CH642821A5 - Pesticidal preparations containing imidazolines, and their use for controlling pests - Google Patents

Description

The invention relates to pesticidal preparations which contain new imidazolines, their use for controlling pests and a method for producing a part of these compounds.

It has been found that compounds of the formula I

(II)

or their acid addition salts with an isocyanate, an isothiocyanate, a ketene, or a compound of the formula Z'-X3, in which X3 is a cleavable group, and that, if appropriate, a free base obtained is converted into an acid addition salt or an acid addition salt obtained into the free one Base transferred.

11. The method according to claim 10, characterized in that a compound of the formula I 'is prepared, in which Ar is an unsubstituted or mono- or polysubstituted by alkyl, preferably methyl, and / or halogen, preferably chlorine, phenyl group, the substituents can be the same or different.

12. The method according to claim 10 or 11, characterized in that one produces a compound of formula I ', wherein Ar is a disubstituted phenyl group, preferably the 2,3-dimethylphenyl group.

13. The method according to any one of claims 10 to 12, characterized in that a connection of the For-

Ar-X-C

(I),

wherein i5 Ar is a phenyl radical which is unsubstituted or mono-, di- or trisubstituted by alkyl, alkoxy, halogen, hydroxyl, cyano, amino, trifluoromethyl or nitro, where the substituents are identical or different and any two adjacent carbon atoms on the phenyl ring 20 are represented by a carbon chain having 3 or 4 carbon atoms may be connected;

X1 is oxygen or NH;

R1 and R2, which are the same or different, are hydrogen or alkyl; and 25 Z is a group of the formula SOnR8 or a group of the formula

-C <

X2 R3

30 where

X2 oxygen, sulfur or NR4;

D 5

R3 is alkyl, aryl, alkoxy, aryloxy or -NC ^;

3s R4 alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio -R5.

or-Nc

-R6,

R5 and R6, which are the same or different, are hydrogen, 40 alkyl, aryl, -COR7 or S02R7 or one of the radicals Rs and R6 is hydrogen and the other cyclohexyl;

R7 is alkyl, aryl, alkoxy or aryloxy;

n 1 or 2;

45 R8 alkyl, aryl or -Nd ^ 10; and

R9 and R10, which are the same or different, represent hydrogen, alkyl or aryl,

mean, provided that when Ar is unsubstituted Phe-50 nyl, X1 NH, R1 and R2 are hydrogen, Z is a group of the formula -Cc £, where X2 is oxygen, R3 is R3

does not mean methyl, and their acid addition salts are effective against arthropods, in particular those of the order Acarina.

From Helv. Chim. Acta 1951, 34.1-17, 1- (methyl-carbonyl) -2- (anilinomethyl) -2-imidazoline is known. In this reference, however, no information is given about the biological activity of this compound.

Halogen in formula I is understood to mean in particular chlorine, bromine and iodine. The alkyl and alkoxy groups generally each have 1 to 4 carbon atoms. Certain compounds of formula I can exist in their solvated forms. The group Ar in formula I is preferably unsubstituted or is substituted by alkyl, preferably methyl, and / or halogen, preferably chlorine.

642 821

4th

In the present case, aryl groups are generally taken to mean unsubstituted or mono- or polysubstituted phenyl or naphthyl, where the substituents can be the same or different and alkyl, alkoxy, halogen, nitro, cyano and amino are preferred as substituents.

The preferred compounds of formula I include those in which:

(A) Ar phenyl or 2,3-dimethylphenyl; and or

(B) Z represents a group of the formula -C ^ j, in which X2 is oxygen or sulfur and R3 is NR5R6.

Particularly preferred compounds of the formula I are: 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline;

l-N- (a-naphthyl) carbamoyl-2- (2,3-dimethylphenoxyme-

thyl) -2-imidazoline; l-N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxyme-

thyl) -2-imidazoline; and l-N- (4-cyanophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline.

The compounds of formula I and their acid addition salts are notable for their activity against arthropods, in particular against the order Acarina. The compounds of formula I can be used to control pests of the species Rhipicephalus appen-diculatus, Boophilus decoloratus, Boophilus microplus, Rhipicephalus evertsi, Amblyomma hebraeum, Psoroptes ovis and Hyaloma in animals and Tetranychus in plants.

The compounds of the formula I can be prepared by methods known for compounds with an analogous structure.

Part of the compounds of the formula I, namely the compounds of the formula I '

wherein

Ar is a phenyl radical which is unsubstituted or mono-, di- or trisubstituted by alkyl, alkoxy, halogen, hydroxy, cyano, amino, trifluoromethyl or nitro, where the substituents are identical or different and any two adjacent carbon atoms on the phenyl ring by a carbon chain with 3 or 4 carbon atoms may be connected;

X1 is oxygen or NH;

R1 and R2, which are the same or different, are hydrogen or alkyl; and

Z 'is a group of the formula SO "R8 or a group of the formula wherein

X2 oxygen or sulfur;

R5

R3 is alkyl, aryl, alkoxy, aryloxy or -NCR6;

R4 alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio R5

or -N <j ^ 6;

R5 and R6, which are the same or different, are hydrogen, alkyl, aryl, -COR7 or S02R7 or one of the radicals Rs and R6 is hydrogen and the other cyclohexyl;

R7 is alkyl, aryl, alkoxy or aryloxy;

n 1 or 2;

R8 is alkyl, aryl or -N <^ 10; and

R9 and R10, which are the same or different, represent hydrogen, alkyl or aryl,

mean, provided that when Ar is unsubstituted phenyl, X1 NH, R1 and R2 are hydrogen, Z 'is a group of

Formula -C ^ j ^, where X2 is oxygen, R3 is not methyl, and their acid addition salts are obtained according to the invention starting from two-substituted imidazolines of the formula II

-C

or their acid addition salts with the aid of an addition reaction using an isocyanate, an isothio-cyanate or a ketene or with the aid of a substitution reaction using a compound of the formula III

Z'-X3 (III),

where X3 is a removable group.

If an isocyanate or an isothiocyanate is used for the addition reaction, a compound of the formula I 'is obtained in which Z' denotes an N-substituted carbamoyl or thiocarbamoyl group; if the reaction is carried out with a ketene, a compound of the formula I 'is obtained in which Z' denotes an acyl group. Preferred compounds of formula III for carrying out the substitution reaction are acid chlorides or halogenformates, i.e. Compounds in which X3 represents halogen, acid anhydrides, i.e. Compounds of formula III wherein X3 represents an acyl group, carbamates, imino esters, thiocarbamates or iminothio esters, i.e. Compounds of the formula III, in which X3 is alkoxy- or alkylthio, or mixed anhydrides, for example compounds of the formula III, in which X3 is sulfonyloxy.

In a preferred application of the above-mentioned substitution reactions for the preparation of compounds of the formula I 'in which Z' is a thiocarbamoyl group, the compound of the formula II used as starting material can be reacted with a compound of the formula III in which Z 'is a thiocarbamoyl group and X3 is one Amìno group mean, ie the compound of formula III is a thiourea.

The reaction can optionally be carried out in water or an organic solvent, e.g. B. chloroform or methylene chloride, preferably in the presence of a base, e.g. B. an alkali metal hydroxide, an alkali metal carbonate or a tertiary organic base, such as triethylamine, pyridine or a substituted pyridine or piperidine,

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

642 821

e.g. Pentamethylpiperidine or tetramethylpiperidine, and generally at a temperature of from -70 to +120 ° C, preferably from -10 to +40 ° C.

Compounds of the formula I, in which X2 denotes -NR4, can be prepared analogously to the process described above, i.e. starting from two-substituted imide azolines of the formula II

Ar-X1-C

(II)

or their acid addition salts by means of an addition reaction using a carbodiimide or by means of a substitution reaction using a compound of the formula III

Z "-X3

(HI),

wherein X3 is a removable group and Z "is a group of the formula

-CC

X2 R3

is where

X2 -NR4 means and

NH

OAlk

R3 and R + have the meanings given above. Compounds of the formula I, in particular those in which Z is not a strongly electron-withdrawing group, can be prepared further by using an ethylenediamine of the formula IV

H, N-CH, CH, NHZ

(IV)

or a salt thereof, with a suitable phenoxyalkyl-io or anilinoalkylcarboxylic acid or a reactive derivative thereof, e.g. B. an imino ester, iminothioester, imido halide, ester, amidine, thioamide, nitrii or alkoxycarbonylthioamide. These phenoxyalkyl or anilino alkyl carboxylic acids or their reactive derivatives can i5 by the formula V

R

20th

Ar-X -C-Q

R

(V),

where Q represents a carboxyl group or a reactive derivative da-25 of. When reacted with the ethylenediamine of the formula IV, the group Q forms the imide azoline ring in the formula I.

The reactive derivatives of the carboxyl group in connection with the formula V include e.g. B. the following groups:

OAlk

(Iminoester),

-C-OAlk (orthoester)

'Ï

OAlk

/ "H / 'H

-CT (iminothioester), -C (imidohalide),

'SAlk shark

/ ° / H

■ q; (Ester), -C (amidine),

'OAlk ^ NH "

/ S

- ■ C '(thioamide), -C ^ J (Nitrii), and

SNH "

/ s

-C (carboxyalkylthioamide).

sNHC02Alk

642 821

6

In the above formulas, Alk means an alkyl group having 1 to 6 carbon atoms.

The conditions under which this reaction can be carried out depend, of course, on the nature of the starting materials used. A liquid medium can be present or absent; high or low temperatures can be used as well as various pressures.

If an imino ester is used as the carboxylic acid derivative, this is preferably in the form of an acid addition salt, e.g. B. a hydrohalide. These compounds can, for example, starting from the corresponding Nitrii by reaction with a suitable aqueous alkanol, e.g. As ethanol or methanol, in the presence of dry kenem diethyl ether or chloroform and hydrogen halide at low temperature. The reaction can generally be carried out at a temperature in the range from -20 ° C to room temperature. The reaction with an ethylenediamine of the formula IV is preferably carried out in an inert anhydrous medium, for example chloroform, methylene chloride or ether. The reactants are preferably heated under reflux until the reaction is complete.

If thioimino esters are used as precursors of formula V, these can be prepared in the form of acid addition salts from the corresponding nitriles by reaction with an alkali mercaptan and a hydrogen halide gas at low temperature (about 0 ° C.) in the presence of dry diethyl ether. The iminothioester thus obtained can then, advantageously in the form of the crude reaction product, be reacted with an ethylenediamine of the formula IV, the reaction being carried out at the reflux temperature of the reaction mixture.

If an ester is used as the precursor of the formula V, it will expediently be prepared from the corresponding acid using known methods. The acid itself can be obtained from the corresponding nitrii. The ester precursor can then be carried out with an ethylenediamine of the formula IV, preferably in the presence of a liquid medium, which can be polar or non-polar. The reaction is preferably carried out at elevated temperature.

If the preparation of the compounds of the formula I is based on imidohalides of the formula V and is reacted with an ethylenediamine of the formula IV, the reaction is preferably carried out under anhydrous conditions in the presence or absence of an acid acceptor and, if appropriate, at elevated temperature. The reaction mixture can be a polar or non-polar liquid medium, e.g. B. contain a lower alcohol or ether.

If one starts from an amidine of the formula V in the form of the base or an acid addition salt, the amidine is preferably converted into a compound of the formula I by refluxing it with an ethylenediamine of the formula V in the presence of a polar or non-polar liquid medium, e.g. a lower alkanol, heated under reflux until the evolution of ammonia has ended. The amidine of the formula V can in turn be prepared by known methods, but it is expediently prepared by reacting the corresponding imino ester with ammonia.

The thioamides and amides of the formula V can be prepared from the corresponding nitriles or by means of other suitable methods and then by heating with an ethylenediamine of the formula IV at reflux temperature or higher temperature in the presence or

Absence of a polar or non-polar solvent can be converted into a compound of formula I. The reactions are advantageously carried out in part under reduced pressure in order to initiate the removal of ammonia and / or hydrogen sulfide from the reaction mixture.

If one starts from a nitrii of formula V, this is reacted in the presence or absence of a liquid medium with an ethylenediamine of formula IV or an io salt thereof. The reaction can be carried out in the presence of hydrogen sulfide. The reaction mixture to which a liquid medium e.g. a lower alkanol, which can be added, can be heated to reflux temperature or a higher temperature in a closed vessel, optionally in the presence of an inert gas such as nitrogen.

If the carboxylic acid, the ester or the thioamide is used as the precursor of the formula V for the reaction with ethylenediamine, the resulting intermediate, 20 i. an acylethylenediamine of the formula VI

25th

R

i I /

Ar-X -C-C

■ W

H

\

N-CH2CH2NH2 (VI),

30 where W is oxygen or sulfur, whereupon these compounds can be converted even in situ into compounds of the formula I, which is generally done either by separate treatment with a dehydrating agent such as calcium oxide, or by continuing the reaction under the original conditions can occur until the reaction to the compound of formula I is complete.

The compounds of formula I can also be prepared by using a phenol or an amine of formula VII

Ar-X1-H (VII)

or an O- or N-metal derivative thereof, with a compound of formula VIII

45

v-c

50

(VIII),

wherein V represents a cleavable group derived from an inorganic or organic acid. The following meanings for V are examples:

Halogen, such as chlorine, iodine or bromine, alkylsulfonyloxy or arylsulfonyloxy, such as p-toluenesulfonyloxy.

The compounds of formula VIII can be in the form of the 60 free bases or their acid addition salts. The reaction is generally carried out in an inert liquid medium, which is preferably a polar liquid, such as acetonitrile or isopropanol. As a liquid medium continue to come, for. B. dimethyl sulfoxide, sul-65 folane, methyl ethyl ketone, dimethylformamide, acetone, dimethylacetamide, N-methyl-2-pyrrolidone or mixtures of these compounds. If V in the compound of formula VIII is chlorine, it is advantageous to give the reac

7

642 821

tion mixture a small catalytically effective amount of an iodine salt, e.g. Sodium iodide, or a phase transfer catalyst, e.g. add a quaternary ammonium salt such as benzyltrimethylammonium chloride. The reactants can be heated together under an inert atmosphere, such as nitrogen, at the reflux temperature of the reaction mixture.

Those compounds of formula I in which Z is one

Group-C ^ 3, where R3 is alkoxy, aryloxy or-NR5 R6

means, corresponds, can also be prepared by using a compound of formula IX

Ar

(IX),

Ì / -t y / \

wherein Y is a cleavable group, e.g. B. halogen, acyl, alkoxy, alkylthio, S ", SH, sulfonyloxy or carbalkoxy, means with an active hydrogen-containing compound of formula X.

R11 -H

(X),

wherein R11 is alkoxy, aryloxy or-NR5R6.

A particular embodiment of this method can be applied to the preparation of compounds of the formula I in which Z represents a carbamoyl group, in such a way that a compound of the formula IX in which Y corresponds to a group -SR ", where R" denotes alkyl, and X2 represents the group NR4, reacted with a suitable active hydrogen-containing compound of the formula X. The compounds of formula IX serving as precursors, in which Y is the group SR "and X2 is the group NR4, can in turn be derived from compounds of the formula XI

Ar

Ì A

I, \

R '

N-

(XI),

S 'NNHR "

be preserved.

Those compounds of formula I in which Z is one

V2

Group of the formula where R3 is the above-mentioned R3

Has meaning, and X2 corresponds to a group NR4, can also be prepared by combining a compound of formula II with an inidoyldihalide of formula XII

R4-N = C (Hal) 2

(XII),

where shark means chlorine, bromine or iodine. This reaction produces an intermediate of formula IX, in which X2 denotes the group NR4 and Y shark, which can then be converted into a compound of formula I using the method described above.

The compounds of formula I can be isolated from the reaction mixture in the form of the free base or in the form of an acid addition salt. The bases can then be converted into their acid addition salts using known io methods with the aid of suitable acids. On the other hand, salts of these compounds obtained can be converted into the free bases or into other acid addition salts.

For use as a pesticide, the compounds of the formula I can be offered in the form of the free bases or in the form of their acid addition salts. Suitable acid addition salts of the compounds of formula I are, for example, the hydrohalides, sulfates, nitrates, phosphates, thiocyanates, acetates, propionates, stearates, naph-20 tenates, perchlorates, benzoates, methanesulfonates, ethanesulfonates, tosylates and benzenesulfonates.

The compounds of formula I can be used to control insects, ticks, mites and other arthropods including wild arthropods and those which live as ectoparasites on plants, mammals and birds. They can be used alone or in combination with one or more additives. Suitable additives include, for example, carriers such as are commonly used in formulation technology, e.g. Wetting agents, diluents, stabilizers, thickeners, emulsifiers, dispersants, surface-active substances or other standard carriers.

The formulations can be in the form of an aqueous solution of an acid addition salt of a compound of the formula I or as a suspension of a compound of the formula I in water; they can be used alone or in combination with suitable surface-active substances. The formulation itself can be applied alone or diluted with water to the pests or their immediate environment, which can be done by spraying or dipping.

The formulations may also be in the form of a miscible oil which is a compound of formula 45 in the form of the free base or together with an equimolar amount of a suitable organic acid, e.g. Oleic acid or naphthenic acid to obtain a salt soluble in organic solvents and containing emulsifiers. These miscible oils can be used as an emulsion by spraying or dipping.

The formulations can moreover be present in the form of non-aqueous solutions or suspensions of compounds of the formula I in a suitable organic medium for direct use by the so-called «infusion method». In addition, the formulations can be made up in the form of mesh powders for dilution with water and application by dipping or spraying. Other solid preparations can be used for direct use without dilution; 60 of these include dusts, powders and granules.

Other forms of preparation include Pastes, fats or gels which contain a compound of formula I and a suitable carrier; they can be applied by brushing the infected area. The compounds of the formula I in the form of the free bases or their acid addition salts are present in the pesticide formulations, preferably in an amount of 5 to 80% by weight, calculated as the base, with particular

642 821

ders preferred formulations contain about 20 wt .-%, calculated as base. The concentration at which a compound of the formula I is applied to the pests or their immediate surroundings is generally in the range from 0.001 to 20% by weight, calculated as the base.

From the foregoing, it can be seen that the following novel features are to be claimed:

(a) Pesticidal preparations which contain new, substituted phenoxyalkyl or anilinoalkylimidazolines of the formula I or their acid addition salts and a carrier;

(b) a process for the preparation of new compounds of the formula I 'and their acid addition salts and

(c) methods for controlling harmful arthropods, in particular those of the Acarina order, by applying a compound of the formula I to the pests or their surroundings;

The following examples serve to explain the invention.

example 1

Preparation of 2- (2,3-dimethyiphenoxymethyl) -l-acetyl-2-imidazoline

A solution of 3.0 ml (0.032 mol) of acetic anhydride in 10 ml of diethyl ether was added dropwise over 10 minutes to a stirred suspension of 6.12 g (0.030 mol) of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline (made from 0-ethyl-2,3-dimethylphenoxyacetiminoester and ethylenediamine) in 100 ml of diethyl ether and the mixture cooled to keep it at a temperature below 20 ° C. After stirring for two hours, the reaction mixture was filtered and the precipitate was recrystallized from acetone. White crystals of 2- (2,3-dimethylphenoxy-methyl) -l-acetyl-2-imidazoline, melting point 127 to 130 ° C., were obtained. Analysis:

calculated: C 68.27 H 7.37 N 11.37%

found: C 68.13 H 7.44 N 11.13%

Example 2

2- (2,3-dimethylphenoxymethyl) -l-N, N-dimethylthio-carbamoyl-2-imidazoline

A solution of 2.47 g (0.020 mol) of dimethylthiocarbamoyl chloride in 10 ml of chloroform was added dropwise over 10 minutes to a stirred solution of 4.08 g (0.020 mol) of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline, prepared as in Example 1, and 2.0 g (0.20 mol) of triethylamine in 50 ml of chloroform were added and cooled to keep the temperature of the mixture below 5 ° C. The temperature was then allowed to rise to room temperature. Finally, the reaction mixture was heated to reflux temperature for 5 hours. After cooling, the reaction mixture was washed with water, dried and evaporated. The residue was recrystallized from isopropanol and gave white crystals of 2- (2,3-dimethylphenoxymethyl) -1 - (N, N-dimethylthiocarbamoyl) -2-imidazoline, melting point 124 to 127 ° C.

Analysis:

calculated: C 61.84 H 7.27 N 14.42%

found: C 62.15 H 7.64 N 14.35%

Example 3

2- (2,3-Dimethylphenoxymethyl) -1 - (N-methylthiocarb-amoyl) -2-imidazoline

A solution of 1.46 g (0.20 mol) of methyl isothiocyanate in 10 ml of chloroform was added dropwise over 10 minutes to a stirred solution of 4.08 g (0.020 mol) of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline, prepared as in Example 1, added in 50 ml of chloroform and cooled to keep the reaction temperature below 5 CC. The reaction mixture was allowed to warm to room temperature and was finally heated under reflux for 5 hours. The chloroform was then evaporated in vacuo and the residue was recrystallized from isopropanol. White crystals of 2- (2,3-dimethylphenoxymethyl) -1-N-methylthiocarbamoyl-2-imidazoline were obtained, melting point about 100 ° C. (dec.).

! H -NMR (Deuterochloroform- Tetramethylsilane inter-lo ner standard):

8.1 to 8.35 6.8 to 7.25 5.0 5

15

3.6 to 4.55 3.1 8 20 2.2 5

IH 3H 2H

4H 3H 6H

broad singlet

Multiplet

Singlet

NMR spectrum agrees with the proposed structure

match

Multiplet

Doublet

Doublet

Example 4

1-N-Phenylcarbamoyl-2- (2,3-dimethylanilinomethyl) -2-imidazoline

25 4.20 g (0.024 mol) of 2- (2,3-dimethylanilinomethyl) -2-imidazoline were stirred in 90 ml of methylene chloride, cooled to 0 ° C. and a solution of 2.84 (0.024 mol) of phenyl isocyanate in 10 ml of methylene chloride added dropwise. A white precipitate quickly formed. After addition, stirring was continued at 0 ° C for 2-3 hours, then the reaction mixture allowed to warm to room temperature and stirring continued overnight. The reaction mixture was then evaporated to dryness under reduced pressure and the solid residue thus obtained was recrystallized from propan-2-ol. White crystals of 1-N-phenylcarbamoyl-2- (2,3-dimethyl-anilinomethyl) -2-imidazoline (0.735 HzO), melting point 137 ° C., were obtained.

40 Example 5

l-N- (2,3-dimethylphenoxycarbonyl) -2- (2,3-dimethyl-

phenoxymethyl) -2-imidazoline 3.0 g (0.0147 mol) of 2- (2,3-dimethylphenoxymethyl) -2-imidazoline were dissolved in approx. 40 ml of dry chloroform and cooled to 0 ° C. 2.07 g (0.0147 mol) of tetramethylpiperidine in about 7 ml of dry chloroform was then added to the cooled, stirred solution. 2.71 g (0.0147 mol) of 2,3-dimethylphenyl chloroformate (as a 30 w / v% solution in benzene) was slowly added. A white precipitate thus formed and stirring was continued for 2 hours at 0 ° C, whereupon the temperature of the reaction mixture was allowed to rise to room temperature. Tetramethylpiperidine hydrochloride was precipitated by adding dry acetone and removed by filtration 55. The filtrate was evaporated to dryness under reduced pressure and the white residue was recrystallized from propan-2-ol. 1-N- (2,3-Dimethylphen-oxycarbonyl) -2- (2,3-dimethylphenoxymethyl) -2-imidazoline was obtained, melting point 126 ° to 127 ° C.

60

Examples 6 to 27 The compounds of Examples 6 to 27 are also prepared analogously to the processes described in Examples 1 to 5:

Example 6

1-N-Methyloxycarbonyl-2- (2,3-dimethylphenoxy-methyl) -2-imidazoline, melting point 120 C.

9

642 821

Example 7

1-N-Methylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 147 to 150 C (dec.)

Example 8

1-N-Phenylthiocarbamoyl-2- (2,3-dimethylphenoxy-methyl) -2-imidazoline, melting point 102 to 104 C.

Example 9

1-N-4-toluenesulfonylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 120 CC.

Example 10

1-N- (a-NaphthyI) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 156 to 158 ° C.

Example 11

l-N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxy-methyl) -2-imidazoline, melting point 132 C.

Example 12

1-N- (4-Cyanophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 172 to 174 ° C.

Example 13

1-N-Phenylcarbamoyl-2-phenoxymethyl-2-imidazoline, melting point 170 ° C.

Example 14

1-N, N-Diphenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 143 to 145 CC.

Example 15

1-N-p-Tolylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 137 ° C.

Example 16

1-N-Phenylcarbamoyl-2- (a-phenyloxyethyl) -2-imide-azoline, melting point 159 ° C.

Example 17

1-N- (a-Naphthyl) carbamoyl-2-phenoxymethyl-2-imide-azoline, melting point 160 to 163 ° C.

Example 18

1-N-Cyclohexylcarbamoyl-2- (2,3-dimethylphenoxy-methyl) -2-imidazoline, melting point 63 ZC.

Example 19

1-N-Phenylcarbamoyl-2- (2-chloroanilinomethyl) -2-imide-azoline, melting point 169 ° C.

Example 20

1- (N-phenyl-N-methyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 112 C.

Example 21

1-N-phenylcarbamoyl-2- (a, oc-dimethylphenoxymethyl) -2-imidazoline, melting point 81 to 85: C.

Example 22

1-N-Hexadecylcarbamoyl-2- (2,3-dimethylphenoxy-methyl) -2-imidazoline, melting point 76 to 77 C.

Example 23

1-N- (a-Naphthyl) carbamoyl-2- (3-methylanilinomethyl) -2-imidazoline, melting point 146 C.

Example 24

1-N-Phenylcarbamoyl-2- (2-chloroanilinomethyl) -2-imide-azoline, melting point 168 to 169 C.

Example 25

l-N- (2,6-dimethylphenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline perchlorate salt, melting point 221 to 222 C.

Example 26

l-N- (2,3-dichlorophenyl) carbamoyl-2- (2,3-dimethylphen-oxymethyl) -2-imidazoline, melting point 175 to 180 C.

Example 27

1-N-phenylcarbamoyl-2- (2,3-methoxyphenoxymethyl) -2-imidazoline, melting point 101 C.

Example 28

Preparation of l-methanesulfonyl-2- (2,3-dimethylphen-oxymethyl) -2-imidazoline

8.0 g (0.0392 mol) of 2- (2,3-dimethylphenoxymethyl) -2-imide-azoline was dissolved in 75 ml of dry ether and sufficient (50 ml) of dry chloroform and the solution was cooled in ice (sufficient chloroform was added used to prevent the precipitation of the imidazoline on cooling). To the cold stirred solution, 4.50 g (0.0393 mol) of methanesulfonyl chloride was added dropwise. When the addition was complete, 6.08 g (0.0392 mol) of pentamethylpiperidine was introduced and the reaction mixture was heated under reflux until thin layer chromatography showed that the reaction was complete (about 3 hours). The reaction mixture was then concentrated under reduced pressure and the residue extracted with a water / chloroform mixture (1: 1, about 100 ml). The chloroform layer was washed with water, dried over magnesium sulfate and evaporated under reduced pressure. A residue was obtained which, after recrystallization from isopropanol, gave I-methanesulfonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline, melting point 142 ° to 143 ° C.

Example 29

Analogously to Example 28, 1-benzenesulfonyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline was produced, melting point 108 to 110 ° C.

Example 30

Preparation of 1-N-phenylcarbamoyl-2- (2,3-dimethyl-phenoxymethyl) -2-imidazoline

(A) A solution of 20.4 g (1.0 mol) of 2- (2,3-dimethyl-phenoxymethyl) -2-imidazoline in 300 ml of methylene chloride was cooled to -65 CC and a solution of 11.9 g ( 1.0 mol) of phenyl isocyanate in 300 ml of methylene chloride was added dropwise over 30 minutes. The reaction mixture was allowed to warm to room temperature and stand for 2 hours, during which a precipitate formed. The reaction mixture was evaporated under reduced pressure and the residue was recrystallized from acetone. This gave 1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imide-azoline, melting point 150 to 152 ° C.

Example 31

Blood-soaked female ticks of the Biarra strain of Boophilus microplus were found in groups of 20

s io

15

20th

25th

30th

35

40

45

50

55

60

65

642 821

10th

Ticks per concentration are immersed in different dilutions of the compound to be examined. The washing liquid was prepared immediately before the test by diluting (with water) the compound to be examined. The essential components can be in the form of preparations with miscible oil or mesh powder. The desired concentration ranges for the experiment are obtained by further diluting the main solution or washing liquid.

The ticks are removed from the washing liquid after 10 minutes, dried and glued with the back down onto double-sided adhesive tape. They remain in this position for 14 days, after which the number of viable egg-laying ticks is determined. From these values, a regression line is plotted (concentration against percentage prevention of egg production) and the IR90 and IR99 (concentrations at which 90% and 99% prevention of egg production takes place) are determined.

The results obtained are shown in Table I.

The following preparations are given to show how the pesticidal compounds according to the invention can be applied to pests or to the environment which is susceptible to pest infestation.

Preparation 1 powder

Active compound 1.0 20.0 parts by weight

Talc 99.0 80.0 parts by weight

100 100.0 parts by weight

Table I

Connection at- IR90 IR99

game IR90 IR99

No.

1-N-phenylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-

imidazoline 30 <0.016% -1 -N- (a-naphthyl) carbamoyl-2-10 (2,3-dimethylphenoxy-

methyl-2-imidazoline 10 0.0032% 0.0054% I -N-phenylcarbamoyl-2-

phenoxymethyl-2-imidazoline 13 <0.2%

15 Example 32

Test compounds were prepared in polyethylene glycol and ticks were injected ventrally at a location in the immediate vicinity of the mouth area. After 14 days, the percentage prevention of egg production 20 (IR) was determined. The results are shown in Table II.

% IR

40% at 0.1 mg / ml 70% at 1.0 mg / ml 100% at 10 mg / ml 50% at 0.1 mg / ml

40% at 0.1 mg / ml

70% at 1.0 mg / ml

70% at 0.1 mg / ml

100% at 1.0 mg / ml 40% at 0.1 mg / ml 90% at 1.0 mg / ml

80% at 1.0 mg / ml 70% at 1.0 mg / ml

0.5 part by weight 79.1 parts by weight

100.0 parts by weight

5.0 parts by weight 85.0 parts by weight 10.0 parts by weight

100.0 parts by weight

6.0 parts by weight 94.0 parts by weight 100.0 parts by weight

Preparation 2 mesh powder

Active compound sodium dioctyl sulfosuccinate «Dispersol ACA»

kaolin

25.0 parts by weight 1.0 part by weight 2.0 parts by weight 72.0 parts by weight

100.0 parts by weight

Preparation 3 Aqueous dispersion

Active compound 20.0 parts by weight

"Keltrol" 0.4 parts by weight

65

/ \ klivc veruiiiuiuig Vaseline

Preparation ^ Miscible oil Compound from Example 22 "Aromasol H" nonylphenol ethoxylate

Table II

Compound Example 1-N-Phenylcarbamaoyl-2- (2,3-dimethylphenoxymethyl) -2-imide-

azoline 30

1-N-phenylcarbomoyl-2-phenoxymethyl-2-imidazoline 13

l-N-phenylcarbamoyl-2- (2,3-dimethylanilinomethyl) -2-imidazoline 4 l-N- (a-naphthyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -

2-imidazoline 10

I-N, N-diphenylcarbomoyl-2- (2,3-dimethylphenoxymethyl) -

2-imidazoline 14

l-N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-

imidazoline 11

l-N- (4-toluenesulfonyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-

imidazoline 9

1 -N- (4-tolyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imide-

azoline 15

1-N-methylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imide-

azoline 7

1 -N- (a-naphthyl) carbamoyl-2-phenoxymethyl-2-imidazoline 17

Sodium dioctyl sulfosuccinate 45 water

Preparation 4 infusion

50 Active compound dimethylformamide castor oil

55 Preparation 5

fat

10.0 parts by weight 70.0 parts by weight 20.0 parts by weight

100.0 parts by weight

Claims (17)

642 821 PATENT CLAIMS 1. Pesticide preparation, characterized in that it is an active component of a compound of formula I (I), wherein Ar is a phenyl radical which is unsubstituted or mono-, di- or trisubstituted by alkyl, alkoxy, halogen, hydroxy, cyano, amino, trifluoromethyl or nitro, where the substituents are identical or different and any two adjacent carbon atoms on the phenyl ring by a carbon chain with 3 or 4 carbon atoms may be connected; X1 is oxygen or NH; R1 and R2, which are the same or different, are hydrogen or alkyl; and Z is a group of the formula SOnR8 or a group of the formula ^ X2 -C ^ R3 ' in which X2 oxygen, sulfur or NR4; R3 is alkyl, aryl, akoxy, aryloxy or -Nc ^ e; R4 alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio R5 or -N; • R6 ' R5 and R6, which are the same or different, are hydrogen, alkyl, aryl, -COR7 or S02R7 or one of the radicals R5 and R6 is hydrogen and the other is cyclohexyl; R7 is alkyl, aryl, alkoxy or aryloxy; n 1 or 2; R9 R8 is alkyl, aryl or -Nc ^, 0; and Contains N- (4-chlorophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof. 6. pesticide preparation according to claim 1 or 2, 5 characterized in that it is an active component 1- Contains N- (4-cyanophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof. 7. pesticide preparation according to claim 1, characterized io that they are 1-N-cyclo- as active component contains hexylcarbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imide-azoline. 8. Method of combating harmful arthropods, characterized in that one looks at the pests 15 or the environment of the pests applies a compound of formula I or its acid addition salts. 9. The method according to claim 8 for controlling pests from the order Acarina. 10. Process for the preparation of compounds of the 20 formula 25th 30 in which Ar is a phenyl radical which is unsubstituted or mono-, di- or trisubstituted by alkyl, alkoxy, halogen, hydroxy, cyano, amino, trifluoromethyl or nitro, where the substituents are identical or different and where 35 has any two adjacent carbon atoms on the phenyl ring by a carbon chain 3 or 4 carbon atoms can be connected; X1 is oxygen or NH; R1 and R2, which are the same or different, are hydrogen 40 or alkyl; and Z 'is a group of the formula SOnR8 or a group of the formula 45 R ° and R10, which are the same or different, represent hydrogen, alkyl or aryl, mean, provided that when Ar is unsubstituted phenyl, X1 NH, R1 and R2 are hydrogen, Z is a group of the form X2 mei -C ,, where X2 corresponds to oxygen, R3 represent K does not mean methyl, or contains an acid addition salt thereof and a carrier. 2. Pesticide preparation according to claim 1, characterized in that the active component is present in an amount of 5 to 80% by weight, preferably in an amount of about 20% by weight, calculated as the base. 3. Pesticidal preparation according to claim 1 or 2, characterized in that it contains 1-N-phenylcarbamoyl-2- (2,3-dimethyl-phenoxymethyl) -2-imidazoline or an acid addition salt thereof as the active component. 4. Pesticidal preparation according to claim 1 or 2, characterized in that it contains 1-N- (a-naphthyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof as the active component. 5. Pesticide preparation according to claim 1 or 2, characterized in that it is an active component 1- _c <X2 U <R3 ' in which X2 oxygen or sulfur; -R5. R3 is alkyl, aryl, alkoxy, aryloxy or -N <^ 6; so R4 alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio or -NC ^ \; R R5 and R6, which are the same or different, are hydrogen, 55 alkyl, aryl, -COR7 or S02R7 or one of the radicals R5 and R6 is hydrogen and the other is cyclohexyl; R7 is alkyl, aryl, alkoxy or aryloxy; n 1 or 2; R9 R8 is alkyl, aryl or -NC ^, 0; and 60 R9 and R10, which are the same or different, represent hydrogen, alkyl or aryl, mean, provided that when Ar is unsubstituted phenyl, X1 NH, R! and R2 is hydrogen, Z 'is a group of 65 * 2 Formula -C <i \, where X2 corresponds to oxygen, R3 R3 does not mean methyl, and from their acid additions 3rd 642 821 salt, characterized in that a compound of formula II mei I 'in which Z' is a group of the formula -C C X2 R3 ' where X2 and R3 have the meaning given in claim 1. 14. The method according to any one of claims 10 to 13, characterized in that one produces a compound of formula Y, wherein Z 'is a group of the formula -C = (0) -NR5R6, or -C = (S) -NR5R6, wherein R5 and R6 have the meaning given in claim 1. 15. The method according to claim 14, characterized in that one produces a compound of formula I ', wherein R5 is hydrogen and R6 aryl. 16. The method according to claim 15, characterized in that one produces a compound of formula I ', wherein R6 is phenyl, 4-chlorophenyl, 4-cyanophenyl or a-naphthyl. 17. The method according to any one of claims 10 to 16, characterized in that 1-N-phenylcarbamoyI-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof is prepared. 18. The method according to any one of claims 10 to 16, characterized in that l-N- (a-naphthyl) -carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof is prepared. 19. The method according to any one of claims 10 to 16, characterized in that l-N- (4-chlorophenyl) car bamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof is prepared. 20. The method according to any one of claims 10 to 16, characterized in that l-N- (4-cyanophenyl) carbamoyl-2- (2,3-dimethylphenoxymethyl) -2-imidazoline or an acid addition salt thereof is prepared.