CH578304A5 - S-(1-benzotriazolyl) dithiophosphates - with insecticidal, acaricidal, fungicidal and nematocidal activity - Google Patents

Abstract

Cpds. of formula (I) (where R1 is Me or Et; R2 is n-Pr, i-Pr, n-Bu, n - pentyl, allyl or proparyl; R3 is H, Cl or CF3) are new cpds. pref. prepd. by reacting the corresp. 1-chloromethyl-benzotriazoles with MSP(O)(OR1)SR2 (M = alkali metal, NH4 or alkylammonium).

Description

  

  
 



   The present invention relates to a pesticide containing a benzotriazolyl derivative as the active component and its use in pest control. The benzotriazolyl derivatives have the formula (1)
EMI1.1
 wherein
R1 methyl or ethyl,
R2 n-propyl, isopropyl, n-butyl, n-pentyl, allyl or propargyl and
R3 is hydrogen, chlorine or trifluoromethyl.



   Because of their action of particular importance are compounds of the formula I in which
R1 ethyl and
R2 mean n-propyl.



   The compounds of the formula I can be prepared by the following process known per se:
EMI1.2

In the formulas II and III, R1 to R3 have the meaning given for the formula I and Me represents an alkali metal, in particular sodium or potassium, ammonium or alkylammonium.



   The reaction is carried out at normal pressure, at a temperature of -10-120 ° C., in particular at + 20-70 ° C., and in solvents or diluents which are inert towards the reactants. As a solvent or diluent, for. B. the following are suitable: aromatic hydrocarbons, such as benzene, toluene, halogenated hydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated alkanes with 1 to 3 carbon atoms, ethers, such as dioxane, tetrahydrofuran; Esters, such as ethyl acetate; Ketones such as acetone, methyl ethyl ketone, diethyl ketone, nitriles, e.g. B. acetonitrile.



   Starting materials of the formula II are known or can be prepared analogously to known methods.



   The compounds of the formula I have a broad biocidal action and are therefore suitable for combating various types of plant and animal pests. But they have in particular insecticidal and acaricidal properties and can be used against all stages of development, such. B. eggs, larvae, pupae, nymphs and adults, are used by insects and representatives of the order Akarina, such as. B. against family insects:
Tettignoiidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae.



   The insecticidal or acaricidal effect can be significantly broadened by adding other insecticides and / or acaricides and adapted to given circumstances.



   Suitable additives are, for. B.



   organic phosphorus compounds,
Derivatives of nitrophenols,
Formamidine,
Ureas,
Carbamates and / or chlorinated hydrocarbons.



   The compounds of the formula I can be used together with suitable carriers and / or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary 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 formulas I and Ia can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in customary formulations, which are common knowledge in application technology.



   Agents according to the invention are prepared in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients.



  The active ingredients can be present and used in the following working-up forms: Solid working-up forms:
Dusts, grit, granules (coating granules, impregnation granules and homogeneous granules); Liquid processing forms: a) Active substance concentrates dispersible in water:
Wettable powders, pastes, emulsions; b) Solutions.



   The content of active ingredient in the agents described above is niche 0.1 to 95%, it should be mentioned that concentrations of up to 99.5% or even pure active ingredient can be used for application from the aircraft or other suitable application devices.



   The active ingredients of the formula I can be formulated as follows, for example: Dusts:
The following substances are used to produce a) 5% and b) 2% dust: a) 5 parts of active ingredient,
95 parts of talc; b) 2 parts of active ingredient,
1 part of highly dispersed silica,
97 parts of talc.



   The active ingredients are mixed and ground with the carrier substances.



  Granules:
The following substances are used to produce 5% granules:
5 parts active ingredient,
0.25 parts epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (grain size 0.3-0.8 mm).



   The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and the acetone is then evaporated in vacuo.



  Wettable powder:
The following ingredients are used to produce a) 40%, b) and c) 25%, d) 10% wettable powder: a) 40 parts of active ingredient,
5 parts of lignin sulfonic acid sodium salt,
1 part dibutylnaphthalenesulfonic acid sodium salt,
54 parts of silica; b) 25 parts of active ingredient,
4.5 parts calcium lignosulfonate,
1.9 parts of champagne chalk / hydroxyethyl cellulose
Mixture (1: 1),
1.5 parts of sodium dibutyl naphthalene sulfonate,
19.5 parts of silica,
19.5 parts of champagne chalk,
28.1 parts of kaolin; c) 25 parts of active ingredient,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts of champagne chalk / hydroxyethyl cellulose
Mixture (1: 1),
8.3 parts sodium aluminum silicate,
16.5 parts kieselguhr,
46 parts of kaolin;

   d) 10 parts of active ingredient,
3 parts mixture of the sodium salts of saturated
Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid / formaldehyde
Condensate,
82 parts of kaolin.



   The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of any desired concentration.



  Emulsifiable concentrates:
The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate: a) 10 parts of active ingredient,
3.4 parts epoxidized vegetable oil,
3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylaryl sulfonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene; b) 25 parts of active ingredient,
2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate / fatty alcohol poly glycol ether mixture,
5 parts of dimethylformamide,
57.5 parts of xylene.



   Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.



  Spray:
The following ingredients are used to make a 5% spray:
5 parts active ingredient,
1 part epichlorohydrin,
94 parts of gasoline (boiling point 160-190 C).



   Manufacturing example
Production of O-ethyl-S- (n) -propyl-S - [(5-chlorobenztriazol-1 -yl) -methyl] -dithiophosphate
20.2 g of 1-chloromethyl-5-chlorobenzotriazole and 23.5 g of potassium salt of dithiophosphoric acid O-ethyl-S- (n) -propyl ester are dissolved in 200 ml of absolute acetone with stirring. The mixture is then heated to 50 ° C. and stirred for 15 hours at this temperature, a fine white precipitate separating out. After this precipitate has been filtered off, the acetone solution is evaporated to dryness at room temperature. The remaining, light brown oil is dissolved in 300 ml of ether. After washing the ethereal solution with 100 ml of ice water, the organic phase is dried with magnesium sulfate and the ether is evaporated.

  The compound of the formula is obtained
EMI2.1
 as a light brown oil, with a refraction of nD40 = 1.6685.



   The following connections are also established in the same way:
EMI2.2
  
EMI3.1

example 1
Insecticidal food poison effect Cotton plants and potato plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate).



   After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis or Heliothis virescens larvae L3 and the potato plants with Colorado beetle larvae (Leptinotarsa decemlineata). The experiment was carried out at 24 C and 60% relative humidity.



   In the above test, the compounds according to the preparation example showed a good insecticidal feed poison action against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.



   Example 2
Effect against Chilo suppressalis
6 rice plants of the Caloro variety were transplanted into plastic pots with an upper diameter of 17 cm and raised to a height of about 60 cm.



  The infestation with Chilo suppressalis larvae (L1; 3-4 mm long) took place 2 days after the addition of the active ingredient in granulate form (application rate 8 kg of active substance per hectare) in the paddy water. The insecticidal activity was evaluated 10 days after the granules had been added.



   The compounds according to the preparation example acted against Chilo suppressalis in the above test.



   Example 3
Action against ticks A. Rhipicephalus bursa
5 adult ticks or 50 tick larvae were counted in a glass tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series with 100, 10, 1 or 0.1 ppm test substance each. The tube was then closed with a standardized cotton ball and turned upside down so that the active ingredient emulsion could be absorbed by the cotton wool.



   The evaluation was carried out after 2 weeks for the adults and after 2 days for the larvae. Two repetitions were run for each attempt.



  B. Boophilus microplus (larvae)
With an analogous dilution series as in test A, 20 sensitive resp. OP-resistant larval experiments were carried out. (The resistance refers to the tolerance of Diazinon.)
The compounds according to the preparation example worked in these tests against adults of larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus.

 

   Example 4
Acaricidal effect
Phaseolus vulgaris (plants) were covered with an infected piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity.



  The overflowing mobile stages were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After two to 7 days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result was expressed as a percentage.



  During the holding time, the treated plants stood in greenhouse cabins at 25 C.



   In the above test, the compounds according to the preparation example acted against adults, larvae and eggs of Tetranychus urticae.

 

Claims (1)

PATENT CLAIM I. Pesticides containing as active component a compound of the formula (I) EMI3.2 wherein R1 methyl or ethyl, R2 n-propyl, isopropyl, n-butyl, n-pentyl, allyl or propargyl and R3 is hydrogen, chlorine or trifluoromethyl. SUBCLAIMS 1. Agent according to claim I, containing a compound of the formula (I) in which R1 ethyl and R2 mean n-propyl. 2. Means according to dependent claim 1, containing a compound of the formula EMI3.3 3. Means according to dependent claim 1, containing a compound of the formula EMI3.4 4. Means according to dependent claim 1, containing a compound of the formula EMI4.1 PATENT CLAIM II Use of an agent according to patent claim I for combating various animal and plant pests. SUBClaim 5. Use according to claim II for combating insects.