CH574713A5 - s-Picolyl phosphoridithioates - useful as insecticides, acaricides and plant-growth regulators - Google Patents

Abstract

New cpds. of formula (I): (where R1 is 1-5C alkyl, pref. Et; R2 is 1-5C alkyl or propargyl; X is H or Cl; n = 1-4, pref. 1 or 2) are prepd. by reacting the corresp. picolyl halide with MS(O)P(SR2)OR1 (where M = alkali metal).

Description

  

  
 



   The present invention relates to pesticides containing a picolyldithiophosphoric acid ester as active component, and their use in pest control.



   The picolyldithiophosphoric acid esters have the formula I.
EMI1.1
 wherein
R1 C1-C5-alkyl,
R2 C1-Cs-alkyl or C3-Cs-alkynyl,
X is halogen and n is zero, 1, 2, 3 or 4.



   Halogen is to be understood as meaning fluorine, chlorine, bromine and / or iodine, but especially chlorine. The alkyl or alkynyl groups that come into consideration for R1 and R2 can be straight-chain or branched. Examples of such groups are: methyl, ethyl, propyl, isopropyl, n-, i-, sec-, tert-, butyl, n-pentyl and its isomers and propargyl.



   Because of their action, compounds of the formula I are preferred in which
R1 ethyl,
R2 n-propyl,
X is chlorine and n is 1 or 2.



   The compounds of formula I can analogously to known methods, for. B. be manufactured as follows:
EMI1.2
 wherein
R1, R2, X and n have the meanings given for formula I and
Hal for a fluorine, chlorine, bromine or iodine atom, in particular for a chlorine or bromine atom and
Me stands for an alkali metal, in particular for sodium or potassium.



   The reaction is carried out at normal pressure, a temperature between 0-150 ° C., in particular between 20-100 ° C., and in solvents or diluents which are inert towards the reactants. Examples of such inert solvents or diluents include. a .: aromatic hydrocarbons such as benzene, toluene, halogenated hydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene; chlorinated alkanes of 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 like acetonitrile etc.



   Some of the 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 can be used to control various types of plant and animal pests.



   They are particularly suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Curculinee, Dermelion, Tenestidae, Tenestidae, Cocidaeidae , Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae and acarids of the families: Ixodidae, Argasidae, Tetranychidae, 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.



   Org. Phosphorus compounds;
Nitrophenols and their derivatives;
Formamidine;
Ureas; Pyrethrin-like compounds;
Carbamates and chlorinated hydrocarbons.



   The compounds of the formula I can be used alone or 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 formula I can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in the customary formulation, which are part of general knowledge in application technology.



   The 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 between 0.1 and 95Wo, it should be mentioned that when applied from an airplane or other suitable application devices, concentrations of up to 99.5% or even pure active ingredient can be used.



   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. This gives wettable powders which can be diluted with water to give 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).

 

   example 1
Production of O-ethyl-S-n-propyl-S-2,6-dichloropicolyl-3-phosphorothiolate
14 g of 2,6-dichloropicolyl-3-chloride is dissolved in 150 ml of acetonitrile. 16.9 g of potassium O-ethyl-S-n-propyldithiophosphate are added in portions to this solution. The reaction mixture is stirred for 16 hours at room temperature. After the solvent has been distilled off, the residue is mixed with ether, washed with water and dried over anhydrous sodium sulfate.



   After evaporation of the ether, the compound of the formula is obtained
EMI2.1
 with a refraction of nD24: 1.5740.



   The following connections are also established in the same way:
EMI2.2
  
EMI3.1
   nD24: 1.6004 nD24: 1.5830 nD20: 1.5738 nD20: 1.5995 nD20: 1.5691 nD20: 1.5530
Example 2 Insecticidal feed poison effect
Potted potato plants in the 4-5 leaf stage were immersed in a 0.1% aqueous active ingredient emulsion (obtained from a 10% emulsifiable concentrate).



   After the coating had dried on, the plants were populated with 5 Colorado beetle larvae (Leptinotarsa decemlineata) in the L-3 stage or with 5 larvae of the species Spodoptera littoralis in the L-3 stage.



   Plastic cylinders, sealed at the top with a wire mesh, were then placed over the treated plants in order to prevent the larvae from migrating.



   A percentage evaluation of the destruction achieved was carried out after 3 days.



      The experiment was carried out at 24O C and 60% relative humidity.



   Results compound% kill
Leptinotarsa Spodoptera decemlineata littoralis
EMI4.1
 100% 100% 100% 100% 100% 100%
0% 0% comparative compound (known from U.S. Patent No. 3,371,095)
Example 3
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 ingredient per hectare) into the
Paddy water. The insecticidal activity was evaluated 10 days after the granules had been added.



   The compounds according to Example 1 worked in the above
Test against chilo suppressalis.



   Example 4
Effect against ticks
A. Rhipicephalus bursa
5 adult ticks and 50 tick larvae were each in one
Glass tubes counted and 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 immersed. 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. Run for every attempt
2 repetitions.



   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 Example 1 were active in these tests against adults and larvae of Rhipicephalus bursa and sensitive, respectively. OP-resistant larvae of Boophilus microplus.

 

   Example 5
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 Example 1 were effective against adults, larvae and eggs of Tetranychus urticae.

 

Claims (1)

PATENT CLAIM I Pesticides containing a compound of the formula I as the active component EMI5.1 wherein R1 C1-C, -alkyl, R2 C1-C5-alkyl or C3-C5-alkynyl, X halogen, Y is oxygen or sulfur and n is zero, 1, 2, 3 or 4. SUBCLAIMS 1. Agent according to claim I, containing a compound of the formula I, in which R1 ethyl, R2 n-propyl, X is chlorine and n is 1 or 2. 2. Means according to dependent claim 1, containing the compound of the formula EMI5.2 5 PATENT CLAIM II Use of an agent according to claim I for Control of pests. SUBClaims t 3. Use according to patent claim II to control insects. 4. Use according to patent claim II for combating representatives of the Akarina order.