LU81394A1 - PROCESS FOR THE PREPARATION OF HETEROCYCLIC COMPOUNDS - Google Patents

Description

DESCRIPTIVE MEMORY

FILED IN SUPPORT OF A REQUEST FOR

.. 1st ADDITIONAL PATENT

PATENT

. N ° 78.718 of December 19, 1977

FORMED BY

THE WELLCOME FOUNDATION LIMITED for

Process for the preparation of heterocyclic compounds.

The present invention relates to imidazolines, their preparation and intermediate compounds for their preparation, the pesticidal compositions containing these imidazolines and their use as pesticides.

The Applicant has in fact discovered that the coipo-es of formula (I) below and their acid addition salts show activity against arthropods and in particular against mites.

Its subject is the compounds of formula: CD .MG .GP · 7 (2F) A JQb J (i)

CO - HH ^ - X

where X represents 0 or HH; and T represents Br, 3 ?, X, -ÎTC ^ r -0E, -CO2E, -CONR ^ R ^ on -002¾¾½. ^,

and, if X represents HH, T can also represent Cl, CH

or an alkyl radical of 1 to 4 carbon atoms, it being understood that R represents an alkyl radical of 1 to 18 carbon atoms and preferably of 1 to 4 or of 12 to 18 carbon atoms; and that 12 R and R, identical or different, each represent a hydrogen atom or an alkyl radical of 1 to 18 carbon atoms (preferably 1 to 4 or 12 to 18 carbon atoms, 1 o preferably only one of the symbols R and E representing a radical of '12 to 18 carbon atoms.

the preferred compounds of formula (I) correspond to the formula: CH, CH, \ 3/3 Γ — C H-

v y— x - ch2 —C

(la) CO - HH - ^ ^ - I1 where X has the meanings given to it above; and T * "represents R, Br,“ HO2, CH ^ O- or -002 ^ 2 ^ on, when X represents HH, 1 represents Cl.

Some of the compounds of formula (I) can exist in solvated form.

The preferred compounds of formula (I) are: 1- [N- (4-methoxyphenyl) carbamoyl] -2- (2,3-dimethylphenoxymé-thyl) -2-imidazoline; 1- [H- (4-chlorophenyl) carbamoyl] -2- (2,3-dimethyl anilinomethyl) -2-imidazoline; 1-DT- (4-bromophenyl) carbamoyl] -2- (2,3-dimethylphenoxymethyl) - 2-imidazoline; 1 a 1- DT- (4-nitrophenyl) carhamoyl] -2- (2,3-dimethylphenoxymethyl) - 2-imidazoline; 1- [ET- (4-fluorophenyl) carhamoyl] -2- (2,3-dimethylphenoxymé-thyl) -2-imidazoline; and 1 - [F- (4-br omophenyl) c arhamoyl] -2- (2,3-dimethylanilinomethyl) - 2-imidazoline.

The compounds of formula (I) and their acid addition salts 1 show activity against arthropods. The compounds of formula (I) are suitable for the fight against harmful organisms, such as the species Bhipicephalus appendicu-latus, Boophilus.decoloratus, Boophilus microplus, Ehipicepha-lus e've ^ tsi, Amblyomma hebraeum, Ps or optes ovis and Eyaloma on animals and Tetranychus on plants.

• The compounds of formula (I) have more stability in an aqueous medium than the known imidazolines.

The compounds of formula (i) can be prepared according to any known process for the synthesis of compounds of an analogous structure.

In particular, the compounds of formula (I) can be prepared from 2-substituted imidazolines of formula (II) or their acid addition salts: ♦ ch3 ch3 Σ - ca, - / C11)

H

where X has the meaning given to it above, either by a direct addition reaction with an isocyanate (leading to the N-substituted carbamoylated compound), or by a substitution reaction with a compound of formula: 1 / T ~ \ (III) xx -co. uh -y-i where T has the meaning given to it above and X1 represents an eliminable radical such as a halogen atom or an acyl, alkoxy (for example carbamates) or sulfonyl-oxy radical.

The reaction can optionally be carried out in water or an organic solvent such as chloroform or methylene chloride, preferably in the presence of a base, such as an alkali metal hydroxide, an alkali metal carbonate or a tertiary organic base. such as triethylamine, pyridine, a substituted pyridine or a substituted piperidine, for example pentamethylpiperidine or tetramethylpiperidine, and generally at a temperature of -70 to + 120 ° C and preferably from -10 to + 40 ° C .

The compounds of formula (I), in particular those whose radical:

-00H5- ^ T

is not strongly electrophilic, can be obtained by reaction of an ethylenediamine of formula (IV) or one of its salts: h2n.ch2cïï2m. co. 1 (iv) where Ύ has the meaning given to it above, with a 2, J-dimethylphenoxyalkylcarboxylic or 2,3-dimethyl-anilinoalkylcarboxylic acid, optionally in the form of a "reactive derivative such as an imidate, thioimidate, imidohalide, ester, amidine, thioamide, nitrile or cartoxyalkylthioamide These reagents have the formula:

Qfe ch5 f / (V) V y- x - ch2— q where X has the meaning given to it above and Q represents a carhoxyl radical or a corresponding reactive derivative leading to an imidazoline cycle of formula (I ) during i reaction with a compound of formula (IV).

Suitable derivatives are in particular:

0A1K

/ l -C (imidate) -C-OAlk (orthoester) \ l 011k 011k -C (thioimidate) -C (imidohalide) ^ .sm: ^ Hal

.0 ^ KH

^ S

—C '(ester) -C (amidine) ^^ OAlk ïfflg

S

S

-C (thioamide) -CsF (nitrile)

, S, L

^ 'S

-G '(N-alkoxycarbonylthioamide) and -0 (thio- \. Ester) XHHCOgAlk BAlk where "Alk" represents an alkyl radical of 1 to 6 carbon atoms and one of the symbols A and B represents S, while l other represents S or 0.

The conditions under which this reaction can be carried out obviously depend on the nature of the starting compounds and the operations can be carried out in the presence or in the absence of a liquid medium, at low or high temperature and under different pressures.

When the carboxylic acid derivative is an imi-date, this is preferably used in the form of an acid addition salt, such as a hydrochloride, and can be prepared from nitrile and a suitable anhydrous alkanol such as ethanol or methanol in the presence of diethyl ether f or dry chloroform and hydrogen chloride at low temperature. The reaction can be carried out at a temperature from -20 ° C to room temperature. The reaction with an ethylenediamine of formula (IV) can be carried out in an inert anhydrous medium, such as chloroform, methylene chloride or ether. The reactants are preferably heated to reflux until the reaction is complete.

The intermediate thioimidate, in the form of salt. acid addition can be prepared from the corresponding nitrile by reaction with an alkyl mercaptan and a hydrogen halide gas at low temperature, namely about 0 ° C, in the presence of dry diethyl ether. The thioimidate can then be reacted with an ethylenediamine of formula (IV), the reaction being carried out at the reflux temperature of the mixture.

The intermediate ester can advantageously be prepared from the corresponding acid according to known techniques and the acid itself can be prepared from the corresponding nitrile. The intermediate ester can then be reacted with an ethylenediamine of formula (IV), preferably in the presence of a liquid medium which can be polar or non-polar. The reaction is preferably carried out at an elevated temperature.

The compounds of formula (I) can be prepared from imidohalo garnies intermediates by reaction with an ethylenediamine of formula (IV) in an anhydrous medium, in the presence or not of an acid acceptor and optionally at an elevated temperature. The reaction mixture can comprise a polar or non-polar liquid medium such as a lower alkanol or an ether.

The intermediate amidine, in the form of the hase or of an acid addition salt, is preferably converted into a compound of formula (I) by heating under reflux with an ethylenediamine of formula (IV) in the presence of a polar or non-polar liquid medium, for example a lower alkanol, until the end of the evolution of ammonia. The intermediate amidine can itself be obtained according to any known but prior process. tagging from the corresponding imidate by reaction with ammonia.

The intermediate thioamide and amide can be prepared from the corresponding nitrile or by any other suitable process and converted into compounds of formula (I) by heating with an ethylenediamine of formula (IV) at reflux temperature or at a higher temperature. high, with or without a polar or non-polar solvent. Advantageously, the reactions are carried out partly under reduced pressure in order to initiate the release of ammonia and / or hydrogen sulfide from the reaction mixture.

The intermediate nitrile can be reacted, in the presence or not of a liquid medium, with an ethylenediamine of formula (XV), optionally in the form of a salt, the reaction being able to be carried out in the presence of hydrogen sulfide. A liquid medium such as a lower alkanol can be added to the reaction mixture which can be heated to reflux temperature or to a higher temperature in a closed container, optionally in the presence of an inert gas such as nitrogen.

It is obvious that, when the intermediate compound is the carboxylic acid, the ester or the thioamide, it is possible to isolate as intermediate compound an acylethylene diamine of formula; · CHX Cïïx w fil / v> - X - CH2 —G.

^ N-GHgGHÿSffik

CO * KH Y

where X and Y have the meanings given to them above and ¥ represents an oxygen or sulfur atom, and these compounds can themselves be converted in situ into compounds of formula (I), either by reaction distinct with a dehydrating agent such as calcium oxide, either by continuing the reaction until its completion under the initial conditions leading to a compound of formula (I).

The compounds of formula (I) can be prepared by reaction of a phenol or an amine of formula (VII), optionally in the form of an O-metallic or K-metallic derivative: CH, CH, γ_ / 5 / \ -Σ-Η (VII) where X has the meaning given to it in formula (I), with a compound of formula: / Λ V-CHp —r VI (wine) H y-, cokh where Y a the meaning which has been given to it in formula (I) and V represents a removable radical originating from an appropriate inorganic or organic acid. Suitable derivatives are those comprising a halogen atom, such as a chlorine, bromine or iodine atom, an alkylsulfonyloxy radical or an arylsulfonylcKy radical such as a p-toluenesulf onyloxy radical.

The compounds of formula (VIII) can be used in the form of their bases or their acid addition salts. The reaction is carried out in an inert liquid medium, which is preferably a polar liquid such as acetonitrile or isopropanol or which may be dimethyl sulfoxide, sul-folane, methyl ethyl ketone, dimethylformamide, acetone, dimethyl acetamide , F-methyl-2-pyrrolidone or a mixture of these compounds. When V represents a chlorine atom in a compound of formula (VIII), a small catalytic amount of a saline iodide such as sodium iodide, or of a phase transfer catalyst, such as a quaternary ammonium salt such that benzyltrimethylammonium chloride, can be added with advantage to the reaction mixture. The reactants can be heated in an inert atmosphere, for example nitrogen, to the reflux temperature of the reaction mixture.

The compounds of formula (I) can also be prepared by reaction of a compound of formula:

0 P

where X has the meaning given to it above and P represents an eliminable radical (such as a halogen atom or an acyl, alkoxy, alkylthio, S-, SH, sulfonyloxy or carbalkoxy radical), with an appropriate active amine of formula: t where ï has the meaning given to it in formula (I).

The compounds of formula (I) can be isolated from the mixture of. reaction in the form of a free base or in the form of an acid addition salt. The bases can be converted to acid addition salts according to known techniques using suitable acids and the salts can be converted to free bases or other acid addition salts.

For use as pesticides, the compounds of formula (I) can be presented in the form of their acid addition salts or preferably of their free bases. Suitable salts of formula (I) are in particular the hydrochlorides, the sulfates, the nitrates, the phosphates, the thiocyanates, the acetates, the propionates, the stearates, the naphthenates, the perchlorates, the benzoates, the methanesulfonates, the ethane-sulfonates , p-toluenesulfonates and benzenesulfonates.

The compounds of formula (I) can be used to combat insects, ticks, mites and other arthropods, in particular those living in the independent state and those living in the state of ectoparasites of plants, mammals and birds, and can be used alone or in combination with an additive, which may comprise one or more vehicles used for the composition, such as wetting agents, diluents, stabilizers, thickeners, emulsifiers, dispersants or surfactants and other vehicles. currents.

A composition can be an aqueous solution of an acid addition salt of a compound of formula (I) or a suspension of a compound of formula (i) in water and can be used alone or in combination combination with suitable surfactants. The composition as such can be used alone or diluted in water for application to harmful organisms or their immediate environment by spraying or immersion. *

A composition may be in the form of a miscible oil comprising a compound of formula (I) in the free base state or with an equimolar amount of a suitable organic acid, such as oleic or naphthenic acid, for the formation of 'a salt soluble in organic solvents, in addition to emulsifiers and can be applied in the emulsion state by spraying or immersion.

A composition may be a non-aqueous solution or suspension of a compound of formula (I) in an organic solvent allowing direct application by spreading. A composition can also take the form of a wettable powder to be diluted with water for application by spraying or. immersion. Other solid compositions are also suitable for direct application without dilution, as there are powders, powders and granules.

Another composition may be a paste, a fat or a gel comprising a compound of formula (I) in a vehicle suitable for application by spreading to infested areas.

An acid addition salt of a compound of formula (I) or the latter in the base state is preferably contained in a pesticidal composition in an amount of 5 to 80%, to be calculated by weight of base, a particularly preferred composition containing approximately 20% of compound, to be calculated by base weight. The concentration of a compound of formula (I) applied to harmful organisms or in their immediate environment can be from 0.001 to 20%, to be calculated by basic weight.

The invention therefore has as a non-limiting object: (a) a new 2,3-dimethylphenoxyalkylimidazoline or 2,3-dimethylanilinoalhylimidazoline of formula (I), optionally in the form of acid addition salt; (b) a process for preparing a new compound of formula (I) and its acid addition salts; (c) a process for combating harmful arthropods and in particular against mites, by applying a compound of formula (i) to them or to their environment; (d) a pesticidal composition comprising a compound of formula (I) and a vehicle; (e) a process for preparing such a composition by mixing a vehicle with a compound of formula (I); and (f) a new intermediate compound formed during the preparation of the imidazolines.

The invention is further illustrated without being limited by the following examples.

EXAMPLE 1.- 1- [U- (4-Chloro-phenyl) carbamoyl 1-2- (2,5-dimethylanilinomethyl) - 2-imidazoline

4.20 g (0.024 mole) of 2- (2,3-dimethylanilinomethyl) -2-imidazoline are incorporated by stirring into 90 ml of methylene chloride cooled to 0 ° 0, then a solution of 3 is added dropwise , 66 g (0.024 mole) of 4-chlorophenyl isocyanate in 10 ml of methylene chloride. A white precipitate forms quickly. Stirring is continued for 2 to 3 hours after the addition at 0 ° 0, then the reaction mixture is allowed to warm to room temperature and stirring is continued overnight. The reaction mixture is then evaporated to dryness under reduced pressure, then the resulting solid residue is recrystallized from 2-propanol to obtain "white crystals of 1- [E- (4-chlorophenyl) car-hamoyl] -2- ( 2,3-methylanilinomethyl) -2-imidazoline melting at * 153-155 ° C.

EXAMPLES 2 TO 6.-

By operating as in Example 1, the compounds of Examples 2 to 6 below are also prepared.

EXAMPLE 2, 1- 1- CU- (4-Bromophenyl.) Carbamoyl] -2- (2,3-dimethylphé-noxymethyl) -2-imidazoline monohydrate melting at 150-151 ° C ("white powder").

EXAMPLE 3 1 - [1T— (4-Methoxyphenyl) carbamoyl] -2- (2,3-dimethyl-phenoxymethyl) -2-imidazoline melting at 126-127 ° C (white powder).

EXAMPLE 4 - 1 - [N— (4-Litrophenyl) carbamoyl] -2- (2,3-dimethylphé-noxyméthyl) -2-imidazoline monohydrate melting at 182-185 ° C (pale yellow powder).

EXAMPLE 5. 1- 1- [Η- (4-Carbethoxyphenyl) carbamoyl] -2- (2,3-dimethyl-phenoxymethyl) -2-imidazoline melting at 153 ° C (powder t> lanche). EXAMPLE 6 1- 1- [ST- (4-Fluorophenyl) c arbamoyl] -2- (2,3-dimethylphé-noxyméthyl) -2-imidazoline containing about 5% of impurities and melting at 172-173 ° G.

EXAMPLE 7, - A. Preparation of 1- [IT- (4-bromophenyl) carbamoyl] -2- (2,3-dimethylphenoxymethyl) -2-imida zolin e> A solution of 20 is cooled to -65 ° 0, 4 g (0.1 mol) of 2- (2,3-dimethylpheno2çymethyl) -2-imidazoline in 300 ml of methylene chloride and a solution of 19.8 g (0, 1 mol) of 4-bromophenyl isocyanate in 300 ml of methylene chloride. The reaction mixture is then allowed to warm to room temperature, then allowed to stand for 2 hours at the end of which a precipitate has formed. The reaction mixture is evaporated under reduced pressure and the residue is recrystallized from acetone to obtain l- [ÏT- (4-bromophenyl) -carbamoylJ-2- (2,3-dimethylphenoxymethyl) -2-imidazoline monohy-dreate melting at 150-151 ° C.

B. Preparation ^ via the adduct P- chlorocarbamoylated of 2- (2,3-dimethylphenoxymethyl-2-imidazoline

3.2 g of a 17% toluene solution containing phosgene (containing 0.5521 g or 0.00549 mole of C0Cl2) is added slowly with stirring at 0 ° C. in a mixture with 15 ml of chloroform at one; * solution of 2.40 g (0.0115 mole) of 2- (2,3-dimethylphenoxymethyl) -; imidazoline in 20 ml of dry chloroform. At the end of the addition, the reaction mixture is left to stand at room temperature for 2 hours, then it is diluted with an equal volume of dry diethyl ether and the mixture is quickly filtered.

1.22 g (0.00714 mole) of freshly distilled dry 4-bromo aniline are added to the filtrate which contains the 2- (2,3-dimethylphenoxymethyl) -2-imidazoline ÜT-chlorocarba-mead adduct. and the mixture is left to stand at ambient temperature overnight, at the end of which the thin layer chromatography indicates that the main compound is the desired product. The mixture is evaporated to dryness under vacuum and the residue is taken up in a mixture of aqueous sodium carbonate and dichloromethane. The organic layer is washed with water, dried over magnesium sulfate and evaporated to dryness to obtain a residue which is purified, as described in (A) above, to collect lai- [IT - (4-bromo-phenyl) carbamoyl] -2- (2,3-dimethylphenoxymethyl) -2-imidazoline identical to the compound prepared in (A) above.

EMPIIES 8 TO 10.- 1 Eh operating as in Example 1, the following compounds are prepared: 1- [ΓΓ- (4-methylphenyl) carbamoyl] -2- (2,3-dimethylanilinomé-thyl) -2- imidazoline melting at 154-155 ° C; 1- DT- (4-cyanophenyl) carbamoyl] -2- (2,3-dimethylanilinomethyl) - 2-imidazoline; and 1- Dr- (4-bromophenyl) carbamoyl] -2- (2,3-dimethylanilinomethyl) - 2-imidazoline melting at 161.6-162.2 ° 0.

EXAMPLE 11, -

Female ticks engorged with the Biarra Boophilus microplus strain are immersed, in groups of 20 per concentration, in different dilutions of the compound to be examined. The bath is prepared immediately before the test by diluting the compound to be examined in water. The constituents can be in the form of miscible oil or wettable powder. The desired concentration range is established by further diluting the solution, mother.

We remove the ticks from the tin after 10 minutes, dry them and glue them back down "on double-sided adhesive paper. We keep them in this position for 14 days at the end of which we determine the number of animals Laying viable eggs. Based on the results, the regression curve is plotted (concentration as a function of percentage of inhibition of lay) and the inhibitory concentration of lay CI99 is determined at which lay is inhibited for $ 99.

The results obtained are collated in Table I.

TABLE I

Compound Example CI99. ______; __ n ° __ 1- [U- (4-Chlorophenyl) c arbamoyl] -2- (2,3- 1 0.029% (dimethylanilinomethyl) -2-imidazoline l- [iT- (4-Bromophenyl) carbamoyl] -2 - (2,3- 2 0.0095% dimethylphenoxymethyl) -2-imidazoline l- [U- (4-Methoxyphenyl) carbamoyl] -2- (2,3- 5 0.0038% dimethylphenoxymethyl) -2-imidazoline l- [U- (4 ~ Uitrophenyl) carbamoyl] -2- (2,3 ~ di- 4 0.010% methylphenoxymethyl) -2-imidazoline hydrated 1- [U- (4-Carb ethoxyphenyl) carbamoyl-2- 0.019% (2 , 3-dimethylphenoxymethyl) -2- imidazoline______.

Example 12

By operating as in Example 1, but without recrystallization, the l- £ N- (4-aimethylsulfonamidophenyl) carba-moyl | -2- (2,3-dimethylamilinomethyl) -2-imidazoline is prepared, melting at 151- 153ÛC.

The following compositions illustrate how the pesticidal compounds of the invention can be applied to pests or to areas likely to be at risk of these ores.

Composition 1 Powder casks

Constituent Parts, by weight

Active agent 1.0 20.0% 99.0 80.0 100.0 100.0

Composition 2 Wet powder

Constituent parts by weight

Active agent 25.0

Sodium dioctylsulfosuccinate 1.0

Dispersol ACA 2.0

Kaolin 72.0 100.0

Composition 5 Aqueous dispersion * Constituent Parts by weight

Active agent 20.0

Keltrol 0.4

Sodium dioctylsulfosuccinate 0.5

Water 79.1 100.0

Composition 4-Composition to be poured - Constituent Parts by weight

Active Agent 5.0

Dimethylformamids 85.0

Castor oil 1Q, Q

100.0

Composition 5 Fat

Constituent parts by weight

Active agent 6.0

Vaseline 94-, 0 100.0

Composition 6 Miscible oil

Constituent parts by weight

Compound of Example 3 10.0

Aromasol H 70.0

Ethylylation product of nonylpienol 20.0 100.0

Stability

The compound of Example 1 has a half-life greater than 6 months in an aqueous medium at pH 7d while the half-life of 1 2- (2,3-dimethylpHénoxy) -2-imidazoliiie is approximately 2 weeks .

9

Claims (29)

1, - Compound of formula: ch5 ch5 Ο-χ- ^ ν'Ί X- 'r (D 1 _ / ~ V CO-NH-V y — Y where X represents 0 or M; and Y represents Br, E, I, '- NO2, -OR, -C02R, -C0NR1R2 or -S02NRLR2 or when Y represents Ni, Y can also represent Cl, CN or an alkyl radical of 1 to V carbon atoms, it being understood that R represents an alkyl radical of 1 to 18 carbon atoms and 1 2 R and R, identical or different, each represent a hydrogen atom or an alkyl radical of 1 to 18 carbon atoms, optionally in the form of addition salt d 'acid. 2. A compound according to claim 2, in the formula of which Y represents -OR or -C02R, it being understood that R represents an alkyl radical of 1 to 4- or 12 to 18 carbon atoms. 3 · - Compound according to claim 1 in the formula 12 12 of which Y represents a radical -CONR R or -SO2NR R, it being understood that R and R, identical or different, each represent a hydrogen atom or an alkyl radical from 1 to 4 or from 12 to 18 carbon atoms. 4 -.- Compound according to claim 3, in form- ’12 ,. mule of which only one of the symbols R and R represents an alkyl radical of 12 to 18 carbon atoms. 5 · - Compound according to claim 1 of formula: H- χ - ^ / ί \ = J \ J (la) NI / ~ "V 1 CO” HH - (ΓΤ- pù X represents 0 or i and Y "** represents F, Br, -NC ^, CH ^ O- or - ^ 202 ^ or X represents MH and Y "* · represents Cl, optionally in the form of an acid addition salt. 6.- Compound chosen from l-Dl- (4-methoxyphenyl) -carbamoyl] -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, 1- [F- (4-Hchlorophenyl) carbamoyl] -2- (2,3-dimethylanilinomethyl) - 2- imidazoline, 1- [H- (4-br omophenyl) carbamoyl] -2- (2,3-dimé-thylphenoxymethyl) -2-imidazoline, 1- [H- ( 4 ~ nitr ophenyl) carba-moyl] -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, l- [M- (4 ~ f luorophenyl) carhamoyl] -2- (2,3-dimethylphenoxymethyl) -2 -imidazoline and 1- [H- (4-'bromophenyl) carhamoyl] -2- (2,3-dimethylanilinomethyl) -2-imidazoline, optionally in the form of acid addition salt. 7- - 1- [F- (4-chlorophenyl) carhamoyl] -2- (2,3-dimethylanilinomethyl) -2-imidazoline, optionally in the form of an acid addition salt. 8- - 1- [H- (4 ~ chlorophenyl) carbamoyl] -2- (2,3-dimethylanilinomethyl) -2-imidazoline. 9.- Process for the preparation of a compound according to any one of Claims 1 to 8, characterized in that: (a) a compound of formula: CH, CHX 3 / \ CX —CHp - is reacted ( '(II) ^ VH where X has the meaning given to it in claim 1, or one of its acid addition salts, with an iso-cyanate or with a compound of formula: X ^ CO. m— ^ Y (III) where Y has the meaning given to it in claim 1 and represents an eliminative radical; I. ·· (Td) a compound of formula is reacted: where Y has the meaning which has was given in claim 1, or a salt thereof with a compound of formula: ch5 CH5 \ ^ ~ X 0H2 'Q (T) a where X has the meaning given to it in claim 1 and Q represents a radical carboxyl or a corresponding reactive derivative; Cïïx GH, u \ 3/3 W ri 7 </ - X - Gïïp - 0 v V = l / 'N-GH2GH2M2 (71) co * my where X and Y have the meanings which their were given in claim 1 e t ¥ represents an oxygen or sulfur atom; (d) · reacting a phenol or an amine of formula: Ö-1- or a corresponding O-metallic or H-metallic derivative, where X 1 with the meaning given to it in claim 1, with a compound of formula: V ~ CH2 - (/ \ J (VIII) corn - ^ y where Y has the meaning given to it in claim 1 and Y represents an eliminin radical radical derived from an inorganic or organic acid, or m of its acid addition salts; (e) a compound of the formula: “· * CH, GH, H., .. * - / ï ^ (32) Ox NP where I has the meaning which has it reacted was given in claim 1 and P represents an eliminable radical, with an amine of, formula: Ό where T has the meaning which was given to it in claim 1,! then, if desired, a compound of formula is converted (I) into an acid addition salt or an acid addition salt of a compound of formula (I) is converted into the free base or into another acid addition salt. 10. Pesticide composition, characterized in that it comprises a compound according to any one of claims 1 to 8 in · association with a vehicle. 11. Composition according to claim 10, characterized in that the vehicle is a surfactant. · 12. Composition according to claim 10, characterized in that the vehicle is a liquid. 13. Composition according to claim 12, characterized in that the vehicle is a suspending agent. 14 -.- Composition according to any one of the res · i * -, ^ N n -7 _____ r *. _ ___ ___L £ ____ the. form of aqueous solution or suspension, miscible oil, non-aqueous solution or suspension, paste, grease, gel, wettable powder, powder, powder or granules. 15. Composition according to any one of claims 10 to 14, characterized in that it comprises 5 to 80% of the compound according to claims 1 to 9? to be calculated as free base weight. 16. Composition according to any one of the res-. Dications 10 to 15, characterized in that it comprises 1- [ÏT- (4-chlorophenyl) carbamoyl] -2- (2,5 -dimethylanïlinomêtiiyl) - 2-imidazoline. 17. Composition according to claim 16, characterized in that it is presented in the form of a wettable powder. 18. Composition according to Claim 16, characterized in that it is presented in the form of a miscible oil. 19. Method for combating harmful arthropods, characterized in that a compound according to any one of claims 1 to 8 is applied to these arthropods or to their environment. 20. Method according to claim 19, characterized in that the harmful organisms are mites. 21. The method of claim 19 or 20, characterized in that the harmful organisms are ectoparasites of mammals or birds. 22. Method according to any one of the claims 19 to 21, characterized in that the compound is applied by spraying, dusting or immersion. 23. A method according to any one of claims 1 · ^ Λ \ ΛΛ. y. / _ ... φ applied to harmful organisms or their environment is 0.001 to 20%, to be calculated as free base weight. 24, - Method according to any one of claims 19 to 23, characterized in that the compound is 1- [E- (4-chlorophenyl) carbamoyl] -2- (2,3-dimethylanilinomethyl) - 2-imidazoline. 25. A method of preparing a composition according to any one of claims 10 to 18, characterized in that a compound according to any one of claims 1 to 8 is mixed with a vehicle. ♦ 26. A compound according to claim 1, prepared in any one of examples 1 to 10. 27. The method of claim 9 in essence as described in any of Examples 1 to 10. 28. A compound according to claim 1, prepared by the process according to claim 9 or 27. 29. Composition according to any one of claims 10 to 18, in substance as described above with reference to any one of compositions 1 to 6. "♦