DE1643354A1 - Methylene bis (phenyl sulfide) -4-alkyl sulfonic acid ester - Google Patents

Description

FARBENFABRIKEN BAYER AG LEVERKUSEN-Bayenvexfc "ce"

O, οβρ. Patent department

Si / Ss. "." ■■

Methylen-bis-CphenylBUlfiaj ^ -alkylsulfonaaureeater

The present invention relates to new methylene bis (phenyl sulfide) -4-alkyl sulfenic acid esters, which acaricidal properties have " as well as several processes for their preparation.

It has already become known that “carbamates are like that 2-isopropoxyphenyl-li-methylcarbamate for the control of insects and acarids can use (German Patent 1 108 202).

It has been found that the new methylene-biB- (phenyl sulfide) 4-alkyl sulfonic acid ester the formula

-S-CH ₂ -S- ξ «\\ -0-SO ₂ R (I)

in which

R stands for alkyl with 1-2 _: G atoms,

R »stands for halogen or alkyl»

R "represents halogen, alkyl or trifluoromethyl,

η is O, 1 or 2 and m is O, 1, 2, 3, 4 or 5,

have strong acaricidal properties. Le A 10 737 109827/179

It has also been found that the sulfonic acid esters of Formula (I) is obtained when one

(a) Thiophenols of the formula

(ID

in which

R "and m have the meaning given above and

A represents hydrogen or an equivalent of a metal,

with phenyl alkylsulfonate of the formula

(III)

in softer

R, R 'and η have the meaning given above and Hal stands for halogen, optionally in the presence of one Acid binder

implements or

(b) methylene bis (phenyl sulfide) of the formula

Le A 10 737 -2-

1098 27/1795

in which

R ¹ , R ", η and m have the meanings given above and

A stands for hydrogen or an equivalent of a metal,

with alkyl sulfonic acid halides of the formula

. HaI-SO ₂ R.

in which ·

R has the meaning given above and

Hai stands for halogen · .- .. ·

optionally reacts in the presence of an acid binder · ^

It is extremely surprising that the According to the invention, methylene-bis (phenylsulphide) -4-alkylsulphonic acid esters a stronger acaricidal and especially ovieide Have more effect than the well-known carbamate.

In the formulas given above, R stands for methyl and ethyl, R ¹ preferably stands for chlorine, bromine and fluorine and alkyl with 1-3 C atoms, R ″ preferably stands for chlorine, bromine, fluorine, alkyl with 1-3 C atoms and Trifluomethyl; η is preferably O or 1, m is 0, 1, 2, V 4 and 5

The course of the reaction in process (a) corresponds to the following Reaction scheme ":

Cl- f ~ \ -SNa + Cl-CH ₂ -S- ^ Λ-0-SO ₂ CH ₃ ^

-S-CH ₂ -S- f \ -0-SO ₂ CH ₅

Le A 10 737 (VI)

-3-

109827/1795

The starting materials (formulas II and III) are already known. The thiophenols are preferred used in the form of alkali metal salts, in particular potassium and atrium and in the form of alkaline earth metal salts, especially of magnesium, calcium and barium.

The reaction is conveniently carried out in a diluent performed. Organic solvents can be used for this. This preferably includes hydrocarbons, such as gasoline and toluene and xylene, ethers such as diethyl ether, dioxari and alcohols such as Methyl alcohols and ethyl alcohol. In some cases ^ water can also be used. However, the reaction can also occur without Diluents are run.

The reaction temperatures can be in a relatively wide range can be varied as the end products are fairly stable compounds. Generally one works between 0 and 180 ° E, preferably between 20 and 150 ° C.

When carrying out the method according to the invention the starting materials are expediently in equimolar proportions a. The reaction product is worked up in the usual way, e.g. by distillation or recrystallization.

If the free thiophenols are used, it is expedient to give them an acid binder. The same as in method (b) are suitable.

The reaction of process (b) corresponds to the following formula scheme ι

Le A 10 ΐγ ~ ⁴ ~

109827/179? ■

Gl-SO ₂ -OH ₅

KaCl

(Til) .- ,: ■■. ■■■ ';^;

All starting materials used compounds dtr formulas (IT "and T) are already known, I _{n of} the formula (IV). A. preferably for hydrogen and one equivalent of an" alkali metal * « _t especially potassium or sodium, and an alkaline earth metal,

especially magnesium, gallium and barium. %

In the formula (V), Hai preferably represents chlorine.

Water and all inert organic solvents can be used as diluents Solvent in question »The same solvents are preferred used as specified for * method (a). "

All common acid-binding agents can be used with Alu acid binders will. When working in an aqueous medium, it is advisable to use Alkali hydroxide, such as potassium hydroxide or sodium hydroxide, and alkali carbonates such as sodium carbonate and potassium carbonate. When working in organic solvents, it is advisable to use tertiary amines such as pyridine, picoline, dimethylaniline, Diethylaniline trimethylamine and triethylamine.

The reaction temperatures are the same for method (b) as with method (a).

L® A 10 737 -5-

BADORf (SITIAL

In carrying out the procedure, (b) it is expedient to use . the starting materials in approximately equimolar proportions. However, deviations from these ratios are possible * This also applies to the dosage of the acid-binding auxiliaries. .

The reaction mixture is worked up in the usual way Way, s.B. by distillation or recrystallization.

The active ingredients according to the invention show at "lower α Phytotoxicity on strong acaricidal effects. The effects set in quickly and last a long time. The active ingredients are therefore used to combat mites (acarina) with good success.

Among the mites, the spider mites (Tetranychidae), such as the common spider mite (Tetranychus urticae), are particularly important. Fruit tree spider mite (Paratetranychus pilosus); Gall mites such as the currant gall mite (Eriophyes ribis) and the tarsonemids such as Tarsonemus pallidus; as well as ticks. The active ingredients W are effective in all development stages of the mites, especially against the eggs «

The active ingredients according to the invention comb into the usual ones Formulations are transferred, such as solutions, emulsions, suspensions, powders, pastes and granules. These are in produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents and / or solids Carriers, if necessary using surface

Le A 10 ΊΎΤ -b-

7 1843354

active agents, ie emulsifiers and / or dispersants. If water is used as an extender, organic solvents can also be used as auxiliary solvents. Liquid solvents are essentially: 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 carrier materials: natural minerals such as kaolins, clays, talc and chalk, and synthetic minerals such as highly dispersed silica and silicates; as emulsifiers: non-organic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkyl, aryl polyglycol ethers, alkyl sulfonates and aryl sulfonates; as dispersants, for example, lignin, waste liquor and methyl cellulose.

The active compounds 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.

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, pastes and granulates can be applied · The application happens in the usual way Way, e.g. through. Pouring, spraying, dusting, scattering or misting.

1098277 ⁷ i795

BAD Ol

The active ingredient concentrations can be in the ready-to-use Preparations in larger areas vary. You are in generally between 0.05 and 5 percent by weight, preferably between 0.1 and 3 percent by weight. '

Le A 10 737 -8-

10982? / 1795

example Tetranychus test.

Solvent 5 weight point dimethylformainicl Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the production of an appropriate preparation of the active substance

1 part by weight of active ingredient is mixed with the specified

Amount of solvent containing the specified amount of emulsifier I

holds «and dilutes the concentrate with water to the desired level

Concentration.

Bean plants (Phaseolus vulgaris), which are approximately 10 - 30 cm high, sprayed dripping wet. These bean plants are strong with all stages of development of the bean spider mite (Tetranychus urtieae) infested. . "■■■■

■ ■ - ■ ■■ Ϊ

After the specified times, the effectiveness of the active compound preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in % . 100 % means that all spider mites have been killed, 0% 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:

Le A 10 737 -9-

10S827 / 1795

40

T a feel 1 e
(plant-damaging mites)

Active ingredients

Active ingredient concentration in #

Degree of destruction in after 8 ^a

-CH (CH ₃ )

(known)

'2

98

Vo-SO ₂ -CH ₃

Cl

Cl

98

80

80

Cl - //

VV-O-SO ₀ -CH ₀ -CH, 0, 2

2 3

9Θ

Le A 10 737

-ΙΟ

9827/179 5

example 1

25.4 g (0.175 mol) of p-chloro-thiophenol are dissolved in 100 ml of ethyl alcohol. An equimolar amount of sodium alcoholate solution is added dropwise to the solution and the mixture is left to stir for 15 minutes. Then 44.3 g of p-chloromethyl mercaptophenyl methanesulfenic acid ester are added and the mixture is refluxed for 1 hour. By adding some sodium alcoholate solution is neutralized μ the approach. It sucks "from the precipitated salt ^c and pour the filtrate into ice water. The precipitated oil is taken up with methylene chloride, washed and dried. The solvent is removed in vacuo. The oily residue can be distilled.
Melting point: 49 °, b.p. 0.01 / 220-250 °, yield: 58 g (91.5 $ d, Th>)

109827 ^ 795

it

Example 2

Cl Cl

56.6 g (0.2 mol) of pentachlorothiophenol are suspended in 500 ml of ethyl alcohol and an equimolar amount of sodium alcoholate solution is added. The mixture is stirred at 50 ° for 15 minutes. The pentachlorothiophenol goes into solution as a phenolate. At that g ^ solution are added 50.6 g Chlormethylm "rcapto-phenyl-methanesulfonic ^v säureester added and the batch is heated for 2 hours under reflux. After cooling, the precipitated product is filtered off with suction and washed several times with water. After drying, the compound has a melting point of 135 °. Yield: 58 g (49 % of theory)) A further amount of the compound can be isolated by working up the mother liquor.

Analogously to the method according to Examples 1 and 2, the in the following table 1 specified further substances B can be produced:

T a b e 1 1 e 1

R. R " 3-Cl Κρ.Ο, Οΐ / Torr R ¹ CH ₃ 2-Cl 4-Cl 230-232 ° n = 0- CH, 3-Cl 4-CH ₃ 230-232 ° n = 0 CH, 4-Cl 220-230 ° n = 0 CH, 2-Cl, 10982 ^ 1 258 ° ■ n = 0. CH, 3-Cl, 258-260 ° n = 0 CH, 3-Cl, 240-242 ° n = 0 C ₂ H ₅ (m = 0) 240 ² n = 0 C ₂ H ₅
Le A 10 7-7 4-Cl 24 6 °
7 95 n = 0

Claims (5)

- f3 1) M * ethylene bis (phenyl sulfide) -4-alkyl sulfonic acid ester of formula (I) in which R stands for alkyl with 1-2 C atoms, R-. ^{1 represents} halogen or alkyl, R "represents halogen, alkyl or trifluoromethyl, η means 0, 1 or 2 and m is 0, 1, 2, 3, 4 or 5. 2) Process for the preparation of methylene bis (phenyl sulfide) -4-alkyl sulfenic acid ester, characterized in that (a) thiophenols of the formula. (II) in which | R "and η have the meaning given above and A represents hydrogen or an equivalent of a metal, with alkyl sulfonic acid ester of the formula HaI-GH ^ -S ~ (ft \ -0-SO ₂ R (III) in which R, R ¹ and η have the meaning given above and Hal stands for halogen, optionally in the presence of an acid binder. Le A 10 757 -15- 109827 f 1795 implements or (>) Methylen-bis-Cphenylsulfide) of the formula 1643354 (RO _n (IV) in which R ', R "n and m have the meaning given above and A represents hydrogen or an equivalent of a metal, with alkylsulfonic acid hylogenides of the formula HaI-SO ₉ R OO C. * r in which R has the meaning given above and Hai stands for halogen optionally reacted in the presence of an acid binder. 3) acaricidal agents, characterized by a content of methylenebis (phenyl sulfide) -4-alkyl sulfenic acid ester according to claim 1. 4) method for combating acarids, characterized in that that one methylene bis (phenyl sulfide) -4-alkyl sulfonic acid ester W according to claim 1 allows acarids or their habitat to act. 5) Process for the preparation of acaricidal agents, thereby characterized in that one methylene bis (phenyl sulfide) -4-alkyl sulfonic acid ester according to claim 1 mixed with extenders and / or surface-active agents. -14- Le A 10 737 1098277 1795