CH592411A5 - Phenoxymethyl- and phenylthiomethyl-pyridine derivs - with insecticidal, acaricidal and plant-growth regulating activity - Google Patents

Abstract

Pyridine derivs. of formula (I) are new: (where Y is CH2, O, CO or S; Z is O or S; R1 is a gp. of formula a-f: R2 is H or Me; A circled negative is a mineral acid residue). Cpds. (I) are insecticides (e.g. active against Dyodercus fasciatus larvae, Aedes aegypti larvae, Tenebrio molitor pupae and Ephestia kuhniella) and acaricides (e.g. active against Tetranychus urticae eggs, larvae and adults); some also have plant-growth regulating activity (unspecified).

Description

  

  
 



   The present invention relates to a pest control agent containing as active component at least one phenylaralkyl ether or thioether of the formula I below and its use in pest control.



   The new phenylaralkyl ethers and thioethers contained in the agents according to the invention have the formula I.
EMI1.1

EMI1.2
 Z -0- or -S-, R1 hydrogen or methyl,
EMI1.3

R3 hydrogen, methyl or ethyl,
R4 is hydrogen, methyl, ethyl, formyl or acetyl and Ae is a mineral acid residue.



   Examples of mineral acid residues are u. a .: Cle, Br3, je, HSO4e, so4ee.



   Because of their action, agents according to the invention are preferred which contain compounds of the formula I in which Y is -CH2-, -0- or
EMI1.4
 z -0, R1 hydrogen,
EMI1.5

R3 is hydrogen, methyl or ethyl and Ae is Cle, Brs or each.



   The compounds of formula I can according to methods known per se by alkylation of a (thio) phenol or (thio) phenolate II, respectively. IV can be prepared with a halide III in the presence of a base or a proton acceptor:
EMI1.6

In the formulas II to IV, Y, Z, R1 and R2 have the meaning given for the formula I, X stands for halogen, in particular for chlorine or bromine, and Me for a metal of the 1st or 2nd main group of the periodic table, in particular for Sodium, potassium, or calcium.



   As acid-binding agents or as bases, for. B. in question: tertiary amines such as trialkylamines, pyridine, dialkylanilines; also inorganic bases such as hydrides, hydroxides; Alkoxides and carbonates of alkali and alkaline earth metals.



  Processes 1) and 2) are carried out at a reaction temperature between 10 and 1500 ° C., preferably between 50 and 130 ° C., under normal pressure and in the presence of inert solvents or diluents.



   Suitable solvents or diluents are, for. B.



  Ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxy ethane, dioxane, tetrahydrofuran; N, N-dialkylated carboxylic acid amides, such as dimethylformamide; Ketones, such as acetone, methyl ethyl ketone or cyclohexanone, and hexamethylphosphoric triamide, dimethyl sulfoxide or C2-Cs alcohols, such as. B. isopropanol. The starting materials of the formulas II to IV are known compounds or can be prepared analogously to methods known and described in the literature.



   The compounds of the compositions according to the invention contained in formula I are suitable for combating various types of pests which infest animals and plants.



  Some compounds of the formula I have a plant growth-regulating effect. In particular, however, the agents according to the invention are suitable for controlling insects of the following families:
Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae and acarids of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.



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



   Suitable additives are, for.



   organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates or chlorinated hydrocarbons.



   The compounds of the formula I can be used formulated with suitable carriers and / or additives. These 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:
Sprays.



   The content of active ingredient in the agents according to the invention is between 0.1 and 95% by weight.



   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 sodium salts of saturated fatty alcohol sulfates,
5 parts naphffialinsulfonic 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,
13.4 parts of a combination emulsifier, consisting of
Fatty alcohol polyglycol ethers and alkylarylsulfonate
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 polyglycol 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).



     The residue tends to further rei chromatographically on silica gel (eluent: methyl acetate-methanol 49: 1), whereby pure 1-phenoxy-4- (3-picolyloxy) -benzene of mp.



     47-48 "C is obtained.



   This base can also be purified using its hydrochloride (melting point 196-197 "C, from methanol) without chromatographic purification.



   B. Preparation of the N-oxide of 1-phenoxy-4 (3-picolyloxy) benzene
example 1
A. Preparation of 1-phenoxy-4- (3-picolyoxy) benzene
A mixture of 22.3 g of 4-phenoxyphenol, 16.4 g of 3-picolyl chloride hydrochloride, 41.4 g of finely powdered, anhydrous potassium carbonate, 0.5 g of potassium iodide, 70 ml of isopropanol and 40 ml of dimethylformamide are added under an N2 atmosphere and stirring heated to 80 ° C. for 24 hours. After this time, the reaction mixture is filtered off from the sediment and the filtrate is largely freed from the solvents in vacuo. The residue is dissolved in approx. 400 ml of ether and the ethereal solution is extracted one after the other Water four times with 10% potassium hydroxide solution and finally with saturated sodium chloride solution.

  The ether solution is then treated with Norit adsorption charcoal and over
Sodium sulfate dried, the solvent was distilled off and
To a solution of 27.7 g of 1-phenoxy-4- (3-picolyloxy) benzene in 100 ml of dichloromethane, the solution of 22 g of approx. 85% 3-chloroperbenzoic acid in 250 g is added dropwise with stirring at 0 ° C. over the course of one hour Methylene chloride diethyl ether (9: 1). After stirring for 4 hours at 0-5 ° C., the reaction mixture is warmed to room temperature and stirred for a further 3 hours at this temperature. For working up, the reaction mixture is filtered and the filtrate is repeatedly washed neutral, first with 5% potassium hydroxide solution and then with water.

  After the organic phase has been dried over sodium sulfate, the solvent is removed in vacuo and the remaining N-oxide of 1-phenoxy-4- (3-picolyloxy) benzene is recrystallized from a little isopropanol (melting point 123 to 125 ° C.).



   The following compounds of the formula I are also prepared in an analogous manner:
EMI3.1
 M.p .: 37-39 "C M.p .: 39-41" C
M.p .: 78-80 "C
M.p .: 172-174 "C
M.p .: 85-86 "C
M.p .: 1900C (decomp.)
EMI4.1

Example 2
A. Contact effect on Dysdercus fasciatus larvae
A certain amount of a 0.1% acetone active substance solution (corresponding to 10 mg AS / m2) was pipetted into an aluminum dish and distributed evenly.



   After the acetone had evaporated, 10 larvae of the 5th instar of Dysdercus fasciatus were placed in the treated dish, which received food and moist cotton wool. The bowl was then covered with a sieve lid. After approx.



  10 days, i.e. H. As soon as the control animals had completed their adult moult, the test animals were examined according to the number of normal adults.



   The compounds according to formula I showed a good effect in the above test.



   B. Contact effect on Aedes aegypti larvae
Approximately 20 two-day larvae of the yellow fever mosquito (Aedes aegypti) were placed in a beaker containing a solution of the active substance (concentration 5 ppm). The cup was then covered with a sieve lid. After the control animals had completed their adult moult, the test animals were examined and the percentage number of normal adults compared to the control was determined.



   The compounds according to formula I showed a good effect in the above test.



   C. Contact effect on Tenebrio molitor pupae
A certain amount of a 0.1% acetone active ingredient solution corresponding to 10 mg AS / m2 was pipetted into an aluminum dish and distributed evenly.



   After the acetone had evaporated, 10 freshly skinned pupae were placed on the treated area. The bowl was covered with a sieve lid.



   After the control animals had left the pupal shell as adults, the test animals were examined for the number of normal adults.



   The compounds according to formula I showed a good effect in the above test.



   Example 3
Effect against Ephestia kühniella
50 g of wheat flour are mixed in two cups with a certain amount of active ingredient formulated as 5% dust, so that the concentration was 0.05%.



   10 larvae of Ephestia kühniella were added to each cup (25 g of flour). The course of the population was recorded over the course of 8 weeks and the number of moths developed was determined.



   The compounds according to formula I showed good activity in this test against Ephestia kühniella.



   Example 4
Effect against spider mites
Phaseolus vulgaris (French beans) were coated 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 from a chromatography atomizer with the emulsified test preparations in a concentration of 0.04%, so that the spray mixture did not run off. After two to seven days, larvae, adults and eggs were evaluated for living and dead individuals under the dissecting microscope, and the result was expressed as a percentage. During the holding time, the treated plants stood in greenhouse cabins at 25 ° C. The compounds according to formula I showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae.

 

   PATENT CLAIM 1
Pesticides containing at least one compound of formula I as active component
EMI4.2

EMI4.3
 Z -0- or -8-, Rl hydrogen or methyl,
EMI4.4
 

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. EMI4.1 Example 2 A. Contact effect on Dysdercus fasciatus larvae A certain amount of a 0.1% acetone active substance solution (corresponding to 10 mg AS / m2) was pipetted into an aluminum dish and distributed evenly. After the acetone had evaporated, 10 larvae of the 5th instar of Dysdercus fasciatus were placed in the treated dish, which received food and moist cotton wool. The bowl was then covered with a sieve lid. After approx. 10 days, i.e. H. As soon as the control animals had completed their adult moult, the test animals were examined according to the number of normal adults. The compounds according to formula I showed a good effect in the above test. B. Contact effect on Aedes aegypti larvae Approximately 20 two-day larvae of the yellow fever mosquito (Aedes aegypti) were placed in a beaker containing a solution of the active substance (concentration 5 ppm). The cup was then covered with a sieve lid. After the control animals had completed their adult moult, the test animals were examined and the percentage number of normal adults compared to the control was determined. The compounds according to formula I showed a good effect in the above test. C. Contact effect on Tenebrio molitor pupae A certain amount of a 0.1% acetone active ingredient solution corresponding to 10 mg AS / m2 was pipetted into an aluminum dish and distributed evenly. After the acetone had evaporated, 10 freshly skinned pupae were placed on the treated area. The bowl was covered with a sieve lid. After the control animals had left the pupal shell as adults, the test animals were examined for the number of normal adults. The compounds according to formula I showed a good effect in the above test. Example 3 Effect against Ephestia kühniella 50 g of wheat flour are mixed in two cups with a certain amount of active ingredient formulated as 5% dust, so that the concentration was 0.05%. 10 larvae of Ephestia kühniella were added to each cup (25 g of flour). The course of the population was recorded over the course of 8 weeks and the number of moths developed was determined. The compounds according to formula I showed good activity in this test against Ephestia kühniella. Example 4 Effect against spider mites Phaseolus vulgaris (French beans) were coated 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 from a chromatography atomizer with the emulsified test preparations in a concentration of 0.04%, so that the spray mixture did not run off. After two to seven days, larvae, adults and eggs were evaluated for living and dead individuals under the dissecting microscope, and the result was expressed as a percentage. During the holding time, the treated plants stood in greenhouse cabins at 25 ° C. The compounds according to formula I showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae. PATENT CLAIM 1 Pesticides containing at least one compound of formula I as active component EMI4.2 EMI4.3 Z -0- or -8-, Rl hydrogen or methyl, EMI4.4 EMI5.1 R3 is hydrogen, methyl or ethyl, R4 is hydrogen, methyl, ethyl, formyl or acetyl and AO is a mineral acid residue. SUBClaims 1. Means according to claim I, containing a connection Z -o-, EMI5.2 Ro hydrogen, EMI5.3 R3 is hydrogen, methyl or ethyl and Ae is CIe, Br '3 or each. 2. Means according to dependent claim 1, containing the compound of the formula EMI5.4 3. Composition according to dependent claim 1, containing the compound of the formula EMI5.5 4. Means according to dependent claim 1, containing the compound of the formula EMI5.6 5. Means according to dependent claim 1, containing the compound of the formula EMI5.7 PATENT CLAIM II Use of the agent according to claim I for combating pests. SUBClaim 6. Use according to claim II for combating insects and representatives of the order Akarina.