnylaxFiyiaEaoniumbroniid 0 ia 1 ky 1 di me thy] a Kf -O-:! ticfcroni id

Alkyldimethylbenzyla ~ ^p scniuir.chlond ·

Alkyl C _n -C ₁ yj 3

Di-isobutyiKresoxyäiTiaxyätbyldiir.ethylbejizylaiiiKiiiiüiiiiEchJorid p-Di-isobutylphenoxyethoxyäthyldifnethylbenzylaeimliiäEchlorld

Gliotoxin ^ ji-Diguanidino-SjSjS-trihydroxycyclohexyl 5-deoiiy-2-0- {2-iJeoxy-2-iiietliylainino-α-L-glucopyranosyl) 3-C-formyl-β-uyxopentofuranoside (STREPTOMYCIN) 7-Chl or-4,6-direthox / cuoaran-S-nn ^ -spiro-l '- (Z'-aettoxy-B'-nethyleye 1 ohex-2'-en-4 On) (GR ISEOFULVIN )

(OXYTETRACYCLIfJ) 7-chloro-4-din; etKy ^! c-ii! io-l, 4,4a, r ', 5a, 6, ll _J ] 2H-octa! iycIro-3,6,10,] 2,] 2a pentahydroxy-B-ethyl-ljll-dioxo-Z -naphthacencarboximid (CHLORTE! RACYEUS) (PIUARICfN) (LANCOMYCIR) (PHLEOMYCIN) (KASUGAMYCIN) (PHYTOACTIN) Df-J-threo ^^ - dichk.rH-tS-hydroxy-a-ihydroxyeetthyylT-p-nihydroxyeETTHYLT-p-nihydroxyeETThyT-p-ni Blasticidin-S-benzylanino-benzenesulfonate

N- (3-nitrophenyl) Ü3ii? TiiHid Phenoxyessigsäjrt sodium-p-dineii.) ] J * J'r: u-ber> zo] o , / osulfonat Acroiein-phenyli,] 'j-'3ii 2-Chl oracetaldt fj d {? _; 4-dinitrop '■, nyl) -hydrazone 2-chloro-3- (tolyL - .. «!« I- ^ D-propi; · -itrile l-chloro-2-phenyl -; -.- "rn- diol (4 / -1hion {3) p-Nonylphenoxypc ¹ , -i :. Jefioxyath- ol-Jod-Koaplex (o-NHroitethyl) -Cc- "c-benzylth · '? iliy 1 aain- hydrochloride 3- ( p.-t.-butyl-p! .c ^ '' aIfonyl) acrylonitrile Oktachl orcyc 1 ohexCäCr Pentachlorbenzylakoh ;!

Pentaclilobenzyl acetate pentachlorobenzaldehyde cyanohydrin 2-norcanphanneti ''; ^r ''? l, 6-SSIS (dir.ei ^'y' ---- '' JyJ -Cr ^i!.) - 'exar "; a.

l- (3-ChIoraJ iyl) -. 3.0 _f 7-triaz3-l-coal tar and ifochcf tar

309811/1196

The compounds of the formula I can preferably be halogenated with Salicylic acid alkylamides and anilides,

with halogenating dipheny! ureas, with halogenating benzoxazoles or benzoxazolones, with polychlorohydroxydiphenylmethanes, with halodihydroxydiphenyl sulfides, with bactericidal 2-iminoimidazolidines or tetrahydropyrimidines or, with bactericidal and fungicidal quaternary compounds or with certain dithiocarbamic acid derivatives, as with tetramethyl thiuram disulfide, with fungicidal amidines, carbainoyloximes, are combined. Possibly Carriers with beneficial inherent effects, such as sulfur as a powder base or zinc stearate as a component, can also be used of ointment bases, used v / ground.

In the following examples, some typical forms of application for various areas of application are described.

St lifting means

To make a 2% dust, the following are used Substances used:

2 parts of active ingredient of formula I.
5 parts of colloidal silica and 93 parts of talc.

The active ingredient is intimately mixed and ground with the carrier substances. The fungicidal dust obtained in this way is used to dust plants.

Spray powder

For the production of a) 25% and b) 40% wettable powder the following substances are used:

a) 25 parts of active ingredient of formula I.

10 parts of a 1: 1 mixture of Cg-Cng-alkanol-polyglycol-

ether and kieselguhr,
35 parts diatomaceous earth and
30 parts of colloidal silica; BAD ORIGINAL

30981 1/1196

b) 40 parts of active ingredient of the formula I.

10 parts of a 2: 3 mixture of Cg-C- ^ g-alkylphenoxy-

polyoxyethylene glycol and silica. and 50 parts of silica.

The active ingredients are absorbed onto the carrier substances and then mixed and ground with the additives listed. A wettable powder with excellent wettability and suspension properties is obtained. Such wettable powders can be diluted with water to obtain suspensions of any desired concentration of active ingredient, which are used to treat crop plants.

- Λ

Emulsion concentrate

For the production of a) 10% and b) 207o emulsion concentrate the following substances are used:

a) 10 parts of active ingredient of the formula I, 15 parts of ethoxyethanol ". 15 parts of dimethylformamide

50 parts mineral oil with a high aromatic content and 10 parts of a combination emulsifier, consisting of the calcium salt of dodecylbenzenesulfonic acid and one Alkylaryl polyglycol ether (e.g. "Emullat P 140 HFP", manufacturer Union Cliimique S.A., Brussels);

b) 20 parts of active ingredient of the formula T and 70 parts of xylene

10 parts of a combination emulsifier, consisting of the Calcium salt of dodecylbenzenesulfonic acid and an alkylaryl polyglycol ether (e.g. "Emullat P 140 HFP", Manufacturer Union Chimique. S.A., Brussels).

The active ingredients are in xylene respectively. the solution-filling mixture loosened and these solutions are then the combination emulsifiers added. . One receives Emulsionr.koiizontratc: which with water to Krii'.i I ·. I ou '. ti jfuli) ^ cü.desired concentrate, ion vonUinnt be konncu. iJolclie Kiiiulnionfii are suitable for treating crops.

30981 1/1 196

ORIGINAL

granules

The following substances are used to produce a 27 _{o granulate:}

4 parts of a 1: 1 mixture of the active ingredient of the formula I with silica

92 parts of granulated limestone
3 parts of a mixture of 0.5 parts of Cg-C ₉ alkylphenoxy «

polyoxyethylene glycol and 2.5 parts of polyethylene glycol and 1 part diatomaceous earth.

The lime grits are impregnated with the polyethylene glycol mixture and then mixed with the mixture of active ingredient and silica. Then kieselguhr is added as an anticaking agent. This granulate is particularly suitable for treating potting soil.

Seed dressings

A. A dry pickling agent of the following composition was used:

20 wt -.% Of a compound of the formula I

1 wt -.% Paraffin oil
79 wt .- # talc.

'"■■ There are 600 g of this agent, which has good adhesion compared to seed grains, with IOD Ug barley seeds placed in a tightly closing rotatable trough. The filled barrel was rotated for 45 minutes, according to v.'C-icher Time was practically the entire amount of the agent used as a coating on the seed grains.

P. Eu became an i; n :: fibnizmittel fol ^ ncior iucc ^ nmensotzuni;

309811/1196 ßAD

23 * 00 wt -.% Of a compound of formula 1 1.65 wt -.% Alkarylpolygiykolärher (Eir.ulgator)

1.65 wt. 7. MaHSO ^ -H ₂ O, finely ground 73.70% by weight of DiSUhylene glycol monoethyl ether acetate. A bath was prepared: consisting of 250 g of the above agent and 15 liters of Hasser at room temperature, this bath preparation being thoroughly mixed. "1-With this aqueous preparation" 100 kg of rye seed would be showered then drain onto a * sieve.

"■ .-- ■■" - ■

leave and then dry well.

C, A wet pickling agent of the following composition was used used: . '"·

65.0% by weight of a compound of the formula I.

18.0% by weight of precipitated, hydrated, amorphous silica 5.0 Gev7.-7o coconut oil / alcohol polyglycolic acid with 8> iol

Ethylene oxide per hol of fatty alcohol 4.0 Ge \: .-% adhesive (containing 5O7 _e polyvinyl

. alcohol),

8.0% by weight kaolin (finely powdered). -

50 g of this agent were dispersed with 3.5 liters of water. With this aqueous "preparation 100 kg Oats — seeds sprayed and worked thoroughly so that all of the liquid sinks from the seed grains has been recorded. After that it was only easy moist seeds dried.

30 9811/1196 sad original

Claims (17)

-tu - Claims Thiadiazo! Derivatives of the formula I • _ JV Jl Γ in which R is hydrogen, an unsuhntituierton or 1-V by halogen, alkoxy or dialkylamino substituted alkyl radical with 1-4 carbon atoms, Alhcuylreß with 2-4 carbon atoms or cycloa]); yl or cycloalkenyl radical with 3-7 carbon atoms, Rp is a straight-chain or branched alkyl radical with 1-4 carbon atoms, and η means 1 or 2. 2. Thiadiazo] d ■ rj vat, characterized by Mispruch] R methyl, ethy J or tri fluorinetbyl, R ₂ alkyl with JI J3 4 carbon atoms and η means 1 or 2 . BATH ORIGINAL 0 9 811/119 - in - 3. thiadiazole derivative according to claim 2, characterized by the formula 4. thiadiazole derivative according to claim 2, characterized by the formula -CI 3 · 5. thiadiazole derivative according to claim 2, characterized by the formula H- "CH XJH. 6. Th.i adiazolder'ivat according to claim 2 _S characterized by the formula fs ■ CFL-Oi L ₃ , ΒΛΟ 30981 1/1196 7. thiadiazole derivative according to claim 2, characterized by the formula Ii 8. thiazolyl derivative according to claim 2, characterized by the formula 9. Process for the preparation of thiadiazole derivatives of the formula I. R ₂ - S (O) _n 309811/1196 2, and R and R are those under formula I in claim 1 in which given ^ meaning, characterized in that one 5-chloro-thiadiazole of the formula II Cl . (II) in soft * - * R-. has the meaning given under formula I, with a compound of formula III R ₂ - - Me (III) in which R has the meaning given under formula I _} η 2 and IVSe is an alkali metal cation, 10. Process for the preparation of thiadiazole derivatives from Forrael T according to claim 1, characterized in that a thiadiazole derivative of formula IV (IV) 309 811/119 6 _ 44 - in which R and R _{p have} the meaning given in claim 1 oxidized. 11. Means for combating harmful microorganisms, characterized by a content of at least one compound according to claims 1 to 8. 12. Composition according to claim 11, which in addition to the active ingredient as a solid or liquid carrier, at least one of the following Additives contains: soaps, surface-active substances, foaming agents, emulsifiers, dispersants or wetting agents, water, organic solvents, light stabilizers, optical brighteners, fungicidal substances, bactericidal substances. 13. Antimicrobial detergent and cleaning agent, marked by a content of at least one compound according to claims 1 to 8. 14. Use of thiadiazoles according to claims 1 to 8 as Fungicides, in particular being soil fungicides. 15 · Use of thiadiazoles according to claims 1 to 8 for Protecting organic materials against the harmful and damaging effects of microorganisms. 16. Seed dressing containing a thiadiazole as active ingredient according to claim 1. 17. Means according to claim l6 characterized by a content to 3-methyl-5-n-propylsulfonyl-1 _i 2, ^J t-thiadiazole, 3-methyl-5-tert.butylsulfonyl-1,2,4-thiadiazole or 3-methyl-5-sec.butylsulfonyl-1, 2,4-thiadiazole. 309811/1196 l8. Methods of combating phytopathogenic fungi and fungal spores that damage seeds in the ground, by treating the seed before sowing with a dressing agent, characterized in that a dressing agent according to Claim 16 and 17 used. PO 3.35 / Eich / sl / ps 309811/1196