DE2702235A1 - 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites - Google Patents

Abstract

Thiourea derivs. of formula (I) are new: In the formula, R1 is alkyl (pref. 1-6C) or cycloalkyl, R2 is >=2C alkyl (pref. 2-6C) or cycloalkyl, R3 is alkyl (pref. 1-6C) cycloalkyl or halo (pref. Cl or Br). n is 0,1 or 2 (pref. 0 or 1) and when n = 2 the R3's can be different, and R4 is H, alkyl (pref. 1-12C) alkenyl (pref. 2-12C), cycloalkyl or cycloalkenyl. All alicyclic gps. pref. have 3-7C. Cpds. (I) are prepd. e.g. by reacting a phenylisothiocyanate with NH2CH2R4, and are useful for control of animal or plant parasites, pref. as ectoparasiticides. (Specifically claimed) insecticides, acaricides, fungicides and nematocides. They are more effective against insects and strains of Boophilus resistant to phosphate esters than the structurally similar cpds. of FR 2193817. They are useful in agriculture, forestry, protection of stored goods and in hygienic applications.

Description

Novel N-aryl-N'-alkyl-thioureas, method

for their production and their use as a means of control of animal and vegetable pests The present invention relates to new ones N-Aryl-N'-alkylthioureas, processes for their preparation and their use as a means of combating animal and vegetable pests, in particular as ectoparasiticides, insecticides and acaricides.

It is already known that N-aryl-N ', N'-dialkyl-thioureas as ectoparasiticides, in particular as tickicides against ticks of the genus boophilus, are effective (see DT-OS 2 337 122).

Show towards the known and chemically related compounds the N-aryl-N'-alkylthioureas according to the invention have a better effect against phosphoric ester-resistant Ticks of the genus boophilus as well a distinctly pronounced insecticidal Effect that the comparative products from DT-OS 2 337 122 lack. They are also Effective in agriculture against insects which are harmful to plants and against mites.

It has now been found that the new N-aryl-N'-alkyl-thioureas of the general formula (I) in which R1 and R2 can be identical or different and represent alkyl or cycloalkyl, and R3 represents alkyl, cycloalkyl or halogen, n represents 0, 1 or 2 and where, if n represents 2, the radicals R3 can be identical or different and R4 stands for hydrogen, alkyl, alkenyl, cycloalkyl or cycloalkenyl have a strong effect on animal and plant pests, in particular an ectoparasiticidal, insecticidal and acaricidal effect.

It has also been found that the new N-aryl-N'-alkylthioureas of the formula (I) are obtained if a) aryl isothiocyanates of the formula with alkylamines of the formula H2N-CH2-R4 (III) or alternatively b) alkyl isothiocyanates of the formula R4-CH2-NCS (IV) with arylamines of the formula reacted, where R1, R2, R3, R4 and n in the formulas (II) to (V) each have the meaning given above in the formula (I).

The novel N-aryl-N'-alkyl-thioureas according to the invention surprisingly show a more pronounced ectoparasiticidal effect than the chemically closely related ones N-aryl-N ', N'-dialkyl-thioureas from DT-OS 2 337 122 as well as an additional insecticidal Effect as well as an effect against mites, which corresponds to the compounds from DT-OS 2 337 122 is missing.

The compounds according to the invention are thus an enrichment of technology.

If, according to preparation variant a), 2,6-di-sec-butylphenyl isothiocyanate and isobutylamine are used as starting materials, the course of the reaction can be represented by the following equation: (Reaction equation A) If, according to preparation variant b), isobutyl isothiocyanate and 2,6-di-sec-butyl-aniline are used as starting materials, the course of the reaction can be represented by the following equation: (Reaction equation B) In the formula (I), the radicals R¹ and R² are preferably alkyl (C1-C6) and cycloalkyl (C3-C7). Examples include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, iso-butyl, tert-butyl, pentyl (2), pentyl (3), tert-pentyl, cyclopentyl, hexyl ( 2), hexyl- (3), cyclohexyl.

The radical R3 preferably stands for alkyl (C1-C6), in particular for Alkyl (C1-C4), for example for methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, iso-butyl, tert-butyl or for halogen, preferably for chlorine or bromine. Farther R3 can stand for cycloalkyl, preferably cycloalkyl- (C3-C7), may be mentioned: Cyclopentyl and cyclohexyl ,.

The radical R4 preferably represents hydrogen or straight-chain Alkyl (C1-C12) for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Octyl, decyl or dodecyl.

Furthermore, R4 can preferably represent branched alkyl (C3-C12) or stand for alkenyl- (C2-C12). Examples include: isopropyl, sec-butyl, iso-butyl, tert-butyl, 2-methyl-butyl, 3-methyl-butyl, tert-pentyl, pentyl- (2), 3-methyl-butyl- (2), 2,3-dimethyl-butyl- (2), 2,3,3-trimethyl-butyl- (2), 2,2-dimethyl-propyl- (1), 2-methyl-butyl- (2), 4,4-dimethyl-pentyl- (2), 2,4,4-trimethyl-pentyl- (2), Hexyl- (2), hexyl- (3), vinyl, 1-methyl-vinyl, 2-methyl-vinyl, 2,2-dimethyl-vinyl, 1,2-dimethyl-vinyl, 1,2,2-trimethyl-vinyl, allyl, crotyl, 1-methyl-allyl, 1,1-dimethyl-allyl, 2-isopropylvinyl, 2-tert-butyl-vinyl, 2-butyl-vinyl, 3,3-dimethylallyl, 3-hexyl-allyl. Finally, R4 can stand for cycloalkyl or cycloalkenyl. (Preferably with each 3 to 7 carbon atoms). Examples include: cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cyclopropyl- (1) -yl- (1), cyclopentene- (1) -yl- (3), cyclopentene- (1) -yl- (3), Cyclohexen- (1) -yl- (3) and 1-methyl-cyclopentyl- (1).

Compounds of the formula according to the invention are particularly preferred in which RI and RII can be identical or different and for alkyl (C1-C6) or cycloalkyl (C3-C7), RIII for alkyl (C1-C6), cycloalkyl (C3-C7), chlorine or bromine, n for 0 or 1 and RIV stand for hydrogen, alkyl (C1-C12), alkenyl (C2-C12), cycloalkyl (C3-C7) or cycloalkenyl (C3-C7).

The aryl isothiocyanates used as starting compounds of the general Formula (II) and alkyl isothiocyanates of the general formula (IV) are known or are known can be prepared by known methods, for example by reaction of arylamines of the general formula (V) or alkylamines of the general formula (III) with thiophosgene, by reaction of N-aryl- or N-alkyl-dithiocarboxylic acids Salts with phosgene or oxidizing agents, or from alkyl halides and alkali thiocyanates or from olefins and hydrogen rhodanide (see also Houben-Weyl, "Methods of organic chemistry ", Volume IX, pages 867-878).

As starting compounds for the according to reaction equation A to be used Aryl isothiocyanates of the general formula (II) may be mentioned, for example: 2,6-dimethylphenyl isothiocyanate 2-methyl-6-ethyl-phenyl isothiocyanate 2,6-diethyl-phenylisothiocyar.at 2-ethyl-6-isopropyl-phenyl isothiocyanate 2,6-Diisopropyl-phenyl-isothiocyanate 2,6-Di-sec-butyl-phenyl-isothiocyanate 2-. Methyl-6-sec-butyl-phenyl isothiocyanate 2-ethyl-6-sec-butyl-phenyl isothiocyanate 2-isopropyl-6-sec-butyl-phenyl isothiocyanate 2-methyl-6-isopropyl-phenyl isothiocyanate, 2-methyl-6-cyclopentyl-phenyl isothicyanate 2-ethyl-6-cyclopentyl-phenyl isothiocyanate 2-isopropyl-6-cyclopentyl-phenyl isothiocyanate, 2,6-di-cyclopentyl-phenyl isothiocyanate 2-methyl-6-tert-butyl-phenyl isothiocyanate, 2-ethyl-6-tert-butyl-phenyl isothiocyanate 2-methyl-6-cyclohexyl-phenyl isothiocyanate, 2-ethyl-6-cyclohexyl-phenyl isothiocyanate 2,4-dimethyl-6-ethyl-phenyl isothiocyanate 2,4-dimethyl-6-isopropyl-phenyl isothiocyanate 2,4-dimethyl-6-sec-butyl-phenyl isothiocyanate 2,4-dimethyl-6-tert-butyl-phenyl isothiocyanate 2,4,6-trimethyl-phenyl-isothiocyanate, 2,6-diethyl-4-methyl-phenyl-isothiocyanate, 2,6-diisopropyl-4-methyl-phenyl-isothiocyanate 3,5-dimethyl-2,6-diethyl phenyl isothiocyanate, 3-methyl-2,6-diethyl phenyl isothiocyanate 3-chloro-2,6-diethyl phenyl isothiocyanate, 4-methyl-2,6-di-sec-phenyl isothiocyanate 2,4,6-triethyl phenyl isothiocyanate 2,4,6-triisopropyl phenyl isothiocyanate 3-chloro-4-methyl-2,6-diethyl phenyl isothiocyanate 3,4-dimethyl-2,6-diethyl phenyl isothiocyanate, 4-chloro-2,6-diethyl phenyl isothiocyanate 4-chloro-3-methyl-2,6-diethyl-phenyl isothiocyanate, 4-methyl-2,6-di-cyclopentyl-phenyl isothiocyanate 4-n-butyl-2,6-diaethyl-phenyl isothiocyanate, 4-isobutyl-2,6-diaethyl-phenyl isothiocyanate 4-tert-butyl-2,6-diaethyl-phenyl isothiocyanate, 4-n-propyl-2,6-diaethyl-phenyl isothiocyanate 4-Cyclohexyl-2,6-diaethyl-phenyl-isothiocyanate, 2-methyl-4,6-di-tert-butyl-phenyl-isothiocyanate the the arylamines of the general types on which the aforementioned aryl isothiocyanates are based Formula (V) can alternatively be used for the preparation of the compound of the general Formula (I) according to reaction equation B can be used.

Examples of alkyl isothiocyanates of the general formula IV are called: 2 "ethyl isothiocyanate Ät: wlisothiocyanflt propylicothiocyanate butyl isothiocyanate Isobutyl isothiocyanate pentyl isothiocyanate neopentyl isothiocyanate 3-methyl-butyl isothiocyanate 2,3-dimethyl-butyl isothiocyanate 2,2,3-trimethyl-butyl isothiocyanate 2,2,3,3-tetramethyl-butyl isothiocyanate 3,3-dimethyl-butyl isothiocyanate, 2-ethyl-butyl isothiocyanate, 2-isopropyl butyl isothiocyanate 2,2-dimethyl-butyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate Decyl isothiocyanate dodccylidothiocyanate 2,4,4-trimethyl-pentyl isothiocyanate 2,2,4-tetramethyl-pentyl isothiocyanate Allyl isothiocyanate 2 - :: ethyl-allyl isothiocyanate, crotyl isothiocyanate 2, 3-dimethyl-allyl isothiocyanate 2,3,3-trimethyl-allyl isothiocyanate, butene- (3) -yl (1) -isothiocyanate, 2,2-dimethyl-buten- (3) -yl- (1) -isothiocyanate 3-isopropyl-allyl-isothiocyanate, 3-tert-butyl-allyl-isothiocyanate, 3-hexyl-allyl-isothiocyanate Cyclopropyl methyl isothiocyanate Cyclopentyl methyl isothiocyanate Cyclopenten- (1) -yl- (1) -methyl isothiocyanate Cyclopenten- (2) -yl- (1) -methyl isothiocyanate Cyclohexyl-methyl isothiocyanate Cyclohexen- (1) -yl- (1) -methyl isothiocyanate The general alkylamines on which the aforementioned alkyl isothiocyanates are based Formula (III) can alternatively be used for the preparation of compounds of the general rornel (I) can be used in analogy to reaction equation A.

According to the invention, as already mentioned above, a) d.e are substituted Aryl isothiocyanates of the general formula (11) with the alkylamines of the general formula Formula (III) or alternatively b) alkyl isothiocyanates of the general formula (IV) reacted with arylamines of the general formula (V).

The conversion takes place in molar or approximately molar ratios, the more volatile or less valuable component being used in excess can be, for example with 5-50% excess. However, it is in a preferred one Embodiment also possible, for example the alkylamines of the general formula (III) in a large excess, namely 2-20 mol, based on 1 mol of aryl isothiocyanate II to use. They thus also serve as a solvent for the resulting Thioureas of the general formula (I) and can after implementation Distillation can be largely recovered.

When carrying out the implementation according to equation A or B can tertiary organic bases are added to accelerate the reaction. One works for example at temperatures of 10 to 1200C, in particular at 20 to 60 ° C. The implementation of the substituted aryl isothiocyanates of the general formula (II) it the Alkylamines of the general formula III or, alternatively, the alkyl isothiocyanates IV with the arylamines of the formula V on without solvent in the melt or under Addition of a solvent and diluent take place. As such, for example are used: hydrocarbons or halogenated hydrocarbons such as petroleum ether, Benzene, ligroin, cyclohexane, benzene, toluene, chlorobenzene, methylene chloride, Chloroform, carbon tetrachloride, water-soluble solvents such as methanol, ethanol, Acetone, acetonitrile, dimethylformamide, if necessary, can continue the approaches inorganic or, as already mentioned above, organic bases as accelerators added are, for example triethylamine, 1,4-daizabicyclo- [2,2,2] -octane (DABCO) 1,5-diaza-bicyclo- [4,3,9] -nonen- (5) (DBN) 1,8-diaza-bicyclo- [5,4,0] -undecen- (7) (DBU), potassium hydroxide, sodium hydroxide, Sodium hydride, sodium oxide.

Depending on the starting compounds, the reactions can be exothermic and depending on the size and the presence of thinner by cooling under Control must be kept or the unsettles must be maintained by heating, for example be accelerated to temperatures of 40-1500C, preferably 50-1000C. The initial conditions are therefore individually different and depend on the type and amount of used Starting materials and the solvent used.

The processing takes place either by distilling off solvents and recrystallizing the reaction product or by pouring it into water or dilute aqueous mineral acids, filtration and drying.

As new N-aryl-N'-alkyl-thioureas of the general formula (I) the following compounds are listed: N- (2,6-diethyl-phenyl) -N'-methyl-thiourea; F: 103-1050C N- (2,6-diethyl-phenyl) -N'-ethyl-thiourea; F: 72-73 ° C N- (2,6-diethyl-phenyl) -N'-propyl-thiourea; F: 58-60 ° C N- (2,6-diethyl-phenyl) -N'-butyl-thiourea; F: 41-43 ° C N- (2,6-diethyl-phenyl) -N'-isobutyl-thiourea; F: 68-70 ° C N- (2,6-diethyl-phenyl) -N'-neopentyl-thiourea; F: 87-890C N- (2,6-diethyl-phenyl) -N'-pentyl-thiourea; (F <30 ° C) N- (2,6-diethyl-phenyl) -N'-hexyl-thiourea; F: 102-105 ° C N- (2,6-diethyl-phenyl) -N'-heptyl-thiourea; (F <30 ° C) N- (2,6-diethyl-phenyl) -N'-octyl-thiourea N- (2,6-diethyl-phenyl) -N'-decyl-thiourea N- (2,6-diethyl-phenyl) -N'-dedecyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-methyl-thiourea; F: 97-1000C N- (4-methyl-2,6-diethyl-phenyl) -N 'ethyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-propyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-butyl-thiourea; F: oil (F <30 ° C) N- (4-methyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea; F: 60-61 ° C N- (4-methyl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea; F: 106-1070C N- (4-methyl-2,6-diethyl-phenyl) -N'-pentyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-hexyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (2,2-dimethyl-butyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - ( 2,3-dimethyl-butyl) thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (2,2,3-trimethyl-butyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - (2,3,3-trimethyl-butyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (2,2,3-tetramethyl-butyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - (3-methylpentyl) thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (2-isopropyl-butyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - (2, 4,4-trimethylpentyl) thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (2,2,4,4-trimethyl-pentyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-allyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-methallyl-thiourea F: 86-88 ° C N- (4-methyl-2,6-diethyl-phenyl) -N'-crotyl- thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (3,3-dimethyl-allyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - ( 2,3-dimethyl-allyl) thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- [buten- (3) -yl- (1)] - thiourea N- (4-methyl-2,6-diethyl-phenyl) - N '- [2,2-dimethyl-buten- (3) -yl- (1) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (3-isopropyl-allyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - (3- tert-butyl-allyl) thiouring agent N- (4-methyl-2,6-diethyl-phenyl) -N '- (3-hexyl-allyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-cyclopropyl-methylthiourea N- (4-methyl-2,6-diethyl-phenyl) -N '(cyclopentyl-methyl) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N' - [cyclopenten- (1) -yl- (1) -methyl] thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-cyclohexyl-thiourea N- (4-methyl-2,6-diethyl-ohenyl) -N '- [cyclohexen- (3) -yl- (1) methyl] thiourea N- (2,6-diethyl-phenyl) -N '- (2,3-dimethyl-butyl) -thiourea N- (2,6-diethyl-phenyl) -N' - (2,2,3-trimethyl- butyl) thiourea N- (2,6-diethyl-phenyl) -N '- (3-methyl-pentyl) thiourea N- (2,6-diethyl-phenyl) -N '- (2,2,4,4-tetramethyl-pentyl) -thiourea N- (2,6-diethyl-phenyl) -N '- (3,3-dimethyl-allyl) -thiourea N- (2,6-diethyl-phenyl) -N' - (2,3-dimethyl-allyl) -thiourea N- (2,6-diethyl-phenyl) -N'-methallyl-thiourea N- (2,6-diethyl-phenyl) -N '- (cyclopentyl-methyl) -thiourea N- (2,6-diethyl-phenyl) -N '- (cyclohexyl-methyl) -thiourea N- (3-methyl-2,6-diethyl-phenyl) -N'-propyl-thiourea N- (3-Met} lyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea N- (3-methyl-2,6-diethyl-plieny L) -N'-neopenty-thiourea F: 102-1040C N- (3-methyl-2,6-diethyl-phenyl) -N'-pentyl-thiourea N- (3-methyl-2,6-diethyl-phenyl) -N'-methaLlyl-thiiourea F: 105-1060C N- (3-methyl-2,6-diethyl-phenyl) -N '- (3-methyl -butyl) -thiourea N- (3-methyl-2,6-diethyl-phenyl) -N '- (2-ethyl-butyl) -thiourea N- (3,5-dimethyl-2,6-diethyl-phenyl) -N'-butyl -thiourea F: 108-1100C N- (3,5-dimethyl-2,6-diethyl-phenyl) -N'-pentyl-thiourea N- (3,5-dimethyl-2,6-diethyl-phenyl) -N'- neopentyl thiourea N- (3,5-Dimethyl-2,6-diethyl-phenyl) -N'-metallyl-thiourea N- (3,5-Dimethyl-2,6-diethyl-phenyl) -N'-pentene- (4) -yl- (l) -thiourea N- (3,5-Dimethyl-2,6-diethyl-phenyl) -N'-cyclopentyl-methylthiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-pentyl-thiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-methallyl-thiourea N- (3-chloro-2,6-diethyl-phenyl) -N'-propyl-thiourea N- (3-chloro-2,6-diethyl-phenyl) -N'-butyl-thiourea F: 108: 1110C N- (3-chloro-2,6-diethyl-phenyl) -N'-neopentyl-thiourea F: 106-1100C N- (3-chloro-2,6-diethyl-phenyl) -N '- (3-methyl-pentyl) -thiourea N- (3-chloro-4-methyl-2,6-diethyl- phenyl) -N'-isobutyl-thiourea N- (3-chloro-4-methyl-2,6-diethyl-phenyl) -N '-neopentyl-thiourea N- (3-chloro-4-methyl-2,6-diethyl-phenyl) -N'- methallyl thiourea N- (2,4,6-trimethyl-phenyl) -N'-neopentyl-thiourea N- (2, q, 6-trimethyl-phenyl) -N'-methallyl-thiourea N- (2,3,4,6-tetramethyl-phenyl) -N'-butyl-thiourea, N- (2,3,4,6-tetramethyl-phenyl) -N'-methallyl-thiourea N- (2,6-Diisopropyl-phenyl) -N'-methyl-thiourea F: 167-1680C N- (2,6-Diisopropyl-phenyl) -N'-ethyl-thiourea N- (2,6-Diisopropyl-phenyl) -N'-propyl-thiourea F: 106-1070C N- (2,6-Diisopropyl-phenyl) -N'-butyl-thiourea F: 99-1030C N- (2,6-diisopropyl-phenyl) -N'-isobutyl-thiourea F: 108-1120C N- (2,6-diisopropyl-phenyl) -N '- (3-methyl-butyl) -thiourea F: 64-680C, N- (2,6-Diisopropyl-phenyl) -N'-pentyl-thiourea. F: 76-830C N- (2,6-Diisopropyl-phenyl) -N'-neopentyl-thiourea F: 150-1550C N- (2,6-diisopropyl-phenyl) -N'-methallyl-thiourea F: 93-950C N- (2,6-diisopropyl-phenyl) -N'-hexyl-thiourea N- (2,6-Di-1sopropyl-phenyl) -N'-dodecyl-thiourea N- (2,6-Diisopropyl-phenyl) -N '- (2-ethyl-butyl) -thiourea N- (2,6-diisopropyl-pl1enyl) -N '- (3,3-dimethyl-butyl) -thiourea N- (2,6-diisopropyl-phenyl) -N' - (2,3-dimethyl-butyl) -thiourea N- (2,6-diisopropyl-phenyl) -N '- (2,2,3-trimethyl-butyl) -thiourea N- (2,6-diisopropyl-phenyl) -N' - (2,2,4- trimethylpentyl thiourea N- (2,6-diisopropyl-1) llenyl) -N '- (2,3,3-trimethyl-allyl) -thiourea N- (2,6-diisopropyl-phenyl) -N' - (cyclopentyl-methyl) -thiourea N- (2-Ethyl-6-isobutyl-phenyl) -N'-methallyl-thiourea F: 105-1060C N- (2-ethyl-6-isobutyl-phenyl) -N'-butyl-thiourea N- (2-ethyl-6-isobutyl-phenyl) -N'-neopentyl-thiourea N- (2-ethyl-6-isobutyl-phenyl) -N-isobutyl-thiourea N- (2-methyl-6-isopropyl-phenyl) -N'-butyl-thiourea, N- (2-methyl-6-isopropyl-phenyl) -N'-isobutyl-thiourea ? - (2-Methyl-6-isoproj) yi-phenyl) -N'-neopentyl-thlourea N- (2-methyl-6-ethyl-phenyl) -N'-isobutyl-thiourea N- (2-methyl-6-ethyl-phenyl) -N '-neopentyl-thiourea N- (2-methyl-6-ethyl-phenyl) -N' - (3,3-dimethyl-butyl) -thiourea N- (2,6-di-sec-butyl-phenyl) -N'-methyl-thiourea N- (2,6-di-sec-butyl-phenyl) -N'-ethyl-thiourea N- (2,6-Di-sec-butyl-phenyl) -N'-propyl-thiourea F: 85-87 ° C N- (2,6-Di-sec-butyl-phenyl) -N'-butyl- thiourea N- (2,6-Di-sec-butyl-phenyl) -N '-isobutyl-thiourea F: 83-850C N- (2,6-Di-sec-butyl-phenyl) -N'-allyl-thiourea F: 83-86 ° C, N- (2,6-Di-sec-butyl-phenyl) -N'-methallyi-thiourea F: 69-720C N- (2,6-Di-sec-butyl-phenyl) -N '-neopentyl-thiourea F: 88-900C N- (2,6-Di-sec-butyl-phenyl) -N'-pentyl-thiourea N- (2,6-Di-sec-butyl-phenyl) -N'-hexyl-thiourea, N- (2,6-Di-sec-butyl-phenyl) -N'-octyl-thiourea N- (2,6-Di-sec-butyl-phenyl) -N'-decyl-thiourea N- (2,6-Di-sec-butyl-phenyl) -N '- (2-ethyl-butyl) -thiourea N- (2,6-di-sec-butyl-phenyl) -N '- (3,3-dimethyl-butyl) -thiourea N- (2,6-di-sec-butyl-phenyl) -N' - ( 2-methylpentyl) thiourea N- (2,6-di-sec-butyl-phenyl) -N '- (2,3,3-trimethyl) -allylthiourea N- (2-methyl-6-sec-butyl-phenyl) -N'- propyl thiourea N- (2-ethyl-6-sec-butyl-phenyl) -N'-methallyl-thiourea N- (2-isopropyl-6-sec-butyl-phenyl) -N'-isobutyl-thiourea N- (2-methyl-2,6-di-sec-phenyl) -N'-isobutyl-thiourea F: 98-1020C N- (4th methyl-2,6-di-sec-butyl-phenyl) -N'-butyl-thiourea F: 97-1000C N- (2,6-Di-cyclopentyl-phenyl) -N'-methyl-thiourea N- (2,6-Di-cyclopentyl-phenyl) -N'-butyl-thiourea N- (2,6-Di-cyclopentyl-phenyl) -N'-isobutyl-thiourea N- (2,6-Di-cyclopentyl-phenyl) -N'-neopentyi-thiourea N- (2,6-di-cyclopentyl-phenyl) -N'-methallyl-thiourea N- (2,6-Di-cyclopentyl-phenyl) -N '- (cyclopropyl-methyl) -thiourea N- (2,6-Di-cyclopentyl-phenyl) -N'-pentyl-thiourea N- (2-Ethyl-6-cyclopentyl-phenyl) -N'-isobutyl-thiourea N- (2-methyl-6-tert-butyl-phenyl) -N'-isobutyl-thiourea N- (2-Methyl-6-tert-butyl-phenyl) -N'-neopentyl-thiourea N- (2-Methyl-6-tert-butyl-phenyl) -N'-methallyl-thiourea N- (2-methyl-6-tert-butyl-phenyl) -N'-pentyl-thiourea, N- (2-methyl-4,6-di-tert-butyl-phenyl) -N'-methyl-thiourea N- (2-methyl-4,6-di-tert-butyl-phenyl) -N'-isobutyl-thiourea N- (2-methyl-4,6-di-tert-butyl-phenyl) -N ' -methallyl thiourea N- (4-methyl-2,6-diisopropyl-phenyl) -N'-methyl-thiourea, N- (4-methyl-2,6-diisopropyl-phenyl) -N'-propyl-thiourea F: 125-1270C N- (4-methyl-2,6-diisopropyl-phenyl) -N'-butyl-thiourea F: 126-1290C, N- (4-methyl-2,6-diisopropyl-phenyl) -N'-isobutyl-thiourea. F: 150-1530C N- (4-methyl-2,6-diisopropyl-phenyl) -N'-neopentyl-thiourea, N- (4-methyl-2,6-diisopropyl-phenyl) -N'-methallyl-thiourea N- (4-methyl-2,6-diisopropyl-phenyl) -N'-hexyl-thiourea, N- (4-ethyl-2,6-diisopropyl-phenyl) -N'-isobutyl-thiourea N- (4-ethyl-2,6-diisopropyl-phenyl) -N'-neopentyl-thiourea, N- (2,4,6-triisopropyl) -N'-methyl-thiourea N- (2,4,6-triisopropyl-phenyl) -N'-butyl-thiourea, N- (2,4,6-triisopropyl-phenyl) -N'-allyl-thiourea N- (2,4,6-triisopropyl) -N'-methallyl-thiourea F: 115-1180C N- (2,4,6-triisopropyl-phenyl) -N '- (3-methyl-pentyl) -thiourea N- (2,4,6-triisopropyl-phenyl) -N # - (2-ethyl-pentyl) -thiourea N- (2,6-dimethyl-phenyl) -N'-butyl-thiourea N- (2,6-Dimethyl-phenyl) -N'-neopentyl-thiourea N- (2,6-Dimethyl-phenyl) -N ' -methallyl-thiourea N- (2,6-dimethyl-phenyl) -N'-isobutyl-thiourea N- (2,6-dimethyl-phenyl) -N'-hexyl-thiourea N- (2-methyl-6-ethyl-phenyl) -N'-methyl-thiourea F: 65-670C N- (2,4-dimethyl-6-ethyl-phenyl) -N'-methyl-thiourea F: 125-1260C N- (2,4,6-trethyl-phenyl) -N'-propyl-thiourea N- (2,4,6-Trethyl-phenyl) -N'-butyl-thiourea, oil (F <30 ° C) N- (2,4,6-Trethyl-phenyl) -N'-isobutyl-thiourea F: 74-76 ° C N- (2,4,6-triethyl-phenyl) -N'-methallyl-thiourea N- (2,4,6-trethyl-phenyl) -N'-neophentyl-thiourea F: 78-80 ° C N- (4-butyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea, oil (F <30 ° C) N- (4-Butyl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea F: 52-540C N- (4-butyl-2,6-diethyl-phenyl) -N'-crotyl-thiourea N- (4-Butyl-2,6-diethyl-phenyl) -N'-heptyl-thiourea N- (4-Cyclohexyl-2,6-diethyl-phenyl) -N'-butyl-thiourea F: 63-660C N- (4-cyclohexyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea F: 118-1200 N- (4-cyclohexyl-2,6-diethyl-phenyl) -N'isobutyl-thiourea N- (4-cyclohexyl-2,6-diethyl-phenyl) -N'-methallyl-thiourea N- (4-cyclopentyl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea N- (4-propyl-2,6-diethyl-phenyl) -N'-n-pentyl-thiourea; Oil (mp 30 ° C) N- (4-isobutyl-2,6-diethyl-phenyl) -N'-methyl-thiourea F: 123-1260C N- (4-isobutyl-2,6-diethyl-phenyl) -N'-n-hexyl-thiourea; oil (F <30 ° C) N- (4-tert-butyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea F: 121-1220C N- (4-tert-butyl-2,6-diethyl-phenyl) -N'-butyl-thiourea F: 81-830C N- (4-tert-butyl-2,6-diethyl-phenyl) -N'-n-pentyl-thiourea, oil (F <30 ° C) N- (2-methyl-4,6-di-tert .-Butyl-phenyl) -N'-isobutyl-thiourea F: 157-16O0C N- (2-methyl-4,6-di-tert-butyl-phenyl) -N'-neopentyl-thiourea F: 157-159 ° C N- (4-Methyl-2,6-di-cyclopentyl-phenyl) -N'-butyl-thiourea F: 151-1530C the Active ingredients are suitable if they are well tolerated by plants and have favorable toxicity to warm-blooded animals for combating animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in storage and material protection as well as in the hygiene sector. They are sensitive and resistant to normal Species as well as effective against all or individual stages of development. To the above mentioned Pests include: From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, for. B. Blaniulus guttulatus.

From the order of the Chilopoda, for. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola, for. B. Onychiurus armatus.

From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorloides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, for. B. Forficula auricularia.

From the order of the Isoptera, for. B. Reticulitermes spp ..

From the order of the Anoplura, e.g. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevlcoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp ..

From the order of the Lepidoptera, for. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuts padella, Plutella masculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulans, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Chorlstoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera, for. B. Anobtum punctatus, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzsephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp .. Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus, spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for. B. Diprion spp. Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stoloxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Sibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyani, Ceratitis capitata, Dacus oleae, Tipula paludosa.

A.s of the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp., From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dcrmanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp, Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., The active compounds according to the invention are used in Form of their customary formulations and / or from these formulations prepared mailing forms.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges.

The active ingredient concentration of the use forms can range from 0.0000001 up to 100% by weight of active ingredient, preferably between 0.01 and 10% by weight.

The application takes place in a customary adapted to the application norms Way.

The active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in Fofl. for example tablets, Capsules, potions, granules, through dermal application in the form of, for example, the Dipping (dipping), spraying (spraying), pouring (puor-on and spot-on) and des Powdering and parenteral use in the form of, for example, injection.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, Pastes, soluble powders, granulates, aerosols, suspension emulsion concentrates, Saatgutucer, active ingredient-impregnated natural and synthetic substances, ultra-fine encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with Burning sets, such as incense cartridges, cans, spirals, etc. as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. by Mixing the active ingredients with extenders, i.e. non-volatile solvents Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g.

organic solvents can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorine fourth aromatics or chlorinated aliphatic Hydrogenates such as chlorobenzenes, chloro-ethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffin, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strong pore e solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous diluents or carriers are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons as Butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic barley in flours, such as fumed silica, alumina and Silicates; as solid carriers for granules: broken and fractionated natural Rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granulates made from inorganic and organic flours and granulates made from organic material such as sawdust, coconut shells, corn cobs, and tobacco stalks; as an emulsifier and / or Foaming agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. Lignin, sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

Example test with parasitic adult beef ticks (Boophilus microplus res.) Solvent: Cremophor For the production of an appropriate preparation of active substance the active substance in question is mixed with the specified solvent in a ratio of 1: 2 and dilute the concentrate obtained in this way with water to the desired Concentration.

10 adult beef ticks (B. microplus res.) Are immersed for 1 min. In the active compound preparation to be tested. After transferring them to plastic beakers and storing them in an air-conditioned room, the degree of destruction is determined in percent, with 100% meaning that all ticks and 0% that none of the ticks have been killed. Active ingredient active ingredient conc. Killing effect in% in ppm Boophilus microplus / Biarra-St. res. CH 3 -CH-C 2H5 H-C511-N-C3H7 10000 30 1 1,000 CH3-H-C2H5 CH3-CH-C2H5 5 + NH-C-NH-C4H9 10,000 100 49 1 1,000 to 50 CH3-CH-C2H5 CH 3-CH-C2H5 1Ii CH, 10 -C-NH-CH 4 1 o ooo 23 1,000> 50 r ~ c8 CM3 PIPE CH3-CH-C 2H5 CH3 / NH-C511-NH-CH 10 °°° °° 000 100 3 ~~ 1 000 50 o CH CH sC H Test with parasitic fly larvae Emulsifier: 80 parts by weight of Cremophor EL To produce a suitable active ingredient preparation, 20 parts by weight of the active substance concerned are mixed with the specified amount of the emulsifier and the resulting mixture is diluted with water to the desired concentration.

About 20 fly larvae (Lucilia cuprina) are placed in a test tube filled with a cotton plug of the appropriate size, which contains about 3 ml of a 20% egg yolk powder suspension in water. 0.5 ml of the active ingredient preparation are applied to this egg yolk powder suspension. The degree of destruction is determined in% after 24 hours. 100% means that all and 0% that none of the larvae have been killed. Active ingredient, active ingredient-killing effect centering in% ppm Lucilia cuprina res. CH iC2H5 5 S 1,000 100 > HC-NH-C3H7 100 100 3 1 C2H5 CH i C2H5 5 CH3 1,000 100 > NH-C-NH-CH2-c-cH3 100 CA3 \ C? H CH3 100 Cfl3 C2H5 CH3 CH i C2E; 5 \ off 000 100 3 <NH-C-NH-CH2-C / H 100 100 \ cH \ C. 10 0 C 2 \ CH3 10 ° 3 C2H5 Example test with parasitic mange mites (Psoroptes cuniculi) Solvent: Cremophor To produce an appropriate preparation of active ingredient, the active substance in question is mixed with the specified solvent in a ratio of 1: 2 and the concentrate thus obtained is diluted with water to the desired concentration.

About 10-25 mange mites (Psoroptes cuniculi) are added to 1 ml of the to Brought testing active ingredient preparation, which in tablet nests of a thermoformed packaging have been pipetted.

After 24 hours, the degree of destruction is determined in percent.

100% means that all mites and 0% that none of the mites have been killed. Active ingredient active ingredient killing agent centering in kung in% ppm Psoroptes cuni- culi CH C2H5 10 S 10 100 5 1 H 3 100 ..HC-NH-C4H9 1 100 C1k0.3 0 C3 C2H5 CH, 5 CH3 100 100 3sGd 3 S CH3 100 100 NH-C-NH-CH2 CHZ '( fi CH 10 100 C3 H3 3 3 100 1 0 Example A Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolue vulgaris), which strongly differ from all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are infected, sprayed dripping wet.

After the specified times, the destruction in X is determined.

100% means that all spider mites have been killed; 0, means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in the following table: Table (plant-damaging mites) Tetranychus test Active ingredients active ingredient killing degree centering in% in% 2 days CH 0.1 60 Cl- 9 -NH-CS-N 0.01 0 H 3 CH3 (known) Active ingredients according to the invention: < NH NH-C "-NH-C3H7 cm 0.1 100 0.1 100 NH-C3H7 0.01 98 3 CH CH3 CH CH3 e NH-C-NH-C3H7 0.1 100 It 3 0.01 95 CH CH3 3 CH-C2H5 S > HC-NH-C3H7 0.1 98 CH-C2H 0.01 95 CH3 CH3 3 xCH3 CH s S 0.1 100 3 <HC-NH-C4H9 0.01 99 CHCH 3 CH3 Table (plant-damaging mites) Tetranychus test Active ingredients active ingredient killing centering in% degrees in% after 2 days CH3 CH-C2H5 S CHH-C "-NH-C4H9 0.1 100 CH-C H 0.01 100 25th CH3 CH C. <1 NH-C-NH-C5H1 aoo CKCH3 511 0.01 99 CH3 CH3 CH-C2H5 S 0.1 0.1 0 1 100 : HC 2Hg CH3 CH CH 3 fiH - NII-CsH13 0.1 100 oCH3 0.01 100 CH 0.01 100 CH Table (plant-damaging mites) Tetranychus test Active ingredients active ingredient killing degree centering in% in% 2 days CH3 1 3 CH CH "NH-C-NH-CH -CFK 3 0.1 100 9 CH3 0.01 100 HC 2H5 CH3 Example B Plutella test Solvent: 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound dewy and populated with caterpillars of the cabbage moth (Plutella maculipennis).

After the specified times, the destruction is determined in%.

100% means that all the caterpillars have been killed; 0% means that no caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in the table below: Table (plant-damaging insects) Plutella test Active ingredients active ingredient killing centering in% degrees in% after 3 days CH3 C1- 0.1 80 Cl-n -NH-CS-N 0.1 80 H cH 0.01 0 3 3 (known) Active ingredients according to the invention: H3 CH S H3 CH3 g NH-C-NH-C 3H7 0.1 100 t 0.01 100 CH3 CH3 CH-C2H5 S 0.1 100 "H-CINH-CqHg 0.01 100 CH-C 2M5 CH3 CH3 CH-C2H CH C2H5 S R3 0.1 100 NH-C-NH-CH2-C100 t2Hg -C \ CH3 CH3 Table (plant damaging insects) Plutella test Active ingredients active ingredient killing degree centering in% in% 3 days CH 3 CH-C2H5 S / CH3 0.1 100 CH3- Q - NH-C-NH-CH2-CH 0.01 100 CH-C2H CH3 C1H-C2H5 CH3 CH3 CH-C2H5 S CH3 0.1 100 NH-C-NH-CH2-C, -CH3 0.01 100 CH-C2H5 CH3 CH3 Example Pyricularia test / rice / systemic solvent: 11.75 parts by weight acetone dispersant: 0.75 parts by weight alkylaryl polyglycol ether water: 987.50 parts by weight water The amount of active ingredient required for the desired concentration of active ingredient in the casting liquid is mixed with the stated amount of the solvent and dispersant and dilute the concentrate with the specified amount of water.

The liquid thus obtained is applied in the desired amount put in saucers, on which pots with holes in the bottom with 30 approx. 2 weeks standing old rice plants.

The test preparations are absorbed through the roots.

After 3 days, during which the plants in a greenhouse at 22 - 24 C and approx. 70% relative humidity remain, the plants will with an aqueous suspension of 100,000 to 200,000 spores / ml Pyricularia oryzae inoculated and in a room at 24-26 ° C. and 100% relative humidity set up.

About 4 days after the inoculation, the infestation is present in all leaves present after inoculation compared to untreated, but also inoculated control plants determined.

The evaluation takes place in numbers from 1 to 9. 1 means 100% effect, 3 = good effect, 5 = moderate effect and 9 = no effect.

Active ingredients, application rates and results are shown in the table below: Table Pyricularia test / rice / systemic Active ingredient expenditure- infestation value number amount (1 = 100% effect) 10 kg / ha (9 = no effect) Control (untreated) 9 Active ingredients according to the invention: C2H5 S CM3 -'- NM-C-NM-C4M9 3 25th CH3'S 1CH3 CM Q -NH-C NH / 3 C2M5 M3 CS Q -NH-C-NH-C2H5 2 25th 2H5 S q NH-C-NH-C3H7 3 C-NH-C3H7 3 C2H58 ß NH-C NH-C4H9 2 CH 2 CM 3 $ NH-C-NH-CH2- / H3 C2H5 CH3 Example / liquid active ingredient preparation Solvent: 11.75 parts by weight acetone Dispersant: 0.75 parts by weight alkylaryl polyglycol ether and 987.50 parts by weight water The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dispersant and the concentrate is diluted with the specified amount of water.

30 rice plants about 14 days old are sprayed with the spray liquid until dripping wet. The plants remain in a greenhouse until they have dried off at temperatures of 22 to 240C and a relative humidity of about 70 %. They are then treated with an aqueous suspension of 100,000 to 200,000 spores / ml inoculated by Pyricularia oryzae and in a room at 24-260C and 100% relative Humidity set up.

5 days after the inoculation, the infestation is in all at the time of Inoculation leaves as a percentage of the untreated, but also inoculated leaves Control plants determined. The evaluation takes place in numbers from 1 to 9. 1 means 100% effect, 3 = good effect, 5 = moderate effect and 9 = no effect.

Active ingredients, active ingredient concentrations and results are shown in the table below: Table Pyricularia test / liquid active ingredient preparation Active ingredient infestation value number (1 = 100% ige Effect, 9 = no effect) with an active ingredient concentration tration of 0.025 percent: CH Cl- <-NH-CS-N 9 5 cd3 CH3 (known) C2M5 5 nS / CH3 v NH-C-NH-CH2-CH3 / CH CH3 C2M5 C2H5 G NH-C-NH-C2H5 3 C2H5 2M5S1 S / CH3 C-NH-CH, -CH 3 2 \ cM 25 3 Preparation Examples Example 1 N- (2,6-diethyl-phenyl) -N'-isobutyl-thiourea 15.0 g of 2,6-diethyl-phenyl isothiocyanate are introduced into 20 g of isobutylamine at 20 ° C. and left to stand for 12 hours. The mixture is then stirred with excess dilute hydrochloric acid until the reaction product, which initially precipitates out as an oily product, crystallizes. It is filtered and washed neutral with water.

Then the filter cake is rubbed evenly with methanol, water added, suctioned off and dried. Yield 19.0g; F: 68-70 ° C.

Elemental analysis and NMR spectrum are with the assumed constitution in accordance.

Analogously, from the corresponding 2,6-diethyl phenyl isothiocyanate and the corresponding aliphatic amines the following N-aryl-N'-alkyl-thioureas are produced: N- (2,6-diethyl-phenyl) -N'-ethyl-thiourea F: 72-73 ° C N- (2,6-diethyl-phenyl) -N'-propyl-thiourea F: 58-60 ° C N- (2,6-diethyl-phenyl) -N'-butyl-thiourea F: 41-43 ° C N- (2,6-diethyl-phenyl) -N'-pentyl-thiourea N- (2,6-Diethyl-phenyl) -N'-neopentyl-thiourea F: 87-89 ° C N- (2,6-Diethyl-phenyl) -N'-hexyl-thiourea N- (2,6-diethyl-phenyl) -N'-heptyl-thiourea, N- (2,6-diethyl-phenyl) -N'-dodecyl-thiourea F: 120-1230C, N- (2,6-diethyl-phenyl) -N'-methallyl-thiourea. F: 65-68 ° C That Starting product 2,6-diethyl-phenyl isothiocyanate can be prepared as follows be: 100 g of 2,6-diethylaniline in 200 ml of methylene chloride are at 0 - SOC below Stir to a mixture of 500 ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 92 g of thiophosgene were added dropwise. Then the mixture is heated to reflux until the evolution of CO 2 is finished. The cooled batch is filtered, the methylene chloride layer is separated off, dried with calcium chloride and fractionated.

Yield 112 g; Bp 101-103 ° C / 1.4 Torr. Example 2 N- (4-MethYl-2,6-diethyl-phenol) -N'-neopentel-thiourea 15.0 g of 4-methyl-2,6-diethyl-phenyl isothiocyanate are dissolved in 9.0 g of 2,2-dimethyl-propylamine at 200C entered, whereby exothermic reaction occurs. After 12 hours, stir with excess dilute hydrochloric acid, filtered, washed with water and dilute Methanol and dries.

Yield 21 g; F: 106-107 ° C.

Elemental analysis and NMR spectrum are with the assumed constitution in accordance.

Similarly, from 4-methyl-2, 6-diethyl phenyl isothiocyanate and the corresponding aliphatic amines the following thioureas are produced: N- (4-methyl-2,6-diethyl-phenyl) -N '-butyl-thiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea F: 60-61 ° C, N- (4-methyl-2,6-diethyl-phenyl) -N'-methallyl-thiourea f: 86-880C 4-methyl-2,6-diethyl phenyl isothiocyanate can be prepared according to the following procedure: 100 g of 4-methyl-2,6-diethyl aniline in 200 ml of methylene chloride at O - 5 0C to a mixture of 500 ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 92 g of thiophosgene were added dropwise with stirring. It is then heated under reflux until the evolution of CO 2 has ended. After this After cooling, the batch is filtered off from solids, the methylene chloride layer separated, dried over calcium chloride and fractionated.

Yield 110 g; Bp: 113-116 ° C / 1.2 Torr.

Example 3 15.0 g of 2,6-diisopropylphenyl isothiocyanate are added at 20.degree entered in 20.0 g of isobutylamine. The reaction is exothermic; one leaves 12 Stand for hours and then stir with excess dilute hydrochloric acid. The crystalline precipitated reaction mixture is filtered off with suction, with water and dilute methanol washed and dried.

Yield 19.0g; 108-112 ° C.

Elemental analysis and NMR spectrum correspond to the assumed constitution.

Similarly, from 2,6-diisopropyl-phenyl isothiocyanate and the corresponding aliphatic amines the following thioureas are produced: N- (2,6-diisopropyl-phenyl) -N'-propyl-thiourea F: 106-107 ° C N- (2,6-diisopropyl-phenyl) -N'-butyl-thiourea, N- (2,6-diisopropyl-phenyl) -N '- (3-methyl-butyl) -thiourea F: 64-680C, N- (2,6-Diisopropyl-phenyl) -N'-pentyl-thiourea. F: 76-830C N- (2,6-Diisopropyl-phenyl) -N'-neopentyl-thiourea F: 150-1550C N- (2,6-diisopropyl-phenyl) -N'-hexyl-thiourea N- (2,6-Diisopropyl-phenyl) -N'-dodecyl-thiourea, N- (2,6-Diisopropyl-phenyl) -N'-methallyl-thiourea F: 93-95 ° C 2,6-Diisopropyl-phenylisothiocyanate can be prepared as follows: 100 g of 2,6-diisopropyl-aniline in 200 ml of methylene chloride are taken at 0-5 ° C Stir to a mixture of 300 ml of water, 500 ml of methylene chloride, 120 g of calcium carbonate and 78 g of thiophosgene were added dropwise. Then it is heated under reflux until the evolution of CO2 is finished.

After cooling, it is filtered, the methylene chloride layer is separated off, dried over calcium chloride and fractionated.

Yield 110 g; Bp: 144-1480C / 11 torr.

Example 4 N- (2,6-Di-sec-butyl-phenyl) -N -methallyl-thiourea 15.0 g of 2,6-di-sec-butyl-phenyl isothiocyanate are dissolved in 12.0 g of methallylamine at -100C registered. Allow to slowly come to + 200C and store at 200C for 12 hours. The batch is then stirred with excess dilute hydrochloric acid, the crystalline one Sucked off the reaction product, washed with water and dilute methanol and dried.

Yield 20.0 g; F: 69-720C.

Similarly, from 2,6-di-sec-butyl-phenyl isothiocyanate and the corresponding aliphatic amines the following thioureas are produced: N- (2,6-di-sec-butyl-phenyl) -N'-propyl-thiourea F: 85-870C N- (2,6-di-sec-butyl-phenyl) -N'-allyl-thiourea F: 83-860C N- (2,6-di-sec-butyl-phenyl) - N'-butyl thiourea F: wax N- (2,6-di-sec-butyl-phenyl) -N'-isobutyl-thiourea F: 83-850C N- (2,6-di-sec-butyl-phenyl) -N ' pentyl thiourea (oily) N- (2,6-di-sec-butyl-phenyl) -N'-neopentyl-thiourea F: 88-900C N- (2,6-di-sec-butyl-phenyl) -n ' -dodecyl thiourea (Elig) 2,6-di-sec-butyl-phenyl isothiocyanate can be prepared as follows: 100 g of 2,6-di-sec-butyl-aniline in 200 ml of methylene chloride are stored at 0 - 50C below Stir to a mixture of 300 ml of water, 500 ml of methylene chloride, 100 g of calcium carbonate and 68 g of thiophosgene were added dropwise. Then the mixture is heated under reflux until the evolution of CO 2 is finished. After cooling, the solids are filtered off, the methylene chloride layer separated off, dried over calcium chloride and fractionated: Yield 112 g, boiling point: 117-1200C / 1.0 torr.

Example 5 N- (4-methyl-2,6-diisopropyl-phenyl) -N'-isobutyl-thiourea 15.0 g of 4-methyl-2,6-diisopropyl-phenylisothiocyanate become 20 g of isobutylamine at 209tin entered and the exothermic reaction moderated by cooling. Leave for 12 hours stand and then stirred with excess dilute hydrochloric acid.

The reaction product which has crystallized out is filtered off with water and dilute methanol and dried.

Yield 18.0 g; F: 150-1530C.

Analogously from 4-methyl-2,6-diisopropyl-phenylisothiocyanate and the following thioureas prepared from the corresponding aliphatic amines become: N- (4-methyl-2,6-diisopropyl-phenyl) -N'-butyl-thiourea F: 126-1290C N- (4-methyl-2,6-diispropyl-phenyl) -N'-propyl-thiourea F: 125-127 ° C From 4-methyl-2,6-di-sec-butyl-phenyl isothiocyanate and isobutylamine is obtained analogously to N- (4-methyl-2,6-di-sec-butyl-phenyl-N'-isobutyl-thiourea F: 98-1020C with n-butylamine N- (4-methyl-2,6-di-sec-butyl-phenyl) -N'-butyl-thiourea F: 97-100 ° C 4-methyl-2,6-diisopropyl-phenyl isothiocyanate can be prepared as follows are: 150 g of 4-methyl-2,6-diisopropyl-aniline in 200 ml of methylene chloride are at 200C to a stirred mixture of 500 ml of methylene chloride, 300 ml of water, 120 g Calcium carbonate and 110 g of thiophosgene were added dropwise. Then it is heated under reflux until the C02 development has ended. The approach is filtered off from solids, the methylene chloride layer separated, dried over calcium chloride and fractionated.

Yield 159 g solidifying oil; Bp: 124-1260C / 1.2 Torr.

Analogously, 4-methyl-2,6-di-sec-butyl-aniline and thiophosgene become 4-methyl-2,6-di-sec-butyl-phenyl isothiocyanate with a boiling point of 130-1320C / 1.2 Torr obtain.

Example 6 N- (3-MethYl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea 15.0 g of 3-methyl-2,6-diethylphenyl isothiocyanate are dissolved in 9.0 g of 2,2-dimethylpropylamine at 200C registered.

The mixture is left to stand for 12 hours and then stirred with excess dilute Hydrochloric acid. The crystallized reaction product is filtered off with suction, with water and washed with dilute methanol and dried. Yield 20.0 g; F: 102-1040C. Elemental analysis and NMR spectrum are in agreement with the assumed constitution.

Similarly, from 3-methyl-2,6-diethylphenyl isothiocyanate and methallylamine N- (3-methyl-2,6-diethyl-phenyl) -N'-methallyl-thiourea F: 105-106 ° C; obtain will; from 3,5-dimethyl-2,6-diethyl-phenyl isothiocyanate and n-butylamine the N- (3,5-dimethyl-2,6-diethyl-phenyl) -N'-butyl-thiourea F: 108-1100C; from 3-chloro-2,6-diethyl-phenyl isothiocyanate and n-butylamine the N- (chloro-2,6-diethyl-phenyl) -N'-butyl-thiourea F: 108-11 ° C; with 2,2-dimethyl-propylamine of N- (3-chloro-2, 6-diethyl-phenyl) -N ' -neopentyl thiourea F: 106-1100C; from 2-ethyl-6-isopropyl-phenyl isothiocyanate and methallylamine N- (2-ethyl-6-isopropyl-phenyl) -N'-methallyl-thiourea F: 50-550C from 2,4,6-triisopropyl-phenyl isothiocyanate and methallylamine the N- (2,4,6-triisopropyl-phenyl) -N'-methallyl-thiourea F: 115-1180C.

The aryl isothiocyanates can be selected from the aryl amines and thiophosgene such as indicated in the preceding examples: 3-methyl-2,6-diethyl-phenyl isothiocyanate; Bp: 110-113 ° / 1.5 Torr 3, 5-dimethyl-2,6-diethylphenyl isothiocyanate: Bp: 119-1270C / 1.2 torr of 3-chloro-2,6-diethyl phenyl isothiocyanate; Bp: 118-121 ° C / 1.2 Torr 2-ethyl-6-isopropyl-phenyl isothiocyanate; Bp 104-106 ° C / 1,2-torr 2,4,6-triisopropyl-phenyl isothiocyanate; Bp: 130-1320C / 1.2 Torr.

Example 7 N- (2,6-Diisopropyl-phenyl) -N '-methyl-thiourea 120 g of 2,6-diisopropyl aniline are dissolved in 100 ml of triethylamine and 53 g of methyl isothiocyanate admitted. The formation of thiourea is slightly exothermic. The mixture is stirred for 12 hours mixed with excess dilute hydrochloric acid, filtered, washed with water and diluted methanol and dries.

Yield 142 g; F: 167-1680C.

Analogously, one obtains from methyl isothiocyanate and the corresponding aniline derivatives the following thioureas: N- (2,6-diethyl-phenyl) -N'-methyl-thiourea F: 103-105 ° C, N- (4-methyl-2,6-diethyl-phenyl) -N'-methyl-thiourea. F: 97-1000C N- (2-methyl-6-ethyl-phenyl) -N'-methyl-thiourea F: 65-670C N- (2,4-dimethyl) -6-ethyl-phenyl) -N'-methyl-thiourea F: 125-1260C.

Claims (12)

Claims 1. N-aryl-N'-alkyl-thioureas of the formula in which R1 and R2 can be identical or different and represent alkyl or cycloalkyl, and R³ represents alkyl, cycloalkyl or halogen, n represents 0, 1 or 2 and where, if n represents 2, the radicals R³ can be identical or different and R4 represents hydrogen, alkyl, alkenyl, cycloalkyl or cycloalkenyl. 2. N-aryl-N'-alkyl-thioureas of the formula in which RI and RII can be identical or different and for alkyl (C1-C6) or cycloalkyl (C3-C7), RIII for alkyl (C1-C6), cycloalkyl (C3-C 7), chlorine or bromine, n for 0 or 1 and RIV are hydrogen, alkyl (C1-C12), alkenyl (C2-C12), cycloalkyl (C3-C7) or cycloalkenyl (C3-C7). 3. Process for the preparation of N-aryl-N'-alkyl-thioureas of the formula in which R1 and R2 can be identical or different and represent alkyl or cycloalkyl, and R3 represents alkyl, cycloalkyl or halogen, n represents 0, 1 or 2 and where, if n represents 2, the radicals R³ can be identical or different and R4 represents hydrogen, alkyl, alkenyl, cycloalkyl or cycloalkenyl, characterized in that either a) aryl isothiocyanates of the formula in which R1, R2, R3 and n have the meaning given above, with alkylamines of the formula H2N-CH2-R (III) in which R4 has the meaning given above, optionally in the presence of solvents, or by reacting b) alkyl isothiocyanates Formula R4-CH2-NCS (IV) in which R4 has the meaning given above, with arylamines of the formula in which R1, R2, R3 and n have the meaning given above, optionally reacted in the presence of solvents. 4. Process for the preparation of compounds of the formula in which R1 and RII can be identical or different and for alkyl (C1-C6) or cycloalkyl (C3-C7), RIII for alkyl (C1-C6), cycloalkyl (C3-C7), chlorine or bromine, n for 0 or 1 and R are hydrogen, alkyl (C1-C12), alkenyl (C2-C12), cycloalkyl (C3-C7) or cycloalkenyl (C3-C7), characterized in that either a) aryl isothiocyanates of the formula in which R1, R11, R and have the meaning given above, with alkylamines of the formula H2N-CH2-RIV (IIIa) in which RIV has the meaning given above, optionally in the presence of inert solvents, or by reacting b) alkyl isothiocyanates Formula RIV-CH2-NCS (IVa) in which RIV has the meaning given above, with arylamines of the formula in which * R, R11, R and n have the meaning given above, optionally reacted in the presence of solvents. 5. The method according to claim 2), characterized in that at variant a) works with an excess of alkylamine. 6. The method according to claim 5), characterized in that the Reaction in the presence of tertiary organic bases at temperatures from 10 to 1200C, performs. 7. The method according to claim 6), characterized in that the Implementation at temperatures of 20 to 600C. 8. Ectoparasiticidal agents, characterized by a content of N-aryl-N'-alkylthioureas according to claim 1). 9. Agents effective against insects and acarids, characterized by a content of N-aryl-N'-alkylthioureas according to claim 1). 10. Process for the preparation of ectoparasiticidal agents, thereby characterized in that N-aryl-N'-alkylthiourea according to claim 1) with inert, mixed with non-toxic diluents and / or carriers. 11. Process for the preparation of agents which against insects and Acarides are effective, characterized in that one N-aryl-N'-alkylthioureas according to claim 1 mixed with suitable diluents and / or carriers. 12. A method for combating ectoparasites, characterized in that that one infected by ectoparasites animals with N-aryl-N'-alkylthioureas according to Claim 1) treated.