WO1982003390A1 - Erivatives of phenoxy-phenyle-isothio-urea,intermediary products based on phenoxy-phenyle-thio-urea,preparation thereof and their utilization against insects - Google Patents

Abstract

N-phenoxy-phenyl-isothio-urea derivatives of formula (FORMULA) in which R1, R2 and R3 separately signify hydrogen, halogen, C1-C4-alkyl, C1-C4 alkoxy, trifluoromethyl or nitro, R4 and R5 mean separately C2-C4-alkyl, R6 mean C1-C6-alkyl, C3-C6-alkenyle or C3-C5-alkinyle, R7 mean C1-C10-alkyl, C3-C5-alkenyle or C3-C6-cyclo-alkyl and R8 signifies hydrogen or C1-C10-alkyl. The invention also describes a process for their preparation and their use in the fight against insects; as well as their intermediate products based on phenoxy-phenyle-thio-urea.

Description

 Phenoxyphenylisothioureas, phenoxyphenylthioureas as intermediates, their production and use in the control of pests

The present invention relates to N-phenoxyphenyl isothioureas, processes for their preparation, pesticide compositions which contain the compounds according to the invention as active co-component, and their use for the pest control of pests on animals and plants.

The N-phenoxyphenyl isothioureas correspond to the Forael

wherein R ₁ , R ₂ and R _{3 are} each hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy,

Trifluomechyl or nitro, R ₄ and R ₅ each C ₂ -C ₄ alkyl, R ₆ C ₁ -C ₆ alkyl, C ₃ -C ₆ alkanesyl, or C ₃ -C ₅ alkynyl, R ₇ C ₁ - C ₁₀ alkyl, C ₃ -C ₅ alkenyl or C ₃ -C ₆ cycloalkyl and R _{8 is} hydrogen or C ₁ -C ₁₀ alkyl.

Halogen is fluorine, chlorine, bromine or iodine, but especially chlorine.

The alkyl, alkoxy, alkenyl and alkynyl groups which are in question in the case of R ₁ to R ₈ can be saturated or bent. Examples of such groups include methyl, methoxy, ethyl, propyl, isopropyl, n-, i-, sec-, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and its isomers, allyl, methallyl, fropargyl.

Cyclopropyl and cyclohexyl are the preferred cycloalkyl groups in R ₇ .

Because of their action, preferred compounds are Forael I, in which R _{1 is} hydrogen, chlorine, methoxy, trifluoroethane or nitro, R ₂ and R _{3 are} each hydrogen or chlorine, R ₄ and R _{5 are} each ethayl, I≤σpropyl, i-butyl, sec .-Butyl or tert.-butyl, R _{6 is} C ₁ -C ₆ alkyl, allyl or fropargyl, R _{7 is} C ₁ -C ₆ alkyl, cyclopropyl or cyclohexyl and R _{8 is} hydrogen.

However, particular preference is given to compounds of Forael I in which R _{1 is} hydrogen, chlorine or trifluoroethane, R _{2 is} hydrogen or chlorine, R _{3 is} hydrogen, R ₄ and R _{5 are} each isonropyl or R _{4 is} ethyl and R ₅ is-butyl, R _{6 is} methyl, R _{7 is} tert-butyl or isopropyl and R _{8 is} hydrogen.

The compounds of Forael I are also in Fora of acid addition salts e.g. Mineral salts before and can be used according to the invention in the form of their salts. The term of the present invention is therefore understood to mean both the free compounds of Forael I and their acid addition salts which are non-toxic to warablütam.

The compounds of Forael I can be converted into their acid salts by methods known per se. For the formation of addition salts are, for example, chloroformic acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, propionic acid, buttaric acid, valeric acid, oxalic acid, malonic acid, succinic acid, malic acid, maleic acid, Fumaric acid, lactic acid, tartaric acid, citric acid, beuzoic acid, phthalic acid, ciatic acid and salicylic acid are suitable.

The compounds of Forael I are prepared analogously to known processes, in dea aan e.g. a thiourea from Forael

ait eines Hälid der Forael

ait a Halid the Forael

R ₆ - Ea1 (III)

converts, in formulas II and III R ₁ to R _{8 have} the meanings already given for Forael I and "Hal" represents a halogen atom, in particular a chlorine or bromine atom.

The process is conveniently carried out at a temperature between 0 and 100 ° C, under normal or slightly elevated pressure and preferably in the presence of a solution or diluent which is inert to the reaction substances. Suitable solvents or diluents are e.g. Ethers and ethereal compounds such as diethyl ether, di-isopropyl ether, dioxane and tatrahydrofuran; aromatic hydrocarbons such as benzene, toluene and sylola; and ketones such as acetone, methyl ethyl ketone and cyclohexanone.

The compounds of Forael II to be used as starting materials are new. They can easily be obtained from known precursors, for example by using an isothiocyanate of Forael IV

with an amine of formula V

R ₇ - NH ₂ (v)

implements, wherein in the formulas IV and VR ₁ to R ₅ and R _{7 have} the meanings already mentioned (see. Example 1).

The process for the preparation of the starting materials of Forael II is preferably carried out in the presence of a solvent or diluent which is inert to the reactants, at a reaction temperature of 0 to 100 ° C. under normal pressure. Suitable solvents and solvents for this process are the substances already mentioned for the process for the preparation of the end product in Formula I.

The compounds of Forael I and the starting materials of Formula II are suitable for controlling pests on animals and plants.

The compounds of formulas I and II are particularly suitable for controlling insects, phytopathogenic mites and ticks, e.g. of the order Lepidoptera, Coleoptera, Homoptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplύra, Siphonaptera, Mallophaga, Thysanura, Isσptera, Psocoptera and Hyaenoptera.

Compounds of formulas I and II are particularly suitable for controlling insects which damage crops, in particular plant-damaging insects, in ornamental and useful plants, in particular in cotton crops (for example against Spodoptera littoralis and Heliothis virescans) and vegetable cultures (for example against Laptinotarsa decamlineata).

Active ingredients of the formulas I and II also have a very favorable action against flies, e.g. Musca domestica and mosquito larvae.

The acaricidal activity of the compounds of Forael I extends both to plant-damaging acarines (mites: 2.3. Of the families Tetranychidae, Tarsonemidae, Eriophydae, Tyroglyphidae and Glycyphagidae) as well as to ectoparasitic acarines (mites and ticks: e.g. of the families Ixidaeidae, , Sarccptidae and Der- manyssidae), which cause damage to farm animals.

With special advantage. Compounds of formulas I and II are also combined with substances which have a synergistic or reinforcing effect. Examples of such connections include Piperouyibutoxid, Propiayläther, Propinyloxiae, Fropinylcarbamate and Propinylphosphonate, 2 .- (3,4-Methylenedioxyphenoxy) -3,6,9-trioxaundecan (Sesaaex or Sesoxane), S, S, S-Tributylphosphorotrithiaata, 1,2-Methyleπdioxy-4 - (2- (octylsulfonyl) propyl) benzene.

The compounds of formulas I and II can also be used in unchanged form or together with the auxiliaries customary in forauling technology as formulations, such as emulsion concentrates, suspension concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusting agents, granules Feineverkapseiungen in polymeric materials and the like, are used in a known manner. The application methods such as spraying, atomizing, dusting, scattering or pouring, depend entirely on the intended use. It should be noted here that the biological behavior of the active ingredient of the formula I or II is not significantly influenced by the application method and the type and amount of auxiliary materials used for the preparation of the formulation. The formulations are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredients with extenders, that is to say with solvents, solid carriers, and, if appropriate, using surface-active substances (surfactants). Possible solvents are: aromatic hydrocarbons, preferably the fractions C ₈ to C ₁₂ , ie xylene gels up to substituted naphthalenes, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, strongly polar solvents such as dimethyl sulfoxide or diaethylformamide, and water. Often, powdered rock is usually used as a solid carrier, for example for dusting agents and dispersible powders. Chemically, calcite, talc, kaolinite, montmorillonite or attapulgite are particularly suitable. To improve the physical properties, highly disperse silicas or highly disperse absorbent polymers can also be added. Porous types such as pumice, broken brick, sepiolite and bentonite can be used as granular carriers, materials such as calcite or sand as non-sorptive carriers. In addition, a large number of pre-granulated materials of inorganic or organic nature can be used, from dolomite to crushed nutshells or corn cobs.

Depending on the polarity of the active ingredient of formula I or II to be formulated, suitable surface-active substances are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties.

Suitable action-active surfactants are, for example, quaternary ammonium compounds, such as, for example, cetyltriaethylammonium bromide. Suitable anionic surfactants are, for example, soaps, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, sodium, calcium or ansaonium lignin sulfonate, butylnaphthalene sulfonate or a mixture of the sodium Diisopropyl and Triisopropylnaphthalenesulfonate. Suitable non-ionic surfactants are, for example, the condensation products of ethylene oxide with fatty alcohols, such as, for example, oleyl alcohol or cetyl alcohol, or with alkyl pheuols, such as, for example, octylphenol, nonylphenol or octylresol. Other non-ionic compounds are the partial esters which are derived from long-chain fatty acids and hexitan hydrides, the condensation products of these partial esters with ethylene oxide or lacithins.

The non-ionic, anionic and cationic tansides commonly used in fonulation technology include: described in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringewood, New Jersey,

Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York.

The formulations generally contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I or II and 0 to 25% of a surfactant and 1 to 99.9% of a solid or liquid additive.

The formulations can also contain additives such as stabilizers, defoamers, viscosity regulators, binders in the adhesive and also fertilizers for producing special effects.

The active compounds of the formula I or II can be formulated, for example, as follows: (data in percent by weight):

Formulation examples for liquid active ingredients of the formula I or II emulsion concentrates a) active ingredient 20%

Ca-dodecylbenzenesulfonate 5%

Castor oil polyglycol ether

C36 mol AeO) 5%

Xylene mixture 70%

b) active ingredient 40%

Ca-dodecylbenzenesulfonate 8%

TributyIphenol polyglycol ether (30 mol AeO) 12%

Cyclohexanone 15%

Xylene mixture 25%

c) active ingredient 50%

Tributylphenol polyglycol ether 4.2%

Calcium dodecylbenzoisulfonate 5.8%

Cyclohexanone 20%

Xylene mixture 20%

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

Solutions a) Active ingredient 80% ethylene glycol monomethyl ether 20%

b) Active ingredient 10% polyethylene glycol 400 70% N-methyl-2-pyrrolidone 20%

c) Active ingredient 5% epoxidized vegetable oil 1% petrol (boiling range 160-190ºC) 94% d) active ingredient 95%

Epoxidized vegetable oil 5%

These solutions are suitable for use in the form of tiny drops.

Granules a) Active ingredient 5%

Kaolin 0.2-0.8 mm 94%

Finely divided silica 1%

b) active ingredient 10%

Attapulgite 90%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.

Dusts a) active ingredient 2%

Finely divided silica 1%

Talc 97%

b) active ingredient 5%

Fumed silica 5%

Kaolin fine 90%

Ready-to-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation examples for solid active ingredients of Forael I or II wettable powders a) Active ingredient 20% Na lignin sulfonate 5% Na lauryl sulfate 3% silica 5% kaolin 67%

b) active ingredient 60%

Na lignin sulfonate 5%

Na diisobutylnaphthalenesulfonate 6%

Octylphenolipolyglycol ether

(7.8 mol AeO) 2%

Finely divided silica 27%

The active ingredient is mixed well with the additives and ground well in a suitable grinder. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

Emulsion concentrate

Active ingredient 10%

Octylphenol polyglycol ether

(4-5 mol AeO) 3%

Ca-dodecylbenzenesulfonate 3%

Eicinusölpolyglykoläther

(36 mol AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water. Dusts a) active ingredient 5% talc 95% b) active ingredient 8% kaolin fine-particle 92%

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding them in a suitable mill.

Extruder granules

Active ingredient 10%

Na lignin sulfonate 2%

Carboxymethyl cellulose 1%

Kaolin finely divided 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extracted and then dried in an air stream.

coating granules

Active ingredient 3%

Polyethylene glycol 200 3%

Kaolin (0.3-0.8 mm) 94%

The finely ground active ingredient is evenly applied in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained. Suspension concentrate

Active ingredient 40%

Δ ethylene glycol 10%

Nonylphenol polyglycol ether (15 mol AeO) 6%

Na lignin sulfonate 10%

Carboxymethyl cellulose 1%

Fσπnalin (35% formaldehyde solution) 0.2%

Silicone oil in the form of a 75% emulsion 0.8%

Water 32%

The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Example 1 :

a) Preparation of 2, 6-Diisoρropyl-4-phenoxy-an i lin

48.9 phenol are dissolved in 500 ml of xylene. 30.2 g of powdered potassium hydroxide are added to this solution in a piece of atmosphere. The reaction mixture is heated to the boiling point with stirring and the water formed is continuously distilled off.

After the addition of 0.6 g of copper chloride and 100 g of 2,6-diisopropyl-4-bromoaniline, the mixture is stirred at 150-155 ° C. for 8 hours, then cooled and suction filtered. The filtrate is washed with 15% sodium hydroxide solution (150 ml) and twice with 150 ml of water. The organic phase is separated off, dried with sodium sulfate, the solvent is distilled off and the product is distilled.

b) Preparation of N- (2,6-diisopropyl-4-phenoxyphenyl) isothiocyanate

8.8 g of thiophosgene and 13.7 g of calcium carbonate are stirred in 60 ml of methyl enchloride and 35 ml of water. At 0 to 5 ° C 17.4 g of 2,6-diisopropyl-4-phenoxy-aniline are added dropwise to this mixture. The reaction mixture is brought to the boil and stirred at reflux for two hours. After cooling, the mixture is filtered off. The organic phase is separated from the filtrate, washed twice with 50 ml of water each time, dried over sodium sulfate and evaporated. The crude product (oil) is used for further implementation without purification.

The following connections are also made in an analogous manner:

c) Preparation of compounds of formula II

19.2 g of N-2,6-diisopropyl-4-phenoxyphenyl isothiocyanate are diluted with 10 ml of toluene and then tert with 13.7 g. Butylamine added, The reaction mixture is then stirred at 20-25 ° C for 12 hours. After evaporation and recrystallization from hexane, the compound of the formula is obtained

Auf analoge Weise werden auch folgende Verbindungen hergestellt:

- 18 -

The following connections are also made in an analogous manner:

- 18 -

d) Herstellung des Endproduktes

d) Production of the end product

11.54 g of N-2,6-diisopropyl-4- (phenoxy-phenyl) -N'-tert-butylthiourea are dissolved in 30 ml of dimethylformamide. At 40 ° C, 5.96 g of methyl iodide is added dropwise to this solution. After standing for twelve hours at room temperature, the reaction mixture is poured into an aqueous solution which has been adjusted and maintained at pH 12 with potassium carbonate. The aqueous solution is extracted with methyl achloride, the organic phase is separated off, dried over potassium carbonate and the methylene chloride is distilled off.

mit einem Schmelzpunkt von 89-92ºC.After recrystallization (Hesanj cooling to -50 ° C), the compound of formula is obtained

with a melting point of 89-92 ° C.

The following connections are also made in an analogous manner:

Example 2: Insecticidal feeding poison effect: Spodoptera littoraiis, Dysdercus fasciams and Heliothis virascens

Cotton plants were sprayed with an aqueous emulsion containing 0.052 of the compound to be tested (obtained from a 10% emulsifiable concentrate).

After the coating had dried on, the plants were each populated with larvae of the species Spodoptera littoraiis (L3-Stadiua) Dysάercus fasciatus (L4) or Heliothis virescens (L3). Has. used two plants per test compound and per test species and an evaluation of the degradation rate achieved was carried out after 2, 4, 24 and 48 hours. The test was carried out at 24 ° C and 60% relative humidity. In the above experiment, compounds according to Example 1 showed good activity against larvae of the species Spodoptera littoraiis, Dysdercus fasciatus and Heliothis virescens.

Example 3: Insecticides feeding poison effect: Laptiaotarsa decemlineata

With the same procedure using larvae of the species Leptinotarsa decealineata (L3) and potato plants instead of Bauayoll plants, the test method described in Example 2 was repeated.

Compounds according to Example 1 had a good activity against larvae of the species Leptinotarsa decemiineata.

Example 4: Action against acarines damaging to plants: Tetranychus urticae (OP-sensitive) and Tetranychus cinnabarinus (OP-colerant)

The primary leaves of Phaseolus vulgaris plants were 16

Hours before testing for acaricidal activity with a piece of iafestiartan leaf from a mass cultivation of Tetranychus urticae (OP-sens.) Or Tetranychus cinnabarinus (OP-tol.). (The tolerance relates to the tolerance of diazinon).

The infected plants treated in this way were sprayed with a test solution containing 400 or 200 ppm of the compound to be tested to the point of dripping wet.

Flat 24 hours and again after 7 days, adults and larvae (all mobile stages) were evaluated under the binocular for living and dead individuals. One plant was used per concentration and per test species. During the course of the experiment, the plants were in greenhouse cabins at 2-5 ° C.

Compounds according to Example 1 showed a positive effect against individuals of the species Tetranychus urticae and Tetranychus cinnabarinus in this experiment.

Example 5: Action against ectoparasitic acarines (ticks) Rhipi - cephalus bursa (adults and larvae), Amblyomma hebraeum (⍛ adults, nymphs and larvae) and Boophilus microplus (larvae - OP-sensitive and OP-coleranr)

Larvae (approx. 50 each), nymphs (approx. 23 each) or adults (approx. 10 each) of the tick species Rhipicephalus bursa, Amblyσmma hebraeum and Boophilus microplus are used as test objects. The test tiara are briefly in an aqueous emulsion or solution containing 0.1; 1.0; 10; 50 or 100 ppm of the compound to be tested immersed.

The emulsions or solutions in the test tubes are then taken up with cotton wool and the wetted tactile animals are left in the tubes contaminated in this way.

The kill rate achieved at each concentration was evaluated after 3 days for larvae and after 14 days for nymphs and adults.

Compounds according to Example 1 showed a good activity against larvae, nymphs and adults of the species Rhipicephalus bursa and Amblyomma hebraeum as well as against larvae (OP-res. And OP-sens.) Of the species Boophilus mircroplus in this experiment.

Claims

Claims 1. A compound of the formula

wherein R ₁ , R ₂ and R _{3 are} each hydrogen, halogen, C ₃ -C ₄ alkyl, C ₁ -C ₄ alkoxy, trifluoromethyl or nitro, R ₄ and R _{5 are} each C ₂ -C ₄ alkyl, R ₆ C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₅ alkisyl, R ₇ C ₁ -C ₁₀ alkyl, C ₃ -C ₅ alkenyl or C ₃ -C ₆ cycloalkyl and R _{8 is} hydrogen or C ₁ -C ₁₀ alkyl. 2. A compound according to claim 1, vorin R _{1 is} hydrogen, wherein R _{1 is} hydrogen, chlorine, methoxy, trifluoromethyl or nitro, R ₂ and R _{3 are} each hydrogen or chlorine, R ₄ and R _{5 are} each ethyl, isopropyl, i-butyl, sec-butyl or tert Butyl, R ₆ C ₁ -C ₆ alkyl, allyl or propargyl, R ₇ C ₁ -C ₆ alkyl, cyclopropyl or cyclohexyl and R _{8 are} hydrogen. 3. A compound according to claim 2, wherein R _{1 is} hydrogen, chlorine or trifluoromethyl, R _{2 is} hydrogen or chlorine, R _{3 is} hydrogen, R ₄ and R _{5 are} each isopropyl or R _{4 is} ethyl and R _{5 is} sec-3uryl, R _{6 is} methyl, R ₇ tart.-butyl or isopropyl and R _{8 is} hydrogen. 4. The compound according to claim 3 of the formula

5. The connection according to claim 3 of the Forael

6. The compound according to claim 3 of the formula

7. The compound according to claim 3 of the formula

8. A process for the preparation of compounds according to claim 1, characterized in that a compound of the formula

with a connection of the Forael R ₆ - Ea1 implemented vorin R ₁ to R _{8 have} the meaning given in claim 1 and shark represents a halogen atom. 9. A pesticide which contains a compound as claimed in claim 1 in addition to a suitable carrier and / or other additive as active component. 10. Use of a compound according to claim 1 for controlling various animal and vegetable pests. 11. Use according to claim 10 for controlling insects and representatives of the order Akarina. 12. A compound of the formula

vorin R ₁ , R ₂ and R ₃ each hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₆ alkoxy, Trifluoromethyl or nitro, R ₄ and R ₅ each C ₂ -C ₄ alkyl, R ₇ C ₁ -C ₁₀ alkyl, C ₃ -C ₅ alkenyl or C ₃ -C ₅ cycloalkyl and R ₈ hydrogen or C ₁ -C ₁₀ alkyl. 13. A pesticide which, in addition to a suitable carrier and / or other additive, contains a compound as claimed in claim 12 as an active component. 14. Use of a compound according to claim 12 for controlling various types of animal and vegetable pests.