CZ279674B6 - Carbamate and urea derivatives with activity of insect juvenile hormone, process of their preparation and insecticidal agent based thereon for fighting insects - Google Patents

Abstract

Carbamate and urea derivatives of a general formula I where n is the integer of one to three, R1 is the oxygen atom, hydroxyl group together with one atom of hydrogen or a group of the general formula: -O-(CH2)m-O- where m is the integer of two or three, R<2> is hydrogen atom, alkyl with one to three carbon atoms, the hydroxyl group, acetyl group or tetrahydropyranyloxy group, R is a group of the general formula (CH2)p-NHCOO-R<3> where p is the integer of two or three and R<3> is alkyl with one to four carbon atoms, alkenyl with two to four carbon atoms or alkinyl with two to four carbon atoms, with the exception that R3 is not an alkyl if n is the integer of one or two or a group of the general formula: (CH2)p-X-CONHR4 where p has the abovementioned meaning and R4 is an alkyl with one to four carbon atoms or alkenyl with two to four carbon atoms or alkinyl with two to four carbon atoms and x is the oxygen atom or the imino group. The derivatives of general formula I are prepared by the reaction of a compound of general formula II where R<1>, R<2> and n have the abovementioned meanings with a compound of the general formula III: Z-(CH2)p-NHCOO-R<3> where R<3> and p have the abovementioned meanings and Z means the chlorine atom, bromine atom or p-toluenesulphonyloxy group, or by the reaction of a compound of general formula II with a compound of general formula IV: Z-(CH2)p-X-CONHR<4> where R<4>, X, Z and p have the abovementioned meanings. The insecticide for the liquidation of insects contains an insecticide effective quantity of the compound of general formula I as the active substance and an inert carrier or solvent, or surfactants and/or an antifungal preparation.

Description

Carbamate and urea derivatives, process for their production and insecticide for insect control

Technical field

The present invention relates to carbamate and urea derivatives having the effect of regulators of insect development (insect juvenile hormone), the molecule of which contains a carbamate or urea group in the side aliphatic chain, a process for their preparation and the possibility of their use in formulations suitable for use in practice.

BACKGROUND OF THE INVENTION

To date, a large number of insect developmental agents, also known as juvenoids, have been described (Sláma et al.: Insect Hormones and Bioanalogues, Springer Verlag, 1974; CA Henrick: in Insecticide Mode of Action, edited by JR Coats), p. 315, Academic Press, 1982; CA Henrick: Insect Chemical Ecology (I. Proud Editor), p. 429, SPB International - Academia, 1991). A common feature of the action of juvenoids, otherwise chemically very different compounds, is the development of developmental disorders in insects, leading ultimately to extinction or a strong suppression of the extent of the population of harmful insects. Their advantage is the relatively high specific activity on some insect species with very low toxicity to vertebrates and a wide range of biological activity, including sterilization and ovicidal effects, undressing disorders and disruption of developmental cycles.

Methods of pest control using juvenoids have led to the development of various formulations, ie dosage forms, which differ from one another mainly according to the intended use and reflect also the specific physico-chemical properties of the biologically active substance, eg solubility, volatility, degradation rate of the active substance The biologically active substance is the most important component of the preparation. The basic criteria according to which suitable juvenoids are selected for use in practically applicable formulations are determined, for example, by the chemical structure of the biologically active substance and its physico-chemical properties, the rate of degradation by abiotic and biotic factors, the toxicity of juvenoid and its potential metabolites for other animals. . Knowledge of the dynamics of residues in the food chain and other components of the natural environment, the occurrence of secondary metabolites of the original juvenoid and last but not least the findings of biological tests, which determine the suitability of the structure for use in the control of specific insect pests, are also decisive. Worldwide attention is paid to the question of research into suitable application forms of juvenoids. Recent works (see, e.g., Retnakaran A., Granett J., Ennis T .: Insect Groeth Regulators, in Comprehensive Insect Physiology, Biochemistry and Pharmacology (GA Kerkut and LI Gilbert, eds.), Vol. 12, pp. 529- 601, Pergamon press 1985, or Kawada H., Dohara K., Shinjo G .: Jpn. J. Sanit. Zool., 39, 339 (1988); and others) summarize the results of these investigations which clearly indicate the importance of juvenoid stability in under the conditions of field trials because these substances must be present in a sufficient concentration in suitable

This is especially at a time when the developmental stage of the insect pest that is sensitive to the effect of juvenoid is rising and culminating.

For the practical use of juvenoids, ie substances affecting the development and reproduction of harmful insects, it is necessary to ensure that an effective amount of the active substance has a uniform and long-lasting effect throughout the treatment site for at least a period such that a substantial part of the susceptible population is affected. juvenoid sensitive) developmental stage. Due to the inhomogeneity of the pest populations in terms of the development of individuals, this period can be quite long, e.g. 6 to 8 weeks. Systems which allow such a uniform and long-term effect of the active substance must meet a number of criteria. E.g. It must allow optimal dispersion of the biologically active substance, juvenoid, in the treated area, it must provide protection of juvenoid against atmospheric oxidation, light and other environmental influences that would reduce and shorten efficiency, be suitable for ease of use and application, ensure constant and reproducible the effect of the biologically active agent over the required time must ensure the efficient use of an expensive chemical compound such as juvenoid, while the use of the co-formulation and the carrier must not adversely affect the desired effect, and finally these systems must be cheap both in production and application. The individual formulations used so far do not meet all these criteria. In addition, the intended method of application should also be considered. Other formulations are suitable for controlling insect pest populations in livestock buildings, medical facilities, warehouses, households, etc., other in field application conditions, resp. in greenhouses against insect pests on agricultural crops.

SUMMARY OF THE INVENTION

The invention relates to carbamate and urea derivatives of the general formula I,

(AND)

where n is an integer one to three, R ¹ is an oxygen atom, a hydroxyl group together with one atom hydrogen or a group of the formula: -O- (CH ₂ m is an integer two or three, ) -0- in which R ² is a hydrogen atom, an alkyl having a carbon number atoms of one to three, hydroxyl, acetyl, pyranyloxy, or tetrahydro- R is a group of the general formula:

-2C 279674 B6 (CH ₂ ) _p -NHCOO-R ³ wherein p is an integer of two or three and R ³ is alkyl of one to four carbon atoms, alkenyl of two to four carbon atoms, or alkynyl of carbon numbers atoms of two to four, with the proviso that R ³ is not alkyl when n is an integer one or two, or a group of the formula:

(CH ₂ ) _p -X-CONHR ⁴ wherein p is as defined above and R ⁴ is alkyl of one to four carbon atoms, or alkenyl of two to four carbon atoms, or alkynyl of two to four carbon atoms, and X is an oxygen atom or an imino group.

Derivatives of formula (II):

I is prepared by reacting the compound

OH (Π) in which R, R and n are as defined above, with a compound of formula III:

-Z- _(CH2) p-CO-R ³ (III) wherein R and p have the abovementioned meanings and Z represents a chlorine atom, a bromine atom or a p-toluenesulfonyloxy group.

The derivatives of formula (I) may also be prepared by reacting a compound of formula (II) with a compound of formula (IV):

-Z- (CH ₂₎ pX-CONHR ⁴ (IV) wherein R ^4, X, Z, and P s maj abovementioned meanings.

The invention also relates to an insecticidal insecticide composition which, according to the invention, contains as an active ingredient an insecticidally effective amount of a derivative of the general formula I and an inert carrier or diluent. It may further comprise a surfactant and / or an antifungal composition.

The composition of the present invention allows a sustained release of a biologically active compound of formula I under the action of some abiotic and biotic factors, while protecting the biologically active compound of formula I from oxidation and other environmental influences, thereby providing a longer biological effect compared to in the form of a chemically pure biologically active substance of the formula I, or in the form of a

Compared to the use of previously known formulations. The juvenilizing effect of the biologically active compound of the formula I results in disturbances in the development of insect individuals of the above-mentioned insect orders and thereby decreases the population density of the next generation of the indicated insect pests on the treated flat. It has been shown experimentally that the biological activity of the composition of the invention remains constant for at least two years under appropriate storage conditions.

Surfactants suitable for all of the above applications may be selected from the group consisting of ionic or non-ionic surfactants. It is often advantageous to use a mixture of both types. As ionic surfactants, for example, sulfates or phosphates of fatty alcohols and ethoxylated fatty alcohols, ethoxylated alkylphenol sulfates, ligninsulfonates, alkylarylsulfonates, salts of sulfonated naphthalene-formaldehyde codenzation products, dialkylsulfosuccinates and the like can be used. As nonionic surfactants, for example, ethylene oxide condensation products with fatty acid esters or amides, fatty alcohols, alkyl-substituted phenols or fatty acid sorbitans and their condensation products with ethylene oxide can be used.

For example, formaldehyde or phenol may be used as the antifungal agent, for example glycol or glycerin may be used as the antifreeze agent.

The composition according to the invention is applied either after dilution with water and thorough mixing, the concentration of the active compound of the formula I in the spray gun being selected according to the application, usually in the range of 0.001 to 0.5% by weight, or the composition according to the invention. by spreading in such an amount that the average concentration of the active compound of the formula I is 0.001 to 1% by weight. or small dishes, boxes, sachets and the like suitable containers are filled with the composition of the invention to allow the application of the composition in an amount of typically 0.5 to 500 grams per cartridge, the treatment term being selected such that a substantial portion of the target population The species of the pest was affected during the period of the sensitive developmental stage.

The composition according to the invention can advantageously be used for reducing the population density of harmful insects of the order Blattoidea (preferably cockroaches), preferably Russian domestic and cockroaches, Coleoptera (beetles), preferably pests of stocks such as tobacco mites (Lasioderma serricorne), Diptera (diptera) , preferably house flies and mosquitoes, Heteroptera (bugs), preferably pests of legumes Netara viridula, Homoptera (even-winged insects), preferably aphids (Aphidoidea), mer Psylloidea), cicadas (Cicadoidea) or worms (Coccoidea) and Isoptera (termiti) . These groups of insects include serious plant pests such as hops, potatoes, beets, fruit trees, rice, vegetables, ornamental plants, pests of stocks, forest crops and structural organic materials (eg wood) and the like. The effect of the active substance can also be manifested in the reduction of the possibility of transmission of viroses in crops of crops, but also in livestock production, which is a particularly important factor of plant and animal production. Ultimately, the same goal is pursued by the application of substances with a juvenilizing effect on insects in health care facilities, possibly - among other health care facilities, eventually

-4GB 279674 B6

- inter alia - in households. The active ingredient may be formulated as a concentrate, an emulsion concentrate in a wettable powder, an aqueous dispersion, a formulation formed with a polymeric carrier, preferably a carrier based on polygalacturonic acid, or preferably a carrier consisting of finely divided polyamide or polyester pre-impregnated with epoxy resin. , or into the form of a fire bait.

DETAILED DESCRIPTION OF THE INVENTION

The following are examples that illustrate the invention without limiting it in any way.

Example 1

N-Ethyl 2 - [4- (2-oxo-cyclohexylmethyl) fenoxyJethylkarbamát (I, ^{R1 =} 0, ^R2 = H, n = 2, R = (CH _{2) 2} OCONHC ₂ H ₅₎

a) To a solution of 2- (4-hydroxybenzyl) -1-cyclohexanone (24.6 mmol) in methanol (50 mL) was added sodium hydroxide (27.1 mmol) and the mixture was refluxed for 30 minutes. After the methanol was evaporated, the remaining sodium salt of the starting ketone was stirred in toluene (60 mL), and ethylene carbonate (88 mmol) was added to the reaction mixture. The reaction mixture was refluxed for 8 hours and then shaken with saturated sodium bicarbonate solution and water until neutral. The extract was dried over sodium sulfate. After evaporation of the solvent, the residue was purified by column chromatography to give 5.43 g (89%) of 2- [4- (2-hydroxyethoxy) benzyl} -1-cyclohexanone.

b) 2- [4- (2-hydroxyethoxy) benzyl] -1-cyclohexanone (20.2 mmol) was dissolved in triethylamine (5 mL) and ethyl isocyanate (28.1 mmol) was added with vigorous stirring to the reaction mixture. mixtures. Stirring was continued for 30 minutes at room temperature and for a total of 4 hours at 50 ° C. The reaction mixture was then diluted with chloroform (50 mL), shaken with 5% hydrochloric acid and water until neutral. The extract was dried over sodium sulfate and after evaporation of the solvent, the crude residue was purified by silica gel column chromatography. 3.28 g (51%) of N-ethyl 2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethylcarbamate was obtained. Constants: IR spectrum: 3458, 1731, 1714, 1615, 1245 cm @ ^-1 .

Example 2

N-Ethyl 2- [4- (2-ethylenedioxy-1-cyclohexylmethyl) phenoxy] ethylcarbamate (I, R ¹ = O (CH 2) 2 O, R ² = H, n = 2, R = (CH 2) ₂ OCONHC ₂ H ₅ )

To a solution of N-ethyl 2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethylcarbamate (3.1 mmol) in benzene (50 mL) was added ethylene glycol (1 mL) and a catalytic amount of p-toluenesulfonic acid. Water was distilled off from the reaction mixture under azeotropic conditions for 6 hours. After cooling, the reaction mixture was shaken with water and the organic layer was dried over sodium sulfate. After evaporation of the solvent, the residue was purified by column chromatography on

Silica gel yielded 0.68 g (60%) of N-ethyl 2- [4- (2-ethylenedioxy-1-cyclohexylmethyl) phenoxy] ethylcarbamate. Constants: IR spectrum: 3459, 1730, 1613, 1245, 1156, 926 cm ^-1 .

Example 3

N-ethyl 2- [4- (2-hydroxy-cyclohexylmethyl) phenoxy] ethylcarbamate (I, ^{R1 =} H, OH, R ² = H, n = 2, R = (CH _{2) 2} OCONHC ₂ H ₅ )

To a solution of N-ethyl 2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethylcarbamate (5.9 mmol) in methanol (90 mL) was added sodium borohydride (55.2 mmol) with stirring and cooling to 0 Deň: 32 ° C. The reaction mixture was then stirred at room temperature for 2 days. Methanol was evaporated under reduced pressure, the residue diluted with saturated sodium chloride solution (20 mL) and the organic layer extracted with ether. After drying over sodium sulfate and evaporation of the solvent, the residue was separated by silica gel column chromatography to obtain 0.77 g (40%) of the cis isomer and 0.53 g (28%) of the trans isomer of N-ethyl 2- [4- (2-hydroxy) -1-cyclohexylmethyl) phenoxy] ethylcarbamate. Constants: IR spectrum (cis isomer): 3616, 3453, 1718, 1612,

1235 cm ^-1 ; (trans isomer): 3609, 3451, 1718, 1612, 1241 cm ^-1 .

Example 4

N-ethyl N-2- [4- (2-oxo-cyclohexylmethyl) phenoxy] ethyl-urea (I, R ¹ = O, R ² = H, n = 2, R = (CH _{2) 2,} NHCONHC ₂ H ₅ )

a) To a mixture of 2- (4-hydroxybenzyl) -1-cyclohexanone (41.7 mmol), water (57 mL) and 1,2-dibromoethane (50 mmol) was added dropwise sodium hydroxide solution (39.8 mmol) in water (11.4 mL). The reaction mixture was heated to 110 ° C with stirring for 7 hours. The completion of the reaction is indicated by changing the pH of the reaction mixture. After cooling, the reaction mixture was extracted with ether and the extract was dried over sodium sulfate. The solvent was evaporated and the residue was purified by silica gel column chromatography. 6 g (46%) of 2- [4- (2-bromoethoxy) benzyl] -1-cyclohexanone were obtained.

b) In a pressure vessel, 2- [4- (2-bromoethoxy) benzyl] -1-cyclohexanone (36.95 mmol) was dissolved in tetrahydrofuran (30 mL). To the solution was added liquid ammonia (30 mL), the vessel sealed and allowed to stand at room temperature for 1 day. Then the same amount of liquid ammonia was added once more and the reaction mixture was allowed to stand again for 1 day. After opening the pressure vessel, it was transferred to a beaker, the vessel rinsed with 5% hydrochloric acid solution. The acid portion was filtered through a frit and made basic with sodium hydroxide. The combined aqueous layers were shaken ten times with 50 ml of ether and the combined extract was dried with sonic sulfate. After evaporation of the solvent, the obtained product, 2- [4- (2-aminoethoxy) benzyl] -1-cyclohexanone (7.5 g; 88%) was used for the next reaction step without further purification.

c) 2- [4- (2-Aminoethoxy) benzyl] -1-cyclohexanone (9 mmol) was dissolved in triethylamine (19 mL) and ethyl isocyanate (13.5 mmol) was added to the reaction mixture with vigorous stirring of the reaction mixture.

-6GB 279674 B6 mixtures. Stirring was continued for 30 minutes at room temperature and for a total of 1 hour at 500 ° C. The reaction mixture was evaporated to dryness and the crude residue was purified by silica gel column chromatography. 1.43 g (50%) of N-ethyl N-2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethyl urea was obtained. Constants: IR spectrum: 3446, 1706, 1612, 1244 cm ^-1 .

Example 5

N-ethyl N-2- [4- (2-ethylenedioxy-1-cyclohexylmethyl) phenoxy] ethyl urea (i, r ¹ = o (ch ₂ ) ₂ 0, r ² = h, n = 2, r = (ch ₂ ) ₂ n hconhc ₂ h ₅ )

Following the procedure described in Example 2, N-ethyl N-2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethyl urea (0.9 mmol) was obtained from N-ethyl N-2- (4- (2-oxo-1-cyclohexylmethyl) phenoxy). -ethylenedioxy-1-cyclohexylmethyl) phenoxy] ethylurea in an amount of 0.26 g (78%) Constants: IR spectrum: 3448, 3381, 1666, 1648, 1240, 1156, 924 cm ^-1 .

Example 6

N-ethyl-N-2- [4- (2-hydroxy-cyclohexylmethyl) phenoxy ethyl-urea (I, R ^{1 =} H), OH, R ² = H, n = 2, R = _{(CH2) 2} NHCONHC ₂ H ₅ )

Following the procedure described in Example 3, N-ethyl N-2- [4- (2-hydroxy) was obtained from N-ethyl N-2- (4- (2-oxo-1-cyclohexylmethyl) phenoxy) ethyl urea (4.8 mmol). 1-cyclohexylmethyl) phenoxyethylurea in an amount of 1.44 g (95%) Constants: IR: 3614, 346, 1665, 1649, 1611, 1243 cm @ ^-1 .

Example 7

N-Methyl 2- [4- (2-oxo-3-methyl-1-cyclopentylmethyl) phenoxy] propylcarbamate (i, r ¹ = o, r ² = ch ₃ , n = i, r = (ch ₂ ) ₃ oconhch ₃ )

Following the procedure described in Example 1, N-methyl 2- [4- (2-oxo-3-yl) -1-cyclopentanone (25 mmol) was obtained from 5-methyl-2- (4-hydroxybenzyl) -1-cyclopentanone (25 mmol) ( 25 mmol) of N-methyl 2- [4- (2-oxo-3-methyl-1-cyclopentylmethyl) phenoxy] propylcarbamate in 50% yield. Constants: IR spectrum: 3458, 1731, 1714, 1615, 1245 cm @ ^-1 .

Example 8

N-Propargyl 2- (4- (2-oxo-1-cycloheptylmethyl) phenoxyethylcarbamate (I, R ¹ = O, R ² = H, n = 3, R = (CH ₂ ) ₂ OCONHCH ₂ C = CH)

-7GB 279674 B6

Following the procedure described in Example 1, N-propargyl 2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethylcarbamate was obtained in 52% yield from 2- (4-hydroxybenzyl) -1-cycloheptanone (20 mmol). Constants: IR spectrum: 3458, 1731, 1714, 1615, 1245 cm @ ^-1 .

Example 9

N-Propargyl 2- [4- (2-ethylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl carbamate (I, R ¹ = O (CH 2) 2 O, R ² = H, n = 3, R = (CH 2) ₂ OCONHCH ₂ C = CH)

Following the procedure described in Example 2, N-propargyl 2- [4- (2-ethylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl was obtained from N-propargyl 2- (4- (2-oxo-1-cycloheptylmethyl) phenoxyethylcarbamate (10 mmol). carbamate in 90% yield Constants: IR spectrum: 3459, 1730, 1613, 1245, 1156, 926 cm ^-1 .

Example 10

N-Propargyl 2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy] ethylcarbamate (I, R ^X = H, OH, R ² = H, n = 3, R = (CH ₂ ) ₂ OCONHCH ₂ C = CH)

Following the procedure described in Example 3, N-propargyl 2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy] ethylcarbamate was obtained from N-propargyl 2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethylcarbamate (15 mmol). in 89% yield (55% cis isomers and 34% trans isomers). Constants: IR spectrum (cis isomer): 3616, 3453, 1718, 1612,

1235 cm ^-1 ; (trans isomer): 3609, 3451, 1718, 1612, 1241 cm ^-1 .

Example 11

N-Allyl 2- (4- (3-Aacetoxy-2-oxo-1-cycloheptylmethyl) phenoxy] ethylcarbamate (I, R ¹ = O, R ² = CH ₃ COO, n = 3, R = (CH ₂ ) ₂ OCONHCH ₂ CH = CH ₂ )

Following the procedure described in Example 1, N-allyl 2- (4- (3-acetoxy-2-oxo-1-cycloheptylmethyl)) was obtained from 3-acetoxy-2- (4-hydroxybenzyl) -1-cycloheptanone (20 mmol). phenoxy ethylcarbamate in 50% yield Constants: IR spectrum: 3458, 1731, 1615, 1245 cm @ ^-1 .

Example 12

N- (3-Buten-1-yl) 2- [4- (3-hydroxy-2-oxo-1-cyclopentylmethyl) phenoxy] ethylcarbamate (i, r ¹ = o, r ² = oh, n = i, r = (ch ₂ ) ₂ oconh (ch ₂ ) ₂ ch = ch ₂ )

Following the procedure described in Example 1, β- (3-buten-1-yl) 2- [4- (3-hydroxy-2-) was obtained from 3-hydroxy-2- (4-hydroxybenzyl) -1-cyclopentanone (20 mmol). oxo-1-cyclopentylmethyl) phenoxy-ethylcarbamate in 56%. Constants: IR spectrum: 3458, 1731, 1714, 1615,

1245 cm ^-1 .

Example 13

N-ethyl 2- [4- (3-tetrahydropyranyloxy-2-oxo-cycloheptylmethyl) phenoxy] propylcarbamate (I, ^R1 = 0, ^R2 = On-THP = 3, R = _{(CH2) 3 2} OCONHC H ₅ )

Following the procedure described in Example 1, N-ethyl 2- [4- (3-tetrahydropyranyloxy-2-oxo-1-cycloheptylmethyl) was obtained from 3-tetrahydropyranyloxy-2- (4-hydroxybenzyl) -1-cycloheptanone (25 mmol). phenoxy] for pylcarbamate in 51% yield. Constants: IR spectrum: 3458, 1731, 1714, 1615, 1245 cm @ ^-1 .

Example 14

N-Methyl N-2- [4- (2-oxo-3-methyl-1-cyclopentylmethyl) phenoxy] propyl urea (i, r ¹ = o, r ² = ch ₃ , n = i, r = (ch ₃ ) ₃ nhconhch ₃ )

Following the procedure described in Example 4, N-methyl N-2- [4- (2-oxo-3-methyl-1-cyclopentylmethyl) was obtained from 5-methyl-2- (4-hydroxybenzyl) -1-cyclopentanone (23 mmol). phenoxypropyl-urea in 52% yield. Constants: IR spectrum: 3446, 1706, 1612, 1244 cm ^-1 .

Example 15

N-Propargyl N-2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethyl urea (I, R ¹ = O, R ² = H, n = 3, R = (CH ₂ ) NHCONHCH ₂ C = CH)

Following the procedure described in Example 4, N-propargyl N-2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethyl urea was obtained from 2- (4-hydroxybenzyl) -1-cycloheptanone (20 mmol) in 54% load. Constants: IR spectrum: 3446, 1706, 1612, 1244 cm ^-1 .

Example 16

N-Propargyl N-2- [4- (2-ethylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl urea (i, r ¹ = o (ch 2) ² 0, r ² = h, n = 3, r- (ch 2) ₂ nhconhch ₂ c = ch)

Following the procedure described in Example 5, N-propargyl N-2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethyl urea (10 mmol) was obtained from N-propargyl N-2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethyl urea. (ethylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl urea in 89% yield. Constants: IR spectrum: 3448, 3381, 1666, 1647, 1240, 1156, 1156, 924 cm ^-1 .

-9EN 279674 B6

Example 17

N-propargyl N-2- [4- (2-hydroxy-cycloheptylmethyl) fenoxyJethyl-urea (I, R ¹ = H, OH, R ² = H, n = 3, R = (CH _{2) 2} NHCONHCH ₂ C = CH)

Following the procedure described in Example 6, N-propargyl N-2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethyl urea (12 mmol) was obtained from N-propargyl] N-2- [4- (2-oxo-1-cycloheptylmethyl) urea. hydroxy-1-cycloheptylmethyl) phenoxyethylurea in 85% yield. Constants: IR spectrum: 3614, 3446, 1665, 1649, 1611, 1243 cm ^-1 .

Example 18

N-Allyl N-2- [4- (3-acetoxy-2-oxo-1-cycloheptylmethyl) phenoxy] ethyl urea (i, r ¹ = o, r ² = ch ₃ coo, n = 3, r = ( ch ₂ ) ₂ nhconhch ₂ ch = ch ₂ )

Following the procedure described in Example 4, N-allyl N-2- [4- (3-acetoxy-2-oxo-1-cycloheptylmethyl) was obtained from 3-acetoxy-2- (4-hydroxybenzyl-1-cycloheptanone (18 mmol)). ) phenoxy] ethyl-urea in 51% yield. constants: IR: 3446, 1706, 1612, 1244 cm ^"3.

Example 19

N- (3-Buten-1-yl) -N-2- [4- (3-hydroxy-2-oxo-1-cyclopentylmethyl) phenoxy] ethyl urea (i, r ¹ = o, r ² = oh, n = i, R = (CH ₂₎ NHCONH _{(CH2) 2} CH = CH ₂₎

Following the procedure described in Example 4, N- (3-buten-1-yl) -N-2- [4- (3-hydroxy-) -benzyl] -1-cyclopentanone (19 mmol) was obtained from 3-hydroxy-2- (4-hydroxybenzyl) -1-cyclopentanone. 2-oxo-1-cyclopentylmethyl) phenoxy] ethyl urea in 53% yield. Constants: IR spectrum: 3446, 1706, 1612,

1244 cm ¹ .

Example 20

N-ethyl N-2- [4- (3-tetrahydropyranyloxy-2-oxo-cycloheptylmethyl) phenoxy] propy1-urea (I, R ^{1 =} O, R ² = O-THP ", n = 3; R = (CH ₂ ) ₃ NHCONHC ₂ H ₅ )

Following the procedure described in Example 4, N-ethyl N-2- [4- (3-tetrahydropyranyloxy-2-oxo-1-) - was obtained from 3-tetrahydropyranyloxy-2- (4-hydroxybenzyl) -1-cycloheptanone (25 mmol). cycloheptylmethyl) phenoxy] propyl 1-urea in 51% yield. Constants: IR spectrum: 3446, 1706, 1612, 1244 cm ^-1 .

-10GB 279674 B6

Example 21

Ethyl N- [2- (4- (2-oxo-cycloheptylmethyl) phenoxy]] ethylcarbamate (I, ^{R1 =} 0, ^R2 = H, n = 3, R = (CH _{2) 2} NHCOOC ₂ H ₅ )

To a solution of 2- (4-hydroxybenzyl) -1-cycloheptanone (5.565 g:

25.5 mmol) in DMFA (35 mL) was added sodium hydride (50% dispersion in mineral oil; 1.835 g; 38.2 mmol) under ice-cooling and stirring. After stirring for 1 hour, the temperature of the reaction mixture was raised to 100 ° C, a solution of ethyl N- (2-chloroethyl) carbamate (8 g; 38.2 mmol) in DMFA (5 mL) was added dropwise and the mixture was heated to 150 ° C for 9 hours. After cooling to 0, the mixture was poured into chilled 5% hydrochloric acid solution (50 mL) and the organic layer was extracted 5 times with 50 mL of ether. After washing the extract with a little water and drying the organic layer with sodium sulfate, the solvent was evaporated and the residue was purified by silica gel column chromatography. 4.75 g (56%) of ethyl N- [2- (4- (2-oxo-1-cycloheptylmethyl) phenoxy] phenoxy] ethylcarbamate were obtained.

Constants: IR spectrum: 3455, 1711, 1612, 1250 cm ^{@ -1} .

Example 22

Ethyl N- [4- [2-ethylenedioxy-1-cycloheptylmethyl) phenoxy] ethylcarbamate (i, r ¹ = o (ch ₂ ) ₂ 0, r ² = h, n = 3, r = (ch ₂ ) ₂ nhcooc ₂ h ₅ )

To a solution of ethyl N- (2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethylcarbamate (1.07 g; 3.2 mmol) in benzene (25 mL) was added ethylene glycol (1 mL) and a catalytic amount The reaction mixture was heated with azeotropic distillation of the reaction water for 14 hours After cooling, the reaction mixture was shaken with water and the organic layer was dried over sodium sulfate, and the solvent was evaporated and the residue was purified by silica gel column chromatography to give 0.854 g (74%). ) ethyl N - [- [4- (2-ethylenedioxy-1-cycloheptylmethyl) phenoxy]] ethylcarbamate Constants: IR: 3455, 1250 cm @ ^-1 .

Example 23

Ethyl N- [2- [4- (2-hydroxy-cycloheptylmethyl) phenoxy]] ethylcarbamate (I, ^{R1 =} H, OH, R ² = H, n = 3, R = _{(CH2) 2} H NHCOOC ₅ )

To a solution of ethyl N- [2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy]] ethylcarbamate (3.15 g; 9.4 mmol) in methanol (45 mL) was cooled to 0 ° C with stirring sodium borohydride (1.73 g; 45.7 mmol) was added. The reaction mixture was stirred at room temperature for an additional 4 hours. Then the methanol was evaporated, the residue was diluted with saturated sodium chloride solution and the organic phase was extracted with ether. After the extract was dried over sodium sulfate and the solvent was evaporated, the residue was separated by column chromatography on silica gel. 2.08 g (66%) of cis-ethyl N- [2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy]] ethylcarbamate and 0.34 g (11%) of trans-ethyl N were obtained. - [2- (2-hydroxycycloheptylmethyl) phenoxy] ethylcarbamate and 0.34 g

-11EN 279674 B6 (11%) trans-ethyl N- [2- [4- (2-hydroxycycloheptylmethyl) phenoxy]] ethylcarbamate. Constants: IR spectrum (cis isomer): 3630, 3465, 1246 cm ^-1 ; (trans isomer): 3625, 3465, 1243 cm ^-1 .

Example 24

Propargyl N- [2- [4- (2-oxo-cyclohexylmethyl) phenoxy] ethylcarbamate (I, ^R1 = 0, ^R2 = H, n = 2, R = (CH _{2) 2} CH = NHCOOCHC)

Following the procedure described in Example 21, 2- (4-hydroxybenzyl) -1-cyclohexane (2 g; 9.8 mmol) and propargyl N- (2-chloroethyl) carbamate (1.36 g; 9 mmol) were obtained. propargyl N- [2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy]] ethylcarbamate in 60% yield. Constants: IR spectrum: 3455, 1711, 1612, 1250 cm ^-1 .

Example 25

Allyl N [2- [4- (2-oxo-1-cyclopentylmethyl) phenoxy]] ethylcarbamate (i, r ¹ = o, r ² = h, n = i, r = (ch ₂ ) ₂ nhcoochc = ch ₂ ) .

Following the procedure described in Example 21, from 2- (4-hydroxybenzyl) -1-cyclopentanone (1.9 g; 9.8 mmol) and allyl N- (2-chloroethyl) carbamate (1.36 g; 9.8 mmol) and allyl N- (2-chloroethyl) carbamate (1.36 g; 9 mmol) gave allyl N- [2- [4- (2-oxo-1-cyclopentylmethyl) phenoxy] ethylcarbamate in 58% yield. Constants: IR spectrum: 3455, 1711, 1612, 1250 cm ^{@ -1} .

Example 26

3-buten-l-yl N- [2- [4- (3-methyl-2-oxo-cyclohexylmethyl) phenoxy]] - ethylcarbamate '(I, R ¹ = 0, R ² = CH _3, n = 2, R = (CH ₂ ) ₂ NHCOOCH ₂ CH ₂ CH = CH ₂ )

As described in Example 21, it was from 6-methyl-2- (4-hydroxybenzyl) -1-cyclohexanone (2.1 g; 9.8 mmol) and 3-buten-1-yl-N- (2-chloroethyl) carbamate. (1.47 g; 9 mmol) of 3-buten-1-yl N- [2- [4- (3-methyl-2-oxo-1-cyclohexylmethyl) -phenoxy]] -ethylcarbamate in 62% yield. Constants: IR spectrum: 3455, 1711, 1612, 1250 cm ^-1 .

Example 27

Methyl N- [2- [4- (3-methyl-2-hydroxy-cycloheptylmethyl) phenoxy]] propylcarbamate (I, ^{R1 =} H, OH, R ² = CH _3, n = 3, R = (CH _{2) 3} NHCOOCH ₃₎

Following the procedure described in Example 23, the methyl N- [2- [4- (3-methyl-2-oxo-1-cycloheptylmethyl) phenoxy]] propylcarbamate (3.1 g; 9 mmol) was obtained from the methyl N- [cis] isomer. 2- [4-3-methyl-2-hydroxy-1-cycloheptylmethyl) phenoxy]] propylcarbamate in 57% yield and the methyl N- [2- [4- (3-methyl-2-hydroxy-1-cycloheptylmethyl) trans isomer Phenylcarbamate in 18% yield yield. Constants: IR spectrum (cis isomer): 3630, 3465, 1246 cm -1 · ¹ ·; (trans isomer):

3625, 3465, 1243 cm ¹ .

Example 28

Propargyl N- [2- [4- (3-acetoxy-2-ethylenedioxy-1-cyclopentylmethyl) -phenoxy]] propyl carbamate (I, r ¹ = o (ch 2) ² 0, R ² = CH ³ COO, n = 1, R = (CH _{2) 3} nhcooch ₂ C = CH)

Following the procedure described in Example 22, propargyl N was obtained from propargyl N- [2- [4- (3-acetoxy-2-ethylenedioxy-1-cyclopentylmethyl) phenoxy]] propylcarbamate (3.2 g; 9.1 mmol). - [2- [4- (3-acetoxy-2 ethylene-2-ethylenedioxy-1-cyclopentylmethyl) phenoxy] propylcarbamate in 51% yield. Constants: IR spectrum: 3455, 1250 cm ^{@ -1} .

Example 29

Propargyl N- [2- [4- (3-hydroxy-2-oxo-cycloheptylmethyl) -phenoxy]] ethylcarbamate (I, R ¹ = 0, R ² = 0H, n = 3, R = (CH ₂ ) ₂ NHCOOOCH ₂ C = CH)

Following the procedure described in Example 21, starting from 7-hydroxy-2- (4-hydroxybenzyl) -1-cycloheptanone (2.52 g; 9.8 mmol) and propargyl N- [2- [4- (3-hydroxy- 2-oxo-1-cycloheptylmethyl) phenoxy]] ethylcarbamate in 45% yield. Constants: IR spectrum: 3455, 1711, 1612, 1250 cm ^-1 .

Example 30

N-Ethyl 2- [4- (2-oxo-1-cyclohexymethyl) phenoxy] methylcarbamate (I, R ¹ = O, R ² = H, n = 2, R = CH ₂ OCONHC. ₂ H ₅ )

Following the procedure described in Example 1, N-ethyl 2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] methylcarbamate was obtained from 2- (4-hydroxybenzyl) -1-cyclohexanone (25 mmol) in 51% yield. Constants: IR spectrum: 3458, 1731, 1714, 1615, 1245 cm @ ^-1 .

Example 31

Propargyl N- [2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] methylcarbamate (I, R ¹ = O, R = CH ₂ NHCOOOCHC = CH)

Following the procedure described in Example 21, propargyl N was obtained from 2- (4-hydroxybenzyl) 1-cyclohexanone (2 g; 9.7 mmol) and propargyl N- (2-chloromethyl) carbamate (1.36 g; 9 mmol). [2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] methylcarbamate in 60% yield. Constants: IR spectrum: 3455, 1711, 1612, 1250 cm ^{@ -1} .

-13GB 279674 B6

Example 32

N-Propargyl N-2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy] methyl urea (I, R ^F = H, OH, R ² = H, n = 3, R = CH ₂ NHCONHCH ₂ C = CH)

Following the procedure described in Example 6, N-propargyl N-2- [4- (2-hydroxy) was obtained from N. prpargyl N-2- [4- (2, oxo-1-cycloheptylmethyl) phenoxy] methyl urea (12 mmol). (1-cycloheptylmethyl) phenoxy] methyl urea in 85% yield. Constants: IR spectrum: 3614, 3446, 1665, 1649, 1611, 1243 cm ^-1 .

Example 33

N-Propargyl 2- [4- (2-propylenedioxy-1-cycloheptylmethyl) phenoxy] ethylcarbamate (I, R ¹ = O (CH 2) 3 O, R ² = H, n = 3, R = (CH 2) ₂ OCONHCH ₂ C = CH)

Following the procedure described in Example 2, N-propargyl 2- [4- (2-propylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl was obtained from N-propargyl 2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy] ethylcarbamate (10 mmol). carbamate in 91% yield. Constants: IR spectrum: 3459, 1730,

1613, 1245, 1156, 926 cm ^-1 .

Example 34

N-Propargyl N-2- [4- (2-propylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl urea (i, r ¹ = o (ch 2) 3 0, r ² = h, n = 3, r = (ch 2) ₂ nhconhch ₂ c = ch)

Following the procedure described in Example 5, N-propargyl N-2- [4- (2-oxo-1-cyclohephylmethyl) phenoxy] ethyl urea (10 mmol) was obtained from N-propargyl N-2- [4- (2-oxo-1-cyclohephylmethyl) phenoxy] ethyl urea. (propylenedioxy-1-cycloheptylmethyl) phenoxy] ethyl urea in 88% yield. Constants: IR: 3448, 3381, 1666, 1240, 1156, 924 cm ^1st

Example 35

The biologically active juvenoid of formula I (40 g) is dissolved in xylene (100 g). 28 g of oxyethylated olein surfactant is added to the solution. The mixture is stirred for 0.5 hour and then made up to 200 g of total weight with xylene. This provides a composition comprising 20 wt. biologically active substances of the general formula I.

Example 36

The biologically active juvenoid of formula I (40 g) is dissolved in vegetable oil (100 g). 28 g of oxyethylated olein surfactant is added to the solution. The mixture is stirred for 0.5 hour and then made up to 200 g of total weight with xylene.

-14GB 279674 B6

This provides a composition comprising 20 wt. biologically active substances of the general formula I.

Example 37

The biologically active juvenoid of formula I (40 g) is dissolved in xylene (100 g). To the solution is added 28 g) of an oxyethylated olein surfactant. The mixture is stirred for 0.5 hour and then made up to 200 g of total weight with xylene. This provides a composition comprising 20 wt. For application, the concentrated formulation is diluted with water (4 m ³ ) to give a formulation of 0.001 wt%. a biologically active substance of the general formula I which is applied by spraying, i.e. in a conventional manner for the treatment of agricultural crops with conventional insecticides, with the proviso that the term of treatment must be chosen such that the target population is affected during the predominantly sensitive developmental stage (e.g. in aphids it is the third larval instar). In this way, the composition can be used against aphids such as peach aphids (Myzus persicae) in greenhouses, potatoes, beets and other crops, poppy aphids (Aphis fabae) on beets, hop aphids (Phorodon humuli) on hops, as well as against the apple tree (Psylla mali) on apple trees, against the spotted apple tree (Psylla pyri) and the apple tree (Psylla pyricola) on pear trees and the like. The results are shown in Table 2.

Example 38

The biologically active juvenoid of formula I (40 g) is dissolved in N-methylpyrrolidone (60 g). 15 g of the condensation product of nonylphenol with ethylene oxide and 5 g of calcium dodecylbenzenesulfonate are added to the solution. The mixture is made up to 200 g of total diesel mass. This provides a composition comprising 20 wt. For application, the concentrated formulation is diluted with water (4 m ³ ) to give a formulation of 0.001 wt%. a biologically active substance of the formula I, which is applied by spraying as described in Example 37 and can be used in the same manner as the composition described in Example 37.

Example 39

A finely ground sample of the biologically active compound of the formula I (50 g) is mixed with sodium lignin sulphonic acid (5 g) and finely ground kaolin (45 g). Mix thoroughly. Before use, the composition is mixed in water (500 L) to form a mixture containing 0.01 wt. The active ingredient is spray-applied as described in Example 37 and can be used in the same manner as the composition described in Example 37.

-15GB 279674 B6

Example 40

A mixture of the biologically active juvenoid of formula I (50 g), sodium lignin sulphonate (25 g) and water (100 ml) is ground into a single dispersion in a bead mill. Ethylene glycol (5 g), a silicone defoamer (0.1 g) and formaldehyde (0.1 g of a 30% aqueous solution) were added to the ground dispersion. The mixture is made up to 200 g with water to give an aqueous dispersion containing 25 wt. Before use, the composition is mixed in water (2.5 m ³ ) to give a mixture containing 0.002% of the active ingredient, which is applied by spraying as described in Example 37 and can be used in the same manner. in the manner described in Example 37.

Example 41

To a solution of the biologically active juvenoid of formula I (0.05 g) in acetone, 2 drops of surfactant (higher fatty acid derivatives such as Tween 20-sorbitan monolaurate) were added, and the resulting mixture was dissolved in 30 ml of 1% alginate . The resulting solution was slowly dripped into 50 mL of a 1% aqueous calcium chloride solution so that the alginate granules formed were of a constant size. Then, the suspension of alginate granules is allowed to stand for 2 hours to adequately solidify the matrix. The alginate granules are separated from the aqueous solution by filtration through a sieve of suitable mesh size and washed with 50 ml of water. They can be kept either wet or dry (24 h at room temperature). The dried granules may be immersed in water and swelled for 24 hours before use. The alginate granules are applied by dusting or spreading on the litter in livestock buildings.

Example 42 ·

To a solution of the biologically active juvenoid of formula I (0.05 g) in acetone was added 2 drops of the surfactant, Tween 20, and the resulting mixture was dissolved in 30 ml of 2% pectate. The resulting solution was slowly dripped into 50 mL of a 1% aqueous calcium chloride solution so that the pectate granules formed were of a constant size. The pectate granule suspension is then allowed to stand for 2 hours to sufficiently consolidate the matrix. The pectate granules are separated from the aqueous solution by filtration through a sieve of suitable mesh size and washed with 50 ml of water. They can be kept either wet or dry (24 h at room temperature). The dried granules may be immersed in water and swelled for 24 hours before use. Pectate granules are applied by dusting or spreading on litter in livestock facilities.

Example 43

To a solution of the biologically active juvenoid of general formula I (0.1 g) in xylene was added a mass formed by finely crushing the polyamide fibers previously impregnated with epoxy resin (1 g). After stirring, the solvent was evaporated under reduced pressure

-16GB 279674 B6 ku. The resulting pulverulent mass contains 10 wt. The active substances of the formula I can be kept for at least two years. Application is by spraying or spreading in the litter in wet livestock buildings.

Example 44

To the loose form of the feed mixture (100 g), composed of proteins (50% by weight), sugars (25% by weight), binder (10% by weight) and fillers (15% by weight), was added finely ground biologically active juvenoid of formula I (2 g) and the resulting mixture was stirred for 1 hour on a roller mixer to homogenize it. Then, the binder components of the feed mixture were added in an amount such that their content in the resulting mixture was 20 wt%. and the resulting mixture was homogenized for 1 hour on a roller mixer. The composition may be stored for at least two years. The containers are filled with the means from which the individual of the insect that is the target of the intervention is ingested. They are particularly suitable for reducing the population density of cockroach insects.

Example 45

Methodology for testing a composition according to the invention for house flies:

Different concentrations of the composition of the invention in the form of a 20% emulsion concentrate were added to the samples of 50g calf litter calves weighing 0.5 g, or a sample of the composition using the polymeric carriers of the invention in an amount of 0.5 to 5 g. In part of the litter samples thus prepared, the larvae of the SRS / WHO domestic sensitive strain in the 3rd developmental stage were exposed immediately after their preparation, in other parts after 17, 31, 42 days. During this time, the water content of the bedding was kept at its original level and the bedding was kept at 22-25 ° C.

Example 46

Methodology for testing the composition of the invention on insects of the order Homoptera and Heteroptera:

One useful use of the composition according to the invention is its application in lures against difficult species of cockroaches, such as the Russian roach (Blatella germanica), the common cockroach (Blatta orientalis) and the American cockroach (Periplaneta amercana). Advantageously, a bait bait composition with an active compound concentration of 0.01-5% by weight can be used for these applications. As a rule, one bait is laid per 10 to 20 m ² , preferably in a larger amount, i.e. up to 50 to 100 g, for a considerable consumption of food by these insects when it is overgrown. The bait is placed in a suitable container, preferably in a box or bag, which is provided with suitable openings allowing the entry of harmful insects and preventing access to non-target organisms. The bait is replenished or renewed every 6 to 8 weeks, if cockroaches occur even for 1 year. Replacement is simple, absolutely does not contaminate or pollute the environment, as the vast majority has so far

-17GB 279674 B6 used equipment. In addition, a well-performed intervention, over a long period of application, results in the aradication of cockroaches at the treated site, while the predominant means have only temporarily reduced the cockroach alnudance, so the environment must be repeatedly burdened with health harmful substances with little effect on target organisms. Indication of a decrease in the population density of insects of the order Blattoidea using the composition according to the invention is very simple, since decreasing the amount thereof increases the time needed to rebuild the bait.

Example 47

Methodology for testing the composition of the invention for Isoptera insects:

In termites (Isoptera), the specialization of individual properties is expressed by the morphological adaptation of individual castes. The differentiation from the morphologically simplest stages of the larvae to the soldier's caste goes through a transitional period of development, the so-called white soldier. The regulating factor of this transformation is the natural phenomenon of juvenile hormone, whose effect can be imitated in laboratory tests or practical applications. by the action of juvenoid. The composition according to the invention in the form of a water-wettable concentrate, emulsion concentrate, aqueous dispersion or powder, containing 0.1 to 0.5% by weight of water. The biological active compounds of the formula I are applied by spraying on wooden objects attacked by the pest. If the wooden object allows it, it is advantageous to use all the possibilities of spraying into the cavities in the wood. Depending on the need and intensity of the pest infestation, it is necessary to repeat the spraying in the range of about 2 to 8 weeks, initially more often.

Example 48

Methodology for testing the composition of the invention for insects of the order Coleoptera:

The efficacy of the composition of the invention was tested by means of a residual spray test. In the case of phytophagous pests of the order Coleoptera, the undersides of the leaves of the test nutrient plant are sprayed with the composition according to the invention in the form of a concentrate, an emulsion concentrate, a water-wettable powder or an aqueous dispersion. The larvae of the above pests are tested on the treated leaves. In the case of storage pests of this order of insects, the composition of the invention should be applied to all suitable species of food serving as pests, as well as to all areas of their potential occurrence or hiding, e.g. , doors, windows, ceiling, around heat conduction and so on. The composition according to the invention in the above forms is applied by spraying, the spraying mixture preferably containing 0.1 to 2% by weight. The results are summarized in Table 3.

Example 49

Testing methodology for ovicidal efficacy:

The laboratory strains of the model pests, ie the Eastern Coater, Cydia molesta and the Marbled Coater, Lobesia botrana, were for

These tests were conducted on semisynthetic diets from standard conditions. The biologically active compounds of the formula I cause disorders and consequent inhibition of embryonic development in carnation eggs and reduce their hatching rate to varying degrees. In the selection tests for compounds of formula I, a residual spray test is used (see Proud and Kuld, IOCB / WPRS Bull. 4, 21-28 (1991)). Freshly prepared 0.1% acetone solutions of the compounds of the formula I emulsified with 0.1% Tween 2é in a volume of 1 ml are applied by spraying in a sedimentation tower by means of a nozzle: a) directly on eggs, laid on a microtene foil, max. or (b) a non-foil film on which an exception is allowed for 24 hours after treatment. Incubation of eggs treated with the compounds of formula I and control eggs treated with water only with an appropriate amount of solvent and emulsifier takes place at a stable temperature, preferably at 21 + 2 ° C, of approximately 59% relative humidity and a photoperiod of 16 h light / 8 h darkness. The biological activity of the compounds of formula I is read after 7 days according to the number of eggs hatched and dead and is expressed as a percentage of inhibited eggs with Abbott correction. The results are summarized in Table 1.

Table 1

Ovicidal activity of compounds of formula I on Eastern and Marbled wrappers compared to standard juvenoid

Species Eastern Wrapper % inhibitory insect Marbled wrapper my eggs% 0.1% 0.01% Substance (concentration) 0.1% 0.01 Ethyl N- [2- [4- (2-oxo-1-cyclopentylmethyl) phenoxy]] ethylcarbamate 91 43 94 46 cis-Ethyl N- [2- [4- (2-hydroxy-1-cyclopentylmethyl) phenoxy]] ethylcarbamate 74 60 82 55 trans-Ethyl N- [2- [4- (2-hydroxy-1-cyclopentylmethyl) phenoxy]] ethylcarbamate 79 13 85 13 Ethyl N- [2- [4- (2-ethylenedioxy-1-cyclopentylmethyl) phenoxy]] ethylcarbamate 82 48 91 82 Ethyl N- [2- [4- (2-oxo-1-cycloheptylmethyl) phenoxy]] ethylcarbamate 85 19 Dec 91 18 Ethyl N- [2- [4- (2-ethylenedioxy-1-cycloheptylmethyl) phenoxy]] ethylcarbamate 92 16 61 15 Dec cis-Ethyl N- [2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy]] ethylcarbamate 85 20 May 89 18 trans-Ethyl N- [2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy]] ethylcarbamate 80 12 92 12 methoprene (standard) 12 9 10 8

-19GB 279674 B6

Table 2

Activity of the compounds of formula I on aphids

Substance

Efficiency (IC 50)

Ethyl N- [2- [4- (2-ethylenedioxy-1-cyclopentylmethyl) phenoxy] ethylcarbamate cis-Ethyl N- [2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy]] ethylcarbamate trans-Ethyl N- [2- [4- (2-hydroxy-1-cycloheptylmethyl) phenoxy] ethylcarbamate

0.035> 0.1

0.07

Table 3

Efficacy of the compounds of formula I on mealworm

Substance

Efficiency (ID 50)

N-Ethyl 2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethylcarbamate

N-Ethyl 2- [4- (2-ethylenedioxy-1-cyclohexylmethyl) phenoxy] ethylcarbamate cis-N-Ethyl 2- [4- (2-hydroxy-1-cyclohexymethyl) phenoxy] ethylcarbamate trans-N-Ethyl 2- [4 - (2-hydroxy-1-cyclohexylmethyl) phenoxyethylcarbamate

N-Ethyl N-2- [4- (2-oxo-1-cyclohexylmethyl) phenoxy] ethyl urea

N-Ethyl N-2- [4- (2-ethylenedioxy-1-cyclohexylmethyl) phenoxy] ethyl urea

N-Ethyl N-2- [4- (2-hydroxy-1-cyclohexylmethyl) phenoxy] ethyl urea

Ethyl N- [2- [4- (3-methyl-2-oxo-1-cyclohexylmethyl) phenoxy] ethylcarbamate

Ethyl N- [2- [4- (3-methyl-2-ethylenedioxy-1-cyclohexylmethyl) phenoxy]] ethylcarbamate cis-Ethyl N- [2- [4- (3-methyl-2-hydroxy-1-cyclohexylmethyl)] phenoxy]] ethyl carbamate trans-Ethyl N- [2- [4- (3-methyl-2-hydroxy-1-cyclohexylmethyl) phenoxy]] ethyl carbamate methoprene (standard)

0.00005

0.000001

0.00001

0.00005

0.005

0.005

0.005

0.00001

0.000005

0.00002

0.00001

0.01

Industrial applicability

The substances according to the invention can be used for the protection of crop plants from insect pests and in the field of combating harmful insects in animal production or in the field of municipal hygiene.

Claims (5)

1. Carbamate and urea derivatives of the general formula I: OR (I) where n is an integer one to three, R ¹ is an oxygen atom, a hydroxyl group together with one hydrogen atom, or a group of the formula: -O- (CH ₂ ) _m -O-, in which m is an integer two or three, R ² is hydrogen, alkyl having a carbon number of one to three, hydroxyl group, an acetyl group or a tetrahydropyranyloxy group, R is a group of the formula: (ΟΗ ₉ ) -.- ΝΗΟΟΟ-Ρ ^{3 p} 8 wherein p is an integer of two or three and R is alkyl of one to four carbon atoms, alkenyl of two to four carbon atoms, or alkynyl of carbon atoms two to four, with the proviso that R ³ is not alkyl when n is an integer one or two, or a group of the formula: (CH _{2) p} -X-CONHR ⁴ in which p is as defined above and R ^4, or j or ^e carbon carbon carbon imino group. one to four, two to four, two to four, and is an alkyl having an alkenyl number having an alkynyl number having an oxygen atom number; or 2. A process for the preparation of a compound of the formula I, characterized in that the compound according to claim 1, characterized in that: OH (Π) Wherein R ¹ , R ² and ⁿ are as defined above, react with a compound of formula III: -Z- _(CH2) p-CO-R ³ (III) wherein R and p have the abovementioned meanings and Z represents a chlorine atom, a bromine atom or a p-toluenesulfonyloxy group. 3. A process according to claim 1 wherein the compound of formula (II): OH (Π) ί o _z in which R, R and n are as defined above, is reacted with a compound of formula IV: Z- (CH ₂ ) _p -X-CONHR ⁴ (IV) wherein R ⁴ , X, Z and p have the meanings given above. 4. An insecticidal insecticide composition comprising, as active ingredient, an insecticidally effective amount of a derivative of the formula I as defined in claim 1 and an inert carrier or diluent. Insecticidal composition according to claim 4, characterized in that it contains surfactants and / or an antifungal composition.