DE1060655B - Pest repellants - Google Patents

Description

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FEDERAL REPUBLIC OF GERMANY

GERMAN / mtm. PATENT OFFICE

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kl. 451 9/12

INTERNAT. KL. A 01 H EXPLAINING PAPER 1060 655

M 35726 IVa / 451

REGISTRATION DATE: OCTOBER 26, 1957

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:

JULY 2, 1959

The present invention relates to new pesticides, whose active ingredients are derived from 1,2-dicyan-1,2-dimcrcapto-ethene. About the biological The effect of this group of substances is not yet known, and only two representatives with a very simple structure are at all (cf. Chemische Technik, Vol. 8, pp. 597, 598 [1956]).

It has been found that derivatives of 1,2-dicyano-1,2-dimercapto-ethene have excellent biocidal effects. It is particularly noticeable that the individual connections appear very different. Representatives of this class of compounds were found to be acaricidal, fungicidal, insecticidal, nematocidal or have several of the mentioned effects. It has been shown that with Preservation of the structure apparently responsible for the biological effect

NC —C-S-

: l
NC-CS-

the groups seated on the free valence valences can be varied as far as possible without the biocidal effect of the respective compound being lost as a result.

The present invention accordingly relates to a damaging device lingsbekämpfungsmittcl, which is characterized by a content of compounds of the general formula Pesticides

Applicant:

E. Merck Aktiengesellschaft, Darmstadt, Frankfurter Str.

NC-CSR ₁

NC —C —S —R, Dr. Albert van Schoor, Traisa on Darmstadt,

Dr. Ernst Jacobi, Dr. Siegmund Lust

and Dr. Horst Flemming, Darmstadt,

have been named as inventors

wherein R ₁ and R _{2 represent} organic radicals which can optionally be linked to one another.

The following table lists some of the compounds tested with their radicals R ₁ and R _2. The corresponding biological effectiveness is given in the right column.

No. of
Ver
do thi ng R, R ₁ = s Physical data
F. I Kp. 168 to 172 ⁰ C
at 0.4 torr effect I. -COO-C ₂ H ₆ -COO-C ₂ H ₅ - - acaricide
fungicide II -CH ₃ -CH ₃ 101 ⁰ C - insecticide
acaricide
nematocide III /
\ - - acaricide IV - - acaricide
fungicide V - CO- S - C ₄ H "(n) - CO —S — C ₄ H ₉ (n) 125 ° C fungicide
neraatocide VI > c = o 117 ° C acaricide
fungicide > C

3 K, 0 κ, Cl 4th - effect No. of
Ver
binding -CH ₂ -COO-C ₂ H ₅ -CH ₂ -COO-C ₂ H ₅ | CH _a Physical data
I · '. Kp. nematocide VII i
0 57 ° C - \ O Cl fungicide VIII A.
v 150 "C O \ / \ ■ --- ) fungicide IX 220 ⁰ C

1,2-Dicyan-1,2-di (carbethoxymercapto) ethene (I) shows a good fungicidal and at the same time an acaricidal effect, so that the connection through its combination effect is particularly suitable for pest control. The tests were carried out e.g. B. with the Mushroom Rhizoctonia solani and the mite Tyrophagus dimidiatus.

1,2-Dicyan-l ^ -di-imethylmercaptoj-ether (II) possesses In addition to excellent acaricidal and nematocidal properties, it also has a good insecticidal effect. the Effect against nematodes was z. B. on Panagrellus zymosiphilus and against mites on Tyropbagus dimidiatus tested. It turns out that the effect of this compound is currently the best special one in practice Acaricide (dichlorobenzilic acid ethyl ester) and most effective nematocide (N -metbyldithiocarbam in acid sodium) quite corresponds. This substance combines excellent nematocidal and acaricidal properties.

4,5-Dicyan-1,3-dithiol-2-one (V) possesses compared to Rhizoctonia solani about twice as strong a fungicidal effect as tetramethylthiuram disulfide. Simultaneously this substance has a nematocidal activity that is equivalent to that of sodium N-methylditbiocarbamic acid. There is thus a combination of excellent fungicidal and nematocidal properties.

4,5-Dicyan-1,3-dithiol-2-thione (VI) has even better nematocidal and fungicidal properties. The usual one Fungicide Tetramethylthiuramdibulfid is exceeded in its effect by this substance 20 times, and the nematocidal properties of the compound are about 4 times that of N-methyklithiocarbamic acid Sodium. This active ingredient is therefore extremely suitable for combating nematodes and fungi.

2,3-Dicyan-1,4-dithiaanthraquinone also has a very good fungicidal effect (TX). The fungicidal effect is particularly pronounced here. She is on average twice as large as the organic fungicides that have been tried and tested in practical crop protection. This connection was tested on the mushrooms Rhizoctonia solani, Venturis, inaequalis, conidiospores, Alternaria spec, and Botrytis cinerea, in comparison with N-trichloromethylthiotetraliydrophthalimide, Zinc dimethyldithiocarbamate and tetramethylthiuram disulfide. Phytotoxic ^ experiments showed that the substance is particularly well tolerated by plants having.

Pesticides, the chemical constitution of which shows a certain similarity with the dithiaanthraquinone derivatives according to the invention, are described in British patent specification 747 909, German patent specification 876018 and USA patent specification 2,547,723. Comparative experiments showed that these compounds have a significantly lower fungicidal and fungistatic activity than the dithiaanthraquinone derivatives disclosed with the present invention.
The invention can claim to have opened up a new group of pesticides, the individual representatives of which have the most varied of biocidal activities, some selectively and some combined.
Jiie compounds according to the invention can, for. B.

can be produced by reacting the alkali salt of 1,2-Dicyan-1,2-dimercapto-ether with the corresponding organic halogen compounds. So you can z. B. 1,2-Dicyan-1,2-di- (butylmcrcapto) -ethcn produce by Sales of the disodium salt of 1,2-dicyano-1,2-dimercapto-ethene with 2 moles of butyl iodide or bromide. The reactions are expediently carried out in the presence an inert solvent, such as. B. methanol, ethanol, xylene or acetone through. The reactions are also successful when working in suspension rather than in solution.

The compounds can be used on all pesticides common application forms. According to known methods, you can spray and dusts or can produce the compounds Add paints or varnishes or soak textile fibers with suitable solutions of the substances. Even processing into solutions or emulsions, which after the anisole process can be sprayed using the solvents customary for this purpose. All application forms generally contain at most 95 percent by weight of active ingredient. Mixtures of the compounds can of course also be used process according to the invention to the usual forms of use in crop protection.

In the context of the present invention, no protection is claimed for the production of the active ingredients.

Examples

1. To a suspension of 3.7 g of the disodium salt

of 1,2-dicyan-1,2-dimercapto-ethene in 50 ecm benzene are 1.5 ecm thiophosgene in about 15 minutes

5 6

Ice cooling and stirring were added dropwise, then boiled for 2 hours through dissolved alcohol. The alcoholic

Stirring further at ordinary temperature, the solution is freed from the solvent in vacuo, the

Reaction brought to an end. After removing the water residue in an ethereal solution, repeat with water

soluble fractions, the benzene is distilled off and washed out and, after drying, with Na ₂ SO ₄

Recrystallized residue from carbon tetrachloride. 5 distilled. 15 g of 1,2-dicyano-1,2-di- (ethyl-

The pure 4,5-dicyan-1,3-dithiol-2-thione crystallizes in mercapto) ethene as a light oil with a boiling point of 133 bis

golden yellow needles and melts at 123 ° C. 135 ° C below 0.3 torr.

2; 3.7 g of the disodium salt of 1,2-dimercapto-8. A mixture of 25.9 g of disodium salt of 1,2-di-

1,2-Dicyan-ethens with 4.6 g of 2,3-dichloro-naphtho- mercapto-1,2-dicyan-Ethens, 22.1 g / 3-Chloräthyl-methyl-

quinone combined in alcoholic solution. The io sulfide and 50 ecm of absolute alcohol is 45 minutes on

Reaction mixture warms to about 4O ⁰ C. reflux condenser cooked. The solvent is removed

By subsequent boiling for an hour or two, the Rcak is vaporized and replaced by ether. Water soluble parts

tion terminated. Cooling to about 1O ⁰ C and aspiration are extracted. Then the Na ₂ SO _{4 is} dried

supplies a crude product containing NaCl. The purification concentrated solution and the residue in vacuo

takes place by leaching with water and recrystallization 15 distilled. After a slight advance go at 185 to

from ethylal or acetone. The 2,3-dicyano 190 ⁰ C produced in this way under about 0.01 Torr 13 g of a light yellow from

1,4-dithiaanthraquinone crystallizes in gray-brown Na- l, 2-Dicyan-l, 2-di - (^ - methylmercapto-ethylmercapto) -

dell with purple metallic shimmer and melts the existing oil over,

9 at 220 ⁰ C. A mixture of 26.4 g Styroldibromid, 15 ecm

3. 14.8 g of the disodium salt of 1,2-dicyan-1,2-di- so acetone and 25.9 g of the disodium salt of 1,2-dimercaptomercapto-ethene are suspended in 50 ecm acetonitrile 1,2-dicyan-ethene is boiled for 1 ^ hours on the reflux and at ^{0 0} C within 15 minutes with a solution of cooler. 18 g of NaBr can be stirred into 8 g of phosgene in 16 ecm of acetonitrile by filtration. It is easy to feel. After evaporation of the acetone, a lively reaction with the development of heat takes place, a syrup permeated with crystals, from which cooling must be carried out. To complete the 25 treatment with trichlorethylene and subsequent UmReaktion is shaken overnight at 25 to 30 ⁰ C. crystallize from CCl ₄ analytically pure 2,3-dicyan-5,6-di-The resulting NaCl is removed by filtration. hydro-5-phenyl-p-dithiin obtained, mp 128-133 ⁰ C. The filtrate yields, after evaporation of the solvent in is.

Vacuum a product still containing NaCl, from which 10. A mixture of 16.8 g of chloromethyl-p-tolyl ketone,

repeated recrystallization from ethyl acetate pure 30 150 ecm acetone and 9.3 g disodium salt of 1,2-di-

4,5-Dicyan-1,3-dithiol-2-one with a melting point of 125 ⁰ C mercapto-1,2-dicyan-ethene are at for 30 hours

can be isolated. Stirred at room temperature. The fixed portions will be

4. 7.45 g of the disodium salt of 1,2-dimercapto-l, 2-dicyan- sucked off, washed with water and after ethens are recrystallized from benzene with 13 ecm butyl bromide and 37 ecm drying. The thus obtained Alcohol boiled for 11 hours. The precipitated common salt 35 l, 2-dicyan-l, 2-di- (p-toluylmercapto) -ethene melts is removed by filtration, the alcohol below 165 to 167 ° C.

distilled under reduced pressure. A dark 11 remains behind. 13 g of the disodium salt of 1,2-di-

Residue, which is dissolved in ether and repeated with water mercapto-1,2-dicyano-ethene in 150 ecm of ether and carries /

is washed out. The ether dried with Na ₂ SO ,, in the course of 20 minutes a solution of 10 g of phthalic

After the solution has been distilled off, the solution leaves acid dichloride in 10 ecm of ether. Here the,

by means of 6.7 g of brown oil, which is kept at about 5 ° C by ice cooling at the subsequent vacuum temperature,

distillation mostly at 147 to 148 ° C below about Then the temperature is allowed to rise to about 20 ° C

0.3 Torr passes. The fraction consists of 1,2-dicyan and is stirred for a further 4 hours at room temperature. That

1,2-di (n-butylmcrcapto) ethene. reaction pro-

5. 6.1 g of chloroacetonitrile in 30 ecm of acetone are filtered off with suction, washed with water and removed dissolves and recrystallized in the course of 30 minutes with 7.4 g of disodium acetone with the addition of a little charcoal, salt of 1,2-dimercapto-l, 2-dicyan-ethene added, whereby the so produced

the temperature is maintained at 19 to 21 ° C. To obtain the tetracyane product, the table salt is replaced by g qq

Filtration separated, the filtrate concentrated and the 50, / \., - '' "" ^

residue obtained from chloroform, then from alcohol ^N ^ ~

umkristallisicrt, reasonable until the melting point to 120 ⁰ C xsr r

has risen. This gives the 1,2-dicyan-1,2-di- (cyano- ^N ^ C _κ "\. ^

methylmercapto) ethene in white prismatic cri- ^N S - CO

stall. 55

6. In a suspension of 7.4 g of the disodium salt which melts at 211 ° C.

l ^ -Dimercapto-l ^ -dicyanethcns are stirred in under ice-cooling 12. 26 g of the disodium salt of 1,2-dimercapto-1,2-dicyanlung 10 ecm of allyl bromide. The ethens will rise in the course of 45 minutes to a temperature of up to 20 ° C. The potassium sulfite and 220 ecm acetone are added by stirring for 10 minutes with a mixture of 22 ecm perchloromethyl mercaptan with 2.6 g room temperature and boiling for 15 minutes, the reaction being completed. The NaBr is suctioned off, the temperature must be kept at 0 to 5 ° C. Subsequently, the filtrate is evaporated and the residue is taken inÄther will be l ^l / ₂ hours shaken long without cooling at Zimmerauf what remains water-soluble substance temperature further stirred. The excreted table salt will be. This is followed by drying with Na ₈ SOj, the residue is removed by filtration and the ether is distilled off with acetone and the ether is washed in vacuo. The solvent is evaporated and the residue. The obtained l, 2-dicyano-l, 2-di- (allylmer- residue boiled with Pctroläther. It will capto) -äthen proceeds at 131 to 133 ⁰ C under 0.3 Torr as crystals, melting. 118 to 12O ⁰ C obtained by Umhelles oil over. crystallize from carbon tetrachloride pure cis-1,2-di-

7. 26 g of the disodium salt of 1,2-dimercapto-1,2-dicyan-cyano-1,2-di- (trichloromethyl-dithio) -ethene with a melting point of 120 bis Ethens will deliver with 25 g of ethyl bromide in 150 ecm abso- 70 122 ° C.

7 8

13. 28 g of the disodium salt of 1,2-dimercapto-l ^ -dicyan- stirred and then boiled for a further 2 hours. The ether ether and 26.5 g sodium thiose sulfate are washed in 280 ml of solution with water at 0 to 5 ° C, dissolved with water and _{dried at about -3 "C with a solution of Na 2} SO ₄ and distilled from the solution of 20 g of chloromcthyhnercaptan in 60 cc of petroleum free medium. in order to accelerate crystal formation ether stirred, to which about 1 hour is needed. 5 dissolve the brown evaporation residue in benzene After I ¹ / _{for 2} hours, further stirring the reaction and decomposes the benzene solution aiii chromatograpraktisch terminated. the After separation of the washed product, two sulfur-free fractions are obtained after drying, which for the most part ^{crystallize in chlorobenzene at about SO 0} C. After concentration has taken place, the undissolved components are contained the disubstituted from benzene is obtained as a tuated isomeric compound which melts at 130 ° C. By recrystallization ren crystal needles of 1,2-dicyan-1,2-di- (N, N-dimethyl chloroform) one obtains the trans-1,2-dicyan-1,2-di-carbamyl-mercaptoj-ethene.

(trichloromethyl-dithio) -ethene in beautiful flakes- 19. A mixture of 15 g of 2-oxy-S-nitro-benzyl chloride,

gen crystals melting at 178 to 18O ⁰ C. 200 cc of ether and 10.4 g of the Dinatriumsalzcs

14. A suspension of 34 g chloroacetanilide in 15 ^ 1 ^ -Dimercapto -dicyan-äthens is 4 hours 75 cc of acetone is stirred over a period of about ¹ J for ₁ hour at ordinary temperature. Dxirch evaporation with 26 g of sodium salt of 1,2-dimercapto-1,2-dicyan- des ether and recrystallization of the resulting ether stirred and the residue from dioxane is obtained by moderate cooling, 1,2-dicyan-1,2-di- Maintained temperature between 25 and 30 ° C. To be (2-hydroxy-5-nitrobenzyl-mercapto) -ethene of F. 135 acceleration of the reaction is then another 1 hour 20 to 1.37 ° C.

long cooked. The acetone is then distilled off and 20. 62 g of the disodium salt of 1,2-dimercapto-l, 2-dicyano

washes the residue, after thorough trituration with ether, suspended in 400 ecm acetone, are dripped

Water, then with alcohol and finally with ether, while stirring, with 31 g of dichloromethyl methylsulfide

the end. 1,2-Dicyan-1,2-di-added are obtained in good yield. The mixture heats up weakly. It will

(N-pbenyl-carbamylmethyl-mercaptoJ-ethene. The sub-25 is stirred for a further 1 hour at room temperature

punch melts after recrystallization from glacial acetic acid and the solvent is distilled off in vacuo, the back

Acetone at 215 ° C. got stripped with water and made up of benzene, then off

15. 7.4 g of the disodium salt of 1,2-dimercapto-1,2-dicyanocarbon tetrachloride recrystallized. Those at 93 to ethens are suspended in 37 ecm of absolute alcohol. 95 ° C-melting yellow crystals consist of is added dropwise at about 20 ⁰ C with stirring, and 30 2-Methyknercapto-4,5-dicyano-l, 3-dithiol.

Does 11.5g of chloroformic acid ß-chloroethyl ester and ßV cool? 50 g disodium salt of 1,2-dimercapto-1,2-dicyan-

stir for a further 2 hours at room temperature. ithens are suspended in 300 ecm of pure acetone,

The resulting mixture is filtered, concentrated and at - 40 ⁰ C cooled. With stirring, 30 g

ethereal solution washed out with water. After acetyl chloride in 60 ecm acetone added dropwise (15 minutes)

Evaporating the solvent and standing for several days, and 35 ^ hour at - held 40 ^0C. The acetone will

crystallizes the l ^ -Dicyan-l ^ -di-dö-chloro-carbäthoxy- distilled off in vacuo, the residue with water

mercapto) ethene. Added by recrystallization from metha-, extracted with ether. The ether is via Na ₂ SO ,,

nol, the substance is obtained in pure form from the F. 87, dried, filtered through charcoal and distilled off. Of the

up to 90 ° C. The residue is after recrystallization from isopropyl

16. There are 8 ecm chloroacetone in 50 cc of acetone, 40 ether, then from cyclohexane 10 gl, 2-dicyano-l, 2-divorgelegt g and at 15 to 20 ⁰ C., while cooling 13 of the (acetylmercapto) -äthen mp 115 ⁰ C, sinters from IU ⁰ C. Dinatrium salt of 1,2-dimercapto-1,2-dicyano-ether is added to the acetone solution after the reaction is stirred in. It is ^{left to stand for a further 1} _{l for 2} hours, often under a lot of water, and the precipitated product is filtered off with suction and shaken. 200 ecm are then added to recrystallize from isopropyl ether, crystals of water are obtained, the precipitate is filtered off with suction and crystallized from a melting point of 81 to 82 ° C. The analyzes of both substances are recrystallized from acetone until the melting point is 153 to 155 ° C equal, so that there are probably cis-trans-isomers, has been reached. 22. 130 g of the disodium salt of 1,2-dimercapto-

The elementary analysis of the slightly yellowish 1,2-dicyano-ethene are in 750 ecm acetone under

Needles corresponds to the compound 1,2-dicyan-1,2-di- stirring with 65 g of bischloromethyl sulfide added

(acetonyl-mercapto) -ethene. 50, the temperature is kept at 30 to 35 ⁰ C. At-

17. While stirring and cooling gently with ice, the mixture is stirred for a further 1 hour at room temperature over the course of about 10 minutes. The acetone is then distilled off in vacuo, water is added to the residue of 13 g of the disodium salt of 1,2-dimercapto and the residue is etherified 4 times from 1,2-dicyano-ether in 50 ecm acetone with 19.3 g chlorine. The ether is _{dried with Na 2} SO ₄ and ethyl formate. After stirring for a further 3 hours, distilled off, finally in vacuo. The residue is filtered off at room temperature, the precipitated is dissolved in benzene and _{chromatographic salt on neutral Al 2} O ₃ , the solvent is evaporated and the graphed is dissolved. Elution with benzene-ethyl acetate 4: 1 residue in ether and wash with water. The _i obtained yellow crystals, melting at 112 to 114 ⁰ C, sinters with Na ₂ SO ₄ dried ether solution is evaporated. : from 109 ° C. Analytical data agree to the Verbin-off the remaining brown oil are deposited over 60! Dung 2,3-dicyano-l _J-4.6 trithiacyclohepten-2.

Night crystals from repeated recrystalli- 23. wettable powder. 80 parts of 2,3-dicyano-1,4-dithiaanthra-

sicren from methanol, shiny, almost colorless needles of quinone, 10 parts of kaolin, 10 parts of the sodium salt of the

F. give 50 to 51 ⁰ C. The results of the elementary densation product from oleic acid and methyl taurine,

analysis show the new compound as 1,2-dicyan- techn. (32 ° / ₀ ig), the necessary fineness

1,2-di- (carboctoxy-mercapto) -ethene. Grind 65. The powder produced in this way can be in the form of

18. 13 g of the disodium salt of the dilute aqueous suspension are suspended or ver-1,2-dimercapto-1,2-dicyano-ethene is injected in 100 ecm of ether and be sprayed.

gradually stirs a solution of 10.8 g of dimethyl 24th emulsion concentrate. 40 parts of 1,2-dicyano-1,2-di-

add carbamic acid chloride in 10 ecm of ether. The mixture (cyclopenten-2'-yl-l'-mercapto) ethene, 12 parts of polyoxy

continue for 20 hours at normal temperature - 70 ethylene sorbitol ester of a mixture of fat and resin

acids combined with a suitable sulfonate, 3 parts sulfonated aliphatic polyester and 45 parts Xylene are mixed together. The resulting solution is emulsified in water and can be splashed or be sprayed.

25. Liquid aerosol. 24 parts of 1,2-dicyan-1,2-di- (carbäthoxymercaptoj-ethene, 76 parts of methylene chloride, 50 parts of difluorodichloromethane, 25 parts of monofluorotrichloromethane ■ and 25 parts techn. Propane-butane mixture are in ■ a liquid gas aerosol spray can is filled and can be sprayed from it.

26. Paints. 15 parts 1,4-endomethylene-11 , ^ - dichlor-S.e-dithia-oJ-dicyan-l, 4,11,12-tetrahydroanthraquinone- (9,10), 10 parts chalk, 8 parts zinc oxide, 8 parts iron oxide, 5 parts copper naphthenate, 8 parts Linseed oil stand oil and 16 parts of maleate resin are made into a paint with a total of 30 parts of solvent processed. It is advisable to use a small part of the solvent (e.g. mineral spirits) rubbed with the substance mixture and then the remaining part of the solvent (e.g. white spirit with an addition of n-butanol) added.

27. 40 parts of 4,5-dicyano-1,3-dithiol, 20 parts of Attaclay (finely powdered attapulgite), 30 parts kaolin, ground,

8 parts of sulfite scrubbing powder, 2 parts of alkyl naphthalene sulfonate are mixed and made into a fine powder marry. Mixing with water gives suspensions that can easily float and can be sprayed or Spraying are suitable.

28. 50 parts of 2,3-dicyan-1,4-ditliia-5.8-endomethylene anthraquinone, 40 parts of kaolin, 10 parts of wetting agent (e.g. sodium salt of the condensation product of oleic acid and methyl taurine), are intimately ground together. The mixture that is easily suspended in water can be splashed or sprayed.

29. 50 parts of 1,2-dicyano-1,2-di- (carbäthoxyäthyl-mercapto) -äthen, 30 parts of xylene and 20 parts of alkylphenols polyglycol ethers are mixed with one another. By Dilution with water gives finely divided emulsions which are suitable for spraying or spraying are.

30. 50 parts of 1,2-dicyano-1,2-di- (carbobutoxy-methylmercapto) -ethene, 30 parts of xylene, 10 parts of tetrachlorethylene and 10 parts of emulsifier (alkylphenol polyglycol ether) are mixed together. This mixture, when poured into water, gives emulsions of finer quality Dispersity.

31. 40 parts of 1,2-dicyano-1,2-di (methylmercapto) ethene, 30 parts of kaolin, 13 parts of precipitated aluminum silicate,

9 parts of the sodium salt of alkylnaphthalene sulfonic acid, 2 parts of the sodium salt of the condensation product Oleic acid and methyl taurine and 3 parts of sodium sulfate are ground to a uniform mixture.

32. wettable powder. 15 parts of 1,2-dicyano-1,2-di- (benzylmercapto) -ethene, 30 parts of attaclay (finely divided attapulgite), 55 parts of slate flour are made to the required Grind fineness. After stirring with water, a sprayable powder is obtained.

33. 25 parts of 1,2-dicyano-l, 2-di- (p-chlorobenzyl-mercapto) -äthen, 50 parts of xylene, 15 parts gasoline fraction (boiling range 145-200 ⁰ C at 18 ° / ₀ aromatics), 5 parts Oxethylated sorbitan monolaurate, 5 parts mixed emulsifier from ethoxylated tall oil fatty acid sorbitol ester and sulfonate are mixed together.

34. Emulsion concentrate. 40 parts of 1,2-dicyan-l, 2-di- (l ', 3'-dithia-2'-oxoheptyl) ethene, 30 parts of cyclohexanone, parts of xylene, 5 parts of alkylaryl polyglycol ether, 5 parts of fatty acid polyglycol ester, mixed with one another, give a solution that can be emulsified in water.

Claims (9)

Claims-. 1. Pesticides, characterized by a content of compounds of the general formula NC —C —S —R NC —C —S —R wherein the radicals R denote organic radicals which can be linked to one another. 2. Pesticides according to claim 1, characterized by a content of compounds the general formula NC —C —S —R Il NC —C —S —R wherein the radicals R are carboxylic acid ester, thiocarboxylic acid ester and / or dithiocarboxylic acid ester groups «5 or hydrocarbon radicals, which optionally can be connected to one another and / or substituted by functional groups and the preferably form a quinoid system or carbon-containing radicals with one or more Represent heteroatoms which preferably form heterocyclic systems and which optionally can be connected to each other. 3. Pesticides according to claim 1, characterized by a content of compounds the general formula NC —C-S, NC-C-S where R> C = O,> C = S,> CH halogen,
> CH - S - alkyl, > chn: R ' R ' or> C = NOR 'and R' is hydrogen or one Mean hydrocarbon residue. 4. Pesticide according to claim 1, characterized by a content of 2,3-dicyan-1,4-dithiaanthraquinone the structural formula NC-C NC-C Considered publications:
German Patent No. 876 018;
British Patent No. 747,909;
U.S. Patent No. 2,547,723. 9 909 559/417 6.59