SE444563B - IMIDAZOLINE DERIVATIVES FOR USE AS INSECTICID OR ACARICID - Google Patents

Description

X 1 is O or NH; VV R 1 and R 2 are the same or different and are hydrogen or (C 1-4) -alkyl; _% ¿ÇX2_ and Z are a group SOZR8 or a group -C. where X 2 is O - R 3 V 'or S; R 3 is (C 1-4) -alkyl, (C 1-4) -alkyloxy, phenoxy optionally substituted by one or more C 1-4 alkyl or NR, R 5 and R 6 are the same or different and are hydrogen, (C 1-4) - alkyl, naphthyl or phenyl optionally substituted with one or more substituents selected from halogen, cyano and C 1-4 alkyl or SO 2 R 2; in R 7 is naphthyl or phenyl which is substituted by one or more substituents selected from halogen, cyano and C 1-4 alkyl; R 8 is (C 1-4) alkyl or naphthyl or phenyl optionally substituted with one or more substituents selected from halogen, cyano and C 1-4 alkyl; V, wherein, when Ar is unsubstituted phenyl, R 1 and R 2 are H; X2 X1 is NH, Z is -C¿%; and X 2 is O, and R B is non-methyl.

R3 I in I formula (I) includes halogen chlorine, bromine and fluorine.

Certain compounds of formula (I) may exist in their solvated forms. The group Ar in formula (I) is preferably unsubstituted or has substituents selected from (C 1-4) alkyl- (preferably methyl) and / or halogen (preferably chloro) groups. As used herein, the term "aryl" includes phenyl or naphthyl either unsubstituted or substituted with one or more substituents, wherein the substituent or substituents are the same or different and are preferably selected from (C 1-4) -alkyl, (C 1-4) -alkoxy, halogen , and cyan. Preferred compounds of formula (I) include those therein: (a) Ar is phenyl or 2,3-dimethylphenyl; and or . x ~ _ - ~ (b) Z is -Cáfá where X2 is O or S and R3 is NRSR6.

Particularly preferred compounds of formula (I) are: 1-N-phenylcarbamoyl-2H (2,3-dimethylphenonimethyl) -2-imidazoline; 1-NF (granaphthyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -1-imidazoline; 1-N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline; and in . o 1-N- (4-cyanophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline.

The compounds of formula (I) and their acid addition salts (have activity against Artropoda, in particular against those of the order Acarina. The compounds of formula (I) can be used to control pests such as Rhipicephalus appendiculatüs, Boophilus decoloratus, Boophilus microplus, Rhipicephalus evertsi hebraeum, Psoroptes ovis and Hyaloma species on animals and Tetranychns species on plants.

The compounds of formula (I) may be prepared in any known manner for the preparation of compounds having an analogous structure.

The compounds of formula (I) may in particular be prepared from 2-substituted imidazolines of formula (II) or an acid di- * f N 1 - fl- xl- - ((II) _ * I2 N »U,. Ar, X 1, R 1 and R 2 are the same as defined above, either by a direct addition reaction with an isocyanate or isothiocyanate (to give a compound of formula (I) in which Z is an N-substituted carbamoyl or thiocarbamoyl group); a chain (to give a compound of formula (I) in which Z is an acyl group) or by a substitution reaction with a compound of formula (III): oz-x '1' (111) wherein Z is the same as defined above and X 'is a leaving group such as halogen (eg in acid chlorides or haloformate esters), acyl (eg in acid anhydrides), acyloxy or alkylthio (eg carbamates, imidates, thiocarbamates or thioimidates) or sulfonyloxy (eg in mixed anhydrides). 'AA' In a particular application of the above substitution reaction, compounds of fo The formula (I) in which Z is a thio-A carbamoyl group is prepared by the reaction between a compound of formula (II) and a compound of formula (III) in which Z is a thiocarbamoyl group and X 'is NH 2 (ie Z = X' is a thiourea).

The reaction may 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, and an alkali metal carbonate or a tertiary organic base such as triethylamine, pyridine or substituted pyridines or piperidines, t ex pentamethylpiperidine or tetramethylpiperidine; and usually at temperatures of -70 ° C to 120 ° C, preferably at temperatures of: -1o ° C to 40 ° C. in which Ar, X f is a carboxyl group or a reactive derivative thereof to give Compounds of formula (I), especially those where Z is not one. strong electron withdrawing group, can be prepared by an ethylenediamine of formula (IV) or salt thereof; H 2 N; CH 2 CH 2 NH.Z (IV), in which Z is the same as defined above, is reacted with a suitable phenoxyalkyl or anilinoalkylcarboxylic acid or a reactive derivative thereof such as imidate, thioimidate, imidohalide, ester, amidine, thioamide, nitrile or carboxyalkylthio. These reactants may conveniently be represented by the formula (V): R 1 Ar-X 1 -C Q R 2 - (V) 11 2, R 1 and R 2 are the same as defined above and the Q imidazoline ring structure of formula (I) when reacted with a Compound of Formula (IV): Suitable Derivative Wine Concepts 11144u1 ~ 9 now in H- »" i 'I onik 444 _ V- -C (imidate), -C-0Alk (orthoester), v. il \ oA1k - A ozuk NH. NH _ _ -Câøá l (thioimidate), -Cááá (imidohalide) | \ sA1k i \ 1 ~ ra1 _ / NH -C (ester), -C (amidine), _ \ oA1k '. -NHZ S _ -Câøá - ( thioamide), -C 2 N (nitrile), and NH 4 -C 44 (carboxyalkylthioamide) NHCO 2 Alk where "Alk" is an alkyl group having 1-6 carbon atoms; The conditions under which this reaction can be carried out depend, of course, on the nature of the starting materials used, and a liquid medium may be either present or absent; high and low temperatures can be used and different pressures can be used.

When the carboxylic acid derivative is an imidate, it is preferably in the form of an acid addition salt such as a hydrogen halide salt, and it can be prepared from the nitrile and a suitable anhydrous alkanol such as ethanol or methanol in the presence of dry diethyl ether or chloroform and hydrogen chloride at a low temperature. The reaction can be carried out at a temperature in the range of -ZQQC to ambient temperature. The reactions. with an ethylenediamine of formula (IV) is carried out in an inert, anhydrous V medium such as chloroform methylene chloride or ether. The reactants are preferably heated under reflux until the reaction is complete.

The thioimidate intermediates in the form of acid addition salts can be prepared from the corresponding nitrile by reaction with an alkyl mercaptan and a hydrogen halide gas at low temperatures of about 0 ° C in the presence of dry diethyl ether. The thioimidate can then be reacted with an ethylenediamine of formula (IV). wherein the reaction is carried out at the reflux temperature of the reaction mixture. The ester intermediates can be conveniently prepared from the corresponding acid by known methods, and the acid itself can be prepared from the corresponding nitrile. They can then be reacted with an ethylenediamine of formula (IV), preferably in the presence of a liquid medium which may be polar or non-polar. The reaction is preferably carried out at an elevated temperature. The compounds of formula (I) may be prepared from the imidohalide intermediates by reaction with an ethylenediamine of formula (IV), under anhydrous conditions in the presence or absence of an acid acceptor and optionally at an elevated temperature.

The reaction mixture may comprise a polar or non-polar liquid medium such as a lower alkanol or an ether.

The amidine intermediate in the form of the base or the acid addition salt thereof 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 evolution of ammonia ceases. The amidine intermediates themselves can be prepared by known methods, but conveniently from the corresponding imidates by reaction with ammonia.

The thioamide and amide intermediates can be prepared from the corresponding nitriles or by any other suitable method and they can be converted to compounds of formula (I) by heating with an ethylenediamine of formula (IV) at reflux temperature or higher * temperature in the presence or absence of a polar or non-polar solvent. Conveniently, the reactions are performed in part under reduced pressure to induce the removal of ammonia and / or hydrogen sulfide from the reaction mixture. The nitrile intermediates are reacted in the presence or absence of a liquid medium having an ethylenediamine of formula (IV) or a salt thereof. The reaction can be carried out in the presence of hydrogen sulfide. A liquid medium such as a lower alkanol may be included in the reaction mixture which may be heated to reflux temperature or to a higher temperature in a closed vessel, optionally in the presence of an inert gas such as nitrogen.

It is well known that when the intermediate is the carboxylic acid, ester or thioimide, the acylethylenediamines of formula (VI) can be isolated as an intermediate: Ar-X1-ï-c / âááå (VI) R2 \\\ Z in which Ar, X1, R1, R2 and Z are the same as defined above and 2 W is oxygen or sulfur and these compounds themselves can be converted in situ to a compound of formula (I), either by separately treating them with a dehydrating agent such as calcium oxide or continuing the reaction to completion under the initial conditions which give a compound of formula (I). The compounds of formula (I) may be prepared by bringing a phenol or amine of formula (VII) or an O- or N-metal compound thereof; Ar-x1-H (v11) in which Ar and X1 are the same as defined for formula (I) to react with a compound of formula (VIII): 2 T / "j vc - (VIII) JSM II in which R1, R2 and Z is the same as defined for formula (I) Kap -_... and V is a leaving group derived from a suitable inorganic or organic acid. Suitable derivatives are halogen, such as chlorine, iodine or bromine, alkylsulfonyloxy or arylsulfonyloxy such as p-toluenesulfonyloxy.

The compounds of formula (VIII) may be in the form of their bases or acid addition salts thereof. The reaction is carried out in an inert liquid medium, which is preferably a polar liquid such as acetonitrile or isopropanol, or may be dimethylsulfoxide, sulfolane, methylethylketone, dimethylformamide, acetone, dimethylacetamide, N-methyl-2-pyrrolidone or mixtures thereof; In the case where V is chlorine in a compound of formula (VIII), a small catalytic amount of an iodine salt, for example sodium iodide or a phase conversion catalyst such as a quaternary ammonium salt, for example benzyltrimethylammonium chloride, may be suitably included in the reaction mixture. - ningen. The reactants can be heated together under an inert gas atmosphere, such as nitrogen, at the reflux temperature of the reaction mixture.

X2 4%? and R 3 R 5 is C 1-4 alkoxy, phenoxy optionally substituted with one or more C 1-4 alkyl or NRSRS can also be prepared by a compound of formula (IX): The compounds of formula (I) in which Z is C k) 'Ar ~ X - (IX) »= É * - g,') ---_“ ns o-4; ¿¿/>? in which Ar, X1, X2, R1 and R2 are the same as defined above and Y is a leaving group (such as halogen, acyl, alkoxy, alkylthio, S2, SH, sulfonyloxy or carbalkoxy) is reacted with a suitable active hydrogen -containing compound of formula (X): stool-H V (x) in which R 11 is the same as above for R 3.

The compounds of formula (I) may be isolated from the reaction mixture as the free base or in the form of an acid addition salt.

The bases can be converted to acid addition salts thereof by known techniques using the appropriate acid, and salts of the compound can also be converted to the free bases or to other acid addition salts. For use as a pesticide, the compounds of formula (I) may be presented in the form of their free bases or as acid addition salts thereof. Suitable salts of formula (I) include hydrogen halide, sulfate, nitrate, phosphate, thiocyanate, acetate, propionate, stearate, naphthenate, perchlorate, benzoate, methanesulfonate, ethane. sulfonate, eosylate and benzenesulfonate acid addition salts thereof.

The compounds of formula (I) may be used to control insects, ticks, mites and other arthropods including free-living arthropods and those which are ectoparasites of plants, mammals and birds and may be used alone or in combination with an «additive, which may be in in the form of one or more of the carriers known in the art of preparation, such as: wetting agents, diluents, stabilizers, thickeners, emulsifiers, dispersants or surfactants or other standard carrier ingredients.

A formulation may be an aqueous solution of an acid addition salt, a compound of formula (I) in water, and may be used alone or in combination with suitable surfactants. The preparation per se can be used alone or diluted in water for application to the pests - or their immediate surroundings by spraying or dipping.

A preparation may be in the form of a miscible oil comprising a compound of formula (I) in the form of its free base or with an equimolar amount of a suitable organic acid such as oleic acid or naphthenic acid to provide a salt which is soluble in organic solvents, and emulsifiers, and applied as an emulsion by spraying or dipping. A formulation may be a non-aqueous solution or suspension of a compound of formula (II) in a suitable organic solvent for direct application by means of a wettable powder for dilution with water and application by dipping or spraying. Other solid formulations. can also be used for direct application without dilution, such as dust, powder and granules.V An additional preparation may be a paste, a fat or, a gel containing a compound of formula (I) and a suitable carrier, and may be applied an acid addition salt or a base of a compound of formula (I) is preferably presented in a pesticide formulation in an amount between 5 and 80%, calculated on the weight of the base, and in particular '- * ------ vngvgw wa 7714407-9 10 drawn preparations contain about 20%, calculated on the weight of the base.

.The concentration of a compound of formula (I) applied to the pests or their immediate surroundings may be in the range of 0.001% - 20%, calculated on the weight of the base. The features of the present invention appear from the appended claims.

The following examples are provided to illustrate the present invention and should not be construed as limiting it in any way.

EXAMPLE 1 šrsaëEëll9ias_§r_š: lšlå: êimsërlfsaeëimsërll: l: §se§r;: Z: imiêsëelin A solution of acetic anhydride (3.0 ml; 0.032 mol) in diethyl ether (10 ml) was added dropwise over 10 minutes to a stirred suspension of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (6.12 g; 0.030 mol) (prepared from O-ethyl-2,3-dimethylphenoxyacetimidate and ethylenediamine) in diethyl ether (100 ml), and the mixture was cooled to keep its temperature below 20 ° C. After stirring for 2 hours, the reaction mixture was filtered and the precipitate was recrystallized from acetone to give white crystals of 2- (2,3-methylphenoxymethyl) -1-acecyl-2-imiaazoline, mp 127-13 ° C. Analysis: Calculated Found 11.37% N 11.13% N 68.27% C 68.13% C 7.37% H 7.44% H EXAMPLE 2 _ _ z fl zrës fi methylphenoximgfyl> -iiurrszgiægzzisieseræêmeutzzimiëëzeiia A solution of aimecylthiocarbamo .47 9; 0.20 mol) in chloroform (10 ml) was added dropwise over 10 minutes to a stirred solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (4.08 g; 0.020 mol) prepared in Example 1, and triethylamine (2.0 g; 0.20 mol) in chloroform (50 ml) and the reaction mixture was cooled to keep its temperature below 5 DEG C. The reaction temperature was then allowed to rise to room temperature and finally the reaction mixture was refluxed for 5 hours. After cooling, the reaction mixture was washed with water, dried and evaporated, the residue was recrystallized from isopropanol to give white crystals of 2- (2,3-dimethylphenoxymethyl) -1- (N, N-dimethylthiocarbamoyl) -2-imidazoline, mp 124- 12700. 8.1 - 8.3 6 1 H broad singlet 6.8 - 7.2 6 3 HV multiplet 5.0 6 A2 H singlet NMR spectra corresponded to 3.6 - 4.5 6 4 H multiplies the proposed structure 3.1 6 3 H doublet 'V 2.2 6 6 H doublet EXAMPLE 4 U 7714407-9 Analxs: Calculated' 61.84% c 1.27% H 14.42% N Found 62.15 % C 7.64% dH 14.35% N EXAMPLE 3 2: 1åråzëimsëxššsasëimsëxll: l: 1§: @ §: x; 2i9ëëzë§m9yll: 2: ¿m¿§§§9lin A solution of methyl isothiocvanate (1.46 g 0.20 mol) in chloroform (10 ml) was added dropwise over 10 minutes to a stirred solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (4.08 g; 0.020 mol) prepared in Example 1, in chloroform (50 ml) and the mixture was cooled to keep its temperature below 5 ° C. The temperature of the reaction mixture was allowed to rise to room temperature and finally the mixture was refluxed for 5 hours. The chloroform was then evaporated in vacuo and the residue recrystallized from isopropanol to give white crystals of 2- (2,3-dimethylphenoxymethyl) -1N-methylthiocarbamoy] -2-imidaz-2-imide , mp about 100 ° C (dec.). 1 H-NMR (deuterochloroform - tetramethylsilane internal standard): - 1-Nisylylcarbamoxyl-2: 52r: λim2Exlenylam2ms2x11: 2: η 2 z9lin 2- (2,3-dimethylanilinomethyl) -2-imidazoline (4.2O g; 0.024 g; ) was stirred in methylene chloride (90 ml), cooled to 0 ° C and a solution of phenyl isocyanate (2.84 g; 0.024 mol) in methylene chloride (10 ml) was then added dropwise. A white precipitate formed quickly. Stirring was continued for 2-3 hours after the addition at 0 ° C, after which the reaction mixture was allowed to reach ambient temperature and stirring was continued overnight. The reaction mixture was evaporated to dryness under reduced pressure and the solid residue thus obtained was recrystallized from propan-2-ol to give white crystals of 1N-phenylcarbamoyl-2- (2,3-dimethylanilinomethyl) -2-imidazoline EXAMPLE 5 gl: N: lZi5: êlmsëxlšsneëiäëfëeayll: 2: l2i§: êim @ §xlâ§n9ëlm§§xll: šzimiêëzsz iir 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (3; O g; 0.014? mol) löst dry chloroform (401 ml) and cooled to 0 DEG C. Tetramethylpiperidine (2.07 g; 0.014 mol) in dry chloroform (fv7 ml) was then added to the cooled, stirred solution. 2,3-dimethylphenylchloroformist (2311 g; o, o147 »m1 son 30 s w / v solution in benzene) was added slowly, a white precipitate formed and stirring was continued at 0 ° C for 2 h, after which the temperature of the reaction mixture was allowed to rise to ambient temperature.Tetramethylpiperidine hydrochloride The precipitate precipitated on addition of dry acetone and was removed by filtration, the filtrate being evaporated to dryness under reduced pressure and the white the residue was recrystallized from propan-2-ol to give 1-N- (2,3-dimethylphenoxycarbonyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 126-127 ° C.

EXAMPLES 6-27 'By procedures analogous to those described in Examples 1-5 above, compounds of Examples 6-27 were prepared below.

EXAMPLE 6 1-N-Methyloxycarbonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 120 ° C. EXAMPLE 7 1-N-methylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 147-150 ° C (dec.).

EXAMPLE 8 1N-Phenylthiocarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 10-120 ° C. IN EXAMPLE 9 1-N-4-toluenesulfonylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 120 ° C.

EXAMPLE 10 1-N- (α-Naphthyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -Zeimidazoline, m.p.

EXAMPLE ll. 1-N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 132 ° C.

EXAMPLE 15 7714407-9 EXAMPLE 12 1- N- (4-cyanophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imazazoline, mp 172-174 ° C.

§; EMPEL 13 _. 9 1-N-phenylcarbamoyl-2-phenoxymethyl-2-imidazoline, mp 170 ° C.

EXAMPLE 14 V 1-N, N-diphenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 143-14 ° C. 1N-β-tolycarbamoyl-2- (2,4-dimethylphenoxymethyl) -2-imidazoline, A mp 1379c. EXAMPLE 16 1-R-Phenylcarbamoyl-2- (uphenyloxyethyl-2-iodobazine, mp 159 ° C, EXAMPLE 17 N-N- (uraphthyl) carbamyl 2-phenoxymethyl-2-imidazoline, mp 160-163 ° C EXAMPLE 18 A 1N-cyclohexylcafbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 63 ° C. EXAMPLE 19 1N-Phenylcarbamoyl-2- (2-chloroanilinomethyl) -2-imidazoline, mp 169 ° C EXAMPLE 20 1- (N-phenyl-N-methyl) carbamoyl-2- (2,3-dimethylphenoxymethyl ) -2- -imiaazoline, mp 112 ° C. EXAMPLE 21 1N-Phenylcarbamoyl-2- (α, α-dimethylphenoxymethyl) -2-imidazoline, mp 81-8 ° C.

EXAMPLE 22 ¶_. 'kH-fnexaáskyikâfßafaæyi-ê-f (å, â-fäifaßtg / i fsaašiøaxe- * èyii: êrimàs 281 m, m.p. 76-77 ° C. -2-imidazoline, mp 146 ° C.

EXAMPLE 24 V 1-N-Phenylcarbamoyl-2- (2-chloroanilinemethyl) -2-imidazoline, mp 168-169 ° C. 0.0392 mol) and the reaction mixture was heated under reflux until EXAMPLE 25, 11N- (2,6-dimethylphenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline perchlorate salt, mp 221-222 ° C. A EXAMPLE 26 V 1N- (2,3-dichlorophenyl) carbamoyl-2- (2,3-dimethyl-phenoxymethyl) -2-imiaazoline, mp 115-100 ° C. EXAMPLE 27k-1N-Phenylcarbamoyl-2- (3-methoxyphenoxymethyl) -2-imidazoline, m.p. 1 ° C. 'A * ^ EXAMPLE 28 Preparations of .ls fl eta fl s fl lfwlßzlz2: 32; âzêiiês: Azls. 2,3-Dimethylphenoxymethyl) -2-imidazoline (8.0 g; 0.0392 mol) was dissolved in dry ether (75 ml) and sufficient dry chloroform (50 ml), and the solution was cooled in ice (sufficient chloroform was used to prevent precipitation of the imidazoline on cooling.) Methanesulfonyl chloride (4; so g; o, o393 flour) was added dropwise to the cooled, stirred solution. When the addition was complete, pentamethylpiperidine (6.08 g; TLC showed that the reaction was complete (IV3 h) the ion mixture was concentrated under reduced pressure and the residue was extracted with a water / chloroform mixture (1: 1; 100 ml). The chloroform layer was washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give a residue, which was recrystallized from isopropanol to give 1-methanesulfonyl--2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 142-143 ° C. V EXAMPLE 29.

By a procedure analogous to that used in Example 28, 1-benzenesulfonyl-2- (2,3-dimethylphenoxymethyl) -2-imiazolein, amp 110 ° C was prepared. Preparation of 1N-phenylcarbamoyl-2- (2β-dimethylphenegimethyl) z = .11 _ =. 1; <1§ze; .1.§ s, (A) A solution of 2- (2,3-dimethylphenoxymethyl ) -2-imidazoline <20, 49; 1; om) 1 methylene chloride (zoomil) is cooled to -ss ° c | ° ch a solution of phenyl isocyanate (11, 9 g; 1.0 mol) in methylene chloride (300 ml) was added dropwise over 30 minutes. The temperature of the reaction mixture was allowed to rise to ambient temperature and the mixture was allowed to stand for 2 hours, after which a precipitate had formed. The reaction mixture was evaporated under reduced pressure and the residue was recrystallized from acetone to give 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, mp 150-125 ° C.

(B)! I§-§: ëlesëssëeæexlssësesse_s! _2: iålå: ëisss2lšsaeëissëxllzê: zimiëëëslie A 17% solution of phosgene in toluene (3.2 g containing 0, 552l g, 0.00549 mol COCl2) in dry chloroform (15 ml) was added slowly with stirring at 0 ° C to a solution of 2- (2,3-dimethylphenoxymethyl) -2-imiaazoline (2.4 g, 0.18s moi) in dry chloroform (zo mi). when the addition was complete, the reaction mixture was allowed to stand at room temperature for 2 hours, after which it was diluted with an equal volume of dry diethyl ether and filtered rapidly. The filtrate, which contained the N-chlorocarbamoyl adduct of 2- (2,3-dimethylphenoxymethyl-2-imidazoline), was treated with freshly distilled dry aniline (0.664 g, 0.00714 mol) and the mixture was allowed to stand at ambient temperature overnight, after which TLC showed that the main compound was the desired product.

The mixture was evaporated to dryness in vacuo and the residue was taken up in a mixture of aqueous sodium carbonate and dichloromethane. The organic layer was washed with water, dried over magnesium sulfate and evaporated to dryness to give a residue, which was purified as described in (A) above to give 1N-phenyl-carbamoyl--2- (2,3-dimethylphenoxymethyl) - 2-imidazoline, which was identical to that obtained in (A) above.

Blood-filled female ticks of the species Biarra by Boophilus microplus were immersed in groups of 20 ticks per concentration in a number of dilutions of the test compound. The solutions were prepared immediately before the test by diluting (with water) the test compound. The ingredients can be in the form of miscible oil formulation or wettable powder formulation. The desired concentration variations for the test were obtained by further diluting the main solution.

The ticks were removed from the solution after 10 minutes, dried and placed with the backs down on a double-sided adhesive tape. They were kept in this position for 14 days, after which the number of ticks laying viable eggs was determined. From these data a regression line was plotted (concentration vs. percent inhibition of egg production) 7714407-9 A16 and IR90 and IR99 (concentrations at which 90% and 99% inhibition of egg production occurred, respectively), bGStämåeS- The results obtained are shown in Table 1. TABLE 11 1. . V _, _. . . , W. . . . _. ,. . . . V. . ~. ,.

Compound, Example No. IR 90 IR 99 E 1-N-phenylcarbamoyl-2- (2,3-dimethyl + 30 <0.0% - phenoxymethyl) -2-imidazoline 1N- (α-naphthyucarbamoyl-z- (2,3 - _ 1ø o, oo32 2, - o, oøs4 z -dimethylphenoxymethyl) -2-imidazoline 1N-phenylcarbamoyl-2-phenoxymethyl-13 V <0.2% å - -2-imidazoline g _ f E Emm-EL 32 p The test compounds were prepared in polyethylene glycol and injected into ticks at a rod just ventral to the oral parts. After 14 days, percent inhibition was determined by egg production (IR). The results are shown in Table 211 - Å »Ä \ v TABLE 2 - I f '', M Compound 1. Example No.% IR% 1N-phenylcarbamoyl-2- (2,3-dimethyl-40% at 0.1 mg / ml Phenoxymethyl] -z-imidazoline 1-10 at 1.0 mg 1 m-1N-phenylcarbamoyl-2-phenximethyl-1 - 100% at 10 mg / ml 1α-2-imidazoline 3 was 1N-phenylcarbamoyl-2- (2,3-dimethyl-A / ml (anilinomethyl) -Zemidazoline - fp of 1N- (u-naphthyncarbamoyl-z- (Ls-ai-V - 10 V š 40 '% at 0.1 .g / ml methyl-phenoxymethyl) -2-imidazoline A' V> ¿__._ .. V¿¿ ;;;;;:..... _,. . . . . . . . . . . . . . . . . . . . . . ..¿. . . _,. . . . . _ nt _ .-- * ma »A'l7 7714407-9 TABLE 2 (fax).

Association.,,_: . . . . . . . Example 1 IR 1 -N, N-diphenylcarbamyl-2- (2,3-methylphenoxymethyl) -2-imidazoline 1N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2 - -imidazoline 1N- (4-toluenesulfonyl) carbamoyl-2- - (2,3-dimethylphenoxymethyl) -2-imidazoline * 1N- (4-tolyl) carbamoyl-2- (2,3--dimethylphenoxymethyl) -2 -imidazoline 1N-methylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline 1N- (naphthyl) carbamoyl-2-phenoxymethyl-2-imidazoline 14 ll 17 70% at 1.0 mg / ml 70% at 0.1 mg / ml 100% at 1.0 mg / ml at 0.1 mg / ml at 1.0 mg / ml 40% 90% 80% at 1.0 mg / ml 70% at 1 0 mg / ml The following formulations are given to illustrate the ways in which the pesticidal compounds of the present invention can be applied to the pests or the environments in which pest infestation can be expected.

Formulation l PêEEêEÉÉ_BBl! §Š YÉÉëêšÉ_BElYÉš Active compound Sodium dioctyl sulfosuccinate Dispersol ACA Kaolin Active compound 1.0 »A Talc 9.0 80.0 100.0 100.0 Formulation 2 * 2o, o_weight weight1of 25.0 parts by weight 2.0 72,0 100,0 i 7 W7ï: Ã04 4 o 7, - 9 Berednin¶ \ 3 YÉÉÉÉEÉÉÉÉPÉEEÉQE Active compound xeltrèl Sodium dioctyl sulfosuccinate Water * Preparation 4 Ešëëlåaias Active compound Dimethylformamide Castor oil ~ ßereanEnning; §A§ëëz_9li§.

Compound of Example 22 Aromasol H Nonyl phenol ethoxylate 18 20.0 parts by weight - 0.4 oys - 79.1 100, o 85.0%, 10 parts by weight 100, 10.0 70.0 70.0 - 20.0 100.0 parts by weight of parts _. _05!

Claims (15)

1. 7 ,, 14 4 @; -9 '19 'PATENwxRAv l. A compound of formula (I), for use as an insecticide or acaricide, .f \' Ar-xl -Å 1 / J (T) l? N - in which Ar is an unsubstituted or mono- or disubstituted V phenyl group wherein the substituents are the same or different and are selected from (C 1-4) -alkyl, (C 1-4) -alkoxy, halogen and cyano, X 1 is O or NH; R 1 and R 2 are the same or different and are hydrogen or (C 1-4) alkyl; X, Z and Z are a group SO 2 R 8 or a group -C 4%; where X 2 is O '\\\ R3 - or S; p. A, R 3 is (C 1-4) -alkyl, - (C 1-4) -alkyloxy, phenoxy optionally substituted by one or more C 1-4 alkyl or NR R; R 5 and R 6 are the same or different and are hydrogen, (C 1-4) -alkyl, naphthyl or phenyl optionally substituted by one or more substituents selected from halogen, cyano and C 1-4 alkyl or SO 2 R 7; . R 7 is naphthyl or phenyl substituted with one or more substituents selected from halogen, cyano and C 1-4 alkyl; and R 8 is (C 1-4) -alkyl or naphthyl or phenyl which is optionally substituted by one or more substituents selected from halogen, cyano and C 1-4 alkyl; wherein, when Ar is unsubstituted phenyl, R 1 and R 2? is H; ~ s wnsn-f-v- fi - 77144o7 + 9 X2 »_ X1 is NH, Z is + C '// and X2 is O, and R or an acid addition salt thereof. _ A compound according to claim 1, characterized in that Ar is unsubstituted phenyl or substituted phenyl having one or more substituents which are the same or different 3 is non-methyl, and is (C 1-4) -alkyl or halogen, and that the other the substituents are the same as defined in requirement l. - k Compound according to Claim 1 or 2, characterized in that Ar is substituted phenyl with one or more substituents which are the same or different and are (C 1-4) -alkyl or halogen, and that the other substituents are the same as defined in claim 1. g VV A compound according to any one of claims 1 to 3, characterized in that Ar is substituted phenyl wherein the substituents are selected from methyl or chlorine, and that the other substituents are the same as defined in claim 1. A compound according to any one of claims 1 to 4, characterized in that Ar is disubstituted phenyl, and in that the other substituents are the same as defined in claim 1. '. A compound according to any one of claims 1-5, characterized in that Ar is 2,3-dimethylphenyl, and that the other substituents are the same as defined in claim 1. g A compound according to any one of claims 1-6, characterized in that Z 2 is a group -C /// wherein X 2 and R 3 are the same as defined in R 1 in claim 1, and in that the other the substituents are the same as defined in claim 1. _ A compound according to any one of claims 1 to 7, characterized in that Z is a _ - %%; O '5 6, group C wherein R and R i' 1 NR 5 R 6 - i are the same as defined in claim 1, and that the other substituents are the same as defined in claim 1. ¥ubs2 V 7714407-9 '21 _ A compound according to any one of claims 1 to 7, characterized in that Z is -C '// 1 wherein R 5 and R 6 are the same as defined NRSRG in claim 1, and that the other substituents are the same as defined in rats in claim l. A compound according to claim 8 or 9, characterized in that R 5 is hydrogen and R 6 is naphthyl or phenyl optionally substituted by one or more substituents selected from halogen, cyano or C 1-4 alkyl, and that the other sub the students are the same as defined in claim 1. 11. ll. A compound according to claim 10, characterized in that R 6 is phenyl, 4-chlorophenyl, 4-cyanophenyl or α-naphthyl, and that the other substituents are the same as defined in claim 1. A compound according to claim 1, wherein it is 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof. A compound according to claim 1, characterized in that it is 1-N- (α-naphthyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof. A compound according to claim 1, wherein it is 1-N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof, A compound according to claim 1, wherein it is 1-N- (4-cyanophenyl) carbamoyl-2- (2,3-dimethylphenokimethyl) -2-imidazoline or an acid addition salt thereof,