CH593006A5 - Phenyl aralkyl-amines, ethers and thioethers - with insecticidal and acaricidal activity - Google Patents

Abstract

Phenyl aralkyl amines, ethers and thioethers of formula (I):- (where Y is S, -CH2.S- or -SO-; Z is S, O or NH; R1 is H, 1-4C alkyl, 1-2C alkoxy, 3-4C alkenyloxy, 3-4C alkynyloxy, 3-4C haloalkenyloxy, CN, NO2, or halogen; R2 is H, 1-4C alkyl, 1-2C alkoxy or halogen; or R1, R2 form a 3,4-methylenedioxy group; R3 is H or Me; R4 is H, Me or halogen), are insecticides, and acaricides in conventional formulations containing 0.1 to 95% of (I); e.g. an insecticidal powder may contain 5 pts. of (I) and 95 pts. of talc, finely ground together.

Description

  

  
 



   The present invention relates to a pesticide containing new phenyl aralkyl ethers, thioethers or amines as active components and its use in pest control. These phenyl aralkyl ethers, thioethers and amines have the formula I.
EMI1.1
 Z -S-, -0- or -NH-, R1 hydrogen, CtC3-alkyl, Ci-C2-alkoxy, C34-alkenyloxy, C3-C4-alkynyloxy, halogen or C3-C4-haloalkenyloxy, R2 hydrogen , Ci-C3-alkyl, Ct-C2-alkoxy or halogen, or Rt and R2 together represent the 3,4-methylenedioxy group, and R3 and R4 are each hydrogen or methyl.



   Halogen is to be understood as meaning fluorine, chlorine, bromine or iodine. The alkyl, alkoxy, alkenyloxy, haloalkenyloxy or alkynyloxy groups specified under R1 and R2 are straight-chain or branched. Examples of such groups are: methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, B-chlorallyloxy, α-chlorallyloxy, allyloxy, propargyloxy.



   Agents according to the invention containing compounds of the formula I in which
EMI1.2
 Z is -O-, -S- or NH-, R1 is hydrogen, chlorine, methoxy, methyl or propargyloxy, R2 is hydrogen or R1 and R2 together are the 3,4-methylenedioxy group, and R3 and R4 are each hydrogen.



   The compounds of the formula I can be prepared by methods known per se, for example as follows
EMI1.3

In the formulas II to VI, R1 to R4 and Y have the meaning given for the formula I and X stands for halogen, in particular for chlorine or bromine, and Me for a metal
1st or 2nd group of the periodic table, especially for sodium, potassium or calcium.



   The starting materials of the formulas II, III, IV, V and VI are known or can be prepared by known methods.



   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; Alkoxyides and carbonates of alkali and alkaline earth metals.



  Processes 1 and 2 are generally carried out at a reaction temperature between 0 and 1300 ° C., preferably at 200 to 1000 ° C., under normal pressure and in the presence of solvents or diluents.



   Suitable solvents or diluents are, for. B.



  Ethers, such as diethyl ether, diisopropyl ether, 1,2-dimethyloxy ethane, dioxane, tetrahydrofuran; N, N-dialkylated carboxamides, such as dimethylformamide; aliphatic and aromatic hydrocarbons, in particular benzene, toluene, xylenes or ethylbenzene, dimethyl sulfoxide; Ketones, such as acetone, methyl ethyl ketone or cyclohexanone and hexymethylphosphoric acid amide.



   The hydrogenation of compounds of formula VI to compounds of formula I is z. B. with catalytically excited hydrogen, expediently between room and boiling temperature of the reaction mixture, and carried out at normal or elevated pressure. Raney nickel or noble metals such as platinum or palladium are preferably suitable as catalysts.



   The agents contained in the compounds of the formula I are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysidae, Pseudococcidae, Chrysidaeelab Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae as well as acarids of the families: Arranidae, Tetranidae,.



   The insecticidal 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,
Nitrophenols and derivatives,
Formamidine, urea,
Carbamates or chlorinated hydrocarbons.



   The compounds of the formula I can be formulated and 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 formula I can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in customary formulations, which are common knowledge in application technology
The compositions according to the invention are produced 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 processing forms: Solid processing forms:

  :
Dusts, grit, granules (coating granules, impregnation granules and homogeneous granules);
Liquid processing forms: a) water-dispersible active concentrates: wettable powders, pastes, emulsions; b) Solutions: sprays.



   The content of active ingredient in the inventive means is between 0.1 to 95% by weight.



   The active ingredients of the formula I can be formulated as follows, for example:
Dust
The following substances are used to produce a) 50 / above and b) 20 / above dusts: 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 50% granules:
5 parts of active ingredient
0.25 part 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 thus obtained is sprayed onto kaolin and then the acetone im
Vacuum evaporates.



   Wettable powder
The following ingredients are used to produce a) 400/0 above, b) and c) 250/0, d) 100/0 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 champagne chalk / hydroxyethyl cellulose mixture (1:

  :1)
8.3 parts of sodium aluminum silicate
16.5 parts of diatomaceous earth
46 parts of kaolin d) 10 parts of active ingredient 3 parts of a mixture of the sodium salts of saturated
Fatty alcohol sulfates
5 series of napbtialinsulphonic 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> 100% and b) 250% 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 alkyl aryl 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.



   Sprays
The following ingredients are used to make a 50 / above spray:
5 parts of active ingredient
1 part epichlorohydrin
94 parts gasoline (boiling limits 160-1900 C).



   example 1
A. Preparation of a-4 (phenylmercapto-phenoxy) -p-xylene
To a solution of 22.2 g (0.11 M) 4-hydroxydiphenyl sulfide in 80 ml anhydrous acetone, 15.5 g (d, 11 M) finely powdered, anhydrous potassium carbonate are added and the mixture is dried at reflux temperature for one hour. A solution of 18.5 g (0.1 M) α-bromo-p-xylene in 30 ml acetone is added dropwise over the course of 30 minutes and the mixture is boiled for a further 4 hours at reflux temperature. For work-up, the reaction solution is filtered off from the sediment and the filtrate is freed from the solvent in vacuo.

 

  The residue obtained is dissolved in ether and washed
Solution three times with 100% potassium hydroxide solution and then four times with saturated saline solution. After drying the ether phase over sodium sulfate, the solvent is im
Distilled off in vacuo and the residue recrystallized from hexane / isopropanol.



  The compound of the formula is obtained
EMI3.1
 as colorless crystals with a melting point of 97 to 97.50 C.



   B. Preparation of the compound of formula
EMI3.2
 a) A solution of 40.4 g (0.2 M) 4-aminodiphenyl sulfide in 100 ml dry benzene is heated to reflux.



  A solution of 30 g (0.2 M) piperonal in 100 ml benzene is added dropwise to this solution over the course of 90 minutes, and the reaction mixture is refluxed for a further 5 hours. After the solvent has been suctioned off on a rotary evaporator, the residue is recrystallized from methanol. The compound of the formula is obtained
EMI3.3
 with a melting point of 78-790 C.



   b) 4 g of 5 o / o Pt-C catalyst are added to 41.3 g (0.12 M) of the imine obtained according to a), dissolved in 420 ml of dioxane, and the mixture is added for 181/2 hours at room temperature and 760 mmHg Pressure 2.72 1 of hydrogen initiated. The reaction mixture is filtered and the filtrate is concentrated on a rotary evaporator. The residue is recrystallized from isopropyl ether. The compound of the formula is obtained
EMI3.4
 with a melting point of 89-900 C.



   The following compounds of the formula I are also prepared in a manner analogous to that described above: Physical compounds
Data
EMI3.5
   82-830 C 93-940 C 61-620 C Compounds Physical
Data
EMI3.6
 65 c
EMI3.7

EMI3.8
   7P750 C
EMI3.9
   62-630 C
EMI3.10

EMI3.11
    7d770 C
85-86 C 115-117 C
EMI3.12

EMI3.13
 128-130 C connections
EMI4.1
 links
EMI4.2
   links
EMI5.1

Example 2
A.

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



   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 molted adults, 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 Aëdes aegypti larvae
Approximately 20 2-day-old 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 0.10 / above 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 envelope 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
A. Action against Musca domestica
50 g of CSMA maggot substrate each were weighed into beakers. From a 10% acetone solution per active substance, 2.5 ml each time were pipetted onto 50 g maggot substrate. After the treated substrate has been thoroughly mixed, the solvent is allowed to evaporate. 25 1-, 2-, and 3-day maggots and approx. 50 fly eggs were then used for each active ingredient. After pupation was complete, the pupae were flushed out and counted. After 10 days, the number of hatched flies was determined and thus a possible influence on the metamorphosis was determined.



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



   B. Action against Ephestia kühniella
50 g of wheat flour were mixed in two cups with a certain amount of active ingredient, formulated as 50 / above 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 that had developed was determined.



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



   Example 4
Effect against spider mites
Phaseolus vulgaris (French beans) were covered with an invested 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 in a concentration of 0.04 o / o from a chromatography atomizer, so that the spray mixture did not run off. After 2 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 25C C.

 

   The compounds according to formula I showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae.



   PATENT CLAIM I Pesticides containing at least one compound of the formula I as active component
EMI5.2
 Z -S-, -0- or -NH-, Rt hydrogen, C1-C3-alkyl, Ci-C2-alkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, halogen or C3-C4-Ha- logenalkenyloxy,

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



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. links EMI5.1 Example 2 A. Contact effect on Dysdercus fasciatus larvae A certain amount of a 0.1% strength acetone solution (corresponding to 10 mg AS / m2) was pipetted into an aluminum dish and evenly distributed. 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 molted adults, 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 Aëdes aegypti larvae Approximately 20 2-day-old 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 0.10 / above 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 envelope 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 A. Action against Musca domestica 50 g of CSMA maggot substrate each were weighed into beakers. From a 10% acetone solution per active substance, 2.5 ml each time were pipetted onto 50 g maggot substrate. After the treated substrate has been thoroughly mixed, the solvent is allowed to evaporate. 25 1-, 2-, and 3-day maggots and approx. 50 fly eggs were then used for each active ingredient. After pupation was complete, the pupae were flushed out and counted. After 10 days, the number of hatched flies was determined and thus a possible influence on the metamorphosis was determined. The compounds according to formula I showed a good effect in the above test. B. Action against Ephestia kühniella 50 g of wheat flour were mixed in two cups with a certain amount of active ingredient, formulated as 50 / above 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 that had developed was determined. The compounds according to formula I showed a good effect in the above test. Example 4 Effect against spider mites Phaseolus vulgaris (French beans) were covered with an invested 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 in a concentration of 0.04 o / o from a chromatography atomizer, so that the spray mixture did not run off. After 2 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 25C C. The compounds according to formula I showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae. PATENT CLAIM I Pesticides containing at least one compound of the formula I as active component EMI5.2 Z -S-, -0- or -NH-, Rt hydrogen, C1-C3-alkyl, Ci-C2-alkoxy, C3-C4-alkenyloxy, C3-C4-alkynyloxy, halogen or C3-C4-Ha- logenalkenyloxy, R2 is hydrogen, Ci-C3-alkyl, C1-C2-alkoxy or halogen or Rt and R2 together represent the 3,4-methylenedioxy group, and R3 and R4 are each hydrogen or methyl. SUBCLAIMS 1. Pesticides according to claim I containing as active component a compound of formula I, wherein EMI6.1 Z -O-, -S- or NH-, R1 is hydrogen, chlorine, methoxy, methyl or propargyloxy, R2 is hydrogen or R1 and R2 together are the 3,4-methylenedioxy group, and R3 and R4 are each hydrogen. 2. Means according to dependent claim 1 containing the compound of the formula EMI6.2 3. Means according to claim 1 containing the compound of the formula EMI6.3 4. Means according to claim 1 containing the compound of the formula EMI6.4 5. Means according to dependent claim 1 containing the compound of the formula EMI6.5 PATENT CLAIM II Use of the agent according to claim I for combating pests. SUBClaim 6. Use according to claim II for combating insects.