DE1793188C3 - O-alkyl-0-phenyl-thiolphosphoric acid ester, process for their preparation and compositions containing them - Google Patents

Description

CH ₃ S

where R and R? for methyl or ethyl, Ri for Are hydrogen or methyl and n is 1 or 2.

2. Process for the preparation of the compounds according to claim J, characterized in that O-alkyl-O-phenylthionophosphoric acid ester halides of the formula are used in a manner known per se
RO S

\ ll

P — Hal (H)

CH.S ^ f VO

R.

alkaline saponified and the saponification products with alkyl mercaptoalkyl halides of the formula

Hal- (CH ₂ ) "- SR ₂

(111)

converts, where Hai stands for a halogen atom.

3. Insecticidal and acaricidal agents, characterized by a content of O-alkyl-O-phenyl-thiolphosphoric acid esters according to claim 1 and customary carriers / auxiliaries.

From German patents 9 49 231 and 10 18 053 and US patent 3156 718 are among other things, optionally chlorinated S-benzyl esters of Ο, Ο-dialkylthiolphosphoric acids are known. To According to the information in the publications mentioned above, these products are characterized by good insecticidal properties and acaricidal effectiveness with simultaneous low toxicity to warm-blooded animals; therefore they find as pesticides in crop protection and on the hygiene gate application.

Furthermore, in the German Auslegeschrift 12 52 961 fungicidal mixtures for use in the Agriculture described the symmetrical 0.0-dialkyl-S- (o) -phenylalkyl) -thiolphosphoric acid ester as the active component with 2 to 10 carbon atoms in the S-alkyl radical.

In contrast, the present invention relates to the subject matter defined in the claim.

The course of the process for the preparation of the new O-alkyl-O-phenyl-thiolphosphoric acid ester is said to be explained in more detail using the following formula scheme (IV):

RO S

ll

P-Hai + 2MeOH

CH3S- / V0

Saponification

3S- I.
R. RO
\ 0
π + HaI- (CH ₂ ) "SR ₂ Γ
R. RO O
, Il "SR ₂ s Il
PS-Me \ Il
P-
/ CH - O > -S (CH ₂

In the above equations, Me stands for a monovalent metal equivalent or the ammonium group. Ri is preferably methyl, while Hai is preferably chlorine or bromine and Me is potassium, Is sodium or ammonium.

The O-alkyl-O-phenylthionophosphoric acid ester halides required as starting materials for the reaction of the formula (II) are partly described in the literature. You can also be in technical Scale according to known methods by reacting the corresponding O-alkyl-thionophosphoric acid monoester dihalides with the relevant 4-methyl mercaptophenols in the presence of acid binders getting produced. The reaction is preferably carried out in an aqueous alkaline solution at room temperature or slightly elevated temperature (see, for example, US Pat. No. 3,163,688).

Also serving as the second reaction component are the alkyl mereapto-alkyl halides of the structure (IM) known from literature.

While the saponification reaction is expedient can run off in aqueous or aqueous-alcoholic solution, are suitable for the following reaction with the Aikyimercaptoilkylhalogenidcn practically all organic Solvents or mixtures thereof. These include aliphatic or aromatic, if appropriate chlorinated hydrocarbons such as gasoline, methylene chloride. Benzene, toluene, chlorobenzene, xylene; Ether, e.g. B. diethyl or di-n-butyl ether. Dioxane or tetrahydrofuran, and low-boiling aliphatic alcohols, ketones and nitriles, for example methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl, methyl isopropyl Methyl isobutyl ketone, aceto- and propionitrile.

Alkajien are mainly used as saponifying agents, preferably aqueous or aqueous-alcoholic sodium or potassium hydroxide solution.

The reaction can be carried out within a relatively wide temperature range. In general, preferably carried out between 20 ° and 100 ° (or the boiling point of the mixture) at 20 to 8O ⁰ C.

As can be seen from the above formula scheme (IV), per mole of O-alkyl-O-phenyl-thionophosphoric acid Reesterhalogenid 2 mol alkali and 1 mol alkyl mercaptoalkyl halide required. It turned out to be Proven to be useful, the aqueous or aqueous-alcoholic solution of the ester chloride with the alkali move, after completion of the saponification without isolation of the intermediate product formed Alkyl mercaptoalkyl halide undiluted or dissolved in one of the aforementioned solvents with stirring To add reaction mixture and the latter then to complete the reaction even longer Time (1 to 3 hours) to reheat to the temperatures given above. You get with this The products work in excellent yields and in excellent purity.

The mixture is worked up in the customary manner; H. by pouring the approach in water, Taking up the same in a water-immiscible solvent, separating the phases, Washing and drying of the organic layer, evaporation of the solvent and optionally fractionated Distillation of the residue.

The O-alkyl-0-phenyl-thiolphosphoric acid esters according to the invention usually occur in the form of colorless to slightly colored water-insoluble oils, which Do not allow it to distill without decomposition even under greatly reduced pressure; however, they can get through so-called "distilling", d. H. short-term heating in a vacuum to moderately elevated temperatures of the last volatile components are freed and cleaned in this way.

The products according to the invention are characterized by an excellent insecticidal, acaricidal and nematicidal effectiveness. Furthermore, they show a clear fungicidal and bactericidal side effect. she have only a low phytotoxicity. The pesticidal effect sets in quickly and lasts a long time. Because of these properties, the new O-alkyl-O-phenylthiolphosphoric acid esters are found in the vegetable and stored products as well as in the hygiene and veterinary sector to combat harmful sucking and biting insects, mites, nematodes. Fungi and bacteria use.

Draw when used against people harmful to hygiene and supplies, especially flies and mosquitoes the process products also have an excellent residual effect on wood and clay as well good alkali stability on limed substrates.

Depending on their intended use, the new active ingredients can be converted into the customary formulations such as solutions, emulsions, suspensions. Powders, pastes and granulates. These are in themselves known way produced »z. B. by mixing the Active ingredients with extenders, d. H. liquid solvents and / or carriers, optionally under Use of surface-active agents, i.e. emulsifiers and / or dispersants.

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

The process products can also be used with good success in the ultra-low-volume process (ULV) where possible, formulations up to 95% or even the 100% active ingredient alone to spread.

The active ingredient concentrations can in one can be varied in a larger area. In general, concentrations of 0.00001 to 20% are used. preferably from 0.01 to 5%.

SCH ₃

C ₂ H ₅ OP ^

S-CH ₂ -CH ₂ -SC ₂ H ₅
0.4 molar approach.

125 g of 0-ethyl-O- (3-methyl-4-methylmercapi0-phenyl) -thionophosphoric acid chloride are dissolved in 200 ecm of ethanol. To this solution one adds 50 ecm of water. Then it is added dropwise with stirring with 48 g of potassium hydroxide - dissolved in 100 ecm of water - mixed. The reaction mixture is stirred for a further 1 hour at 50 to 60 ° C. and then added dropwise 50 g / J-ethyl mercapto ethyl chloride to the mixture. The latter is then heated to 70 ° C. for a further 2 hours. Finally, the reaction mixture is in 400 ecm Poured ice water, the organic layer taken up with benzene, the benzene solution separated off with water washed until it reacts neutral and dried over sodium sulfate. After distilling off the Solvent obtained 123 g (84% of theory) of the O-ethyl-O- (3-methyl-4-methylmercapto-phenyl -) - S - (^ - ethylmercapto-ethyl) -thiolphosphoric acid ester as a water-insoluble, yellow oil.

In the same way as described above, but using ethyl mercaptomethyl chloride, becomes the connection of the following constitution

CH ₃ S

S CrI? oC-5 ri «

C ₂ H ₅ O

obtained with a yield of 87% of theory.

Ci3H2iCbPS3 (molecular weight 352):
Calculated; S 27.3, P 8.8%;
found: S 27.1, P 9.07%.

Example 2

PS-CH ₂ -CH ₂ -SC ₂ H ₅

CH ₃ O

A solution of 118 g (0.4 mol) of O-methyl-O- (3-methyM-methylmercapto-phenyO-thionophosphoric acid ester chloride (manufactured according to the information in US Pat. No. 3,163,668) in 200 ecm of ethanol and 50 ecm of water are mixed with 48 g of chewing hydroxide in 100 ecm of water. The mixture is then 1

IO

■ Stirred for 5 hours until a neutral reaction has occurred. 50 g of ß-ethyl mercaptoethyl chloride are then added to the reaction mixture and the latter is stirred for a further 2 hours at 70 ° C. The mixture is then poured into water, the separated oil is taken up with benzene, the benzene solution is washed neutral, dried, the solvent is evaporated and the residue is removed 86 g (b1% of theory) of the O-methyl-O- (j-methyl-4-methylnate; iptophenyl -) - S - ()? - ethyl mercapto-ethyl) - thiol phosphoric acid ester are obtained in the form of a water-insoluble, non-distillable ester Oil.

CuHjiOjPSj (molecular weight 352):
Calculated: S 27.2. P 8.8%:
found. S 27.4, P 8.4%.

Claims (1)

Patent claims:
L O-alkyl-O-phenyl-thiolphosphoric acid ester of RO O Ρ — S— (CH ₂ ) ,, - S — R ₂ Vo ⁷ (D Shape!