DE1670757A1 - Process for the preparation of alkyl-substituted ethylene thiuram monosulfides - Google Patents

Description

PAINT FACTORY BAYERAG 1670767 LEVERKUSEN-Bayerweik t ALI Patent department

ST / Ma

Process for the preparation of alkyl-substituted ethylene thiuram monosulfides

The present invention relates to novel alkyl-substituted ethylene thiuram monosulfides which have acaricidal properties have and a process for their manufacture.

It has already become known that one unsubstituted Ethylene thiuram monosulfide is obtained by using ethylene-bis-dithiocarbaminate oxidized in aqueous solution with air or oxygen. The crude reaction product obtained, however, persists only a small part of ethylene thiuram monosulfide, at most about $ 20. The major part of the reaction product consists of polymer compounds.

While the crude product only has a low fungicidal effect has, a purified ethylene thiuram monosulfide has one significantly higher fungicidal effectiveness.

It has also become known that to improve the production of Äthylenthiurammonosulfid the oxidation of the corresponding bis-dithiocarbarainate not with air or

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Carries out oxygen, but with other oxidizing agents, e.g. hydrogen peroxide or ammonium persulphate. But also with In addition to the desired end product, this method creates considerable amounts of by-products, as can be derived from the corresponding Can see thin-layer chromatograms.

Finally it has become known that one can do the following Compounds as acaricidal active ingredients can be used: 0,0-Dläthyl-o- (p-nitrophenol) -thionophosphate and 0,0-Dimethyl-S- (2-ethylinercaptoethyl) -phosphate. It has been found that one can easily and in high yield the new, acaricidally active alkyl-substituted ones Ethylene thiuram monosulfides of the formula

R * 2 HN-CR - CH-NH

t · ι

S = C ^ C * S

(D

in which

R stands for lower alkyl and

R .. and R _{2 represent} hydrogen and lower alkyl

obtained when at 0 to 7O ⁰ C in a water-containing solution of ethylene-bis-dithiocarbaminates of the formula

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-so ^R 2 HN-CR ₁ -CH-NH S = C
I. C = S
I. S.
Me S.
Me

(H)

in which

R, R ₁ and R _{9 have} the meaning given above and Me stands for a monovalent metal,

Air or oxygen introduces and the pH during the Holds total response between 7 and 9t5.

The alkyl-substituted ethylene thiuram mono sulfides obtained contain only the sulfur that is inevitably produced in the reaction, but no by-products such as polymeric compounds.

It can be described as extremely surprising that the alkyl-substituted ethylene thiuram monosulfides are obtained without by-products even when oxidized with oxygen or air, while the unsubscribed ethylene thiuram monoulfide contributes Carrying out the reaction using air or oxygen in a mixture with polymeric compounds is obtained, which the make up the majority of the raw product.

The good results in the method according to the invention are but only achieved if two conditions are met. Once the ethylene-bis-dithiocarbattinate has to be replaced by an alkyl group substitutes S3 in and on the other must during the entire

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Oxidation a certain pH value must be maintained.

It is also surprising that the alkyl-substituted ethylene thiuram monosulfides have a better acaricidal activity than the above-mentioned previously known acaricidal active ingredients *

If methyl ethylene-bis-dithiocarbamic acid, sodium and oxygen are used as starting materials, the course of the reaction can be represented by the following equation:

CH, CH,

HN-CH-CH ₀ -NH O + H ₀ O HN-CH-CH ₀ -NH + S + 2NaOH 2, 2_ ^, Z ₁

ss *** ^ * s ^ ⁰ ^

Na Na _(m)

The starting materials are clearly characterized by the formula (II) given above. In this formula, R preferably stands for alkyl with 1 to 5 carbon atoms, such as methyl, ethyl, propyl and butyl, R ₁ and R _g for hydrogen and alkyl with 1 to 3 carbon atoms, such as methyl, ethyl and propyl.

These starting materials are widely known. For example, it is known Methylethylene-bis-dithiocarbaminate, 1,1-dimethylethylene-bisdithiocarbaminate and 1 ^ -dimethylethylene-bis-dithiocarbaminate.

The as yet unknown carbaminates can be used in the same way like the well-known carbaoinates from the corresponding diamines getting produced.

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However, some of the diamines are not yet known either. she are produced in the same way as the known ones according to the usual methods.

For example, 1-pentylethylenediainine can be prepared by adding 14.1 kg of water to 4 · 3 kg of 1,2-dibromoheptane and placing it in a 50 l autoclave at a pressure of 5 atmospheres. and 70 to 80 ^° C. with 7.1 kg of NH can react. Vpm undissolved 1,2-dibromoheptane and is deposited in a water jet vacuum is concentrated to dryness einge- Λ. The residue is dissolved in 6 l of water and the base is deposited with 3.85 kg of potassium hydroxide. 1.4 kg of crude product are obtained, which are purified by distillation. 1-Pentyläthylendiamin goes with Kp 84-94 ⁰ C / 10 Torr.

In addition to air, pure oxygen or mixtures of oxygen with other inert gases can also be used as the oxidizing agent.

Suitable as a diluent for the implementation according to the invention especially water. However, mixtures of water and other strongly polar liquids can also be used. Therefore Alcohols such as methanol and ethanol come into question as well Dimethylformamide.

Catalysts can be used to accelerate the oxidation Add metal salts that contain metals as cations, which occur in different valency levels. As examples are called:

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Nickel (II) nitrate, manganese (II) sulfate, iron (II) chloride.

Salts of the alkyl substituted ones are particularly suitable • Ethylene-bis-dithiocarbamic acids, as they are used for the main conversion. The hangan salt of these carbamic acids is preferably used.

The reaction temperatures can be varied over a wide range. In general, one works between 0 and 70 ^° C., preferably between 15 and 30 ^° C.

The reaction can be carried out under normal pressure or under increased pressure carry out.

When carrying out the process according to the invention, 0.1 to 30% solutions of the carbaroinate are expediently provided. It is particularly advantageous to work with solutions which contain 0.1 to 5 l of carbamate. ) It should be ensured at the initiation of oxygen that it is finely dispersed in the aqueous solution as possible. This can be achieved, for example, particularly easily by using an aeration stirrer.

During the oxidation, the pH is between 7 and 9 _± 5, preferably between 7.3 and 9%. Since a metal hydroxide is formed during the reaction, it is necessary to continuously add a little acid. The usual inorganic and organic acids such as hydrochloric acid, sulfuric acid and p-toluenesulfonic acid are suitable for this. The catalysts are used in amounts of Ό.001 ' * · '* ^{10 2} 4 ¹ 009852/2194

-γ-

up to 1 percent by weight, based on the carbamate.

The reaction mixture is worked up in the customary manner performed. When using an aqueous solution, the falls Active ingredient and can be sucked off directly.

The active ingredients according to the invention have strong acaricidal effects with low warm-blooded toxicity and phytotoxicity. The effects set in quickly and last for a long time «The active ingredients can therefore be used with good success to combat mites» (Acerina) can be used.

Among the mites, the spider mites (Tetranychidee), like the common spider mite (Tetranychus urticae), are particularly important Fruit tree spider mite (Paratetranychus piloeus); Gall mites, like the currant mite (Eriophyes ribis) and the tarsonemids such as Tarsonemus pallidus; as well as ticks.

It is particularly important that the active ingredients also counteract such Spider mite species are effective which have now become completely or partially real against the acaricides used up to now.

The active compounds according to the invention can be converted into the customary Formulations are transferred, such as solutions, emulsions, suspensions, powders, pastes and granules. These will produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solutions agents and / or solid carriers, optionally

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using surface-active agents, i.e. emulsifiers and / or dispersants. In case of Using water as an extender, e.g. organic solvents can also be used as auxiliary solvents will. The main liquid solvents that can be used are: aromatics, such as xylene and benzene, chlorinated aromatics, such as chlorobenzenes, paraffins, such as petroleum fractions, alcohols, such as methanol and butanol, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; as solid carriers: natural rock flour, such as kaolins, Clays, talc and chalk, and synthetic minerals, such as highly dispersed silicic acid and silicates; as emulsifiers: non-ionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates and arysulfonete; as a dispersant, e.g. Lognin, Sulphite liquors and methyl cellulose.

The active ingredients according to the invention can be used in the formulations present in a mixture with other known active ingredients.

The formulations generally contain between 0.1 and 95 percent by weight active ingredient, preferably between 0.5 and 90.

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The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use Solutions, emulsions, suspensions, powders, and fasting Granules are applied.

It is used in the usual way, e.g. by spraying, misting, dusting, scattering or pouring

The active ingredient concentration in the ready-to-use active ingredient preparations can fluctuate over a wide range. in the in general, it is between 0.5 and 0.001 percent by weight, preferably between 0.1 and 0.005

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Example A: Tetranychus tea Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Bean plants (Fhaseolus vulgaris), which are approximately 10 - 30 cm high, sprayed dripping wet. These bean plants are strong with all stages of development against organic phosphoric acid esters already somewhat resistant strain of the common spider mite (Tetranychus urticae) infested.

After the specified times, the effectiveness of the active ingredient preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in i » . 100 1 » means that all spider mites have been killed, 0 i» means that none of the spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and '. The results are shown in the table below:

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Table (plant-damaging mites)

Active ingredients Active ingredient concentration degree of destruction in % in j » after 48 h 8 d

C ₂ H ₅ O (known)

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0.1 65 70 0.05 20th 50 0.02 0 0 0.01 0 0 0.004 0 0

PS * CH _n * CH / »· SCnH. CH, 0.1 90 80-95 / ^{2 2 2} - HN-CH ₀ CH-NH ^} 0.05 50 70-80 CH, 0 t 2, 0.02 10 0 j S = C C = S 0.01 O 0 (confesses) 0.004 O 0 0 0.1 mn 100 0.05 100 100 0.02 90 100 0.01 80 95 0.004 40 50

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Example 1:

Methyl Ethylene-Muramino Sulphide In 2 1 of water, 118.8 g of a 25.7 # solution of Natriuoi-iDethyl-ethylene-bis-dithiocarbaminat and 8 mg of solid Manganese-methylethylene-hie-dithiocarbafiiinat is given.

With the aid of a gassing stirrer, the mixture is passed at room temperature Air into the solution, adding dilute hydrochloric acid ensures that the pH is kept at 8 to 9. The deposited precipitate is filtered off and at room temperature dried. In the Pil is stepped with water-soluble) zinc salt no more dithiocarbamate detectable.

Exploiter 16.6 g of a yellowish substance at 14O ⁰ C. melts, dissolves clearly in chloroform and can be crystallized from methanol.

Ia thin-layer chromatography it can be seen that the substance contains about 12% elemental sulfur, but is otherwise uniform. After recrystallization from methanol, the substance melts at 148 ^° C. and still contains 4 to 5 % elemental sulfur. The elemental analysis gives the following values: Found ι C 28.88 f> Calculated; C $ 31.3

H $ 3.22 H 4.2 *

M 13.61 + H 14.6 lbs

S 54.4 # S 50.0 %

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Taking into account the 4 to 5 # elemental sulfur that have been detected in the thin film history, they are correct

Analysis values agree well with the calculated values.

The following overview shows that the pH value is critical to the formation of the desired end product;

Reactions were carried out as indicated in the above example, only the pH was varied.

pH Yield Melting point ä

6 1.25 g Pp. 112 - 119 ⁰ C.

7-8 18,00g mp. 140-142 ⁰ C

10 0.00 g (after 15 hours)

12 0.00g (after t5 hours)

8 * ^ 0.90 g decomposition P » ⁰

*) The pH-value was not regulated during the introduction of the irrigation system and rose. '

From the following experiments it emerges that a uniform End product only in the case of alkyl-substituted ethyl bis ^ dithiocarbaminates, but not in the case of unsubstituted persons:

If, instead of sodium methyläthylen-bis-dithiocarba * aluminate .Natriumäthylen-bis-dithiocarbamict and it operates according to the above example, we obtain 10.4 g of a substance from the Pp. 135-143 ⁰ C, which is very bad in chloroform lögt and shows four other substances in addition to 30 # sulfur in the thin / echichtehromatogram.

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The following examples show that S nan does not obtain a uniform alkyl-substituted thiurammon monoeuifide if, in accordance with the process according to the invention, a certain pH value is maintained, but the oxidation is not carried out with air but with hydrogen peroxide or with ammonium persulphate *

a) To a solution of 3.37 1 of water and 51 * 2 g of 26.4% aqueous Ha-triuBtne thy ethylene-bis-dithiocarbaminate solution is added in about 5 minutes 6.8 g of 49.3% hydrogen peroxide in 10, 0 ml. Water. The pH value is kept at 8 by adding n-sulfuric acid. When the precipitation is complete, it is suctioned off. Yield: 4.6 g pp. 116 to 118 ^° C. A total of 4 substances can be seen in the thin-layer chromatogram * of which about 30 pounds are elemental sulfur.

b) Same approach as a), but kept at pH 7. Yield 6.7. G. Mp. 9O ⁰ C. At least four components, of which about 20 £ elemental sulfur.

c) Same approach as a), but kept at pH 9. yield 3.1 g. Mp. 123 to 125 ° C inconsistent end product, at least 40 $ elemental sulfur

d) 0.1 mol ■ ethyläthylen-bis-dlthiocarbaminsaurea sodium in the form of an aqueous solution were oxidized with ammonium persulfate. The oxidation product was filtered off with suction and suspended in 250 ml of methanol and heated ^{to 50 ° C. with stirring.} After suction was washed with Methanoi and dried. Yield 3.4g. Melting point 102 to 103 C. Make the thin-layer chromatogram that *

, Product au ca, 90 % from sulfur.

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Example 2;

t, 1-dimethylethylene thiurate, donosulf id 70 g of a 10.7 # aqueous solution are added to 2 l of water of Katrium-ttt-diiDethyläthyleai-bia-dithiocarbtminat and 20 mg Manganese sulfate given * with the help of a gas stirrer «directs one at room temperature air in the solution, whereby one through Addition of dilute hydrochloric acid keeps the pH at 8.5.

The deposited precipitate is filtered off and at room temperature dried.

The crude product is briefly heated to boiling in ethanol and the undissolved material is filtered off. The solution is cooled to room temperature, some sulfur precipitating out. The filtrate freed from the sulfur is concentrated to dryness. A crystalline syrup remains, which ^{liquefies at 80 to 90 °} C. and dissolves very easily in chloroform. The thin-layer chromatogram shows that the substance is a uniform product in addition to small amounts of sulfur.

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Example 3? ■ '.. ■■ - -. ■

Pentylethylene-thiuraimöönoaulfid

Z 1 water warden 4O ₁ 3 g of 18 "7 5 * wäeejigen strength solution of Hetriue-pentyläthylen-biedithiöcarbaiBinat added. With the help of a gassing stirrer, air is drawn into the solution when the clearing ice is clear, whereby »an addition of dilute hydrochloric acid ensures that a pH of 7 · 5 remains ·

The deposited precipitate is sucked up and at room temperature dried.

The crude product is boiled in chloroform, filtered and the mother liquor is evaporated to dryness. There remains a syrup which gradually dwrchkristallisiert and achnilzt at 70 to 75 ⁰ C. In the thin-layer chrome plating one can see that the substance is uniform along with traces of sulfur.

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Claims (10)

ft claims 1) Process for the division of alkyl-substituted ethylene thiuram monosulfites, marked by the fact that at O up to 70 ^ 0 in a water-containing solution of ethylene-bie-dithlC! earbaminaten of the formula -QH-IiIf I. S. S. Me Me in which R stands for lower alkyl R ₁ and R ₂ for hydrogen if <f is lower than alkyl or the like Me for ^ a monovalent metal tlt Introducing air or oxygen and m $ pH-W pt # throughout the reaction zwieohen wnÄ 7 9 "5 2) The method according to claim t "because it denotes that Ban carries out ^{the reaction at temperatures between 15 and ^ 0 Q i3"} 3) method pursuant to the second * claims 1 and l _t £ characterized in DA8 the prepared water-containing solution contains 0.1 to 5 Gewiohtaprozent Garbaminat, 4) procedure; according to claims 1 to 3 »by virtue of the fact that 4 · γ pH- ¥ »rt listed between? T3 and 9 Lt K 10 24t 5) Process according to claims 1 bia 4, characterized in that »that the reaction solution 0.001 is 1 percent by weight of a metal eel contains, the cation of which is a metal, which in various Valence levels can exist- 6) Process according to Claims 1 to 5 »characterized in that the reaction solution ale the catalyst the jtonganealz of the implementation arriving alkyl-substituted ethylene-bis-dithiocarba- W minic acid contains « 7) AUEjleMbetitwierte Xthylentöiure ^ cmoaiilfide. the »Ι * HR-GR ₁ ^ OH-SH in which - R is not even alkyl M ^ un4 Bg for tasaeratoff and lower alkyl atehen * 8) Akarisidle means _f characterized by a Sehalt of alkylsubatitpierten. Ethylene thiurao * onoeulfici * n according to claim 7. 9) Ter | ahr # n for combating AMpridfiii characterized in that nan alky! Substituted Ethyienthiureisaorioöulfide according to Anapruefe 7 «vjf the Akaridan adtr d« r * ii Iteb # itar «uiir lets act * ^: .-Le A-IO Hi . ". · '. 10). Process for the production of "kari & iden smocks." characterized ü j "U ®sü" allqrlBübeiitulerte Äthylenthlur * a3-TDonosulfide geffiäß An "pri2ob 1 with extenders ^ and / or substances oberflUcbenaktiviii. Le A 10 241 000852/2194