DE2249462C3 - - Google Patents

Description

where X is hydrogen and Y is chlorine or X is chlorine and Y is bromine

2. Process for the preparation of compounds according to Claim!, Characterized in that a halophosphate of the formula is used in a manner known per se

20th

Np- (

> P-Cl

(n) C ₃ H ₇ S

in the presence of an acid-binding agent with a phenol of the formula

or with a phenolate of the formula
X

MeO

> - Br

reacts where Me stands for an alkali metal, ammonium or an alkylammonium group.

3 pesticides which, as an active component, contain a compound according to claim 1 and contain suitable carriers and / or other additives.

4 pesticides according to claim 3 for combating insects and representatives of the order Akarina.

5 pesticides according to claim 4 for combating cotton and Vegetable pests.

The invention relates to that characterized in the claims Object. The connection is preferred of formula I, in which X is hydrogen and ^ is chlorine.

The compounds of the formula I can be prepared by the following methods known per se:

C ₂ H ₅ O °
la) ^) P-Cl

(n) C ₃ H-, S

(H)

acid binding agent

C ₂ H ₅ O

(H) C ₃ H ₇ S

(II)

C ₂ H _S O.?
2) ^) P-CI

Cl

(Vl

+ HO - ζ // - Br

(ΙΠ)

+ HSC ₃ H ₇ (Ii)

acid binding agent

C ₂ H ₅ O

P-O- ^, Λ — Br (VlI)

(VI)

(IX)

(R) ₃

C ₂ H ₅ O

+ MeSC ₃ H ₇ (n) (VIII)

(X)

\ L-A.,

(XII)

PI)

(IX)

S (XIII)

ROC-SMe or MeSR (XIV) or Me ₂ S or MeSH S

Il

or (RO) ₁ P-SMe (XlI)
(n) C ₃ H ₇ Hal

In the formulas IV, VIII, X to XV, Me stands for an alkali metal, in particular sodium or potassium, ammonium or alkylammonium, and R for C _{1 -C 4} -alkyl. such as methyl or ethyl and Hai for a halogen atom, such as chlorine, bromine or iodine.

Suitable acid-binding agents are: tertiary amines, e.g. B. Trialkylamines. Pyridine, dialkylanilines; inorganic bases such as hydrides. Hydroxides; Carbonates and bicarbonates of alkali and alkaline earth metals. Depending on the experimental conditions, it can be advantageous to increase the yield or Shortening the reaction time Catalysts, such as. B. copper or copper chloride to be used. the Process 1 a) to 3b) are at a reaction temperature between 0 and 130 C. at normal Pressure and in solvents or diluents which are inert towards the reactants

Suitable inert solvents or diluents are, for. B. the usual ether and ethereal Compounds, amides, aliphatic and aromatic, optionally halogenated hydrocarbons, nitriles or dimethyl sulfoxide. Alcohols are also suitable for processes 3 a) and 3 b).

The starting materials of the formula 11 can be described analogously to known ones, for example in J. org. Chem. 30, 3217 (1965) Methods are made.

From DT-OS 21 11414, among other things, 0 _: S-dialkyl-O-di- and trihalogen-phenyl-dithiophosphates are known. The compounds according to the invention have a similar spectrum of activity. but are surprisingly much more active. Compared to similar compounds from GB-PS 9 69 029 and CA-PS 8 33 039 ", they are also surprisingly better insecticidal and, moreover, have a more favorable toxicity.

The compounds of formula 1 have a broad insecticidal and acaricidal spectrum, including itire effectiveness against phytopathogenic pests to highlight. The compounds act against • Hern as contact and feeding poisons and can so are used against sucking, chewing and breaking insects and against mites, whereby all stages of development, how eggs, larvae, nymphs, pupae and adults are recorded. Pests this. Art find z. B. in P-eb, soy, corn, tobacco and forestry ι ο as can be found in the store. The compounds according to the invention render particularly valuable services however, when checking cotton and vegetable säcilingen. In this context the following families of insects and acarina should be mentioned: Chrysomelidae, TetHgoniidae, Gryllidae, Gryllotalpidae, Blattidae, Curculionidae, Dermestidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Nitidulidae, Tenebrionidae, Anthomyiidae, Aleyrodidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Psyllidae, Tenthredinidae, Gelechiidae, Geometridae, Coccinellidae, Hyponomeutidae, Lymantriidae, Lyoneliidae, Bruchidae, Tineidae, Noctuidae, Olethreutidae, Culicdae, Tipulidae, Stomoxydae, Trypetidae, Phaloniidae, Pieridae, Plutellidae, Pyralidae, Muscidae, Calliphoridae, Pulicidae, Tortricidae, Ixodidae, Argasidae, Tetranychidae, Thripidae and Dermanyssidae.

The insecticidal and / or acaricidal effect can be achieved by adding other insecticides and / or Substantially widen acaricides and adapt to the given circumstances.

Suitable additives include organic phosphorus compounds, nitrophenols and their derivatives, Ureas, carbamates, chlorinated hydrocarbons, pyrethrin-like compounds and amidines, especially formamidines.

The compounds of the formula I can be used alone or together with suitable carriers and / or Aggregates are used. Suitable carriers and aggregates can be solid or liquid and correspond to the substances commonly used in formulation technology, such as B. natural or regenerated Substances, solvents, dispersants, wetting agents, adhesives, thickeners. Binders and / or fertilizers.

For application, the compounds of the formula I can be processed into customary preparations, which are used either as concentrates or in diluted form. Examples of such preparations are in

55

solid form:

Dust, grit,
Granules (coated granules,
Impregnation granules and
Homogeneous granules);

liquid form:

a) Active substance concentrates dispersible in water: wettable powders, pastes, Emulsions;

b) Solutions.

The production of Milte according to the invention! takes place in a manner known per se by intimate Vennischen and / or grinding of active ingredients of formula 1 with the egg-containing carriers, optionally under Addition of dispersants or solvents which are inert towards the active ingredients.

The content of active ingredient in the agents described is between 0.1 and 95%, preferably between 2 and 50%. With the application you can but also means with active ingredient concentrations of up to 99.5% or even pure active ingredient used will.

example 1

31.1 g (0.15 mol) of 2-chloro-4-bromophenol are dissolved in 150 ml of benzene, then 15.1 g of triethylamine are added. At 10 to 15 ° C, 32.0 g of O-ethyl-Sn-propylchlorothiophosphate are added dropwise with constant stirring. Stirring is then continued for a further 12 hours at room temperature. The mixture is washed with water, 3% Na ₂ CO ₃ solution and again with water and dried over anhydrous sodium sulfate. The benzene is distilled off and the residue is purified by distillation (at 13O ⁰ OO ₅ OO Torr). 49 g of the ester of the form are obtained!

C, H _S O

with a refraction of 11S ¹ 1.5466.

In an analogous manner, the compound of the formula

C ₂ H ₅ O

(n) C ₃ H ₇ S

(ηϊ 1.5719).

Example 2

a) Potted cotton or tobacco plants were sprayed with 125 ppm of active ingredient in the form of an aqueous emulsion. When the spray coating was dry. the plants were _{infected with L 3} larvae of Heliothis virescens. The test was carried out under greenhouse conditions at 24 ° C. and 60% relative humidity. The evaluation of the initial effect in the case of the immediate effect was carried out after 4, 24 and 48 hours. The evaluation of the initial effect in the case of the permanent effect was carried out 2 and 8 days after the spraying had taken place, with controls being carried out after 4, 24 and 48 hours after the infestation.

links

C ₂ H ₅ OO

sprayed in the form of an aqueous emulsion was carried out with the following compounds:

C ₂ H ₅ OW

Cl
Cl

Br connection 1

Cl CA-PS 8 33 039

Compound 92

time in
hours

Mortality. %
Connection University: I.

Connection 11

Immediate effect

100
100
100

Permanent effect

(2d) (8d)

100
100
100

50
100
100

Immediate effect

80

90

100

Permanent effect

Ud) (Sd)

50 100 100

100 aC., H ₇ S

Ο

> —Ζ

III
IV

O
O

H
Cl
H

Cl

Cl
Br
Cl

Br

Br
Cl

Cl Cl

Connection 1 Connection 2 DT-OS 21 11414 Connection 2 DT-OS 21 11414 connection 5

The evaluation of the initial effect for the permanent effect took place 8 days after the spraying, controls were made 4 and 24 hours after infestation.

(%) Mortality

Connect- Connect- Connect- Connect

dung 1 dung HI dung IV dung V

Compound I shows 90 50 0 40 in both immediate and 8 T 4 h

the long-term effect has a significantly better initial 35 8 T 24 h 100 100 40 70

effect.

b) An analogous experiment as described under a) Here, too, there is a significantly better initial effect

- however, the plants could be recognized with 500 ppm of active ingredient compounds 1 and III.

Example 3
Acaricidal effect

Phaseolus vulgaris (French beans) were tested for acaricidal activity with an infected leaf piece from a mass cultivation of Tetranychus urticae. The defected movable Stages were shaped like this from a chromatography nebulizer with 10 ppm active ingredient an emulsified test preparation dusted so that no runoff of the spray liquor occurred. After 2 days larvae, adults and eggs were evaluated under the binocular, reviving and dead individuals and that Result expressed as a percentage. During the "holding time" the treated plants stood in greenhouse cabins at 25 ° C. The compounds I and III showed a 90% and 80% activity, respectively, while compounds IV and V were ineffective

Claims (1)

Patent claims: 1. O, S - dialkyl - O - phenylthiophosphoric acid ester the formula C ₂ H ₅ O f \ p — o (H) C ₃ H ₇ S (D