DE3138702A1 - Novel carbamates - Google Patents

Abstract

There are described N-carbonylimidazolyl-N-methylcarbamates of the formula <IMAGE> in which R1 and R2 in each case are hydrogen or C1-C4-alkyl, a process for the preparation of these carbamates, and their use in pest control.

Description

New carbamates

The present invention relates to N-carbonylimidazolyl-N-methylcarbamate, Process for their production and their use in pest control.

The N-carbonylimidazolyl-N-methylcarbamates have the formula where R1 and R2 are each hydrogen or C1-C4-alkyl.

The Cl-C4-alkyl groups are: methyl, ethyl, propyl, isopropyl, n-, i-, sec- or tert-butyl, but preferably methyl or ethyl.

The compounds of the formula I can be prepared by methods known per se, for example as follows: In formula II, R1 and R2 have the meanings given for formula I. In formula III, X is a halogen atom, in particular.

for a chlorine atom.

The process is carried out at a reaction temperature between -500C and + 1300C, preferably between IOCC and + 1000C, with normal or slightly increased Pressure and in the presence of a solution inert to the reactants or diluent made.

Tertiary ones, in particular, are suitable bases for the process Amines, such as trialkylamines, pyridines and dialkylanilines, and also hydroxides; Oxides, carbonates and bicarbonates of alkali and alkaline earth metals as well as alkali metal alcoholates such as e.g. potassium tert-butoxide and sodium methylate.

Suitable solvents or diluents are, for example, ethers and ethereal ones Compounds such as diethyl ether, di-iso-propyl ether, dioxane, tetrahydrofuran; aliphatic and aromatic hydrocarbons, especially benzene, toluene, xylenes; and ketones such as acetone, methyl ethyl ketone and cyclohexanone.

The starting materials of the formulas II and III are known or can be prepared analogously to known methods.

The compounds of the formula I are suitable for combating pests on animals and plants. So these compounds have fungicidal and plant regulatory Properties.

The compounds of the formula I are particularly suitable for combating of insects, phytopathogenic mites and ticks, e.g. of the order Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.

In particular, compounds of the formula 1 are suitable for combating plant damaging Insects, in particular plant-damaging feeding insects, in ornamental and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable cultures (e.g. against Leptinotarsa decemlineata and Myzus persicae).

In this context, it should be emphasized that the compounds mentioned both through a strongly pronounced systemic and contact effect against sucking insects, in particular against sucking insects of the order Homoptera and especially against insects of the Aphididae family (such as Aphis fabae, Aphis craccivora and Myzus persicae), which are difficult to control with known means, distinguish.

Active ingredients of the formula I also show a very beneficial effect against Flies such as Musca domestica and mosquito larvae. In addition, the connections stand out of formula I by a broad ovicidal and ovilarvicidal action.

In addition, the compounds of the formula I have a valuable one Action against plant-parasitic nematodes and against ectoparasitic mites and Ticks e.g. of the families Ixodidae, Argasidae and Dermanyssidae.

The compounds of the formula I are used in unchanged form or, preferably used together with the auxiliaries customary in formulation technology and are therefore e.g. emulsion concentrates, suspension concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, Dusts, granulates, also encapsulations in e.g. polymeric substances in well-known Way processed. The application methods such as spraying, misting, dusting, Scattering or pouring will be the same as the type of funds depending on the ones sought Chosen according to goals and the given circumstances.

The formulations i.e. those containing the active ingredient of the formula I. Means, preparations and compositions are produced in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with extenders, such as with solvents, solid carriers, and optionally surface-active substances Substances (surfactants). The following solvents can be used in Page: Aromatic hydrocarbons, preferably the fractions C8 to C12, e.g.

Xylene mixtures or substituted naphthalenes, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, Ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as water. As solid carriers, e.g. for dust and dispersible powders, natural rock flour are usually used, such as calcite, talc, kaolinite, montmorillonite or attapulgite. To improve the Physical properties can also include highly dispersed or highly dispersed silica absorbent polymers are added. As granular, adsorptive granulate carriers Porous types such as pumice stone, broken bricks, sepiolite and bentonite come as non-sorptive carrier materials e.g. calcite or sand are possible. In addition, can a variety of pre-granulated materials of inorganic or organic nature such as dolomite in particular, through to crushed plant residues will.

As surface-active substances come depending on the polarity of the The active ingredient of the formula I to be formulated is nonionic, cationic and / or anionic Surfactants with good emulsifying, dispersing and wetting properties are suitable. Under Surfactants are also to be understood as meaning mixtures of surfactants.

Suitable cationic surfactants are, for example, quaternary ammonium compounds, such as cetyl trimethyl ammonium bromide. Suitable anion-active surfactants are e.g. Soaps, salts of aliphatic monoesters of sulfuric acid or orthophosphoric acid, such as sodium lauryl sulfate, Sulfonated aromatic salts Compounds such as sodium and calcium dodecylbenzenesulfonate, sodium, calcium and Ammonium lignosulfonate, butylnaphthalene sulfonate and a mixture of the sodium salts of diisopropyl and triisopropyl naphthalene sulfonate and sodium diisobutyl naphthalene sulfonate. Suitable nonionic surfactants are, for example, the condensation products of Ethylene oxide with fatty alcohols, such as oleyl alcohol or cetyl alcohol, or with Alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. Other non-ionic Means include partial esters, which are derived from long-chain fatty acids and hexitanhydrides derive the condensation products of these partial esters with ethylene oxide and lecithins.

The nonionic, anionic and common in formulation technology Cation-active surfactants are described in the following publication, among others.

'NC Cutcheon's Detergents and Emulsifiers Annual "MC Publishing Corp., Ringewood, New Jersey, 1979.

The formulated agents usually contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I, 1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25%, of a surfactant.

While concentrated resources are preferred for trading, as a rule, rather dilute means are used in practice.

The agents can also contain other additives such as stabilizers, defoamers, Viscosity regulators, binders, adhesives, as well as fertilizers or other active ingredients included to achieve special effects.

Formulation examples for liquid active ingredients of the formula I (% n percent by weight) Emulsion concentrates a) Active ingredient 20% calcium dodecylbenzenesulfonate 5 Z castor oil polyglycol ether (36 mol AeO) 5% xylene mixture 70% b) active ingredient 40 Z Ca-dodecylbenzenesulfonate 8 X tributylphenol polyglycol ether (30 mol AeO) 12 Z cyclohexanone 15 z Y.ylene mixture 25% c) Active ingredient 50% tributylphenol polyglycol ether 4.2% calcium dodecylbenzenesulfonate 5.8% cyclohexanone 20% xylene mixture 20 Z From such concentrates can through By diluting with water emulsions of any desired concentration can be made.

Solutions a) Active ingredient 80% ethylene glycol monomethyl ether 20% b) Active ingredient 10 z polyethylene glycol 400 70% N-methyl-2-pyrrolidone 20 z c) active ingredient 5 z Epoxidized coconut oil 1% petrol (boiling point 160-1900C) 94% d) active ingredient 95 z Epoxidized Coconut Oil 5% These solutions are for use in the form of the smallest Suitable for drops.

Granules a) Active ingredient 5 kaolin 94% highly disperse silica 1 z b) Active ingredient 10% attapulgite 90% The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent then evaporated in vacuo.

Dusts a) Active ingredient 2% highly disperse silica 1% talc 97% b) Active ingredient 5% Highly disperse silica 5% Kaolin 90% By thorough mixing the carrier materials with the active ingredient, ready-to-use dusts are obtained.

Formulation examples for solid active ingredients of the formula I - = weight percent) Wettable powder a) Active ingredient 20 X Na lignin sulfonate 5 X Na lauryl sulfonate 3 Z silica 5 X kaolin 67 X b) active ingredient 60% sodium lignin sulfonate 5% sodium diisobutyl naphthalene sulfonate 6% octylphenol polyglycol ether (7-8 mol AeO) 2% highly disperse silica 27% The active ingredient is mixed well with the additives and placed in a suitable mill grind. Spray powder is obtained which can be mixed with water to form any desired suspensions Allow concentration to dilute.

Emulsion concentrate active ingredient 10% octylphenyl polyglycol ether (4-5 Mol AeO) 3% calcium dodecylbenzenesulfonate 3 Z castor oil polyglycol ether (36 mol AeO) 4% Cyclohexanone 30 z Xylene mixture 50 z This concentrate can be diluted emulsions of any desired concentration can be made with water.

Dust a) Active ingredient 5 Z Talc 95 z b) Active ingredient 8% kaolin 92 Z Ready-to-use dusts are obtained by mixing the active ingredient with the carrier mixed and ground on a suitable mill.

Extruder granulate active ingredient 10% sodium lignin sulfonate 2% carboxymethyl cellulose 1% Kaolin 87% The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then in a stream of air dried.

Coating granulate active ingredient 3% polyethylene glycol 3% kaolin 94 % The finely ground active ingredient is added to the polyethylene glycol in a mixer moistened kaolin applied evenly. In this way you get dust-free Coating granules.

Suspension concentrate active ingredient 40 X ethylene glycol 10% nonylphenyl polyglycol ether (15 mol AeO) 6% Na lignin sulfonate 10 z carboxymethyl cellulose 1% 37% formaldehyde solution 0.2% silicone oil in the form of a 75 own emulsion 0.8% water 32 z The finely ground Active ingredient is intimately mixed with the additives. A suspension concentrate is obtained, from which by diluting with water suspensions of any desired concentration can be produced.

Example 1: Preparation of N- (l-imidazolylcarbonyl) -N-methyl-2,2-dimethyl-dihydrobenzofuranyl- (7) -carbamate 2.83 g of N-chlorocarbonyl-N-methyl-2,2-dimethyldihydrobenzofuranyl- (7 ) carbamate are dissolved in 50 ml of chloroform. A mixture of 0.68 g of imidazole and 1.53 g of triethylamine is added dropwise to this solution while stirring. The reaction mixture is stirred at 20 "C. for ten hours and at 40 to 50" C. for two hours. The salts formed are washed out with water. After drying the organic layer over sodium sulfate and distilling off the solvent, the compound of the formula is obtained 250 with a refraction of ND: 1.5420. The following connections are also established in the same way: Example 2: Insecticidal feed poison effect: Spodoptera littoralis, Dysdercus fasciatus and Heliothis virescens cotton plants were sprayed with a test solution containing 50, 100, 200 or 400 pp of the compound to be tested.

After the covering had dried on, the plants each had larvae of the species Spodoptera littoralis (L3 stage), Dysdercus fasciatus (L4) or Helothis virescens (L3) occupied. One used per test compound and per test species two plants, and an evaluation of the mortality rate achieved was carried out after 2, 4, 24 and 48 hours.

The experiment was carried out at 24 ° C. and 60% relative humidity.

Within the concentration limits given above, Verb in preparations according to preparation example 1 100% action against larvae of the species Spotoptera littoralis, Dysdercus fasciatus and Heliothis virescens.

Example 3: Insecticidal Contact Effect: Myzus persicae In Water Before the start of the experiment, plants (Vicia fabae) were grown with about 200 individuals each colonized by the species Myzus persicae.

The plants treated in this way were treated with a solution 3 days later containing 10 or 1 ppm of the compound to be tested from a distance of 30 cm to dripping wet sprayed. Two plants were used per test compound and per concentration, and an evaluation of the mortality rate achieved was carried out after a further 24 hours.

Compounds showed within the concentration limits given above according to Example 1, a 10% activity against insects of the species Myzus persicae.

Example 4: Insecticidal Systemic Action: Aphis craccivora Rooted Bean plants were transplanted into pots containing 600 cc of soil. Afterward 50 ml of a test solution containing 25 ppm, 5 ppm and 1 ppm of the test solution were used Compound poured directly onto the earth.

After 24 hours, aphids were found on the above-ground parts of the plant (Aphis craccivora) and the plants with a plastic cylinder tied at the bottom slipped over to protect the lice from any contact or gas effect of the test substance to protect.

The destruction achieved was evaluated 24 and 48 hours later Start of experiment. For each concentration dose of test substance, two plants, one each in a separate pot, used. The experiment became more relative at 250C and 70% Humidity carried out.

Compounds showed within the concentration limits given above according to Example 1, a 100% systemic action against insects of the Aphis species craccivora.

Claims (6)

Claims 1. An N-carbonylimidazolyl-N-methylcarbamate of the formula where R1 and R2 are each hydrogen or C1-C4-alkyl. 2. The compound according to claim 1 of the formula 3. A process for the preparation of compounds according to claim 1, characterized in that in the presence of a base, a compound of the formula with a compound of the formula lets react, in which R1 and R2 have the meaning given in claim 1 and X stands for a halogen atom. 4. A pesticide that acts as an active component a compound according to claim 1 contains. 5. The use of a compound according to claim 1 for combating of pests on animals and plants. 6. The use according to claim 5 for combating insects and Representatives of the order Akarina.