CH600769A5 - 3-(Phenoxy or phenylthio)-phenyl alkynyl ethers - Google Patents

Abstract

3-(Phenoxy or phenylthio)-phenyl alkynyl ethers prepd. by reacting 3-substd. phenolates with alkynyl phenolates

Description

  

  
 



   The present invention relates to a pesticide containing new phenylalkynyl ether as active component and its use in pest control.



   The phenyl alkynyl ethers contained in the agents according to the invention have the formula I.
EMI1.1
 where n is the number 0 or 2, Y is oxygen or sulfur, R1 is hydrogen, methyl or halogen and R2 is hydrogen or methyl.



   Halogen for R1 means fluorine, chlorine, bromine or iodine, but in particular chlorine or bromine.



   Because of their action, agents according to the invention are preferred which contain compounds of the formula I in which n is the number 0 or 2, Y is oxygen or sulfur and R1 and R2 are each hydrogen.



   The compounds of formula I can by known methods, for. B. can be produced as follows:
EMI1.2

In formulas II and III, n, Y, R1 and R2 have the meaning given under formula I, X stands for a halogen atom, 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 a base for the above process, e.g. B. tertiary amines, such as trialkylamines, pyridine, dialkylanilines, and also inorganic bases, such as hydrides, hydroxides, alkoxides and carbonates of alkali and alkaline earth metals.



  The process is generally carried out at a reaction temperature of 0 to 150 ° C., preferably between 0 to 80 ° C., under normal pressure and in the presence of inert solvents or diluents.



  Suitable solvents or diluents are e.g. B.



     ether, such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dioxane, tetrahydrofuran; N, N-dialkylated carboxamides, such as dimethylformamide; Ketones such as acetone, methylethyiketone or cyclohexanone; Hexa methylphosphoric triamide; Dimethyl sulfoxide; or C2-Cs alcohols, such as. B. isopropanol.



   The starting materials of the formulas II and III are known compounds and / or can be prepared analogously to the known methyls described in the literature.



   The compounds of the formula I containing compositions according to the invention are suitable for controlling various types of animal and vegetable pests, it being possible for some compounds of the formula I to be used as synergists of insecticides and acaricides.

  They are particularly suitable for controlling insects of the families: Acrididae, Blattidae Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae , Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae, as well as for the control of Akarids of the families: Ixodidae, Argasidae, Tetranychidae.



   The pesticidal effect can be broadened considerably by adding other insecticides and / or acaricides and adapted to the given circumstances.



  Suitable additives are z. E.g .: organic phosphorus compounds,
Nitrophenols and derivatives,
Formamidines, ureas,
Carbamates or chlorinated hydrocarbons.



   The compounds of formula I can be formulated together with suitable carriers and / or additives. Suitable triggers and additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g.

  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 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 suitable carriers, optionally with the addition of dispersants or solvents which are inert to the active ingredients.

  The active ingredients can be present and used in the following processing forms: Solid processing forms: dusts, scattering agents,
Granules (coated granules, impregnated granules and homogeneous granules); Liquid processing forms: a) Water-dispersible spray powder (wettable pow
Active ingredient concentrates: ders), pastes, emulsions b) solutions
The content of active ingredient in the agents described above is 0.1 to 95% by weight.



   The active compounds of the formula I can be formulated, for example, as follows:
Dusts: The following substances are used to produce a) 5% and b) 2% dusts: a) 5 parts of active ingredient
95 parts talc b) 2 parts active ingredient
1 part of highly disperse silica
97 parts of talc
The active substances are mixed and ground with the tri-substances.



   Granules: The following substances are used to produce 5% granules:
5 parts of active ingredient
0.25 part epichlorohydrin
0.25 parts 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 the acetone is subsequently evaporated in vacuo.



   Spray powder: The following components are used to produce a) 40%, b) and c) 25%, d) 10% spray powder: a) 40 parts of active ingredient
5 parts of lignosulfonic acid sodium salt
1 part dibutylnaphthalenesulfonic acid sodium salt
54 parts of silica;

   b) 25 parts of active ingredient
4.5 parts calcium lignin sulfonate
1.9 parts champagne chalk / hydroxyethyl cellulose
Mixture (1: 1)
1.5 parts of sodium dibutyl naphthalenesulfonate
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 mixture of saturated sodium salts
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.

  Spray powder is 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 of epoxidized vegetable oil
3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt
40 parts of dimethylformamide
43.2 parts of xylene b) 25 parts of active ingredient
2.5 parts of epoxidized vegetable oil
10 parts of an alkylarylsulfonate-fatty alcohol polyglycol ether mixture
5 parts of dimethylformamide
57.5 parts xylene
Such concentrates can be used to dilute them with water to produce emulsions of any desired concentration.



     Sprays: The following ingredients are used to make a 5% sprayer:
5 parts of active ingredient
1 part epichlorohydrin
94 parts of gasoline (boiling limits 160-190oC).



   example 1
Preparation of 1-propargyloxy-3 phenyl-mercapto-benzene
To a solution of 15.2 g (0.075 M) of 3-hydroxydiphenyl sulfide in 80 ml of anhydrous acetone are added 10.8 g (0.078 M) of finely powdered, anhydrous potassium carbonate, and the mixture is boiled for 1 hour. 9.5 g (0.08 M) of propargyl bromide are added dropwise within 15 minutes and the mixture is boiled at the reflux temperature for a further 4 hours. For working up, the reaction solution is filtered off from the bottom body and the filtrate is freed from solvent in vacuo.

 

  The residue is dissolved in anther, the solution is washed three times with 10% potassium hydroxide solution and then four times with saturated sodium chloride solution. After the ether phase has dried over sodium sulfate, the solvent is distilled off in vacuo. The compound of the formula is obtained
EMI2.1
 as Ul with a refractive index of nDU = 1.6219.

  The following connections can also be made in an analogous manner:
EMI2.2
  
EMI3.1
  
EMI4.1

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



   After the acetone had evaporated, 10 larvae of the 5th stage of Dysdercus fasciatus were added to the treated dish, which contained feed and moist cotton wool.



  The bowl was then covered with a sieve cover.



   After about 10 days, that is, as soon as the control animals had performed the adult hemorrhage, the test animals were examined for the number of normal adults.



   B) Contact effect on Andes aegypti larvae
About 20 two-day larvae of the yellow fever mosquito (A & es aegypti) were set up in a beaker containing a solution of the active substance (concentration 5 ppm). The cup was then covered with a strainer lid. After the control animals had completed their moult, the test animals were examined and the percentage of normal adults compared to the control was determined.



   The compounds according to formula I showed good activity in tests A and B above.



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



   After the acetone had evaporated, 10 freshly reliefed dolls were placed on the treated area. The bowl was covered with a sieve cover.



   After the control animals left the doll's shell as adults, the experimental animals were
Number of normal adults examined.



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



   Example 3
Effect against Ephestia kiihniella
50 g of wheat flour was mixed in two beakers with a certain amount of active ingredient (formulated as 5% dust), so that an active ingredient concentration of 0.05% by weight was obtained.



   10 larvae of Ephestia kiihniella were set up per beaker (25 g of flour). The course of the population was recorded over a period of 8 weeks and the number of developed moths determined.



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



   Example 4
Action against spider mites (acaricidal action)
Phaseolus vulgaris (bush beans) was covered with an infested leaf stalk from a mass cultivation of Tetranychus urticae 12 hours before the test. The overflowed mobile stages were sprayed with the emulsified test preparations in a concentration of 0.04% by weight using a chromatography atomizer, so that none
The spray liquid ran out.

  After two and seven days, larvae, adults and eggs were examined under the binocular for living and dead individuals, and the result of the evaluation was expressed as a percentage. During the holding period, 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 I pesticide containing at least one compound of the formula I as active component
EMI4.2
 

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



   

 

Claims (1)

** WARNING ** Start 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 ingredient solution (corresponding to 10 mg active ingredient / m2) was pipetted into an aluminum dish and distributed evenly. After the acetone had evaporated, 10 larvae of the 5th stage of Dysdercus fasciatus were added to the treated dish, which contained feed and moist cotton wool. The bowl was then covered with a sieve cover. After about 10 days, that is, as soon as the control animals had performed the adult hemorrhage, the test animals were examined for the number of normal adults. B) Contact effect on Andes aegypti larvae About 20 two-day larvae of the yellow fever mosquito (A & es aegypti) were set up in a beaker containing a solution of the active substance (concentration 5 ppm). The cup was then covered with a strainer lid. After the control animals had completed their moult, the test animals were examined and the percentage of normal adults compared to the control was determined. The compounds according to formula I showed good activity in tests A and B above. C) Contact effect on Tenebrio molitor dolls A certain amount of a 0.1% acetone active ingredient solution corresponding to 10 mg active ingredient / m2 was pipetted into an aluminum dish and distributed evenly. After the acetone had evaporated, 10 freshly reliefed dolls were placed on the treated area. The bowl was covered with a sieve cover. After the control animals left the doll's shell as adults, the experimental animals were Number of normal adults examined. The compounds according to formula I showed good activity in the above test. Example 3 Effect against Ephestia kiihniella 50 g of wheat flour was mixed in two beakers with a certain amount of active ingredient (formulated as 5% dust), so that an active ingredient concentration of 0.05% by weight was obtained. 10 larvae of Ephestia kiihniella were set up per beaker (25 g of flour). The course of the population was recorded over a period of 8 weeks and the number of developed moths determined. The compounds according to formula I showed good activity in this test against Ephestia kiihniella. Example 4 Action against spider mites (acaricidal action) Phaseolus vulgaris (bush beans) was covered with an infested leaf stalk from a mass cultivation of Tetranychus urticae 12 hours before the test. The overflowed mobile stages were sprayed with the emulsified test preparations in a concentration of 0.04% by weight using a chromatography atomizer, so that none The spray liquid ran out. After two and seven days, larvae, adults and eggs were examined under the binocular for living and dead individuals, and the result of the evaluation was expressed as a percentage. During the holding period, 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 I pesticide containing at least one compound of the formula I as active component EMI4.2 where n is the numbers 0 to 2, Y is oxygen or sulfur, R1 is hydrogen, methyl or halogen and R2 is hydrogen or methyl. SUB-CLAIMS 1. Agent according to claim I, containing a compound of formula I, wherein n is the numbers 0 to 2, Y is oxygen or sulfur and R1 and Ri are each hydrogen. 2. Agent according to sub-claim 1 containing the compound of the formula EMI5.1 3. Remiss subclaim 1 containing the compound of formula EMI5.2 4. Agent according to subclaim 1 containing the compound of the formula EMI5.3 5. Composition according to subclaim 1 containing the compound of the formula EMI5.4 PATENT CLAIM II Use of an agent according to claim I for combating pests. SUB-CLAIM 6. Use according to claim II to control insects and representatives of the order Akarina.