DE2454795A1 - HETEROCYCLIC COMPOUNDS AND THEIR USE AS PEST CONTROL AGENTS - Google Patents

Description

DR. BERG DIPL.-ING. STAPF
DIPL.-ING. SCHWABE DR. DR. SANDMATR

PATENT LAWYERS O A * A 7 Q ■?

MUNICH 86, POST BOX 860245 £ H O * ♦ / <3 O

Addition to patent application P 22 60 025.5 dated December 7, 1972, attorney's file 25 579 -jg »ny

Be / Sch

! EHE BOOTS COMPANY LIMITED Nottingham / England

"Heterocyclic compounds and their use as pesticides"

The present invention relates to chemical compounds, pesticides, using these compounds as
Containing active ingredients, and the use of the compounds for controlling pests.

The compounds of the invention have the following all case 549 S09822 / 103 3,. · ' ² '

mean formula

I,

-XC-NR ¹

wherein X is an oxygen or sulfur atom, R ^ is an optionally substituted alkylthio, alkenylthio, aralkylthio, Alkoxyalkyl or alkylthioalkyl group, R is a

1 alkyl or cycloalkyl group and each of the radicals R and R an alkyl, alkenyl, alkoxyalkyl or haloalkyl group

12th

or the radicals R and R together with the nitrogen atom, to which they are connected, an optionally substituted heterocyclic ring, namely a morpholino, Thiamorpholino, 1-pyrrolidinyl and / or 1-piperidino group form, and their salts.

1 2
The radicals R and R can be identical or different and if they are alkyl groups they preferably contain 1 to 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl and η-butyl groups, with methyl groups being particularly preferred.

A p

If the radicals ¹ R or R are an alkenyl group, this preferably contains 2 to 4 carbon atoms and it can be, for example, an allyl or 2-methylallyl group.

509822/1033

If the radicals R ^ or R ^{2 are} an alkoxyalkyl radical, this preferably contains 2 to 4 carbon atoms and they can be, for example, a 2-methoxyethyl or 2-ethoxyethyl group. The radicals R or R, when they are haloalkyl radicals, preferably contain 1 to 4 carbon atoms and they are then suitably substituted with a single halogen atom, namely chlorine, fluorine and bromine, and such radicals include, for example, chloromethyl and 2-chloroethyl radicals.

Ί P

When the group NR R is a substituted heterocyclic Ring, this can be, for example, by 1 to 4-alkyl groups, in particular methyl groups, the substituents with df./ .. carbon atoms of the heterocyclic Rings are connected. To such alkyl-substituted heterocyclic groups include, for example

2,6-dimethylmorpholino-, 4-methyl-1-piperidino-, 2-methyl-1-piperidino-, 2,6-dimethyl-1-piperidino and 2-ethyl-1-piperidino groups. The heterocyclic radical NR R is preferably composed of 1-pyrrolidinyl, 1-piperidino and in particular Morpholino groups selected.

Preferred groups of compounds are those in which (a) both radicals R ¹ and R ^{2 are} methyl groups, (b) R * ^{1 is} a methyl and R is a methyl, ethyl or propyl group and (c) the radicals R * ¹ and R ² together with the nitrogen atom to which they are attached form a morpholino group. It is also preferred that X is an oxygen atom.

609822/1053 -4-

The radical R ^ is optionally a substituted alkylthio, alkenyl thio, aralkylthio, alkoxyalkyl or alkyl thioalkyl group. When optionally substituted alkylthio, the remainder may or may not be branched and examples include methylthio, ethylthio, propylthio, isopropylthio, butylthio _? sec-butylthio, pentylthio and hexylthio groups. The alkylthio group preferably contains 1 to 4 carbon atoms and methylthio and ethylthio radicals are particularly preferred. The alkylthio group may be substituted with one or more substituents such as one or more halogen atoms, an alkoxy group, an alkoxy carbonyl group, an altylthio group, an alkenyloxy group or a dialkylamino group. Examples of such substituents include chlorine, bromine, fluorine, methoxy, ithoxy, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, vinyloxy, dimethylamino and diethylamino groups. Particularly preferred R radicals, if they are a substituted alkylthio group, are methoxymethylthio, ethoxycarbonylmethylthio, methylthiomethylthio, vinyloxyethylthio and dimethylaminoethylthio radicals.

When R ^ is an optionally substituted alkenylthio group is, this can be branched or unbranched and, for example, an optionally substituted allylthio, 2-methylallylthio, Prop-2-enylthio or but-2-enylthio group, preferably containing 2 to 4 carbon atoms. When the radical is substituted, preferred are substituents

609622/1033 " ⁵ "

one or two halogen atoms, such as bromine, fluorine and especially chlorine atoms.

When R ^ is an optionally substituted aralkylthio group it is preferably a benzylthio group or a benzylthio group having one or more substituents is substituted, such as with halogen, nitro, alkoxy, trihalomethyl or alkyl, especially methyl groups. One or two substituents on the are particularly useful Phenyl ring. Examples of such groups are benzylthio, 4- Chlorobenzylthio, 2,4-dichlorobenzylthio, 2-methyl-4-chloro, benzylthio, 2-methylbenzylthio, 2,4-dimethylbenzylthio, 3-nitrobenzylthio, 2-methoxybenzylthio, 4-methoxybenzylthio and 3-trifluoromethylbenzylthio groups.

When R * is an optionally substituted alkoxyalkyl or Is alkylthioalkyl group, it preferably contains 2 to 4 carbon atoms, with methoxymethyl and methylthiomethyl, methoxymethyl groups are particularly preferred.

The radical R is an alkyl or cycloalkyl group and contains preferably up to 10 carbon atoms. If R ^ a Is alkyl, it can be straight or branched and it can be, for example, methyl, ethyl, propyl,. Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 1-ethylpropyl, pentyl, tert-pentyl, hexyl, Li ^ rTrimethylpropyl-, heptyl-, 1.1-Diä.thylpropyl-, 2.3-3- ·

509822/1033

Trimethylbut-2-yl, octyl, 2-ethylhexyl, nonyl or

/ I

Be decyl group. Preferably R contains 3 to 5 carbon

H.

Substance atoms and particularly preferred are R radicals if the Alkyl group an isopropyl, tert-butyl, sec-butyl, 1-

Il

Ethylpropyl and tert-pentyl group. When R is a cycloalkyl group is, it can contain, for example, up to 8 and in particular 3 to 7 carbon atoms in the cyclo-ring. The cycloalkyl group can optionally have one or more substituents on the ring, for example one or several lower alkyl, e.g. methyl, substituents. A lower alkyl substituent is preferably in the 1-position with the cycloalkyl carbon atom that with the imidazole ring is connected, and if there are more than one substituent on the cycloalkyl group, these can be the same or different. For example, R radicals can be cyclopropyl, cyclobutyl, 1-methylcyclobutyl, cyclopentyl, 1-methylcyclopentyl-, cyclohexyl-, 1-methylcyclohexyl-, Be 1-methylcyclohexyl radicals, the 1, 2 or 3 others Methyl substituents, such as 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, cycloheptyl or cyclooctyl groups contain. If the radical R is preferably a cycloalkyl group, this contains 5 or 6 carbon atoms in the cycloring and is a cyclopentyl radical with optionally 1 to 3 methyl substituents or cyclohexyl radical with optionally 1 to 3 methyl substituents.

A special group of the compounds of the formula I.

ORIGINAL INSPECTED

include those in which X is an oxygen or sulfur atom, R ^ is an alkylthio, alkenylthio, aralkylthio or alkoxyalkyl group, R ^ is an alkyl or cyclic alkyl group and each of the radicals r ' ¹ and R ^{2 is} an alkyl, alkenyl , Alkoxyalkyl or haloalyl group or the radicals R and R with the nitrogen atom to which they are connected form a heterocyclic ring which optionally contains 1 to 4 alkyl substituents which are connected to the carbon atoms of the heterocyclic ring, namely morpholino, thiamorpholino -, 1-pyrrolidinyl and I-piperidino groups.

Particularly preferred is a compound of the formula I where $ n X is an oxygen atom, 'S? an alkylthio, R an alkyl group

1 2
and both radicals R ¹ and R are methyl groups or the

1 2
R and R radicals together with the nitrogen atom to which they are connected form an optionally substituted morpholino group. The compounds of the formula I in which the group

pe NR ¹ R is a morpholino group have the further advantage of low mammalian toxicity.

If the compounds of the invention because of their pest control properties are to be used, they are preferably used as free. Base used, however can also be used as acid addition salts which are formed with an inorganic or organic acid can, such as with salt, hydrogen bromide, hydrogen iodide, hydrogen fluoride, sulfur, nitric,

■ -8-

SÖ9822 / 1033

Phosphorus, perchlorine, sulfamine, ant, vinegar, trichloroacetic, Oxal, picrin, benzenesulfon, dodecylbenzenesulfon, p-toluenesulphonic, stearic, flavian, embon or tetraodophthalic acids. Such salts are effective as pesticides because of the imidazole cation content of the salt.

The compounds of the present invention have been found to be useful as pesticides and that they can be used, for example, to control insects. "They are particularly useful to control aphids such as Aphis fabae, Megoura viciae, Myzus persicae, Phorodon humuli, Eriosoma lanigerum, Brevicoryne brassicae and Acyrthosiphon pisum. For more insect species that are associated with the compounds of the invention can be controlled, include, for example, the larvae of the cabbage moth (Plutella m'aculipennis), the larvae the codling moth (Cydia pomonella), caterpillars such as those of the great cabbage white butterfly (Pieris brassicae) and hopping insects such as the green rice leafhopper (Nephotettix cincticeps). Furthermore, the connections effective against (sheep) blowflies (Lucilia sericata) and acarids such as mature spider mites (Tetranychus urticae).

The invention also includes a preparation suitable for pest, preferably insect control, which is a compound of the invention as an active ingredient

509622/1033

ait contains an extender. The extender can be a Solid or a liquid, optionally together with a surface-active agent, for example a dis- ^ v to be emulsifying or wetting agents.

More than one compound of the invention can be used in this preparation be introduced. If desired, the preparation can furthermore contain one or more further pesticides such as compounds known to be fungicides, acatficides or insecticides Have effectiveness. Insecticidal compounds include organochlorine compounds such as DDT, benzene hexachloride or dicofol; Organophosphorus compounds such as, for example, fenitrothion, azinphos-methyl, demeton or dimethoate; or a carbamate such as carbaryl. Fungicidal compounds that can be used are, for example Binapacryl, Benomyl, Captan and Maneb.

The formulations of the invention can be in forms that are known in the art for the formulation of pesticides may be converted, for example in the form of solutions, aqueous dispersions ,, aqueous .Emulsionen, ^x dusting powders, dispergier.bare powder, smoke agent, emulsifiable concentrates and Granules · Such preparations include not only preparations in a form suitable for the application, but also concentrated primary preparations that can be diluted with a suitable amount

-10-

Water or other extender required before use do. Dispersible powders and emulsifiable concentrates are typical examples of such primary preparations.

As a dispersion, the preparation contains a compound of Invention dispersed in an aqueous medium. It is often useful to give the consumer a primary preparation available that can be diluted with water to give a dispersion of the desired concentration obtain. The primary preparation can be marketed in any of the following forms. It can be a dispersible solution containing a compound of the invention dissolved in an aqueous-miscible solvent having with the addition of a dispersant. But it can also be a dispersible powder that is a compound of the Invention and a dispersant contains. Furthermore, a compound of the invention can be in the form of a finely divided Powder together with a dispersant and intimately mixed with water as a paste or cream, which, if desired, an oil-in-water emulsion to form a Dispersion of the active ingredient in an aqueous oil emulsion was added can be.

An emulsion contains a compound of the invention dissolved in a water-immiscible solvent, whereby it into the emulsion form with water in the presence of an emulsifying agent

500822/1033

is brought by means. An emulsion of the desired concentration can be formed from a primary preparation of the following types. It can be a concentrated emulsion to be put on the market containing a compound of the invention together with an emulsifying agent, water and a water-immiscible solvent. However, an emulsifiable concentrate can also be supplied to the user that is a solution of a compound of the invention in a water-immiscible solvent that is a Contains emulsifier.

A dust powder contains a compound of the invention intimately mixed and ground with a solid powdery one Extenders, for example kaolin.

A granular pesticide contains a compound of the invention together with similar extenders as they are used with dust powders, the mixture by means of known Process is granulated. But it can also be the active ingredient on a preformed granular extender, for example Fuller's earth, attapulgite or limestone rock be absorbed or adsorbed.

The concentration of the active ingredient in a preparation, Ad »to j intended for direct use against the pests, is generally in the range from 0.001 to 10 wt. in particular 0.005 to 5% by weight. In a primary

-12-

60S822- / 1Ö33

Preparation may vary widely, the amount of active ingredient and can be, for example 5 to 95 wt.% Of the preparation.

A method also falls within the scope of the invention for pest control, which consists in placing a compound of the present invention at the location j an which the pests occur, i.e. apply to the pests or their whereabouts. A particular embodiment of the invention is a method for protecting plants to insects, particularly aphids, which consists in having a compound of the present invention on plants or their surroundings.

To control pests, the active ingredient can be used as such or, preferably, in the form of the preparations described above be applied. Immediate treatment is often the preferred method, such as spraying, Pollination or fumigation of plants infested with insects. But the active ingredient can also be in the soil, in which the plants grow, are introduced in the form of granules or as a root drink. In such cases it will the active ingredient is absorbed through the roots of the plant and thus forms a protection against the insects. A preferred one The application ratio of the active ingredient is in the range from 0.0056 to 11.210 kg / ha (0.005 to 10 Ib./acre), especially 0.011 to 5.605 kg / ha (0.01 to 5 lb / acre). the

SÖ9822 / 1Ö33

Compounds of the present invention can be used to protect aphids can be used against a variety of plants, such as ornamental plants such as roses and useful plants such as fruit trees, vegetables, potatoes, hops, sugar beets, cotton, corn, rice and tobacco.

The compounds of the present invention can be prepared by means of a process, including an imidazole of the general formula

R ⁴ - 'N

. H ■ z tL

in which the radicals R- ^ and R have the meaning defined above, with a carbamoyl halide or thiocarbamoyl halide of the general formula Z-CXNR R | III), in which the radicals R, R and X have the meaning defined above and Z is a halogen, for example chlorine or bromine, preferably chlorine atom is, implements. The reaction is most conveniently carried out in the presence of an inert organic liquid as the reaction medium, which is preferably a solvent for the reaction · partner is carried out. Advantageously, the reaction in the presence of a suitable base, for example a tertiary amine such as triethylamine, pyridine or alkali metal carbonate carried out in order to take up the hydrogen halide formed in the reaction. But it can also be the imidazole with an alkali metal hydride, such as sodium hydride, under

Formation of an N-alkali metal derivative can be reacted with a halide of the formula III before the reaction. If the connections are made in this way, the reac-. tion partners are preferably reacted with one another at a temperature of from 0 to 12O ⁰ C, for example 50 to 95 ° C. The salts of the invention can easily ^v by treating the product with acid nach.bekannten method thus formed are prepared.

The imidazole compounds of the formula ..II, wherein R ^ an optionally substituted alkylthio, alkenylthio, aralkylthio, alkoxyalkyl or alkylthioalkyl group and R is a Cycloalkyl or alkyl groups with more than one carbon atom are new compounds.

The compounds of the formula II in which R * is optionally substituted alkylthio, alkenylthio or aralkylthio group can be prepared, for example, that an alkali metal thiocyanate with a suitable aminomethyl ketone of the general formula

R ⁴ COCH ₂ NH ₂ with formation of a thiol of the following formula

R ⁴ -r- N

IJ-

IV

SH

-15-

609822 / 103-3

implements, which in turn by means of well-known processes alkylated to form the compounds of formula II, can be alkenylated or aralkylated. There can also be compounds of the formula II in which R * is optionally substituted alkylthio, alkenylthio or aralkylthio group is, be prepared by, in the presence of alkali, an et-haloketone of the general formula R ^ COCHpZ, where Z is a halogen atom, with an S-alkylisothiouronium salt the following formula

where Έ? ' has the meaning defined immediately above and A is a suitable anion, for example a sulfate or halide, is converted.

The ..: Compounds of the formula II in which R- 'is an optionally substituted alkoxyalkyl or alkylthioalkyl group can be prepared, for example, by adding an aldehyde of the general formula R * CHO, in which R * is an optionally substituted alkoxyalkyl or alkylthioalkyl group , with an acyloxylated ketone of the general formula R COQH ₂ B, wherein. B a «presence of ammonia condensed.

mean formula R COQH ₂ B, in which. B is an acyloxy group in

Carbamoyl halides or thiocarbamoyl halides of the general Formula III can be prepared by

509822/1033

Λ 2
a secondary amine of the formula RR NH with a carbonyl

halide or thiocarbonyl halide of the general formula / CXZp, where Z is a halogen atom, preferably a chlorine atom, implemented according to known methods.

The compounds of the present invention can further be prepared by a process, including a carbamoyl halide or thiocarbamoyl halide of the general • formula

■ χ Il

wherein the radicals R, R and X have the meaning defined above and Z is a halogen, preferably chlorine, atom with

Ί 2 a secondary amine of the general formula RR NH, in which the radicals R ¹ and R have the meaning defined above. The compound of the formula V can be prepared by reacting an imidazole of the formula II with a carbamoyl or iEhiocarbamoylhalogenid CXZ ₂ »where Z is a halogen atom.

According to another method of making the compounds of the invention can be a carbonyl bisimidazole or thiocarbonyl bisimidazole the general formula

S09Ö22 / 1Ö33

wherein the radicals R *, R and X have the meaning defined above, with a secondary amine of the general formula
E ¹ R NH, in which R and R have the meaning defined above, are reacted. The compound of formula VI can be prepared by reacting an imidazole of formula II with about 0.5 molecular parts of a carbamoyl or thiocarbamoyl halide CXZ ^, where Z is a halogen atom.

It should be pointed out that the reactions described above for the preparation of the compounds of the formula I yield one or both of the two isomeric products, depending on whether the nitrogen atom in the imidazole ring is substituted (the free hydrogen of the imidazole molecule of the formula II can with each of the ring nitrogen atoms connected). The products
of the present invention can be conveniently used as
1- (NN-disubstituted carbamoyl- or -thiocarbamoyl) -2-R * - 4- (5) -R -imidazoles and this designation
corresponds to formula I, which includes the two isomeric forms. According to the experiments of the applicant, it emerges that the solid products of the reactions described above, after purification by means of conventional methods, such as by ΛΙβκ--

600852 / 1033--

crystallize, are obtained in many cases as essentially pure ^ -substituted compounds. Continue to be in many cases the liquid products of those described above Reactions after isolation by conventional 'methods, such as by distillation under vacuum * in many Cases predominantly in the 4-substituted isomer

Maintain shape. Such 4-substituted isomers can be used as 1- (N.N-disubstituted carbamoyl- or thiocarbamoyl) -2-R * - 4-R-imidazole.

The following examples illustrate the invention. Provided The physical properties of the compounds given are solids by melting point and liquids characterized by boiling point information.

This example illustrates the preparation of compounds according to the invention.

5.1 ml of dimethylcarbamoyl chloride in 20 ml of dry dioxane was added to a mixture of 9 »2 g of 2-ethylthio-4-tert-butylimidazole and 8.4 ml of triethylamine in ^ O ml of dry dioxane. After heating the mixture on the steam bath for 24 hours, the triethylamine hydrochloride was removed and the product, 1-dimethylcarbamoyl-2-ethylthio-4 (5) -tert.-butylimidazole, was distilled. It had a boiling point of 108 to 111 ° C / 0.10 to 0.12 Torr and crystallized nae \

S09S22 / 1Ö33

Cool to a solid with a melting point of

The 2-ethylthio-4-tert-butylimidazole used in the given reaction was made in the following manner.

104 g of potassium thaiimide were suspended in a solution of 100 g of bromopinacolone in 300 ml of dry toluene. This reaction mixture was stirred on the steam bath for 18 hours and the solid precipitate filtered off and washed with toluene. The wash liquors were added to the filtrate, which was heated on the steam bath to concentrate. The product "domestic product, J ^ -dimethyl-i-phthalimidobutan ^ -one, crystallized on cooling. It was washed with light petroleum (bp 80 to 100 ⁰ C) and its melting point was 97 to 101.5 ° C. 82.6 3.3-dimethyl-1-phthalimidobutan-2-one g was refluxed for 10 hours with a mixture of 460 ml concentrated hydrochloric acid, 400 ml water and 324 ml acetic acid, the mixture was evaporated, 360 ml water was added and the solution in ice The phthalic acid was filtered off and the solution evaporated again, the residual solid being dissolved in warm absolute alcohol. Ether was added to the cooled solution and 1-amino-3,3-dimethylbutan-2-one hydrochloride was obtained as a precipitate, melting point 199 up to 200 ⁰ C.

35 »2 g of 1-amino-3,3-cLimethylbutane-2-rone hydrochloride and 30 g Potassium thiocyanate in 50 ml of water were on the for 2 hours

-20-

Steam bath heated. After cooling the solid formed was collected, washed with water, dried and recrystallized from denatured alcohol, -wodurch one 4-tert.Butylimidazol-2-thiol, mp 232 to 234 ⁰ G, received. A solution / suspension of this material in denatured alcohol was added to a solution of 4.5 g sodium hydroxide in 100 ml water. 17 »6 g of ethyl iodide were then added and the mixture shaken for 20 minutes. The product obtained was neutralized by bubbling into carbon dioxide and the denatured alcohol was removed by evaporation. The solid was collected, washed with water, dried and gave after recrystallisation from toluene, 2-ethylthio-4-tert.butylimidazöl, melting point 116.5 to 120 ⁰ C.

Example 2

This example illustrates a process for the preparation of 1-dimethylcarbamoyl-2-methylthio-4 (5) -tert.butylimidaz oil.

1.2 g of sodium hydrod in mineral oil (50 # dispersion) were added to 3 »4 g of 2-Methylthi0-4-tert-butylimidazöl in dry Tetrahydrofuran added. After the hydrogen evolution ceased, 2.7 g of dimethylcarbamoyl chloride was carefully added admitted. Heat developed and a precipitate formed. After one hour the solid was removed and the product is distilled. It was 1-dimethylcarba- moyl-2-methylthio-4 (5) -tert.butylimidazole, boiling point 107 ° C / 0.07 torr.

-21-

S0S822 / 1Ö33

The imidazole reactant used in the above procedure was similar to that described in Example 1 2-Ethylthio-4-tert.butylimidazole produced.

Example 3

This example illustrates another process for the preparation of compounds according to the invention.

While stirring, 11.5 g of 2-methoxymethyl-4-tert-butylimidazole were added to a solution in 30. ml of tetrahydrofuran and 20 ml of triethylamine 8 g of dimethylcarbamoyl chloride. The received The mixture was refluxed for 3 hours and then diluted with methylene chloride, washed with water and the Methylene chloride solution then dried over magnesium sulfate. After evaporation of the solvent, a residue was obtained which distills under reduced pressure, the product, 1-dimethylcarbamoyl-2-methoxymethyl-4 (5) -tert.butylimidazole, Boiling point 106-108 ° C / 0.1 torr.

The imidazole reactant used in the previous procedure was made in the following manner.

To a solution of 123 g of potassium acetate in 1200 ml of methanol they gave 143 g of brompinacolone. This reaction mixture was refluxed for two hours then cooled and filtered. The filtrate was added to a solution of 320 g with stirring Copper (II) acetate monohydrate in 1600 ml of 25 # ammonia and

-22-

60 & 822/1033.

1400 ml of water, after which 100: g of 77 # strength aqueous solution of methoxyacetaldehyde. admitted. The temperature of the reaction mixture was kept at JO to 40 ^° C. for 1 hour and the mixture was then heated on the steam bath for a further 4 hours. After cooling overnight, the insoluble copper salt was collected, washed with water and suspended in 500 ml of 4N acetic acid. A solution of 133 g of potassium iron III cyanide in 400 ml of water was added and the precipitated copper complex was removed and washed with water. The combined supernatant washes were basified (pjj 9-10) with 5N sodium hydroxide and extracted with ether. The ether extracts were combined, washed with water and dried over magnesium sulfate. The solvent was evaporated and the residue recrystallized from petroleum ether (boiling point 60 to 80 ⁰ C) to give 2-methoxymethyl-4-tert.butylimidazol, melting point 65 to Section 6 ° C, the product was obtained.

The following compounds were made in an analogous manner manufactured.

i-Dimethylcarbamoyl-2-methoxymethyl-4 (5) -sec.butylimidazole, Boiling point 108 - 110 ° C / 0.01 Torr

1-dimethylcarbamoyl-2-methoxymethyl-4 (5) - (1-methylcyclopentyl) imidazole, Boiling point 132-134 ° C / 0.2 Torr

1-morpholinocarbonyl-2-methöxymethyl-4 (5) - (1-methylcyclopentyl) imidazole, m.p. 150-152 ⁰ C.

-23- 509822/1033

i-CN-methyl-N-ethylcarbamoyl) -2-methoxymethyl-4 (5) -tert. butylimidazole, Boiling point 112-114 ° C / 0.2 Torr

1 _ (N-methyl-N-ethylcarbamoyl) -2-methoxymethyl ~ 4 (5) -sec. butylimidaz oil, Boiling point 116 - 118 ° C / 0.25 Torr

1-Dimet] aylcarbamoyl-2-inetliöxymetliyl-4 (5) - (1-ethylpropyl) -imidazo !, Boiling point 118 - 120 ° C / 0.1 0? Orr

1-Dimetb.ylcarbamoyl-2-methoxymethyl-4 (5) - (1 -methylcyclohexyl) imidaz oil,. Boiling point 14-5 - 146 ° C / O, 1 Torr

1-dimethylcarbamoyl-2-methOxymethyl-4 (5) -tert.pentylimidazole, Boiling point 115 ° C / O, 2 Torr

1-Morpholinocarbonyl-2-methoxymethyl- ^z t- (5) -tert.pentylimidazole, boiling point 158-140 ° C / 0.1 Torr

1 -Morpholinocarbonyl ^ -methoxymethyl- · 4- ert (5) -t butylimidazole, mp. 57 - 58 ⁰ C

The following intermediates were made in the course of manufacture of the above compounds - isolated.

2-methoxymethyl-4-sec.butyli ^ nidazole, boiling point 122 - 124 ⁰ g / 0.6 torr

2-methoxymethyl-4- (1-methylcyclopentyl) -imidaz oil, Boiling point 126 - 128 ° C / 0.3 Torr

2-methoxymethyl-4- (1-ethylpropyl) imidaz oil, Boiling point 126 - 128 ° C / 0.2 Torr '"

2-methoxymethyl-4- (1-methylcyclohexyl) imidaz oil, Boiling point 142 - 144 ° C / 0.5 Torr

2-methoxymethyl-4-tert.pentylimidazole, '

Boiling point 116 - 118 ° C / 0.4 Torr

5098 ^ 2/1033

Example 4-

The following carbamoyliinidazole compounds. of the general formula I (X = oxygen) were prepared in a manner similar to that described in Example 1.

R-

methyl methyl Benzylthio tert-butyl π R. 4-chlorobenzylthio η π η Propyl thio π ethyl ethyl Methylthio R. methyl methyl Is opr opylthi ο H η η Allylthio η R. η n-pentylthio η η η n-butylthio R. π η lthylthio sec-butyl η π Methylthio η η Propylthio « η η Ethylthiο Isopropyl R. η Methylthio η π π π 1-Medicine π η Ethylthiο H π π Propylthio ' M.

Physical state and constant

solid, 65-67 ⁰ C solid, 96-97 ⁰ C solid, 69-71 ° C liquid, 114 ~ 116 ° C / 0.1 Torr solid, 64-66 ⁰ C solid, 65 "- 67 ° C liquid, 132-136 ° C / O, 08 torr 'liquid, 126-128 ° C / 0.2 torr £ liquid, 103 ° C / O, 08 torr liquid, 100 ° C / O, 05 torr liquid, 108 ° C / 0.06 torr liquid, 115 ° C / O, 11 torr liquid, 116-12O ° C / O, 65 torr

solid, 114-117 C determines 62-64- ⁰ C

ro

cn

CO CJl

methyl

11 η η ti η π

Physical state and constant

methyl Methylthio π Ethylthio ethyl " methyl η η - π M ' 2-methylal It Ethylthio

1-ethylpropyl

liquid, 120-122 ° C / 0.15 torr "liquid, 120-122 ° C / 0.15 torr

tert-butyl solid, 93-94 ⁰ C cyclohexyl solid, 148 ⁰ C 1-methylcyclopentyl liquid, 126-128 ° C / 0.05 Torr tert-butyl liquid, 116-118 ° C / 0.1 Torr

tert-pentyl

liquid, 1-14-116 ° 0 / 0.1 torr

cn

CO

cn

Intermediate product e , ■ "'/'.

The following imidazoles of the general formula II were prepared in a similar manner

as is the case for the preparation of 2-ethylthio-4-tert.butylimidazole in Example 1 "was described ·

crt
ο
co

Έ?

Benzylthio

4-chlorobenzylthio

Propylthio

Methylthiο

Isopropylthio

Allylthio

n-pentylthio

n-butylthio

Ethylthio

Methylthio

Propylthio

lthylthio

Methylthio

Methylthio

lthylthio

Propylthio

tert .Butyl dd R. π π η η η sec. Butyl It

Isopropyl

Il

1-methylcyclohexyl

ti

Physical state and constant

fixed,. 133 ⁰ C solid, 176 ⁰ C solid, 101-103 ⁰ C solid, 149 ° C solid, 160-162 ⁰ C solid, 118-119 ° C solid, 96-98 ° C solid, 79-80 ° C liquid, 115 ° C / O, 16 Torr solid, liquid 74 ⁰ C, 106 ⁰ C / O, 04 Torr solid, 96-98 ° C solid, 96-98 ⁰ C liquid, 126-130 ° C / 0.1 Torr fixed , 74-75 ° C solid, 105-106 ⁰ C.

ro

cn

-ε-

CD

cn

ϋη O CO

Methylthio ethylthio

2-methylallylthio Ethylthio

1-ethylpropyl

Cyclohexyl
1-methylcyclopentyl
tert-butyl
tert-pentyl

Physical state and constant

liquid, 116-118 ° C / 0.2 0? orr liquid, 118-120 ° C / 0.1 torr solid, 110-111 ⁰ C
solid, 69-70 ⁰ C
fixed, 1 (W-105 ° ö
solid, 85 ° C

ro

cn

CD

cn

The intermediates of the formula TV were prepared in a manner similar to that described in Example 1.

R Physical state and constant

sec-butyl determines 109-112 ⁰ C.

Isopropyl solid, 147-15O ° C

1-methylcyclohexyl solid, 205 ^° C

1-ethylpropyl determines 171 ⁰ C.

, Cyclohexyl determines 260-261 ⁰ C.

1-methylcyclopentyl solid, 182-183 ° C

tertiary pentyl solid,

509822/1033

Example 5 Compounds of the invention

The following carbamoylimidazole compounds of the general formula I (X = oxygen) were prepared in a manner similar to that described in Example 2.

R ¹
methyl

H
M.
R.

η
η '
η

methyl
η

ethyl

Propyl

methyl

H
R.

Allyl
methyl

Propylthio

Methylthio

But-2-enylthio

Methylthio

Ethylthio

Methylthio

tert-pentyl

ethyl

tert-butyl

Propyl

tert-butyl

1-methylbutyl cyclohexyl

Propylthio

Butylthio

Methylthio

1-methyleyclohexyl tert-butyl '2-methylallylthio 1-methylcyclohexyl

"Cyclohexyl isopropylthio. Sec-butyl Allylthio "

Physical state and constant

liquid, 122-124 ° C / O, 1 Torr liquid, 100-102 ° C / 0.1 Torr liquid, 124-128 ° C / O, 1 Torr liquid, 106-108 ° C / 0.09 Torr solid, 84-85 ⁰ C

fixed, 100 ⁰ C

liquid, 112 ° C / 0.04 Torr determines 89-90 ⁰ C

liquid, 156-158 ° C / 0.2 Torr determines 42-44 ⁰ C

liquid, 154 ° C / 1.5 torr liquid, 158-160 ° C / 0.2 torr liquid, 166-168 ° C / 0.25 torr liquid, 128 ° C / 0.1 torr • liquid, 124-126 ° C / 0.1 torr

ro

methyl

on O to

It

n η η η η η η η η η

methyl

η η

η η η

Ethyl methyl

Butylthio sec-butyl Il Pentylthio M. Methylthio. Isobutyl Ethylthio η Propylthio 1-ethylpropyl Methylthio methyl η 1-methylcyclopentyl η 1.1.2-trimethylpropyl Ethylthio 1.1.2-trimethylpropyl Propylthio 1-methylcyclopentyl Methylthio tert-pentyl η 1-methylcyclohexyl Ethoxyearbonyl
methylthio tert-butyl 2-vinyloxyethyl
thio Il Methylthiomethyl "
thio ' 2-chloroprop-2-
enylthio

Physical condition
and constant;

liquid, 132-136 ° C / Ö, 1 Torr liquid, 135-159 ° C / O, O8 Torr liquid, 124-128 ° C / 0.1-0.13 0? orr liquid, 12O ° C / O, 07 Torr
liquid, 13O-132 ° C / O, 2 Torr solid, 87 _T 89 ° 0

liquid, 122-124 ° C / 0.1 Torr solid, 50-52 ⁰ C

liquid, 118-120 ° C / 0.1 Torr ι liquid, 134 ~ 136 ° C / 0.05 2? orr ^ liquid, 110-112 ° C / 0.1 torr, liquid, 150-16000 / 0.3 torr liquid, 140-150 ° C / O, 3 torr

liquid, 14-0-14-2 ° C / 0.15 torr liquid, 150-152 ° C / Q, 2 torr

liquid, 136-140 ° C / 0.2 torr

crt ο cc oo

methyl

methyl

2-dimethylamino tert-butyl ethylthio

Methoxymethyl- ^M thio

p enylthio

2-Dimethylamino- sec.Butyl äthylthio Physical state and constant

liquid, 138-140 ° C / 0.1 torr liquid, 145-155 ° C / O, 15 torr liquid, W-149 ° C / 0.2 torr liquid, 150-152 ° C / O, 1 torr

Intermediates ..

The following imidazoles of the general formula II "have been isolated, and they are similar in ^ Way as described for the preparation of 2 ^ ethylthio-4-tert.butylimidazole in Example 1, were manufactured. .

Propylthio Methylthio but-2-methylthio ethylthio methylthio

Propylthio

tert-pentyl

ethyl

tert-butyl

Propyl

tert-butyl

1-methylbutyl

Cyclohexyl Physical state and constant

solid, 85-85.5 ° C solid, 60-61 ⁰ C solid, 84-85 ° C solid, 53 ° C solid, 120 ⁰ C liquid, 118-120 ° C / 0.05 Torr solid, 13O-131 ° C solid, 100-101 ⁰ C

R-

Butylthio 2-methylallylthio

ti

Is opropylthi ο Allylthio Butylthio Pentylthio Methylthio Ethylthio Propylthio methylthio

Propylthio methylthio ethoxycarbonylmethylthxo methylthipmethylthio 2-chloroprop-2-enylthio 2-dimethylaminoethylthio 3-chloroprop-2-enylthio 2-dimethylaminoethy1thio

E.
1-methylcyclohexyl

Il

Cyclohexyl
sec-butyl

Physical state and constant

solid, 80-82 ⁰ C

solid, 115 ° C

solid, 140 ° C

solid, 103-106 ⁰ C

liquid, 134-136 ° C / 0.8 torr

liquid, 138-140 ° C / 0.07 torr

liquid, 155-158 ° C / 0.1 torr

Isobutyl fixed, 60-61 ~ C Il fixed, 66 ⁰ C 1-ethylpropyl fixed, 65-67 ° C methyl fixed, 88-90 ⁰ C 1-methylcyclopentyl fixed, 71-73 ⁰ C η fixed, 59-61 ⁰ C tert-pentyl fixed, 93-94 ⁰ C tert-butyl fixed, 77-79 ⁰ C η fixed, 131-132 ^O C ti fixed, 116-118 ⁰ C η fixed, 66-68 ⁰ C M. fixed, 94-96 ⁰ C sec-butyl liquid, 140-14

ro

Intermediates of formula IV were prepared in a similar way, as described in Example 1, prepared.

4. Physical state and constant

Solid ethyl, 163-165 ° 0

Propyl solid, 183-184 ° C

1-methylbutyl solid, 88-90 ⁰ g

isobutyl solid, 185-186 ⁰ O

Solid methyl, 246 ^° C

1-ethylpropyl solid, ⁰

Example 6

This example illustrates the preparation of compounds

the invention,

1.8 g of sodium hydride in mineral oil (50% dispersion) were gradually added to a solution of 5-4 g of 4-isopropyl-2-methylthioimidazole in 30 ml of dry tetrahydrofuran. After 30 minutes, 5.05 g of morpholinocarbonyl chloride was added. Heat developed and the mixture was refluxed for 1 hour. The tetrahydrofuran was filtered and evaporated to give a residue, which after recrystallization from petroleum ether (boiling point 100 to 120 ° C) the product, 1-morpholinocarbonyl-2-methylthio-4 (5) -isopropylimidazole, mp 63-65 ⁰ G gave .

The imidazole used in the previous procedure. ·

509822/1033

Reactant was prepared in the following manner.

126 g of 3-methylbutane-2-clay in 600 ml of methanol were treated with? 4 ml of bromine, which was added dropwise at a temperature of about 10 ^° G. The solution was chilled on ice and the bromoketone then separated and washed with water. The aqueous alkalis were extracted three times with 50 ml of petroleum ether and the combined bromoketone and petroleum parts were added to 216 g of potassium phthalimide in 500 ml of dimethylformamide. The mixture was then heated with stirring on the steam bath for 2 hours, then filtered to remove insoluble material and poured into 3 liters of water with stirring. The solid was collected, dried and recrystallized from denatured alcohol to give 3-methyl-1-phthalimidep-butan-2-one, m.p. 98-99 ° C.

176.3 g of phthalimidoketone were refluxed for 20 minutes with a mixture of 1 liter of concentrated hydrochloric acid, 1020 ml of water and 710 ml of acetic acid. The solution was evaporated and the residue was taken up in 800 ml of water. After the phthalic acid had been separated off, the solution was evaporated to dryness. The solid was air dried for freedom of excess acid to give i-amino-3-methyl butan-2-one hydrochloride, m.p. 155-158 ⁰ C, obtained.

An aqueous solution of 98.8 g of aminoketone and 63.6 g of potassium

-35-

509822/1033

thiocyanate is heated on a steam bath for 2 1/2 hours. . The oil that settles solidifies to form 4-isopropylimidazole-2-thiol, melting point ⁰

A solution of 6.16 g of potassium hydroxide in 50 ml of denatured alcohol was added to 14.2 g of 4-isopropylimidazole-2-thiol in 150 ml of denatured alcohol, after which 15.6 g of methyl iodide were added. The solution was refluxed for 11/2 hours and the solvent then evaporated. After treatment-of the residue with water, the remaining solid was collected and recrystallized from ethyl acetate. "It was 2-methylthio-4-isopropylimidazole, melting point 96 to 98 ⁰ C.

The following compounds of the general formula I were produced in an analogous manner.

-36- 509822/1033

R ¹ R ² NCX-

Morpholino carbonyl

Physical state and constant

π η

Pyrrolidinylcarb onyl morpholinocarbonyl η}

R M H R R

Methylthio tert-butyl Cyclohexyl solid, 70-72 ° C Ethylthio tert-pentyl R. solid, 79-80 ° C Propylthio R. tert-butyl solid, 63.5-64.5 ° C 2-methylallylthio tert-butyl 1-methyleye1ohexyl liquid, 140-142 ° C / 0.1 Torr Methylthio Propyl solid, 90-92 ⁰ C Ethylthio sec-butyl solid, 94-96 ⁰ C Methylthio R. solid, 99-1O1 ° C Ethylthio H liquid, 186-188 ° C / 0.2 torr Methylthio R. solid, 78-80 ° C ». R. solid, 70-72 ⁰ C Ethylthio H solid, 73-75 ° G Butylthio tert-butyl liquid, 153-157 ° C / O, 1 torr Propylthio R. solid, 34-36 ° C Is opropylthio Isobutyl • POO + - IlM.mmU.fk C
1 CS U f 111 \ J \ j Pentylthio η liquid, 161-166 ° C / 0.1 torr Methylthio Isopropyl solid, 95-97 ° C Ethylthio determines 100-102 ⁰ C. Methylthio solid, 70-72 ° C Ethylthio solid, 63-65 ° C ro R. solid, 59-61 ⁰ C £ j CD CJl

cn o co

R ¹ R ² NCX-

Morpholinocarbonyl

It

η η η ti

Piperidinocarbonyl morpholinocarbonyl

Methylthio Isopropyl Ethylthio 1-ethyl prop Propylth'io η Methylthio N methyl η 1-methyleye η t.ert.Pentyl 2-chloroprop-
2-enylthio tert-butyl Methylthio
metb.yltb.io U Ethylthio η 2-dimethylamino
ethyltbio sec-butyl

Physical state and constant

solid, 63-65 ° C

liquid, 14-2-14-5 ° C / 0.2 Torr liquid, 146-148 ° C / 0.15 Torr liquid, 146-14-8 ° C / 0.2 Torr solid, 81-83 ⁰ C

solid, 90-91 ⁰ C

solid, 85-86 ⁰ C

liquid, 166-168 ° C / 0.25 torr

liquid, 170-172 ° C / 0.2 Torr '

fixed, 63-65 ⁰ C ι

liquid, 164-166 ° C / 0.1 torr

CD CJl

Example 7

This example describes the production of thiocarba

moylimidazole compounds of the invention.

17.0 g of 2-methylthio-4-tert-butylimidazole were dissolved in 200 ml of dry dioxane, after which 13.9 ml of triethylamine and 12.3 g of dimethylthiocarbamoyl chloride were added. The mixture was refluxed for 8 hours, then cooled and the precipitate of triethylamine hydrochloride was filtered off. After the dioxane had been distilled off, a brown oil remained. This oil was extracted with two 50 ml portions of petroleum ether (boiling point 60-8O ⁰ O) and, after cooling, a solid was precipitated, which was collected and recrystallized from petroleum ether (boiling point 80-100 ⁰ C) using charcoal, whereby 1- -tert.butylimidazol dimethylthiocarbamoyl-2-methylthio-4 (5), melting point 94-96 ⁰ C, obtained.

The following compounds were prepared in an analogous manner.

1-dimethylthiocarbamoyl-2-ethylthio-4 (5) - (1-methylcyclohexyl) imidazole, Boiling point 180-190 ° C / O, 2 torr

1-Dimethylthi oc arbamoyl-2-methylthi o-4 (5) -t ert.ρ entylimidazole, Boiling point 126-130 ° C / 0.1 Torr.

-39-

509822/1033

- 59 -

Example 8

This example describes the preparation of 1- (N ~ methyl-N-2 ~ ethoxyethyl) -carbamoyl-a-metliylthio- ^ C 5) -tert .butyl-

imidazole and related compounds.

A solution of 7 g of 2-methylthio-4-tert-butylimidazole in 45 ml of dry tetrahydrofuran became 2, & 2 g of sodium hydride in mineral oil (60 # dispersion) added. The resulting mixture was heated to a temperature between 0 and 5 ° C cooled and then gave 10 g of 1- (N-methyl-N-2-ethoxyethyl) carbamoyl chloride while keeping the reaction mixture below 5 ° C. After filtering to remove the solid precipitate the filtrate was refluxed on the steam bath for two hours. After distilling the product, 1- (N-methyl-S-2-ethoxyethyl) -carbamoyl-2-methylthio-4 (5) -tert-butylimidazole was obtained collected, boiling point 130-134 ° G / O, 1 torr.

The following compounds were made, in a similar manner manufactured.

1- (N-methyl-N-2-ethoxyethyl) -carbamoyl-2-methylthio-4 (5) -isopropylimidazole, boiling point 132-134 ° C / O _r 1 torr

1- (N-methyl-N-2-ethoxyethyl) -carbamoyl-2-methylthio-4 (5) - (1-methylcyclohexyl) r-imidazole _i · boiling point 166-168 ° C / 0.2 Torr.j

Example 9

This example illustrates another method of manufacturing

. -40- 509822/1033

position of the intermediate 2-methylthio-4-tert.butylimidazole of formula II in a way that consists in. that one λ-haloketone with an S-alkylisothiouronium salt implements.

A mixture of 17.9 g of -bromopinacolone, 16.7 g of S-methyl isothiouronium sulfate and 32 g of sodium carbonate in 100 ml of water and 100 ml of ethanol is stirred under reflux for 1 hour. The Etha nol was distilled off and, after adding a further amount of 100 ml of water, 150 ml of toluene were added. The mixture was stirred vigorously for 10 minutes and the hot toluene separated and washed with 100 ml of hot water. 70 ml of toluene and traces of water were distilled off and the remaining toluene solution was stirred at ⁰ ° C. for 30 minutes, whereupon crystalline 2-methylthio-4-tert-butylimidazole separated off. The product was filtered, washed with cold toluene, and dried, mp ^149-0

Example 10

This example describes the preparation of salts of the

Invention.

A concentrated solution of 1.2 g of 1-dimethylcarbamoyl-2-methylthio-4 (5) -tert.butylimidazole in 50 ml of ether was added to a concentrated solution of 1.5 g of flavic acid in 4 liters of ether. The flaviate crystallized on standing and it was filtered off, melting point 205-206 ⁰ G

-41- S09822 / 1033

under decay. After recrystallization from denatured alcohol, a pure sample was obtained, melting point 206 ^° C. with disintegration.

Similarly, the following acid addition salts were made manufactured.

salt Melting point bromide 185 ° C decay Picrat 169-171 ⁰ C. nitrate 152 ⁰ C decay Example 11

This example illustrates the production of emulsifiable ones Concentrates according to the invention.

Emulsifiable concentrates for dilution with water are suitable to form an aqueous emulsion, were prepared from the following ingredients:

# Weight AoI.

Active ingredient 25.0. ■

Calcium dodecylbenzenesulfonate 3.0

N onylphenoxypolyethoxyethanol ⁺ - 3.0 xylene. to 100.0% vol.

Contained nonylphenol ethylene oxide condensate on average 14'MoI of ethylene oxide per mole of nonylphenol.

. -42-

509822/1033

Emulsifiable concentrates containing the following compounds contained, were produced:

1-Dimethylcarbamoyl-2-methylthio-4 (5) -tert.butylimidaz oil 1-Dimethylcarbamoyl-2rathylthio-4 (5) -tert.butylimidaz oil 1-Dimethylcarbamoyl-2-methoxymethyl-4 (5) -tert-butylimidazole 1-morpholinocarbonyl-2-methylthio-4 (5) ^ tert-butylimidazole

Example 12

This example illustrates the production of granules according to the invention.

Granules with a content · .of 5 # w / w. the one in example 11 compounds were prepared in such a way that granules of Fuller's earth (mesh size 0.8 to 0.39 mm) impregnated with a solution of the carbamoylimidazole compound in methylene chloride and then the Methylene chloride evaporates from the impregnated granules.

Example 13

This example explains the production of dispersing

bar powders according to the invention.

Dispersible powders were made from the following ingredients manufactured:

509822/1033

. % W / w

Active ingredient 25.0

Kieaic acid 25.0

Calcium lignosulfonate. 10.0 sodium dioctyl sulfosuccinate 0.5

Kaolin to 100.0

Dispersible powders containing the compounds of Example contained, were produced-

Example 14- -

This example explains the properties of the active ingredients

Compounds of the invention against aphids.

Broad beans, 3 to 5 cm high, were infected with aphids (Megoura viciae) and then sprayed with an aqueous dispersion containing 250 ppm by weight of AoI. the carbamoylimidazole compound .dtmgen of Examples 1 to 8 and 10 included. Each plant was kept under a glass cover for 24 hours and then examined. It was found that at least 5Q # of the aphids were killed. The aphid population of the control plants which were treated with an aqueous spray without the active ingredient was not affected.

Example 15 '

This example explains the properties of the Compounds of the invention versus Ap & iden.

-44-509822 / 1033

Broad beans, 3 to 5 inches high, were made with the black bean aphid (Aphis fabae) occupied and then sprayed with an aqueous dispersion containing 100 ppm w / v. from each of the Contained active ingredients specified above. The plants were kept under glass for 24 hours and then examined. In all Cases, at least 50 # of the aphids were killed. Of the Aphid stocking of the control plants, which were treated with an aqueous spray solution without active ingredient, was not influenced.

The following agents were used;

1-Dimethylcarbamoyl-2-methylthio-4 (5) -tert.butylimidazole 1-morpholinocarbonyl-2-methylthio-4 (5) -tert.butylimidaz oil 1-Morpholinoearbonyl-2-methylthio-4 (5) -sec.butylimidazole 1-Morpholinocarbonyl-2-methylthio-4 (5) -is opropylimidaz oil 1-morpholinocarbonyl-2-methylthio-4 (5) -1-ethylpropylimidazole 1-Dimethylcarbamoyl-2-methylthio-4 (5) -isobutylimidazole

Example 16

This example illustrates the systemic activity of the compounds of the invention against the aphids Megoura viciae.

The compounds under test were used as floor drinkers. With 25 ml of the aqueous test solution the bottom of a plant dish with a diameter of 8 cm, which contained a single broad bean plant, was

-45-509822 / 1033

245A795

waters. A cardboard sign was placed around each plant so that only part of the plant protruded. This . was filled with aphids. After three days, the aphids were assessed by counting the living and dead aphids certainly.

The following compounds were found to have a at less than 100 ppm.

1-Dimethylcarb amoyl-2-methylthio-4 (5) -tert.butylimidaz oil 1-Dimethylthiocarbamoyl-2-methylthio-4 (5) -tert.butylimidazole

thio 1 -Morpholinocarbonyl-2-methy] / - ^/ l- (5) -t ert .butyl imidaz oil

1-Dimethylcarbamoyl-2-allylthio-4 (5) -sec.butylimidazole

1-Dimethylcarbamoyl-2-ethylthio-4 (5) - (1-methylcyclopentyl) imidazole

1-Dimethylcarbamoyl-2-but-2-enylthio-4 (5) -tert.pentylimidazole

Example 17

This example illustrates the effectiveness of 1-dimethylcarbamoyl-2-methylthio-4 (5) -tert.butylimidazole against larvae of the large cabbage white butterfly (Pieris brassicae).

Ten larvae were placed on a cabbage leaf, 'which one preceded immersed in the test solution and allowed to dry. After 24 hours, untreated cabbage was considered Food was added and after a further 24 hours the mortality of the larvae was determined by counting the number of live

-46- 509822/1033

- ■ 46 -

and dead insects.

Two repetitions were performed, one being one Test solution of 200 ppm used. At this concentration, more than 50% was achieved with the active substance Control of the larvae.

-Patent claims-

509822/1033

Claims (16)

Patent claims: "1. Compound of the general formula 1-2. X = CM ¹ IT where X is an oxygen or sulfur atom, Ir is an optionally substituted alkylthio, alkenylthio, aralkylthio, Alkoxyalkyl or alkylthioalkyl group, R- an alkyl or Ί 2 cycloalkyl groups and each of the radicals R and R is an alkyl, Is alkenyl, alkpxyalkcl or haloalkyl, or the radicals R and R together with the nitrogen atom with to which they are connected, an optionally substituted heberocyclic ring, namely a morpholino, thiamorpholino, 1-pyrrolidinyl and / or 1-piperidino group and their salts. 2. A compound according to claim 1, characterized in that X is an oxygen or sulfur atom, R ^ is an alkylthio, alkenylthio, aralkylthio or alkoxyalkyl group, R is an alkyl or cycloalkyl group and each of the radicals R 'and R is an alkyl -, alkenyl, alkoxyalkyl or haloalkyl group, or the radicals r ' ¹ and R together with the nitrogen atom to which they are connected form a heterocyclic ring, which is optionally 1 to 4 -48- . 509822/1033 the
Contains alkyl substituents / are connected to the carbon atoms of the heterocyclic ring, namely form a morpholino, thiamorpholino, 1-pyrrolidinyl and / or 1-piperidino group. 3. Compound according to claim 2, characterized that X is an oxygen atom 4. A compound according to claim 3 »characterized in that Ή? is an alkylthio group with 1 to 4 carbon atoms 5. A compound according to claim 3 »characterized that Ir is an alkoxyalkyl group having 2 to 4 carbon atoms. 6. A compound according to any one of claims 2 to 5 »characterized in that R is an alkyl · is a group with 3 to 5 carbon atoms. 7. A compound according to any one of claims 2 to 6, characterized in that both radicals R ^ and R ^{2 are} methyl groups. 8. A compound according to any one of claims 2 to 6, characterized in that the radicals R ^ -49- 509822/1033 R together with the nitrogen atom with which it is connected. which are to form a morpholine group. 9. pesticides, characterized that there is a compound according to any one of claims 1 to 8 together with as active ingredient contains an extender. 10. Insecticides means, characterized in that that it contains as active ingredient a compound according to any one of claims 1 to 7 together with an extender. · 11. Insecticidal agent, characterized in that that it contains as active ingredient a compound according to claim "8 together with an extender *. 12. Insecticidal agent according to one of claims 10 and 11, characterized in that the Extender is a solid or a liquid together with a surfactant. 13. Method of combating insects, thereby marked that a connection can be established in accordance with any one of claims 1 to 7 for the insects or theirs Common rooms. -50-509822 / 1033 14. Method of combating insects, thereby characterized in that a compound according to claim 8 is applied to the insects or their lounges applies. 15 · Method of combating aphids, thereby characterized in that a compound according to any one of claims 1 to 8 against the aphids or their lounges in the form of sprays or granules applies. 16. A method for producing a compound according to claim 1, characterized in that that one is an imidazole of the general formula R ^: wherein the radicals R * and R have the meaning defined in claim 1 have, with a garbamoyl halide or thiocarbamoyl halide of the general formula Z-CXNR R, wherein the 1 2
_{E 1} R and X radicals have the meaning defined in claim 1 and Z is a halogen atom. · 17 · connection, provided they claim according to a method 16 is made. 509822/1033