DE2924715A1 - IMIDAZOLINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PESTICIDE - Google Patents

Description

DR. BERG DIFL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. 3ANDMAIR

PATENTANWÄLTE Postfach 860245 8000 München / Vl

Dr. Berg Dipi.-Ing. SUpf and Partner, POBox 860245, 8000 Munich 86 "

Your sign Yourref.

Our sign

Oiirref. 3O

Mauerkircherstraße 45

8000 MUNICH 80 June 19, 1979

Lawyer file no .: 30

THE WELLCOME FOUNDATION LIPiITED London, Ν.ΐί. 1 / England

Imidazoline derivatives , process for their preparation and their use as pesticides

Addendum to patent _._. _i ._._.._ (P 27_56 63g.8)

• (089) 988272 988273 988274 983310

Telegrams: BERGSTAPFPATENT MUnchen TELEX: 0524560BERGd

"Uijöol / U794

Bank accounts: Hypo-Bank MUnchen 4410122850 (BLZ 70020011) Swift Code: HYPO DE MM Bayer. Vereinsbank Munich 453100 (BLZ 70020270) Post check Munich 65343-808 (BLZ 70010080)

These; Frfindunr relates to imidazolines, their preparation and intermediates therefor, pesticide formulations wel che these imidazolines containing them and their use as te st ic icle.

"π was found. that the compounds of the below standing formula I and its acid addition salts active ^ e ^ en arthropods, for example cegen members of the order Acarina, are.

Compounds of the general formula I

are those in which the radical X has the meaning G or UH and the radical Y is Br, F, J, -MO ₂ , -OR, -CO ₃ R, -COIiF ¹ R ² or -SO ₂ NR ¹ R ² , and, if the pest X is NH, it can also be Cl, CN or an alkyl radical having 1 to 4 carbon atoms, where the radical R is an alkyl group having 1 to

18 carbon atoms, preferably with 1 to 4 or 12 to

1 2 18 carbon atoms, and each of the radicals R and R

BATH ORIGINAL

- 2Γ-

may be the same or different, and V / on Hydrogen or a Alkyigruppe having 1 to 18 carbon atoms, with 1 to vorzugsvei.se h carbon atoms or having 12 to 13 carbon atoms, where preferably only one of the radicals

1 2
R ur.d R is an alkyl group rr with 12 to 18 carbon atoms

Preferred compounds of the general formula I are those of the general formula Ia

(Ia)

wherein the radical X has the same meaning as above and the radical Y ¹ F ₃ Br ₃ -NO ₂ , CtUO-, or -Cö ^ N, -, or the radical X the ßedeutunq; NH and the radical Y has the meaning Cl

Oewisse compounds of general formula 1 can be used in their solvated forms occur.

Preferred compounds of the general formula I are: 1- (ri- (4-kethoxyphenyl) carbamoyl) -2- (2,3 ~ dimethylphenoxymethyl) -2-imidazoline,

BATH

-y-

1- ( V, - (ü-chlorophenyl) carbamoyl) -2- (2,3-ciimethylanilinomethyl) -2-imidazoline,

1- (;. ^: - (^ -liroinphenyl) carbair.oyl) -2- (2 ₃ 3 ~ d vr.iethylphenoxynethyl) -2-imi .-. Iazoline,

1- (!: - (4-nitrophenyl) carbamoyl) -2- (2,3- ^ inethyIphenoxymethy1) 2-imidazoIi η,

1- (i · - (4-fluorophenyl) carbarioy 1) -2- (2,3-dyne: ethylphenoxyir.ethyl) 2-irnidazolirij and

1- (ϊ, '- (4-F _i romphenyl) carbairio; ^r l) -2- (2,3-dimethylanilinomethyl) -2-imidazoline.

The compounds of general formula I and their acid addition salts have activity towards arthropods. The compounds of general formula I can be used to treat pests such as Rhipicephalus appendiculatus, Boophilus decoloratus, Eoophilus microplus, Rhipicephalus evertsi, Amblyomma hebraeum, Psoroptes ovis and Hyaloma species in animals and Tetranychus species in plants.

The compounds of the general formula T show an improved Stability in aqueous media, corresponding to the known imidazolines.

The compounds of the general formula I can be

BATH ORIGINAL

good known methods of making compounds produced by an analogous structure.

In particular, the compounds of the general formula I from 2-substituted imidazolines of the general formula Ii

.CK-

(II)

or an acid addition salt thereof, in which the radical X has the same meaning as above, either through a direct addition reaction with an isocyanate (to form the !! - substituted garbamoyl compound) or by a Substitution reaction with a compound of the general formula III

χ ¹ —CO — MH— ff NV-Y (III)

in which the radical Y has the same meaning as above and the radical X is a leaving group, such as, for example Halogen, acyl, alkoxy (e.g. carbamate) or sulfonyloxy>, getting produced.

909881/0794

ORIGINAL

The reaction can optionally be carried out in water or in an organic solvent such as chloroform or methylone chloride, preferably in the presence of an alkali metal hydroxide, an alkali metal carbonate, or a tertiary organic base such as triethylamine, pyridine or substituted pyridines or piperidines, e.g. pentanethylpiperidine or tetramethyl ! piperidine, and usually at temperatures in the range from -70 ° C. to 120 ° C., preferably at temperatures in the range from -10 ° C. to ² JO ⁰ C ₃ .

Compounds of general formula I _5, in particular those in which the group

—CONH-

is not strongly electron withdrawing, can by reacting a Kthylenediamines of the general formula IV

H ₂ ! J — CH ₂ CH ₂ NH — CO — NH— ('N) —Y (IV)

or a salt thereof, in which the radical Y has the same meaning as above, with a suitable 2,3-dimethylphenoxyalkyl- or 2,3-dimethylanilinoalkylcarboxylic acid, or a reactive derivative thereof, such as an imidate, thioimidate, imidohalide, ester, amidine,

§09881 / 0704 " ^{/ T} "

7924715

Thicamide, nitrile or carboxyalkylthioamide will. These reaction devices may prove suitable by the alice my formula V

CH-

.χ — CH ₂ —Ο

(V)

are reproduced, in which the radical X has the same meaning as above and the radical Q is a carboxyl group, or is a reactive derivative thereof which provides the imidazoline ring structure of the general formula I, when it is reacted with a compound of the general formula IV.

Suitable derivatives include the structures given below:

NH

Ii

—C — OAIk

(Imidate),

NH

If (thioimidate), -C-SAIk

OAIk

—C — OAIk (orthoester), OAIk

MII j I

—C — shark

(Imidohalide),

| f (ester), -C-OAIk

HH

JL

—HH,

(Amidine),

(Thioaraid),

■ '■■ "2

C - ;; i-ICO ₂ Alk

(li-alkoxycarbonylthJ oarnici)

-C = :: (ritrile) j and

Ii

C-FAIk

(Thioester)

in which "Alk" is an alkyl group of 1 to 6 carbon atoms and one of the radicals A and E is S and the other radical is S or 0.

The conditions under which this reaction can be carried out depends, of course, on the maturity of the one used Starting materials, and a liquid medium may be present or absent; high and low temperatures and various prints can be applied.

If the carboxylic acid derivative is an imidate, this preferably has and it may take the form of an acid addition salt such as a hydrogen halide salt from the Mitril and a suitable anhydrous alkanol, such as ethanol or methanol, in the presence of dry diethyl ether or chloroform and hydrogen chloride can be made at a low temperature. The reaction can be carried out at a temperature in the range from -20 ° C to Room temperature. The reaction with one

909881/0794

Ethylenediamine of the general formula IV can be in an inert anhydrous medium, such as chloroform, ethylene chloride or ether, can be carried out. The respondents are preferably refluxed until the reaction is complete.

The thioimidate intermediates in the form of the S / Jura addition salts can be made from the corresponding nitrile by reacting with an alkylr-iercaptan 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 the general formula IV, the reaction at the reflux temperature the reaction mixture is carried out.

The ester intermediates can suitably be obtained from the corresponding acids by known methods and the acid itself can be prepared from the corresponding ilitrile. You can then with an Xthylenediamine of the general formula IV, preferably in the presence of a liquid medium that can be polar or non-polar can be implemented. The reaction is preferably carried out at an elevated temperature.

The compounds of general formula I can be selected from

§O9881 / O? Ö4

Imidohalide intermediates by reaction with an ethylenediamine of the general formula IV under anhydrous Conditions in the presence or absence of an acid acceptor, and optionally at an elevated temperature getting produced. The reaction mixture can be a polar or non-polar liquid medium such as a lower alkanol or an ether.

The arnidine intermediate in the form of the base or the acid addition salt thereof, is preferably converted into a compound of general formula I by refluxing with an ethylenediamine of the general formula IV in the presence of a polar or non-polar, liquid medium, for example of a lower alkanol, carried out until the evolution of ammonia has ceased. The amidine intermediates themselves can be prepared by any known method, but suitably from the appropriate ones Imidates by reaction with ammonia.

The thioamide and amide intermediates can be prepared from the corresponding Nitriles or by any other suitable method and incorporated into the compounds of the general formula I by heating with an ethylenediamine of the general formula IV at reflux temperature or a higher temperature in the presence or absence

- / 11 -

9801/079 *

a polar or non-polar solvent. Suitably the reactions are partial carried out under reduced pressure to induce the removal of ammonia and / or hydrogen sulfide from the reaction mixture.

The citrile intermediates can be in the presence or absence of a liquid medium with an ethylenediamine of the general formula IV, or a salt thereof, are reacted. The reaction can be carried out in the presence of hydrogen sulfide. A liquid medium such as a lower alkanol, can be in the reaction mixture, which is down to reflux temperature, or in a closed Vessel can be heated to a temperature above this, if appropriate in the presence of an inert gas, such as for example nitrogen.

Of course, where the intermediate product is the carboxylic acid of the ester or the thioamide, the acylethylenediamines can be used of the general formula VI

(VI)

OC — NH-

§09801 / 0794

vrorin the radicals X and Y have the same meaning as above and the radical V. is oxygen or sulfur, isolate as intermediates, and these compounds as such can be converted in situ into a compound of the general formula I, either by separate treatment with a dehydrating agent such as calcium oxide, or by continuing the reaction under the original conditions to completion to form a compound of general formula I.

The compounds of the general formula I can by reacting a phenol or an amine of the general Formula VII

H, C CH, 3/3

(/ \) - X-II (VII)

in which the radical X has the same meaning as in general Formula I, or an O- or N-metal compound same, with a compound of the general formula VIII

(VIII)

OC — NH-

- / 13 §09801 / 0704

in which the radical Y has the same meaning as in general formula I and the radical V is a leaving group derived from a suitable inorganic or organic acid. Suitable derivatives are halogen, such as, for example, chlorine, iodine or bromine, alkylsulfonyloxy or arylsulfonyloxy, such as, for example p-toluenesulfonyloxy.

The compounds of the general formula VIII can be in the form of their bases or their acid addition salts. the The reaction can be carried out in an inert liquid medium, such as a polar liquid for example acetonitrile or isopropanol, or dimethyl sulfoxide, SuIfolan, methyl ethyl ketone, dimethylformamide, Acetone, dimethyl acetamide, N-methyl-2-pyrrolidone, or mixtures of the above solvents. In cases where a compound of the general formula VIII the remainder V is chlorine, a small catalytic amount of an iodide salt, for example x-feise sodium iodide, or a phase transfer catalyst, such as a quaternary ammonium salt such as benzyltrimethylammonium chloride, are present be. The reactants can reflux under an inert atmosphere such as nitrogen the reaction mixture are heated.

§09881 / 0794

The compounds of the general formula I can also be prepared by reacting a compound of the general formula IX

(ix)

OC-F

in which the reads Z has the same meaning v: ie above and the radical P is a leaving group (such as halogen, acyl, alkoxy, alkylthio, S-, SK ₃ sulfonyloxy or carbalkoxy), with a suitable active amine of the general formula X

(X)

in which the radical Y has the same meaning as in general Formula I has to be made.

The compounds of the general formula I can be prepared from these reaction mixtures in the form of the free base or in the form an acid addition salt can be isolated. The bases can be converted into their acid addition salts using known procedures be converted with the help of the appropriate acid

- / 15 -

§09801 / 0794

den, and the salts of the compound can also be converted into the free bases or into other acid addition salts will.

For their use as a pesticide, the compounds of general formula I can be used in the form of their acid addition salts, or particularly preferably in the form of their free bases. Suitable salts of compounds of the general formula 1 include the hydrogen halide, sulfate, mitrate, phosphate, thiocyanate, acetate, propionate, stearate, Naphthenate, perchlorate, benzoate, methanesulfonate, kthanesulfonate, Tosylate and benzenesulfonate acid addition salts.

The compounds of the general formula I can be used as pesticides for combating insects, ticks, lilbs and others Arthropods, including the wild arthropods and those which are ectoparasites on plants, mammals, and birds, and used alone or in combination may be used with an additive which may be in the form of one or more carriers as the applicable A person skilled in the art uses in his formulations, for example wetting, diluting, stabilizing, thickening, emulsifying, Dispersants or surfactants or others usual carrier components.

- / 16 -

A formulation can be an aqueous solution of a snure reaction salt or a compound of the general formula I ₅ or a suspension of a compound of the more general: formula I in barrels and can be used alone or in combination with suitable mineral-active agents . The formulation as such can be used alone or diluted in /.'ass it for application to the pests or their lifeblood. by spraying or immersion 'used' - / ground.

A formulation can be in the form of a mixable QI, the one compound of general formula I in the form of its free base or with an equimolar amount of one suitable organic acid, such as oleic acid or ilaphthenic acid, to contain an organic solvent and emulsifiers to create soluble salt, and they can be applied as an emulsion by spraying or dipping will.

A formulation can be a ignorant solution or Suspension of a compound of general formula I in a suitable organic solvent for the direct "Pour" method of application. A formulation can also take the form of a wettable powder for dilution with water and application by means of immersion or Have spraying. Other fixed «formulations can

- / 17 -

Ö098Ö1 / 079 4

Also used for direct application without dilution are j such as dusts, powders and granulates.

A further formulation can be a paste, a fat or a gel which contains a compound of the general formula I. and a suitable carrier, and applied by spreading the formulation over the infected area can.

An acid addition salt or a base of a compound of general formula I is preferably used in a pesticidal formulation in an amount between 5 and 80% _y weight of the Ease, present, and particularly preferred formulations contain about 20%, based on the weight of the base . The concentration of a compound of the general formula I ₃ which is applied to the pests or their immediate habitat can be in the range from 0.001 % to 20 %, based on the weight of the base.

It can be seen from the foregoing description that the present application is primarily and not exclusively for example the following new features include: (a) A new 2,3-dimethylphenoxyalkyl or 2,3-dimethylanilinoalkyl-imidazoline compound of the general formula I and their acid addition salts;

Ö09881 / 0794 - / 18 -

(b) a process for the preparation of a new compound of the general formula I and its acid addition salts;

(c) a method of keeping arthropod pests under control, especially members of the order Acarina, by applying a connection of the general Formula I on the Sehäldlinge or their habitat;

(d) a pesticidal formulation which contains a compound of the general formula I and a carrier therefor;

(e) a process for preparing a formulation comprised of a mixture of a carrier and a compound of the general formula I; and

(f) a new intermediate product formed in the manufacture of imidazolines.

In summary, the present invention relates to pesticidal imidazolines of the general formula I.

in which the radical X has the meaning 0 or NH, and the radical Y is Br, F ₅ J, -WO ₂ , -OR, -CO ₃ R, -CONR ¹ R ² or -SO ₂ NR ¹ R ² , and , if the radical X has the meaning NH, also Cl,

§09881 / 0794 ~ ^{/ 19} "

CN or an alkyl radical having 1 to 4 carbon atoms, where the radical R is an alkyl group having 1 to 18 carbon atoms and each of the radicals R and R _3, which can be the same or different, is hydrogen or an alkyl group having 1 to 18 carbon atoms. Pesticidal acid addition salts of the imidazolines are also created. The process for the production of the pesticides is described, together with the intermediate products formed in the production process. Pesticide formulations which contain the pesticides and their use are also explained.

The pesticides can be used against arthropods, e.g. against Acarina.

The following examples serve to further illustrate the invention and are not intended to restrict it in any way

example 1

1- (M- (4-chloropheny1) carbamoyl) -2- (2,3 ~ dimethylanilinomethyl) -2-imidazoline

2- (2,3-Dimethylanilinomethyl) -2-imidazoline (4.20 g; 0.024 mol) was stirred in methylene chloride (90 ml) which had been cooled to 0 ° C., and a solution of 4-chlorophenyl isocyanate (3j66 _g; 0.024 mol) in methylene chloride (10 ml) dropwise

- / 20 -

§09801 / 0704

- ac -

added. A hot precipitate quickly formed. .- ■ as stirring was continued for 2 to 3 hours after completion of the addition at O ^J C, the reaction mixture was brought slowly to room temperature and stirring continued over laugh!. The reaction mixture was then evaporated to dryness under reduced pressure and the solid residue thus obtained was recrystallized from propan-2-ol. . "lan obtained white crystals of 1 - (!! - (■} -Chlorpheny 1) carbamoyl) -2- (2,3-diraethylanilinomethyl) -2-imidazoline; melting point 153 ° to 155 ° C

Examples 2 to 6

The compounds of Examples 2 to 6 below were prepared in a manner analogous to that in Example 1.

Example 2

1- (U- (4-bromophenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) 2-imidazoline monohydrate; Melting point 150 ° to 151 ° C (White dust).

Example 3

1- (IJ (4-Methoxypheny1) carbamoyl) -2- (2, 3-Dimet hy lphenoxymethyl) -2-imidazoline; Melting point 126 ° to 127 ° C (white powder).

- / 21

§09881 / 0784

Example 4

1- (H- (4-nitrophenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) 2-imidazoline monohydrate j Melting point 182 ° to 185 ° C (light yellow Powder).

Example 5

1- (N - (^ - carbethoxyphenyl) earbamoyl) -2- (2,3-dimethylpbenoxymethyl) -2-imidazoline; Melting point 153 ° C (white powder).

Example 6

1- (ri- (4-fluorophenyl) carbamoyl) -2- (2J3 ~ dimethylphenoxymethyl) -2-imidazoline; Melting point (about 5 % impurity) 172-173 ° C

Example 7

Preparation of 1- (H- (4-bromophenyl) carbamoyl) -2- (2 _? 3-dimethylphenoxymethyl) -2-imidazoline

(A) A solution of 2- (2,3 ~ dimethylphenoxymethyl) -2-imidazoline (20.4 g; 1.0 mol) in methylene chloride (300 ml) was cooled to -65 ° C and a solution of 4-bromophenyl isocyanate (19.8 g; 1.0 mol) in methylene chloride (300 ml) was added dropwise over 30 minutes. The reaction mixture was then slowly brought to room temperature and set aside for 2 hours when a precipitate formed had formed. The reaction mixture was taking

- / 22 -

809881/0794

concentrated under reduced pressure and the residue was crystallized from acetone. Γ-'an received 1- ( ^T I- (4-i? Rcmphenyl) carbanoyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline. ^r ionohydrate; Melting point 150 ° to 151 ° C.

(B) via the N-chlorocarbamoyl adduct of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline

A 17% solution of phosgene in toluene (3.2 g with a content of 0.5521 g; 0.00549 mol of COCl ₂ ) in a dry. Chloroform (15 ml) was slowly added with stirring at 0 ° C to a solution of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (2.40 g; 0.0115 mol) in dry chloroform (20 ml). After the addition was complete, the reaction mixture was left to stand at room temperature for 2 hours, diluted with an equal volume of dry diethyl ether and quickly filtered. The filtrate, which contained the K-chlorocarbamoyl adduct of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline, was treated with freshly distilled, dry 4-eromaniline (1.22 g, 0.00714 XoI) and the mixture allowed to stand at room temperature overnight, after which time thin layer chromatography showed that the main compound was the desired product. The mixture was concentrated to dryness in vacuo and the residue was taken up in a mixture of aqueous sodium carbonate and dichloromethane. The organic layer was washed over with water

- / 23 - 909881/0794

Magnesium sulfate dried and evaporated to dryness. A residue was obtained which, as described above under (A), has been cleaned. 1- (N- (4-bromophenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, which with the compound obtained under (A) was identical.

Examples 8-10

Using procedures analogous to Example 1, the following Connections made:

1- (N- (4-methylphenyl) carbamoyl) -2- (2,3-dimethylanilinomethyl) -2-imidazoline (melting point 154-155 ° C),

1- (N- (4-cyanophenyl) carbamoyl) -2- (2,3-dimethylanilinomethyl) -2-imidazoline, and

1- (N- (4-bromophenyl) carbamoyl) -2- (2,3-dimethylanilinomethyl) -2-imidazolin (melting point 161.6 ° to 162.2 ⁰ C).

Example 10a

Following the procedure of Example 1, but without recrystallization, became 1- (N-4-dimethyl-aminosulfonyl phenyl) carbamoyl) -2- (2,3-dimethylanilinomethyl) -2-imidazoline (M.p. 151-153 ° C).

- / 24 -

Ö09881 / 079Ä

Example 11

Bulging female ticks of the Biarra strain of Boophilus microplus were tested in groups of 20 ticks in a solution of a certain concentration from a row immersed in solutions with various degrees of dilution of the compound to be examined. The solution was immediate prepared before the experiment by diluting (with water) the compound to be examined. The ingredients can be in the form of a miscible oil or a wettable powder formulation. The desired range of concentrations for the experiment is obtained by further dilution of the stock solution.

The ticks were removed from the solution after 10 minutes, dried and attached to double-sided tape with the back stapled down. They remained in this position for 14 days, after which the number of ticks was determined, who laid viable eggs. A regression line is plotted from these results (concentration versus percentage Inhibition of egg production) and the IR99 (concentration at which a 99% inhibition of egg production occurs) derived.

The results obtained are set out in the table below.

- / 25 -

80S881 / 0794

^ s

Tabel

Verb i η d u η g

example

No. IR99

1- (H- (4-chlorophenyl) carbamoyl) -2- (2 j 3-dimethylanilinomethyl) -2-imidazoline

1- (1T- (4-bromophenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline

1- (M- (^ -Kethoxyphenyl) carbamoyl) 2- ( 2,3-dimethylphenoxymethyl1) -2-imidazoline

1- (Ii- (4-l-nitrophenyl) carbamoyl) -2- (2nd j 3-dimethylphenoxymethy1) -2-imidazoline hydrate

1- (N- (h -carbethoxyphenyl) carbamoyl) · 2- (23-dimethylphenoxymethyl) -2-imidazoline

1 0.029 %

2 0.0095 %

3 0.0038 % H 0.010 % 5 0.019 %

The following formulations serve to explain the manner in which the pesticides according to the invention Compounds applied to pests or their habitats that are sensitive to pest attack can be.

formulation

Dust powder Active compound I ₃ O 20.0 parts

Talc 99.0

100.0 80.0 parts by weight
100.0

009881/0794 - / 26 -

formulation Wettable powder

Active compound 25.0 parts by weight

I-atrium dioctyl sulfosuccinate 1.0 part by weight

L'iscersöl ACA 2.0 parts by weight

i'aolin 72.0 weight parts

100.0

Formulation 3
V.'f-'sser ige dispersion

Active compound 20.0 parts by weight

Keltrol 0.4 part by weight

iiatriurndioetylsulfosuccinat 0.5 weight parts

V / ater 79.1 weight parts

100.0

Formulation 4 Infusion

Active compound 5.0 parts by weight

Dimethylformamide 85.0 parts by weight

Castor oil 10.0 parts by weight

100.0

- / 27 -

909881/0794

- ar- -

31-

Formulation; 5 fat

Active connection 6, 0 parts by weight

Yaseline 9 ^, 0 parts by weight

100.0

Formulation 6 Mixable oil

Connection; ^from Example 3 .... 1O ₃ O parts by weight

Arorriasol II 70.0 parts by weight

:; onylphenol / thoxylate 2Q ₃ O parts by weight

100.0

stability

The compound of Example 1 had a calf life of more than 6 months ₃ in an aqueous medium with a p n value of 7, whereas the half-life of 2- (2,3-dimethylphenoxy) -2-imidazoline was approximately 2 weeks.

Ö09881 / 079 *

Claims (1)

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR PATENTANWÄLTE PO Box 860245 8000 Munich Dr. Berg Dipl.-Ing. Stapf and Partner, POBox 860245, 8000 Munich 86 ^- Your mark
Your ref. Our mark Our ref. 30 Mauerkircherstraße 45 8000 MUNICH 80 i j.979 Anvraltsakte-Hr . : 30 THE WELLCOME FOUNDATION LIMITED Patent to s ρ r- ü ch e 1. Compound of the general formula I • X — CK (D or an acid addition salt thereof, in which the radical X is 0 or UH and the radical Y is Br, F, J, -UO ₂ , -OR, -CO ₂ R, -CONR ¹ R ² or -SO ₂ MR ¹ R ² , or, if the radical X has the meaning NH, can also be Cl, CM or an alkyl radical having 1 to 4 carbon atoms, where the X / R 809881 / 07SU P (089) 988272 988273 988274 983310 : ase Ä584 Telegrams: BERGSTAPFPATENT Munich TELEX: 0524560 BERG d Bank accounts: Hypo-Bank Munich 4410122850 (BLZ 70020011) Swift Code: HYPO DE MM Bayer Vereinsbank Munich 453100 (BLZ 70020270) Post check Munich 65343-808 (BLZ 70010080) K is an alkyl group having 1 to 18 carbon atoms 1 2
and each of the radicals R and K can be identical or different and denotes hydrogen or an alkyl group having 1 to 16 carbon atoms. 2. Compound according to claim 1, characterized in that that the radical Y is -OR or -CO "R, where R is an alkyl group with 1 to 4 or 12 to 15 carbon atoms is. 3. Compound according to claim 1, characterized zei ch η et that the radical Y is -CONR ¹ R ² or -SO ₂ ^ R ¹ R ² , 1 2
wherein each of the radicals R and R, which can be the same or different, is hydrogen or an alkyl group having 1 to 4 or 12 to 18 carbon atoms. 4. Compound according to claim 3, characterized in that that no more than one of the radicals R and R is an alkyl group of 12 to 18 carbon atoms. 5 · Compound according to claim 1 of the general formula la (Ia) or an acid addition salt thereof, characterized ^e ~ G denotes that the radical X is 0 or has MH and the rest of YF, Br ₃ -HO _2, or -CO ₂ CIwO- CPUC is or the radical X has the meaning NH and the radical Y the meaning Cl has. 6. 1- (II- (4-I-? Ethoxyphenyl) carbaraoyl-2- (2,3-dimethylphenoxymethyi) -2-irriidazoline, 1- (N- (4-chlorophenyl) carbamoyl) -2- (2 ₅ 3-dimethylanilinomethyl) -2-imidazoline, 1- (H- (4-Brontnphenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, 1- (II- (4-nitrophenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) -2-iiidazoline ₅ 1- (H- (4-fluorophenyl) carbamoyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline, and 1- (M- (4-bromophenyl) carbamoyl) -2- (2,3-dimethylanilinomethyl) -2-imidazoline, or an acid addition salt of these compounds. 7. 1- (N- (4-chlorophenyl) carbamoyl) -2- (2,3-dimethylanilinometh; yl) -2-imidazoline or an acid addition salt of this compound. 3. 1- (iI- (4-chlorophenyl) carbamoyl) -2- (2j3-dimethylanilinomethyl) -2-imidazoline. §09861 / 0914 292A715 9. A process for the preparation of a compound rjercäii- one of claims 1 to 8, characterized in that η e tj
(a) a compound of the general formula II (II) or an acid addition salt thereof, in which the radical X has the same meaning as in claim 1, with an isocyanate, or with a compound of the general formula III χ ¹ —CC — UK (Ill) vrorin the radical Y has the same meaning as in claim 1 and the radical X is a leaving group;
(b) a compound of the general formula IV II-CH ₂ CH ₂ NH-CO-NH (IV) or a salt of the same, -, 'Torin the remainder Y the same Has meaning v / ie in claim 1, with a compound the general formula V -Ch ₉ - 0 (V) wherein the radical X has the same meaning as in claim and the radical 0 is a carboxyl group or a reactive derivative thereof; (c) a compound of the general formula VI H, C C CH, (VI) OC—: ·: in which the radicals X and Y have the same meaning as in claim 1 and the radical M is oxygen or selulfur, cyclized; (d) a phenol or an amine of the general formula VII CH. H ₃ C -X-H (VII) BATH ORIGINAL or an 0- or i>!. etallverbiridun ["of the same, v: orin the radical X has the same meaning as in claim 1 with a compound of the general formula VIII V- - CIi (VIII) OC— Π or an acid addition salt thereof, wherein the reads Y has the same meaning as in claim 1 and the radical V is a leaving group which is derived from an inorganic or organic acid;
(e) its compound of the general formula IX (IX) OC-P in which the radical X has the same meaning as in claim 1 and the radical P denotes a leaving group, with an amine of the general formula Ä (X) 909881 / 07Θ4 in which the radical Y has the same meaning trie in claim 1; and then, if desired, a compound of the general formula I in an acid addition salt, or an acid addition salt a compound of the general formula I is converted into the free base or another acid addition salt. 10. Pesticide preparation, characterized in that that it contains a compound according to any one of claims 1 to δ together with a carrier therefor. 11. Preparation according to claim 10, characterized in that that the carrier is a surfactant. 12. Preparation according to claim 10, characterized in that that the carrier is a liquid. 13 · Preparation according to claim 12, characterized in that that the carrier is a suspending agent. 14. Preparation according to one of claims 10 to 13 , characterized in that it is in the form 909881/0764 an aqueous solution or suspension, a miscible oil, a non-aqueous solution or suspension, a Paste, a fat, a gel, a wettable powder, a dust, a powder or granules. 15. Preparation according to one of claims 10 to 14, characterized in that it contains from 5 to 80 % of the compound defined in one of claims 1 to 9, based on the weight of the free base. 16. Preparation according to one of claims 10 to 15 »characterized in that it is 1- (IJ- (4-chlorophenyl) carbamoyl) -2- (2,3-dimethylanilinomethyl) -2-imidazoline contains. 17. Preparation according to claim 16, characterized in that that it is in the form of a wettable powder. 18. Preparation according to claim 16, characterized in that it is marked It seems that it is in the form of a miscible oil. 19.Methods for keeping arthropod pests under control, characterized, §09881 / 0794 that it is the application of a compound according to one of the claims 1 to 8 on the pests or their habitat. 20. The method according to claim 19, characterized in that that it concerns pests of the order Acarina. 21. The method according to any one of claims 19 and 2O _3, characterized in that the pests are ectoparasites of mammals or birds. 22. The method according to any one of claims 19 to 21, characterized in that the connection is applied by spraying, dusting or dipping. 23. The method according to any one of claims 19 to 22, characterized in that the concentration of the compound applied to the pests or their habitat is in the range from 0.001 to 20 %, based on the weight of the free turf. 24. The method according to any one of claims 19 to 23, characterized in that the connection 1- (N - (^ - Chloropheny1) carbamoyl) -2- (2,3-dimethylanilinomethyl) 2-imidazoline is. 909831/0794 2 ^r ). A process for Ferstellun "? · A preparation according to any one of claims 10 to 18, characterized £ · Eke η η z calibration η e t in that it dac mixing comprises a compound gen". ', Any one of claims 1 to 8 with a carrier. 2c. A compound according to claim 1, wherein a denotes d u r c h ^ e, that she pemüß one of the examples 1 to 10 of the present specification have been produced is. 27. The method according to claim 9, characterized in that that it is essentially as described in one of Examples 1 to 10 of the present description, has been carried out. 28. A compound according to claim 1, characterized in that it according to the method of claim 9 or of claim 27 has been produced. 29. Preparation according to one of claims 10 to 18, characterized in that it contains the composition on v / e is essentially as described in one of the formulations 1 to 6 of the present description has been. 809881 / om