DD246917A5 - ACYLASTIC SUBSTANCES CONTAINING INSECTICIDES - Google Patents

Abstract

The invention relates to insecticidal agents containing novel acyl ureas of the general formula in which the substituents which have the meaning given in the description in admixture with excipients and / or auxiliaries. It is already known that certain acylureas have insecticidal properties (DE-OS 2,123,236, DE-OS 2,601,780, DE-OS 2,928,410). Surprisingly, it is possible with the agents according to the invention to selectively combat important insects, in particular from the orders of the Diptera, Coleoptera, Lepidoptera and Hymenoptera. formula

Description

^R 2

R

Halogen, C _r C ₆ -alkyl or -C ₆ haloalkyl, hydrogen or halogen,

R ₄ and R ₅ are each hydrogen, halogen or -C ₆ alkyl, R 7 and R ₃ are each hydrogen, C ₁ -C ₆ -alkyl, aryl or halogen, R ₁₀ are identical or different and are hydrogen or fluorine, oxygen or sulfur and η 0,1,2oder3

'mean, in mixture with carriers and / or excipients.

Field of application of the invention

The invention relates to insecticidal agents which contain as active ingredient new acyl ureas in addition to carriers and / or excipients.

Characteristic of the known technical solutions

It is already known that certain acyl ureas have insecticidal properties (DE-OS 2123236, DE-OS 2601780, DE-OS 2928410).

Object of the invention

With the invention, insecticidal agents are provided with which significant insect pests, in particular from the orders of Diptera, Coleoptera, Lepidoptera and Hymenoptera can be selectively controlled.

Explanation of the essence of the invention

The object of the present invention is the provision of agents which control insects much better than the agents known for this purpose.

It has now been found that compounds containing compounds of the general formula

in the

N ^ \

O - (CH ₂ ) _n -

Halogen, C _r C ₆ alkyl or C _r C ₆ -halo, hydrogen or halogen,

R ₄ and R ₅ are each hydrogen, halogen or C ₁ -C ₆ -alkyl, R ₇ and R ₈ are each hydrogen, Ci-C ₆ alkyl, aryl or halogen, and R ₁₀ are identical or different and denote hydrogen or fluorine,

X oxygen or sulfur and

η 0,1,2 or 3

have a significantly better insecticidal effect than known, effect-like means analogous constitution possess. ,

Surprisingly, significant insect pests, in particular from the orders of the Diptera, Coleoptera, Lepidoptera and Hymenoptera, can be selectively controlled with the agents according to the invention.

The term C _r C ₆ alkyl includes, for example, the radicals methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, n-pentyl, n-hexyl and others.

Aryl is intended to mean, for example, phenyl or naphthyl optionally substituted for example by halogen, such as chlorine, or alkyl, such as methyl.

Halogen can be fluorine, chlorine, bromine or iodine. '

As compounds having a particular insecticidal activity, those are to be mentioned in which in the general formula I

Ri is chlorine or fluorine,

R _{2 is} hydrogen, chlorine or fluorine,

R _{3 is} hydrogen, chlorine or methyl,

R _{4 is} hydrogen, chlorine or methyl,

R _{5 is} hydrogen, chlorine or methyl,

R _{6 is} hydrogen, chlorine or methyl,

R _{7 is} hydrogen or methyl,

R _{8 is} hydrogen or methyl,

R ₉ and R ₁₀ fluorine, *

X oxygen and

η 0,1,2 and 3 mean.

The application of the compositions of the invention can be carried out in concentrations ranging from 0.0005 to 5.0% of _Λ preferably from 0.001 to 0.1%.

The compositions of the invention can be used either alone, in admixture with each other or with other insecticidal agents. Optionally, other crop protection or pest control agents such as acaricides or fungicides may be added according to the desired purpose.

Promoting the intensity of action and the rate of action can be achieved, for example, by effect enhancing additives such as organic solvents, wetting agents and oils. Such additives may therefore allow a reduction in the dosage of active ingredient.

The labeled active substances or mixtures thereof are expediently used in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally of wetting agents, tackifiers, emulsifiers and / or or dispersing agents applied.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, furthermore cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and mineral oil fractions.

Suitable solid carriers are mineral earths, for example tonsil, silica gel, talc, kaolin, Attaklay, limestone, silica and vegetable products, for example flours.

Surfactants include, for example: calcium lignin surfactant, polyoxyethylene-alkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.

The proportion of or of the active ingredient (s) in the various preparations can vary within wide limits. For example, the compositions contain about 5 to 80% by weight of active compounds, about 95 to 20% by weight of liquid or solid carriers and optionally up to 20% by weight of surface-active substances.

The application of the agents can be carried out in a customary manner, for example with water as carrier in Spritzbrühmengen of about 100 to 3000 liters / ha. An application of the funds in the so-called low-volume and ultra-low-volume method is just as possible as their application in the form of so-called microgranules.

The preparation of these preparations can be carried out in a manner known per se, for example by milling or mixing methods. If desired, the individual components can also be mixed shortly before use, as is carried out, for example, in the so-called tank mix method in practice.

For the preparation of the preparations, for example, the following constituents are used:

A) 20% by weight of active ingredient 35% by weight of bentonite

8% by weight of calcium salt of lignin sulphonic acid 2% by weight of sodium salt of N-methyl-N-olein-taurine 35% by weight of silica

B) 45% by weight of active ingredient

5% by weight of sodium aluminum silicate, 10% by weight of o-cetyl polyglycol ether with 8 mol of ethylene oxide

2% by weight spindle oil 10% by weight polyethylene glycol 23 parts water

C) 20% by weight of active ingredient 75% by weight of isophorone

5% by weight mixture of ionic and nonionic surfactants

The compounds to be used according to the invention can be prepared by reacting a) alkoxyanilines of the general formula

Λ /

^R to ^ q

Λ, ^R 7

with benzoyl isocyanates or Benzoylisothiocyanaten the general formula

O U

optionally using a solvent and a catalyst for the reaction bring or b) alkoxyphenyl isocyanates or alkoxyphenylisothiocyanates of the general formula

X = C = N-

IV

with benzamides of the general formula

optionally in the presence of a solvent and a catalyst, wherein Ri, R ₂ , R3, R <t, R5, R6, R7 / Rs / R9, R10, X

and η are as defined above.

Suitable solvents for the reactants are inert substances such as aliphatic, alicyclic and aromatic hydrocarbons, which may each be optionally chlorinated, such as hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, meth'ylene chloride, trichlorethylene and chlorobenzene; Ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; Ketones, such as acetone, methyl ethyl ketone; Nitriles such as acetonitrile, propionitrile and benzonitrile; Esters such as ethyl acetate and amyl acetate; Acid amides, such as dimethylformamide and dimethylacetamide; Sulfones and

Sulfoxides, such as dimethyl sulfoxide and sulfolane.

The reaction variant a) can be carried out within a wide temperature range. In general, it is at a temperature between -20 ⁰ C and the boiling point of the reaction mixture, preferably between 20 ⁰ C and 200 ⁰ C.

carried out. '

The reaction variant is preferably carried out under the pressure of the environment, although it also at elevated or

reduced pressure can be performed.

The reaction variant b) can be carried out under the same reaction conditions with respect to temperature and pressure as mentioned for the reaction variant a) in the above.

The acyl ureas to be used according to the invention are colorless and odorless crystalline compounds. They dissolve only very poorly in water or toluene, better in ethyl acetate and good in dimethylformamide.

The benzamides of the general formula V to be used as starting materials and the benzoyl isocyanates and benzoyl isothiocyanates of the general formula III are known per se or can be prepared by known methods

become.

The starting materials of the general formula II are obtained, for example, by the following preparation processes: anilines of the general formula

~ ^R 8

R, R-,. ο 7

where η = 1,2 and 3,

can be prepared by nitrophenols of the general formula

R ₃ R,

with alkenyl halides of the general formula

VII

etherified. The reaction with difluorocarbene and the subsequent reduction by conventional methods provides the desired aniline.

Anilines of general formula II, wherein η = 0, can be prepared by reacting nitrophenols of the general formula VI with vinyl acetate in the presence of catalytic amounts of mercury acetate and acids _f such as conc. H ₂ SO ₄ , p-toluenesulfonic acid or BF ₃ ether to give vinyl ethers. Subsequently, it is reacted with difluorocarbene and converted by reduction into the desired aniline. , .

The cited vinyl ethers can also be prepared in a two-stage reaction by first reacting the phenols with 1,2-dibromoethane in the presence of a weak base such as potassium carbonate to bromoethyl ether and this with a strong base such as potassium hydroxide or potassium tert-butoxide dehydrobrominated to the vinyl ether. Particularly suitable for the last reaction are bicyclic amidines such as 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and tert. Amines such as triethylamine and 1,4-diazabicyclo [2.2.2] octane (DABCO). Anilines of the general formula II, where η = 1, 2 and 3, can also be prepared by direct etherification of aminophenols, by aminophenols of the general formula

VIII

^{5 with} difluorocyclopropylalkyl bromides of the general formula

/ \ ^IX

Br- (CH.) - A X - R ₀

2 η Γ Ι 8

etherified. ^ 5 ^ 7

The following examples illustrate the preparation of the compounds to be used according to the invention.

embodiments example 1

1- (2,6-Difluorobenzyl) -3- {4 (2,2-difluorocyclopropyloxy) -phenyl} -urea 1.0g (5.4mlV! Ol) of 4- (2 _/ 2-difluorocyclopropyloxy) -aniline was dissolved in 10ml THF and added Room temperature with 988 mg (5.4 mmol) of 2,6-difluorobenzoyl isocyanate, dissolved in 1OmI THF added.

After one hour, 150 ml of pentane are added and the precipitate is filtered off with suction.

It is washed with pentane and dried at 50 ⁰ C in a vacuum (200 Torr).

Yield: 1.8g (92% of theory)

Mp: 194-195 ° C. ,

TLC: * eluent: CH ₂ Cl ₂ : MeOH = 95: 5

R _F value: 0.71 Analysis: Calculated: C, 55.44, H, 3.29, N, 7.61, F, 20.64

Found: C 55.06 H 3.33 N 7.28 F 20.52

Example 2 1- (2-Chlorobenzoyl) -3- [4- {2,2-difluorocyclopropylmethoxy) -3,5-d] methylphenyl] urea 2.1 g (9.2 mmol) of 4- (2,2- Difluorcyclopropylmethoxy) -3,5-dimethylaniline are dissolved in 10 ml of tetrahydrofuran and treated at room temperature with 1.82 g (10.2 mmol) of 2-chlorobenzoyl isocyanate, dissolved in 10 ml of tetrahydrofuran.

After one hour you add 150ml pentane and sucks off the precipitate. It is washed with pentane and at

5O ⁰ C in a vacuum (200 Torr) dried.

Yield: 2.9 g = 77% of theory

Mp .: 164-165 ⁰ C

TLC: eluent: CH ₂ Cl ₂ : MeOH = 95: 5

R _f value: 0.81. ·

Analysis: Calculated: C 58.75 H 4.68 N 6.85 Cl 8.67 F9.29%

Found: C58.57 H4.78 N 6.40 CI8.30 F9.36%

Example 3 1- [4- {1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2,6-difluorobenzoyl) urea 1.25 g (4.8 mmol) of 4- (1 -Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dimethylaniline are dissolved in 10 ml of tetrahydrofuran (THF) and treated at room temperature with 0.87 g (4.8 mmol) of 2,6-difluorobenzoyl isocyanate dissolved in 10 ml of THF , After one hour, 150 ml of pentane are added and the precipitate is filtered off with suction. It is washed with pentane and at 5O ⁰ C in a vacuum (200 Torr)

dried.

Yield: 1.55 g = 73% of theory

Mp .: 176-177 ⁰ C

DC:. Eluent: CH ₂ Cl ₂ : MeOH = 95: 5

Rf value: 0.74 Analysis: Calculated: C 53.99 H 3.85 N 6.29 Cl 7.97 F 17.08

Found: C53.95 H3.88 N6.06 Cl 8.03 F16.85

In an analogous manner, the following compounds were prepared:

Example Name of the connection No.

Physical constant

4 1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3,5-dimethylphenyl] -

urea mp: 184-185 ° C

5 1- (2-chlorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3,5-dimethylphenyi] urea

Fabric Fp.:201-202°C

6 1- [3,5-dichloro-4- (2,2-difluoro-cyclopropyloxy) -phenyl] -3- (2,6-difluorobenzoyl) -

Urea Fp .: 184-185T

7 1- [3,5-dichloro-4- [2,2-difluorocyclopropyloxy) -phenyl] -3- (2-chlorobenzoyl) -urea

fabric mp: 211-212 ° C

8th _,. 1- (2-chloro-6-fluorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethyl-

Phenylj-Mamm Fp .: 232 ⁰ C

9 1- (2,6-dichlorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3,5-dimethylphenyl] -

urea · m.:240°C

10 1- [4- (2,2-Difluorocyclopropyloxy) -3,5-dimethylphenyl] -3- (2-fluorobenzoyl) urea

fabric mp: 123 ° C

11 1- [4- (2,2-difluorocyclopropyloxy) -3,5-dimethylphenyl] -3- (2-methylbenzoyl) -

urea Mp.: 178 ° C

12 1- (2-bromobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3,5-dimethylphenyl] urea

fabric Fp.:229°C

13 1- [3-chloro-4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2,6-difluorobenzoyl) -ham-

Fabric Fp.:171-172°C

14 1- [3-Chloro-4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2-chlorobenzoyl) -urea M.p .: 166-167 ° C

15 1- [3-chloro-4- (2,2-difluorcyclopropyloxy) -phenyl] -3- (2-fluorobenzoyl) urea m.p .: 171-172 ⁰ C.

16 1- [3-chloro-4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2-chloro-6-fluorobenzoyl) -

urea mp .: 181-182 ° C

example

Name of the connection

-b-

Physical constant

17 1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3-methylphenyl] -ham-

material . 'Mp .: 161 ⁰ C

18. 1- (2-chlorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3-methylphenyl] -urea m.p .: 181 ⁰ C.

19 · 1- (2-chloro-6-fluorobenzoyl) -3- (4- (2,2-difluorocyclopropyloxy) -3-methylphenyl] -

urea mp .: 184 ⁰ C

20 1- (4- (2,2-Difluorcyclopropyloxy) -3-methylphenyl] -3- (2-fluorobenzoyl) urea m.p .: 140 ⁰ C.

21 1- [3,5-Dibromo-4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2,6-difluorobenzoyl) -

, , urea '... Mp .: 205-206 ° C

22 1- (2,6-difluorobenzoyl) -3- {4- [2,2-difluorocyclopropyl) ethoxy] -3,5-dimethyl

phenyl} -hamstoff m.p .: 174-174 ⁰ C.

23 1- (2-chlorobenzoyl) -3- {4- [2- (2,2-difluorocyclopropyl) ethoxy] -3,5-dimethyl

phenyl} -hamstoff '' m.p .: 144-145 ⁰ C.

24 1- {3,5-dichloro-4- [2- {2,2-difluorocyclopropyl) -ethoxy] -phenyl} -3- (2,6-

Difluorobenzene D-H 2 Mb: 167-168 ⁰ C

25 1- {3,5-dichloro-4- [2- (2,2-difluorocyclopropyl) -ethoxy] -phenyl} -3- {2-

Chlorobenzoyl-urea mp .: 190-191 ⁰ C

26 1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorocyclopropoxy) -3,5-dimethylphenyl] -

thiourea, m.:144°C

27 1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropoxy) phenyl] thiourea m.p .: 171-172 ⁰ C.

28 1- [4- (2,2-Difluorocyclopropyloxy) -phenyl] -3- (2-methylbenzoyl) -urea M.p .: 172-173 ° C

29 1- (2,6-Difluorbenzoyi) -3- {4- [3- (2,2-difluorcyc! Opropyl) propoxy] -3,5-dimethylphenyQ-urea · m.p .: 154-155 ⁰ C.

30 1- (2-Chlorobenzoyl) -3- {4- [3- (2,2-difluorocyclopropyl) propoxy] -3,5-dimethylphenyl} urea __. · Mp .: 146-147 ° C

31 1- {3,5-dichloro-4- [3- (2,2-difluorocyclopropyl) propoxy] phenyl} -3- (2,6-difluorbenzoyO-urea m.p .: 158-159 ⁰ C.

32 1- {3,5-dichloro-4- [3- (2,2-difluorocyclopropyl) -propoxy] -phenyl} -3- (2-chlorobenzoic-urea M.p .: 179-180 ° C

33 1- {4- [3- (2,2-difluorocyclopropyl) -propoxy] -3,5-dimethylphenyl} -3- (2-fluoro)

BenzoyDurea Mp: 117-118 ° C

34 1- {3,5-dichloro-4- [3- (2,2-difluorocyclopropyl) propoxy] phenyl} -3- (2-fluorbenzoyD-urea m.p .: 139-140 ⁰ C.

35 1- {4- [2- (2,2-Difluorocyclopropyl) -ethoxy] -3,5-dimethylphenyl} -3- (2-fluorobenzoyO-urea 'M.p .: 140-141 ° C

36 1- [3,5-dichloro-4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2-fluorobenzoyl) -

urea mp: 167-168 ° C

37 1- {3,5-dichloro-4- [2- (2 _/ 2-difluorocyclopropyl) -ethoxy] -phenyl} -3- (2-

fluorobenzo-urea 'mp .: 164-165 ° C

38 '1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropylmethoxy) phenyl] urea. M.p.:179 ° C

39 1- (2-chlorobenzoyl) -3- [4- (2,2-difluorcyclopropylrnethoxy) -phenyl] -hamstoff m.p .: 165 ⁰ C.

40 1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropylmethoxy) -3,5-dimethylphenyl] urea M.p.:152 ° C

41 1- [3,5-dichloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2,6-difluorobenzoyD-urea m.p .: 170-171 ° C

42 1- [3,5-dichloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -

h-substance, mp .: 193-194 ° C

43 '1- [3-Chloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2,6-difluorobenzoyl) -

urea mp .: 169-17O ⁰ C

44 1- [3-chloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -

urea mp: 159-160 ⁰ C

45 '1- [3-chloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

urea mp .: 164-165 ⁰ C

46 1- [3-Chloro-4- (2,2-difluorocyclopropylmethoxy) -phepyl] -3- (2-chloro-6-fluorobenzoyl-urea. M.p .: 182-183X

47 1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorocyclopropylmethoxy) -3-methylphenyl] -

urea mp .: 162-163 ° C

48 1- (2-chlorobenzoyl) -3- [4- (2,2-difluoro-cyclopropylmethoxy) -3-methylphenyl] -

urea mp: 151-152 ° C

49 1- (2-Chloro-6-fluorobenzoyl) -3- [4- (2,2-difluorocyclopropylmethoxy) -3-methyl-phenyl] -urea M.p .: 151-152 ° C

50 1- [4- (2,2-difluorocyclopropylmethoxy) -3-methylphenyl] -3- (2-fluorobenzoyl) -

urea 'mp .: 131-132 ° C

51 1- [3,5-dibromo-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2,6-difluorobenzoyD-urea M.p .: 16-167 ° C

52 1- [3 _/ 5-dibromo-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -

urea Mp .: 191-192X

53 1- [3,5-dibromo-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2,6-

example

Name of the connection

Physical constant

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- {2-bromobenzoyl) -

urea mp: 182-183 ° C

1- (2,6-Difluorben2oyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5-diiodophenyl] -

urea mp .: 204-205 ⁰ C

1- (2,6-Difluörbenzoyl) -3- [4- (2,2-difluoro-1-methyicyclopropylmethoxy) -3,5-dimethylphenyl] -urea m.p .: 186 ⁰ C.

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluoro-3-methyrcyclopropylmethoxy) -3,5-dimethylphenyll-urea. · Fp.:151°C

1- (2,6-Difluorobenzoyl) -3-L4- (2,2-difluoro-3-phenylcyclopropylmethoxy) -3,5-dimethylphenyi] urea. M.p .: 120-121 ° C

1- (2-Chlorobenzoyl) -3- [4- (2,2-difluoro-1-methylcyclopropylmethoxy) -3,5-dimethyiphenyll-urea M.p .: 198 ° C

1- (2-Chlorobenzoyl) -3- [4- (2,2-difluoro-3-phenylcyclopropylmethoxy) -3,5-dimethyl-phenyl] -butyrate M.p .: 112-113 ° C

1- (2-Chlorobenzoyl) -3- [4- (2,2-difluoro-3-methylcyolopropyimethoxy) -3,5-dimethylphenyll-urea M.p.:156°C

, 1- [3,5-dichloro-4- (2,2-dif] fluoro-1-methylcyclopropylmethoxy) -phenyl] -3- (2,6-

difluorobenzoic urea mp: 180 ^° C

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- {2,6-difluorobenzoyD-urea M.p .: 140 ° C

1- [3,5-dichloro-4- (2,2-difluoro-3-phenylcyclopropylmethoxy) -phenyl] -3-

(2,6-difluorobenzoyl} urea mp .: 145-146 ⁰ C

65. 1- [3,5-dichloro-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3- '

(2-chlorobenzoyi) urea _v . Fp.:220°C ·

1- [3,5-Dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -urea '' Mp .: 183 ⁰ C.

1- [3,5-dichloro-4- (2,2-difluoro-3-phenylcyclopropylmethoxy) -phenyl] -3- (2-chlorbenzoyi) -urea m.p .: 147-148 ⁰ C.

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-methyl-

Benzoydurea Mp .: 191-192 ⁰ C

1- -3- [3,5-Dichloro-4-phenyl (2,2-dif! Uorcyclopropylmethoxy)] (2-methyi-

ben2oyl) urea mp .: 189-19O ⁰ C

1- [3,5-dichloro-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3- (2-methylbenzoyl) -urea 'M.p .: 21O ⁰ C

1- [4- (2,2-Difluorcyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2-fluorobenzoyl) -

urea mp .: 110-111 ⁰ C

'1- [3,5-dichloro-4- (2 _/ 2-difluorocyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

urea mp .: 160-161 ⁰ C

1- [3,5-Dibrorri-4- (2,2-difiuorcyclopropyl-methoxy) phenyl] -3- (2-fluorobenzoyl) -

urea mp .: 173-174 ° C

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyciopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) urea m.p .: 148-149 ⁰ C.

1- [3,5-dibromo-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- {2-fluorobenzoyl) urea m.p .: 150-151 ⁰ C.

1- [3,5-dibromo-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -urea M.p .: 160-161 ° C

(1- [3,5-dibromo-4- {2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- (2,6-difiuorbenzoyl) -urea m.p .: 160-161 ⁰ C.

1- [3,5-dibromo-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -urea m.p .: 178-179 ⁰ C.

1- [3,5-dibromo-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3- (2,6-difluorobenzoyl) -urea. M.p .: 188-189 ° C

1- [3,5-dibromo-4- (2 _/ 2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -urea. M.p .: 197-198 ° C

1- [4- (2,2-Difluoro-1-methylcyclopropylmethoxy) -3 _/ 5-dimethylphenyl) -3- (2-fluorobenzyl) -urea M.p .: 162-163 ° C

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5

difluorophenyll-urea 'mp: 173-174 ⁰ C

1- [4- (2,2-Difluorcyclopropylmethoxy) -3,5-difluorophenyl] -3-2-fluorobenzoyl)! -

urea mp .: 146-147 ⁰ C

1- (2-chlorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5-difluorophenyl] -

urea mp .: 149-150 ° C

iKd-Chloro-difluorocyclopropyl-methoxyl-S, -dimethylphenyi-S- (2-chlorobenzoyl) -urea '. · Mp .: 192-193 ⁰ C

Example Name of the connection _. Physical constant

No. ·

86 i - ^ - ii-chloro ^^ - difluorocyclopropyimethoxyl-S.B-dimethyiphenyl-S-

(2-fluorobenzoyl) -urea 'm.p .: 145-146 ⁰ C.

• 87 i - ^ - d-chloro ^^ - difluorocyclopropylmethoxyl-S.B-dimethylphenyll-S

(2-chloro-6-fluorobenzoyl) -urea m.p .: 204-205 ⁰ C.

88 1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluoro-3,3-dimethylcyclopropylmethoxy) -3,5-dimethylphenyl] -urea. M.p.:175 ° C

89 1- (2-chlorobenzoyl) -3- [4- (2,2-difluoro-3,3-dimethylcyclopropylmethoxy) -3,5-dimethylphenyl] -urea. Fp.:172°C

90 1- [3,5-dichloro-4- (2,2-difluoro-3: 3-dimethylcyciopropylmethoxy) -phenyl!] - 3- (2,6-difluorobenzoyl) -urea M. M.p .: 17O ⁰ C

91 1- (2-chlorobenzoyl) -3- [3,5-dichloro-4- (2,2-difluoro-3,3-dimethylcyclopropylmethoxy) phenyl] urea M.p.

92 H4- (1-Chloro-2,2 <L-fluorocyclopropylmethoxy) -3,5-dichlorobenzyl-3- (2,6-difluorobenzoylo) urea. M.p .: 171-172 ° C

93. 1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dichlorophenyl] -3-

(2-chlorobenzoyl) -urea m.p .: 202-203 ⁰ C.

94 1- [4- (1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2-chloro-6-fluorobenzoyl) urea. 'Mp .: 182-183 ° C

95 1- [4- (1-Chloro-2,2-diflurocyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2-fluorobenzoyl) -urea M.p .: 160-161 ° C

96 1- [4- (1-chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichlorophenyl!] - 3

i2,6difluorobenzoyl) 4hiourea -... - - mp: 147-148 ° C

97 '1- (3,5-dichloro-4-cyciopropylmethoxyphenyl) -3- (2,6-difluorobenzoyl) urea. M.p .: 180-18 ° C

98 1- _{(3/5-dichloro-4-cyclopropylmethoxyphenyl)} -3- (2-fluorobenzoyl) urea m.p .: 159-160 ⁰ C.

The following examples illustrate the preparation of the starting compounds of general formula II.

EXAMPLE 99 4- (2,2-Difluorocyclopropyloxy) -3,5-dimethylaniline

50 g (0.30 mol) of 4-nitro-2,6-dimethylphenol, 45.4 g (0.33 mol) of potassium carbonate and 1.5 g of 18-crown-6 are mixed with 250 ml of 1,2-dibromoethane and stirred for 8 hours 100 ^° C. Subsequently, it is added to ice-water and extracted with chloroform. The chloroform phase is washed with 10% sodium hydroxide solution and four times with water, dried over magnesium sulfate and evaporated in vacuo. From hexane, 67 g (82% of theory, 0.24 mol) of 2-bromoethyl-2,6-dimethyl-4-nitrophenyl ether are obtained

(Mp .: 86-87 ° C). '. '

The entire amount of substance is dissolved in 300 ml of toluene, treated with 2g 18-crown-6 and 30g (0.54 mol) of potassium hydroxide and stirred at 60 ⁰ C for 6 hours. After cooling, the toluene phase is washed with water, dried and concentrated in vacuo. From hexane to obtain 31.6 g (67% of theory) of 2,6-dimethyl-4-nitrophenylvinylether (mp.: 78 ° C).

15 g (78 mmol) of this vinyl ether, dissolved in 100 ml of diglyme is added at 165 ° C internal temperature within 2 hours with a solution of 59.1 g (388 mmol) of sodium chloride in 100 ml of diglyme. The mixture is stirred for 1 hour at 165 ⁰ C, allowed to cool, filtered from the inorganic constituents and concentrated in vacuo (0.1 Torr, 50 ⁰ C). The residue, which is purified by column chromatography (hexane: toluene, 9: 1), gives 14.6 g (77% of theory) of 4- (2,2-difluorocyclopropyloxy) -3,5-dimethylnitrobenzene (mp. 63-64 ⁰ C).

8 g (33 mmol) of 4- (2,2-difluorocyclopropyloxy) -3,5-dimethylnitrobenzene are suspended in 45 ml of water and 75 ml of ethanol and, after addition of 3.27 g (61.8 mmol) of ammonium chloride, added in portions within 10 minutes 16, 5g (248 mmol) of zinc powder added. The temperature rises to 40-45 ⁰ C on. After one hour, the zinc hydroxide is filtered off with suction, ethanol is carefully removed under reduced pressure and the residue is taken up in ethyl acetate. The aqueous phase is separated and the solvent evaporated in vacuo. From hexane, colorless crystals are obtained, which are dried at room temperature (200 Torr).

Yield: 6.5 g = 93% of theory

Mp .: 78-79 ⁰ C

TLC: eluent: CH ₂ Cl ₂ : MeOH = 95: 5

R _r Value: 0.61 Analysis: ¹ Calculated: C61.96% H6.14% N6.56% F17.82% '

Found: C 62.33% H 6.02% N6.49% F17.52%

EXAMPLE 100 4- (2,2-Difluorocyclopropylmethoxy) -3,5-dimethylaniline

To 50 g (0.30 mol) of 2,6-dimethyl-4-nitrophenol, 55.6 g (0.40 mol) of potassium carbonate and 7.5 g of potassium iodide in 400 ml of dimethylformamide is added at room temperature 28.3 ml (0.33 mol) allyl bromide. The mixture is stirred for 1.5 h at 70 ⁰ C, allowed to cool and filtered from the inorganic components.

It is then evaporated in vacuo, mixed with ethyl acetate and the organic phase is washed with water.

Concentration and drying (room temperature, 0.1 Torr) yield 61.9 g (100%) of crystalline 2,6-dimethyl-4-nitrophenyl-3-propenyl ether; Mp .: 35 ⁰ C ₁

20 g (96.5 mmol) of this allyl ether, dissolved in 120 ml of Digiym, are added at 165 ⁰ C internal temperature within 2 hours |

with a solution of 73.6 g (482 mmol) of sodium chloride-fluoroacetate in 150 ml of Digiym. The mixture is stirred for 1 hour at 165 ⁰ C, leaves]

After cooling, the inorganic components are filtered off and concentrated in vacuo (0.1 torr; 50 ^° C.). The residue, which is purified by column chromatography (hexane: toluene, 9: 1), gives 6.3 g (26% of theory) of 4- (2,2-difluorocyclopropylmethoxy) -3,5-dimethylnitrobenzene (n _D 20 = 1 , 5198) and 7g (35%) of starting material.

5.04 g (19.6 mmol) of 4- (2,2-difluorocyclopropylmethoxy) -3,5-dimethylnitrobenzene are suspended in 30 ml of water and 50 ml. Ethanol and added after addition of 1.91 g (36.7 mmol) of ammonium chloride within 10 minutes in portions 9.77 g j

(147 mmol) added zinc powder. The temperature rises to 40-50 ° C. After one hour, the zinc hydroxide is sucked off,)

Ethanol carefully removed in vacuo and the residue taken up in ethyl acetate. The aqueous phase is separated and the solvent is evaporated in vacuo. From hexane, colorless crystals are obtained, which are dried at room temperature (200 Torr). ,

'Yield: 3.5 g = 79% derTheorie m.p .: 71-72 ⁰ C.

TLC: eluent: CH ₂ Cl ₂ : MeOH = 95: 5 R _r value: 0.73

Analysis: Calculated: C63.41% H6.65% N6.16% F 16.72% Found: C63.29% H 6.70% N 5.91% F16.76%

EXAMPLE 101 3-B-dichloro-4- (2,2-difluorocyclopropylmethoxy) -anHin

To a suspension of 4,16g (23.4 mmol) of 4-amino-2,6-dichlorophenol, 3.54 g (25.7 mmol) of potassium carbonate and 0.74 g of potassium iodide in dimethylformamide (50ml) is added dropwise at 100 ⁰ C ( Bath temperature) 4.0 g (23.4 mmol) of 2,2-difluorocyclopropylmethylbromide dissolved in 15 ml of dimethylformamide.

After one hour, concentrate in vacuo. The residue is taken up in ethyl acetate and washed with water (2 ×). After drying over magnesium sulfate, pentane is added and the crystals are filtered off with suction, yield: 2.9 g = 46% of theory. , _v

mp .: 89-90 ° C CH ₂ Cl ₂ : MeOH = 95: i C 44.79% H 3.38% 5 N 5.22% DC: Eluent: RF value: 0.61 C 44.51% H 3.70% N 5.03% Calculated: Analysis: Found: , F14,17 F 14,32

EXAMPLE 102 4- (1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichloroaniline

To 20 g (96.8 mmol) of 2,6-dichloro-4-nitrophenol, 17.9 g (0.13 mol) of potassium carbonate and 2.4 g of potassium iodide in 200 ml of dimethylformamide is added at room temperature 11.8 g (0.1 mol) of 2 , 3-dichloro-1-propene. The mixture is stirred for 1.5 h at 7O ⁰ C, allowed to cool and the organic components are filtered off. It is then evaporated in vacuo, mixed with ethyl acetate and the organic phase is washed with water. After concentration, recrystallization from isopropanol and drying (room temperature, 0.1 Torr), 12.0 g (44% of theory) of crystalline 4- (2-chloro-2-propenyloxy) -3,5-dichloronitrobenzene (mp. : 53-54 ⁰ C).

12 g (42.5 mmol) of this phenol ether, dissolved in 150 ml of Digiym, are added at 165 ⁰ C internal temperature within 2 hours with a solution of 32.4 g (212 mmol) of sodium chlorodifluoroacetate in 150ml Digiym. The mixture is stirred for 1 hour at 165 ⁰ C, allowed to cool, filtered from the inorganic constituents and concentrated in vacuo (0.1 Torr, 50 ⁰ C). The residue, which is purified by column chromatography (hexane: toluene, 9: 1), gives 10.5 g (74.8% of theory) of 4- (1-chloro-2,2-difluorocyclopropylmethoxyl-S) -dichloronitrobenzene ( mp .: 44-45 ⁰ C).

7.11 (21.4 mmol) of 4- (1-chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichloronitrobenzene are suspended in 35 ml of water and 50 ml of ethanol and, after adding 2 g (40 mmol) of ammonium chloride, added within 10 minutes add in portions 10.65 g (160 mmol) of zinc powder. The temperature rises to 40-50 ⁰ C on. After one hour, the zinc hydroxide is sucked off. Ethanol carefully removed in vacuo and the residue taken up in ethyl acetate. The aqueous phase is separated and the solvent evaporated in vacuo. A colorless oil is obtained which, after drying (0.1 torr;

Yield: 6.3 g = 97% of theory

TLC: eluent: hexane / ethyl acetate8: 2

Rf value: 0.30 ¹ H-NMR: (CDCl ₃ ; TMS; 80 MHz)

s 6.52 ppm (2H, Ar-H)

_Br , 4.17 ppm (2H ₁ -O-CH ₂ -)

S _br 3,5 pprn (2H ₇ -NH ₂ ). m1.6-2.4 _P pm _(2H F

-ί- 248

EXAMPLE 103 ^ {^ - Difluoro-S ^ -dimethylcyclopropylmethoxy-S-S-dichloroaniline

To a suspension of 4.45 g (25 mmol) of 4-amino-2,6-dichlorphenoi, 4,54g (33 mmol) of potassium carbonate and 0.5 g of potassium iodide in 50 ml of dimethylformamide is added dropwise at 100 ⁰ C (bath temperature) for 5, 0g (25 mmol) 2,2-difluoro-3,3-

Dimethylcyclopropylmethylbromid dissolved in 15ml dimethylformamide. After one hour, concentrate in vacuo. The residue is taken up in ethyl acetate and washed with water (2mai). After drying delivers the

Column chromatography (hexane / ethyl acetate, 7: 3) a colorless oil.

Yield: 4.1 g = 55% of theory

TLC: mobile solvent = hexane / ethyl acetate 1: 1 '

RrWart: 0.79. · -

Analysis: Calculated: C 48.67% H 4.42% N 4.73% F 12.83%

Found: C48.46% H4.40% N4.43% F12.65% '

The following examples serve to illustrate the possible uses of the agents according to the invention, which took place in the form of their preparations.

EXAMPLE 104

Killing Effect on Larvae (L2) of the Egyptian Cotton Owl (Spodoptera littoralis)

The substances according to the invention were prepared as an aqueous emulsion having an active ingredient concentration of 0.1% and 0.01%, respectively.

used.

Lilac leaves of the broad bean (Vicia faba) were dipped in these preparations. After drying the preparation broth on the dipped lilac leaves, 10 caterpillars of the Egyptian B.aumwolleule (Spodoptera littoralis) in the second instar were placed per experimental member together with three pairs of lilac leaves in a glass Petri halls (0 12cm)

included.- These test elements were set up for 5 days under long day laboratory conditions.

The criterion for the impact assessment was the mortality of the caterpillars. In% after 5 days of trial.

Inventive. , Active substance concentration effect

Connections in% in%

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -phenyl] -urea 0.1 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethylphenyl] -

urea · 0.1 100

1- (2-chlorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethylphenyl] -

urea 0.1 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropyloxy) phenyl] -3- (2,6-difluorobenzoyl) -

urea 0.1 100

1- [3,5-dichloro-4- [2,2-difluorcyclopropyloxy) -phenyl] -3- (2-chlorobenzoyl) -harn-

substance 0.1 100

, 1- (2-Chloro-6-fluorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethyl-

phenyl-urea .0,1 100

1- (2,6-dichlorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethylphenyl] -

urea 0.1 100

1- [4- (2,2-Difluorcyclopropyloxy) -3,5-dimethylphenyl] -3- (2-fluorobenzoyl) -harn-

substance "· 0.1 100

1- [4- (2,2-Difluorcyclopropyloxy) -3,5-dimethylphenyl] -3- (2-methylbenzoyl) -

urea 0.1 100

1- (2-bromobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethylphenyl] -harn-

substance 0.1 100

1- [3-chloro-4- (2,2-difluorcyclopropyloxy) phenyl] -3- (2,6-difluorobenzoyl) -harn-

substance 0.1 100

1- [3-Chloro-4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2-chlorobenzoyl) -urea 0.1 100

1- [3-Chloro-4 - (. 2,2-difluorocyclopropyloxy) -phenyl] -3- (2-fluorobenzoyl) -urea 0.1 100

1- [3-chloro-4- (2,2-difluorcyclopropyloxy) -phenyl] -3- (2-chloro-6-fluorobenzoyl) -

urea 0.1 100

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3-methylphenyl] urea

material . , 0.1 100

1- (2-Chlorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3-methylphenyl] -urea 0.1 100

1- (2-chloro-6-fluorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3-methylphenyl] -

urea 0.1 100

1- [4- (2,2-Difluorocyclopropyloxy) -3-methylphenyl] -3- (2-fluorobenzoyl) urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluorcycIopropyIoxy) phenyl] -3- (2,6-difluorobenzoyl) -

urea 0.1 100

1- (2,6-difluorobenzoyl) -3- {4- [2,2-difluorocyclopropyl) -ethoxy] -3,5-dimethyl-

phenyl} -urea 0.1 100

1- (2-Chlorobenzoyl) -3- {4- [2- (2,2-difluorocyclopropyl) ethoxy] -3,5-dimethylphenyl} urea. 0.1 100

Inventive drug concentration effect

Connections in% · in%

1- {3,5-dichloro-4- [2- (2,2-difluorocyclopropyl) -ethoxy] -phenyl} -3- (2,6-

difluorobenzene-urea 0.1 1D0

1- {3,5-dichloro-4- [2- (2,2-difluorocyclopropyl) -ethoxy] -phenyl} -3- (2-

ChlorobenzoOurea 0.1 100

1- {2,6-Difluorbenzoyi) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethylphenyl] -

thiourea 0.1 100

1- {2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -phenyl] thiourea 0.1 100!

1- [4- (2,2-difluorocyclopropyloxy) -phenyl] -3- (2-methylbenzoyl) -urea 0.1 100 j

1- (2,6-difluorobenzoyl) -3- {4- [3- (2,2-difluorocyclopropyl) -propoxy] -3,5-. <, I

dimethylphenyi-urea 0.1 100 |

1- {2-chlorobenzoyl) -3- {4- [3- (2,2-difluorocyclopropyl) propoxy] -3,5-

dimethylphenyl} urea 0.1 100

1- {3,5-dichloro-4- [3- (2,2-difluorcyclopropyi) propoxy] phenyl} -3- (2,6-

difluorobenzoyl) urea 0.1 100

1- {3,5-dichloro-4- [3- (2,2-difluorocyclopropyl) -propoxy] -phenyl} -3- (2-, '.

ChlorobenzoO-heme 0.1 100

1- {4- [3- (2,2-difluorocyclopropyl) -propoxy] -3,5-dimethylphenyl} -3- (2-fluoro

Benzoydurea, 0.1 100

1- {3,5-dichloro-4- [3- (2,2-difluorocyclopropyl) propoxy] phenyl} -3- {2-

fluorobenzoic acid · 0.1 100

1- {4- [2- (2,2-difluorocyclopropyl) -ethoxy] -3,5-dimethylphenyl} -3- (2-

fluorobenzoic urea. · ', 0.1 100

1- [3,5-dichloro-4- (2,2 ^l difluorocyclopropyloxy) -phenyl] -3- (2-fluorobenzoyi) -

urea. , 0.1 100

1- {3,5-dichloro-4- [2- ^(2,2: difiuorcyclopropyl) -ethoxy] -phenyl} -3- (2-

Fluorobenzo-O-Matter 0.1 100

1- {2-chlorobenzene) -3- [4- {2,2-difluorcyclopropyimethoxy) -3,5-dimethylphenyl] -

urea 0.1 100

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropylmethoxy) phenyl] urea 0.1 100

1- (2-chlorobenzoyl) -3-r4- (2,2-difluorocyclopropylmethoxy) -phenyl] -urea '0.1 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropyimethoxy) -3,5

dimethylphenyl] urea '0.1 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl!] - 3- (2,6-

difluorobenzene-urea 0.1 '100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -

urea 0.1 100

1- [3-chloro-4- (2,2-difluorocyclopropyl-methoxy) phenyl] -3- (2,6-difluorobenzoyl) -

urea ·. 0.1 100

1- [3-chloro-4- (2,2-difluorocyclopropyl-methoxy) phenyl] -3- (2-chlorobenzoyl) -

urea - 0.1 "100

1- [3-chloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

urea 0.1 100

1- [3-chloro-4- (2,2-difluorcyciopropylmethoxy) -phenyl] -3- (2-chloro-6-

fluorobenzoyl) urea 0.1 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3-methyl phenyl!] -

urea 0.1 100

1- (2-chlorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3-methylphenyl] -

urea 0.1-100

1- (2-chloro-6-fluorbenzoy!) - 3- [4- (2,2-difluorcyclopropylmethoxy) -3-

methylphenyl] urea 0.1 100

1- [4- (2,2-Difluorcyclopropy methoxy!) -3-methylphenyl] -3- (2-fluorobenzoyl) -

urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2,6-

difluorobenzene-urea · 0.1-100

1- [3,5-dibromo-4- (2,2-dif uorcyclopropylmethoxy!) Phenyl] -3- (2-chlorobenzoyl) -

urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2,6-

dichlorobenzoylurea. .100

Inventive drug concentration effect

Connections in% in%

1-t3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-bromobenzoyl) -

urea. 0.1 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5-diiodophenyl] -

urea 0.1 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluoro-1-methylcyclopropylmethoxy) -3,5-

Dimethylphenylj-urea, 0.1 x 100

1- (2-chlorobenzoyl) -3- [4- (2,2-difluoro-1-methyleyclopropylmethoxy) -3,5

dimethyl phenylurea 0.1 100

1- [3,5-dichloro-4- (2,2-difluoro-1-methyicyclopropylmethoxy) phenyl] -3-

(2,6-difluorobenzoyl) -urea '0.1 x 100

1- [3,5-dichloro-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3-

(2-chlorobenzoyl) urea '0.1' 100

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-methyl-

benzoylurea 0.1 100

1- [3,5-Dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-methyl-

BenzoyU-urea 0.1 100

1- [3,5-dichloro-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3-

(2-methylbenzoyl) urea 0.1 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluoro-3-methylcyclopropylmethoxy) -3,5-

Dimethylphenylj-urea 0.1 100

1- (2,6-Difluorbenzyoyl) -3- [4- (2,2-difluoro-3-phenylcyclopropylmethoxy) -3,5

dimethylphenyllurea. , 0.1 100

1- (2-chlorobenzoyl) -3- [4- (2,2-difluoro-3-phen'y! Cyclopropylmethoxy) -3,5-

dimethyiphenyi] urea 0.1 100

1- (2-chlorobenzoyl) -3- [4- (2,2-difluoro-3-methylcyciopropylmethoxy) -3,5

dimethylphenyl] urea 0.1 100

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3-

(2,6-difluorobenzoic diurea 0.1 100

1- [3,5-dichloro-4- (2,2-difluoro-3-phenylcyclopropylmethoxy) phenyl] -3-

(2,6-difluorobenzoyl) urea. 0.1 100

1- [4- (2,2-Difluorcyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2-fluorobenzoyl) -

urea '0.1 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

urea 0.1 100

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy-phenyl] -3-

{2-chlorobenzoyl) urea 0.1. , 100

1- [3,5-Diohlor-4- (2,2-difluoro-3-phenylcyclopropylmethoxy) phenyl] -3-

(2-chlorobenzoyl) urea 0.1 100 ×

1- [3,5-dibromo-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3-

(2-chlorobenzoyl) urea 0.1 100

1- [4- (2,2-difluoro-1-methylcyclopropylmethoxy) -3,5-dimethylphenyl] -3-

(2-fluorobenzoyl) urea 0.1-100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5

difluorophenylj-urea 0.1 x 100

1- [4-2.2-Difluorcyclopropylmethoxy) -3,5-difluorophenyl] -3- (2-fluorbenzoyi) -

urea 0.1 100

1- (2-chlorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5-difluorophenyl] -

urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

urea ·. 0.1 100

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- (2-fluoro

benzoyi) urea "'0.1 x 100

1- [3,5-dibromo-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- (2-fiuor-

benzoyl) urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3-

(2-fluorobenzene!) - urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluoro-3-methyicyclopropylmethoxy) phenyl] -3-

(2,6-difluorobenzoyl) urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- (2-chloro-

benzoyl) urea 0.1 100

1- [3,5-dibromo-4- (2,2-difluoro-1-methylcyclopropylmethoxy) -phenyl] -3-

(2,6-difluorobenzoyl) urea 0.1 100

1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dimethylphenyl] -3-

(2,6-difluorobenzoyl) -urea 0.01 100

Inventive "" active ingredient concentration effect

Connections -in% in%

1- [4- (t-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2-chloro-

Benzoyo-urea. 0.01 '100

1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2-fluoro

Benzoyo-urea 0.01. 100

1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2-chloro-

6-fluorobenzoyl) urea 0.01 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-diftuor-3-dimethylcyclopropyloxy) -3,5

dimethylphenyl] urea '' 0.01 ''

1 - (- 2-chlorobenzoyl) -3- [4- (! 2,2-dif fluoro-3,3-d'imethylcyclopropyloxy) -3,5

dimethylphenyl] urea 0.01 100

1- [3,5'-dichloro-4- (2 ₍ 2-difluoro-3-dim8thylcyclopropyloxy) -phenyl] -3-

(2,6-difluorobenzyl diurea 0.01 100

1- (2-chlorobenzoyl) -3- [3,5-dichloro-4- (2,2-difluoro-3,3-dimethylcyclopropyl

methoxy) phenyl] urea "- 0.01 100

1- [4- (1-chloro-2,2-difiuorcyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2,6-difluoro

Benzoydurea 0.01 100

1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2-chloro-

benzpyo-urea ·. 0.01 100

1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2-chloro-

6-fluorobenzoyl) urea 0.01 100

1- [4- (1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2-fluoro-)

benzoyD urea. ~ 0.01. 100

1- [4- (1-chloro-2,2-difluorcyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2,6-difluoro

Benzoyo-thiourea 0.01 100

1- {2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5-dimethylphenyl] -

urea 0.01 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropyloxy) -phenyl] -3- (2,6-difluorobenzoyl) -

urea. 0.01 100

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyciopropylmethoxy) -3,5-dimethyl-

phenyll-urea '0.01 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) phenyl] -3- (2,6-difluoro

BenzoyDurea · 0.01 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -

urea 0.01 100

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) phenyl] -3- (2,6-difluoro

benzoyi) urea 0.01 100

1- (2,6-difluorobenzoyl-3- [4- (2,2-difluoro-1-methylcyclopropylmethoxy) -3,5-

dimethylphenyl] -urea 0.01 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

urea 0.01 100

1- [3, S-dichloro-4- {2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3-

(2,6-DifluorobenzoyO-urea 0.01 100

1- (3,5-dichloro-4-cyclopropylmethoxyphenyl) -3- {2,6-difluorobenzoyl) urea .0100

1- (3,5-dichloro-4-cyclopropylmethoxyphenyl) -3- (2-fluorobenzoyl) -urea 0.01 100

COMPARISON MEDIUM

N- (2,6-difluorobenzoyl) -N '- (p-chlorophenyl) -urea (according to DE-OS 2123236) 0.01

N- (2-chlorobenzoyl) -N '- (p-trifluorometboxyphenyl) -urea' ''

(according to DE-OS 2601780) 0.01 50

EXAMPLE 105

Killing Effect on Larvae (L3) of the Mexican Bean Beetle (Epilachna varivestis)

The substances according to the invention were used as aqueous emulsions with the active ingredient concentrations 0.01% and 0.001%. Likewise, the comparison agents were used as aqueous suspensions.

In this active ingredient preparations bush bean plants (Phaseolus vulgaris) were dipped in the primary leaf stage. Three plant stems with a total of 6 primary leaves were placed in water-filled glass vases per test member and caged in glass cylinders. After the preparation broth had been dried on the treated leaves, 5 larvae of the Mexican bean beetle (Epilachna varivestis) in the 3rd instar larvae were counted into the glass cylinders and kept there for 5 days under long-day conditions.

The criterion for the impact assessment was the mortality of the larvae in% after a 5-day trial period.

Compounds according to the invention - Active substance concentration effect

  in% in%

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropyloxy) -3,5-01,100

dimethylphenyl] urea 0.001. 80

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluorocyclopropylmethoxy) -3,5-0.0180

dimethylphenylj-urea 0.001. 60

1- [3,5-dichloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2,6-difluoro-0.01-100

benzoylurea 0.001 100

1- [3,5-dichloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) - , 0.01. 100

urea. ^: '0.001 .100

1- [3,5-dibromo-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2,6-difluoro-0.01-100

benzoylurea 0.001 100

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluoro-1-methylcyclopropylmethoxy) -3,5-01,100

dimethylphenyl] urea 0.001 90

1- [3,5-dichloro-4- (2,2-difluorocyclopropylmethoxy) -phenyl] -3- (2-fluorobenzyl-0.01-0.01

urea. 0.001 100

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3- 0.01 100

2,6-difluorobenzoyl) urea. 0.001 100

VERGLEiCHSMlTTEL

N- (2,6-Difluorobenzoyl) -N '- (p-chlorophenyl) -urea 0.01 100

(according to DE-OS 2123236) '0.001 0

N- (2-chlorobenzoyl-N '- (p-trifluoromethoxyphenyl) urea 0.01-40

(according to DE-OS 2601780) - 0.001 0

EXAMPLE 108

Ovicidal effect on egg yolks of the Mexican bean beetle (Epilachna varivestis) The compounds according to the invention were used as aqueous emulsions having an active ingredient concentration of 0.01%.

Likewise, the comparison agents were used as aqueous suspensions.

1 day old egg shells, which had been deposited on brush beans by fertilized beetle females, were immersed in these preparations until completely wetted and placed in closed Petri dishes for 7 days.

The criterion for the impact assessment was the percentage of slippage prevention compared to untreated eggs.

Compounds of the invention Active substance concentration effect

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropyloxy) -3,5

dimethylphenyllurea 0.01 95

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5-dimethyl-

phenyl urea 0.01 'x 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) phenyl] -3- (2,6-difluoro

benzoylurea 0.01 100

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-chlorbenzoyD-

urea 0.01 100

1- [3,5-dibromo-4- (2,2-difluorcyclopropylmethoxy) phenyl] -3- (2,6-difluoro

BenzoyU-urea 0.01 80

1- (2,6-DifluorbenzoyD-3- [4- (2,2-difluoro-1-methylcyclopropylmethoxy) -3,5-

dimethylphenyl] urea. '0.01 100

1- [3,5-dichloro-4- (2,2-difluoro-3-methylcyclopropylmethoxy) -phenyl] -3-

2,6-difluorobenzoyl) urea 0.01 100

COMPARISON MEDIUM

N- (2,6-difluorobenzoyl) -N '- (p-chlorpheny!) - urea

(according to DE-OS 2123236) 0.01 50

N- (2-chlorobenzoyl) -N '- (p-trifluoromethoxyphenyl) -urea

(according to DE-OS 2601780) 0.01. , 0

all following according to DE-OS 2928410:

1- [4- (2,2-Dichlorcyclopropylmethoxy) -3,5-dimethyl-phenyl] -3- (2,6-dichloro-

benzoylurea 0.01 0

1- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) phenyl] -3- (2,6-dichIor-

benzoylurea 0.01 0

1- [3-chloro-4- (2,2-dichlorcyclopropylmethoxy) -phenyl] -3- (2-chlorbenzoyD-

urea 0.01 0

1-t3-chloro-4- (2,2-dichlorcyclopropylmethoxy) (2-chloro-6-fluoro-phenyl] -3-

Benzoydurea 0.01 0

1- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) -phenyl] -3- (2-methyl-

benzoylurea · 0.01 0

1- [3-chloro-4- (2,2-dichlorcyclopropylmethoxy) -phenyl] -3- (2-methylbenzoyD-

urea 0.01 0

Compounds of the invention.

drug concentration

effect

1- (2-chlorobenzoyl) -3- [3,5-dichloro-4- (2,2-dichloro-cyclopropylmethoxy] phenyl) -

urea 0.01 0

1- (2-chloro-6-fIuorbenzoyl) -3- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) -

phenylamine, 0.01-0

1- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) phenyl] -3- (2,6-difluoro

Benzoydurea 0.01 · 0

EXAMPLE 107. ,

Ovicidal effect on egg yolk of the Egyptian Cotton Euie (Spodoptera littoralis)

The compounds according to the invention were used as aqueous emulsions having an active ingredient concentration of 0.0016%.

Likewise, the comparison agents were used as aqueous suspensions. In this preparation of active ingredient 1 day old egg shells, which had been deposited by fertilized female females on filter paper, dipped to complete wetting and

deposited for 4 days in closed Petri dishes. , , ,

The criterion for impact assessment was the percentage of slippage prevention compared to untreated eggs.

Compounds of the invention

Active substance concentration effect

1- (2,6-difluorobenzoyl) -3- [4- (2,2-difluorcyclopropylmethoxy) -3,5-dimethyl-

phenyl] -urea 0.0016 80

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) phenyl] -3- (2,6-difiuor-

benzoyo-urea 0.0016 75

1 [4- (2,2, -Difluorcyclopropylmethoxy) -3,5-dimethyl-phenyl] -3- (2-fluorobenzoyl) -

urea '. 0.0016 80

1- [3,5-dichloro-4- (2,2-difluorcyclopropylmethoxy) -phenyl] -3- (2-fluorobenzoyl) -

Urea "· '- 0.0016 100

comparison means

N- (2,6-difluorobenzoyl) -N '- (p-chlorophenyl) urea

(according to DE-OS 2123236) 0.0016 70

N- (2-chlorobenzoyl) -N '- (p-trifluoromethoxyphenyl) -urea

(according to DE-OS 2601780) 0.0016 '70

all following according to DE-OS 2928410:

1- [4- (2,2-Dichlorcyclopropylmethoxy) -3,5-dimethyl-phenyl] -3- (2,6-dichloro-

benzoyo-urea 0.0016 0

1- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) phenyl] -3- (2,6-dichloro-

benzoyl) urea 0.0016 0

1- (2-chlorobenzoyl) -3- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) phenyl] -

urea 0.0016 · 0

1- (2-chloro-6-fluorobenzoyl) -3- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) -

phenyl] -urea. 0.0016 '.0

1- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) phenyl] -3- (2,6-difluoro

BenzoyDurea 0.0016 0

1- [3,5-dichloro-4- (2,2-dichlorcyclopropylmethoxy) -phenyl] -3- (2-methyl-

benzoyo-urea 0.0016 0

1- [3-chloro-4- (2,2-dichlorcyclopropylmethoxy) -phenyl] -3- (2-methylbenzoyl) -

urea 0.0016 .0

1- [3-chloro-4- (2,2-dichlorcyciopropylmethoxy) -phenyl] -3- (2-chlorobenzoyl) -

urea. 0.0016 0

1- [3-chloro-4- (2,2-dichlorcyclopropylmethoxy) -phenyl] -3- (2-chloro-6-fluoro-

benzoyD urea. ~ 0.0016 0

Beispiel108

Killing Effect on Larvae (L3) of the Mexican Bean Beetle (Epilachna verivestis)

The Substenzen are used as aqueous emulsions with the active ingredient concentration 0.1%. In this active ingredient preparations, bush bean plants (Phaseolus vulgaris) are dipped in the primary leaf stage. Three plant stems with a total of 6 primary leaves per sample are placed in glass vases filled with water and placed in glass cylinders. After the preparation broths have been dried on the treated leaves, 5 larvae of the Mexican bean beetle (Epilachna varivestis) in the third larval stage are counted into the glass cylinders and kept there for 5 days under long-term conditions. The criterion for the impact assessment is the mortality of the larvae in% after a 5-day trial period.

Compounds of the invention

Active substance concentration effect

1- [4- (1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2,6-0.1

difluorobenzoyl) urea

1- [4- (1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dimethylphenyl] -3- (2-

chlorobenzoyl) -urea

i- ^ d-Chloro ^^ - difluorocyclopropylmethoxyl-S ^ dimethylphenyn-S-0.1

(2-fluorobenzoyl) urea

100 100 100

Compounds according to the invention Active substance concentration effect

! - .0,1 100

(2-chloro-6-fluorobenzoyl) -urea

1- (2,6-Difluorobenzoyl) -3- [4- (2,2-difluoro-3,3-dimethylcyclopropylmethoxy) -0.100

3,5-dimethylphenylj-urea

1- (2-Chlorobenzoyl) -3- [4- (2,2-difluoro-3,3-dimethylcyclopropylmethoxy) -1,100

3.5 dimethylpheny] - urea

1- [3,5-dichloro-4- (2,2-difluoro-3,3-dimethylcyclopropylmethoxy) -phenyl] -1,100

3- (2,6-difluorobenzoyl) urea. , , - - ..

1- (2-Chlorobenzoyl) -3- [3,5-dichloro-4- (2,2-difluoro-3,3-dimethylcyclopropyl-0.1, 100

methoxy) -phenyl] -urea

1- [4- (1-chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2,6- 0.1, 100

difluorbenzoyll urea

i- ^ d-Chloro ^^ - difluorocyclopropylmethoxy ^ B-dichlorophenyl-S- · 0.1 100

(2-chlorobenzoyl) -urea

 i ^ -d-Chloro ^^ - difiuorcyclopropylmethoxyl-S ^ dichlorphenylJ-S-0.1 100

(2-chloro-6-fluorobenzoyi! Urea

1- [4- (1-Chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2-0,100

fluorobenzoyl) -urea

1- [4 (1-chloro-2,2-difluorocyclopropylmethoxy) -3,5-dichlorophenyl] -3- (2,6- 0,1 100

difluorobenzoyl) thiourea

Claims (1)

Invention claim: Insecticidal compositions, characterized in that they contain at least one acylurea of the general formula R ₁ R ₂ R ₃ , R ₆ , R 9 '.X Q) _0- (CH ₂ , _n -