DE2702235A1 - 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites - Google Patents
1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasitesInfo
- Publication number
- DE2702235A1 DE2702235A1 DE19772702235 DE2702235A DE2702235A1 DE 2702235 A1 DE2702235 A1 DE 2702235A1 DE 19772702235 DE19772702235 DE 19772702235 DE 2702235 A DE2702235 A DE 2702235A DE 2702235 A1 DE2702235 A1 DE 2702235A1
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- Prior art keywords
- phenyl
- thiourea
- alkyl
- methyl
- butyl
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Description
Neue N-Aryl-N'-alkyl-thioharnstoffe, Verfahren Novel N-aryl-N'-alkyl-thioureas, method
zu ihrer Herstellung sowie ihre Verwendung als Mittel zur Bekämpfung von tierischen und pflanzlichen Schädlingen Die vorliegende Erfindung betrifft neue N-Aryl-N'-alkylthioharnstoffe, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Mittel zur Bekämpfung von tierischen und pflanzlichen Schädlingen, insbesondere als Ektoparasitizide, Insektizide und Akarizide. 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.
Es ist bereits bekannt geworden, daß N-Aryl-N',N'-dialkyl-thioharnstoffe als Ektoparasitizide, insbesondere als Tickizide gegen Zecken der Gattung boophilus, wirksam sind (s. dazu DT-OS 2 337 122).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).
Gegenüber den bekannten und chemisch verwandten Verbindungen zeigen die erfindungsgemäßen N-Aryl-N'-alkylthioharnstoffe eine bessere Wirkung gegen Phosphorester-resistente Zecken der Gattung boophilus sowie eine deutlich ausgeprägte insektizide Wirkung, die den Vergleichsprodukten aus DT-OS 2 337 122 fehlt. Sie sind außerdem in der Landwirtschaft wirksam gegen pflanzenschädigende Insekten und gegen Milben.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.
Es wurde nun gefunden, daß die neuen N-Aryl-N'-alkyl-thioharnstoffe der allgemeinen Formel (I) in welcher R1 und R2 gleich oder verschieden sein können und für Alkyl oder Cycloalkyl stehen, und R3 für Alkyl, cycloalkyl oder Halogen, n für 0, 1 oder 2 und wobei, falls n für 2 steht, die Reste R3 gleich oder verschieden sein können und R4 für Wasserstoff, Alkyl, Alkenyl, Cycloalkyl oder Cycloalkenyl stehen eine starke Wirkung gegenüber tierischen und pflanzlichen Schädlingen, insbesondere eine ektoparasitizide, insektizide und akarizide Wirkung besitzen.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.
Weiterhin wurde gefunden, daß man die neuen N-Aryl-N'-alkylthioharnstoffe der Formel (I) erhält, wenn man a) Arylisothiocyanate der Formel mit Alkylaminen der Formel H2N-CH2-R4 (III) oder alternativ b) Alkylisothiocyanate der Formel R4-CH2-NCS (IV) mit Arylaminen der Formel umsetzt, wobei R1 ,R2,R3 ,R4 und n in den Formeln (II) bis (V) jeweils die oben in der Formel (I) angegebene Bedeutung besitzen.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).
Uberraschenderweise zeigen die erfindungsgemäßen neuen N-Aryl-N' -alkyl-thioharnstoffe eine stärker ausgeprägte ektoparasitizide Wirkung als die chemisch nahe verwandten N-Aryl-N', N'-dialkyl-thioharnstoffe aus DT-OS 2 337 122 sowie zusätzlich eine insektizide Wirkung sowie eine Wirkung gegen Milben, welche den Verbindungen aus der DT-OS 2 337 122 fehlt.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.
Die erfindungsgemäßen Verbindungen stellen somit eine Bereicherung der Technik dar.The compounds according to the invention are thus an enrichment of technology.
Verwendet man nach Herstellungsvariante a) 2,6-Di-sek.-butylphenylisothiocyanat und Isobutylamin als Ausgangsstoffe, so kann der Reaktionsablauf durch folgendes Formelschema wiedergegeben werden: (Reaktionsgleichung A) Verwendet man nach Herstellungsvariante b) Isobutylisothiocyanat und 2,6-Di-sek.-butvl-anilin als Ausgangsstoffe, so kann der Reaktionsablauf durch folgendes Formelschema wiedergegeben werden: (Reaktionsgleichung B) In der Formel (I) stehen die Reste R¹ und R², vorzugsweise für Alkyl-(C1-C6) sowie für Cycloalkyl-(C3-C7). Beispielsweise seien genannt: Methyl, Äthyl, Propyl, Isopropyl, Butyl, sec.-Butyl, iso-Butyl, tert.-Butyl, Pentyl-(2), Pentyl-(3), tert.-Pentyl, Cyclopentyl, Hexyl-(2), Hexyl-(3), Cyclohexyl.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.
Der Rest R3 steht vorzugsweise für Alkyl-(C1-C6), insbesondere für Alkyl-(C1-C4), beispielsweise für Methyl, Äthyl, Propyl, Isopropyl, Butyl, sec.-Butyl, iso-Butyl, tert.-Butyl oder für Halogen, vorzugsweise für Chlor oder Brom. Weiterhin kann R3 für Cycloalkyl, vorzugsweise Cycloalkyl-(C3-C7) stehen, genannt seien: Cyclopentyl und 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 ,.
Der Rest R4 steht vorzugsweise für Wasserstoff oder geradkettiges Alkyl-(C1-C12) beispielsweise Methyl, Äthyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Oktyl, Decyl oder Dodecyl.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.
Weiterhin kann R4 vorzugsweise für verzweigtes Alkyl-(C3-C12) oder für Alkenyl-(C2-C12) stehen. Beispielsweise seien genannt: Isopropyl, sek.-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-Dimethylvinyl, 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. Schließlich kann R4 für Cycloalkyl-oder Cycloalkenyl stehen. (Vorzugsweise mit jeweils 3 bis 7 Kohlenstoffatomen). Beispielsweise seien genannt: Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cyclopropyl-(1)-yl-(1), Cyclopenten-(1) -yl-(3), Cyclopenten-(1)-yl-(3), Cyclohexen-(1)-yl-(3) und 1-Methyl-cyclopentyl-(1).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).
Besonders bevorzugt sind erfindungsgemäße Verbindungen der Formel in welcher RI und RII gleich oder verschieden sein können und für Alkyl (C1-C6) oder Cycloalkyl (C3-C7), RIII für Alkyl (C1-C6),Cycloalkyl (C3-C7),Chlor oder Brom, n für 0 oder 1 und RIV für Wasserstoff, Alkyl(C1-C12), Alkenyl (C2-C12), Cycloalkyl (C3-C7) oder Cycloalkenyl(C3-C7) stehen.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).
Die als Ausgangsverbindungen verwendeten Arylisothiocyanate der allgemeinen Formel (II) sowie Alkylisothiocyanate der allgemeinen Formel (IV) sind bekannt oder können nach bekannten Methoden hergestellt werden, beispielsweise durch Umsetzung von Arylaminen der allgemeinen Formel (V) oder Alkylaminen der allgemeinen Formel (III) mit Thiophosgen, durch Umsetzung von N-Aryl- oder N-Alkyl-dithiocarbonsauren Salzen mit Phosgen oder Oxidationsmitteln, oder aus Alkylhalogeniden und Alkalithiocyanaten oder aus Olefinen und Rhodanwasserstoff (siehe dazu u.a. Houben-Weyl, "Methoden der organischen Chemie", Band IX, Seiten 867-878).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).
Als Ausgangsverbindungen für die gemäß Reaktionsgleichung A einzusetzenden Arylisothiocyanate der allgemeinen Formel (II) seien beispielsweise genannt: 2,6-Dimethyl-phenylisothiocyanat 2-Methyl-6-äthyl-phenylisothiocyanat 2,6-Diäthyl-phenylisothiocyar.at 2-Ätyl-6-isopropyl-phenylisothiocyanat 2, 6-Diisopropyl-phenylisothiocyanat 2,6-Di-sek.-butyl-phenylisothiocyanat 2-.'Gethyl-6-sek.-butyl-phenylisothiocyanat 2-Äthyl-6-sek.-butyl-phenylisothiocyanat 2-isopropyl-6-sek.-butyl-phenylisothiocyanat 2-Methyl-6-isopropyl-phenylisothiocyanat 2-Methyl-6-cyclopentyl-phenylisothicyanat 2-Äthyl-6-cyclopentyl-phenylisothiocyanat 2-Isopropyl-6-cyclopentyl-phenylisothiocyanat 2,6-Di-cyclopentyl-phenylisothiocyanat 2-Methyl-6-tert.-butyl-phenylisothiocyanat 2-Äthyl-6-tert.-butyl-phenylisothiocyanat 2-Methyl-6-cyclohexyl-phenylisothiocyanat 2-Äthyl-6-cyclohexyl-phenylisothiocyanat 2,4-Dimethyl-6-äthyl-phenylisothiocyanat 2,4-Dimethyl-6-isopropyl-phenylisothiocyanat 2,4-Dimethyl-6-sek.-butyl-phenylisothiocyanat 2,4-Dimethyl-6-tert.-butyl-phenylisothiocyanat 2,4,6-Trimethyl-phenylisothiocyanat 2,6-Diäthyl-4-methyl-phenylisothiocyanat 2,6-Diisopropyl-4-methyl-phenylisothiocyanat 3,5-Dimethyl-2,6-diäthyl-phenylisothiocyanat 3-Methyl-2,6-diäthyl-phenylisothiocyanat 3-Chlor-2,6-diäthyl-phenylisothiocyanat 4-Methyl-2,6-di-sek.-phenylisothiocyanat 2,4,6-Triäthyl-phenylisothiocyanat 2,4,6-Triisopropyl-phenylisothiocyanat 3-Chlor-4-methyl-2,6-diäthyl-phenylisothiocyanat 3,4-Dimethyl-2,6-diäthyl-phenylisothiocyanat 4-Chlor-2,6-diäthyl-phenylisothiocyanat 4-Chlor-3-methyl-2,6-diäthyl-phenylisothiocyanat 4-Methyl-2,6-di-Cyclopentyl-phenylisothiocyanat 4-n-Butyl-2,6-diaethyl-phenylisothiocyanat 4-Isobutyl-2,6-diaethyl-phenylisothiocyanat 4-tert.-Butyl-2,6-diaethyl-phenylisothiocyanat 4-n-Propyl-2,6-diaethyl-phenylisothiocyanat 4-Cyclohexyl-2,6-diaethyl-phenylisothiocyanat 2-Methyl-4,6-di-tert.-butyl-phenylisothiocyanat Die den vorgenannten Arylisothiocyanaten zugrundeliegenden Arylamine der allgemeinen Formel (V) können alternativ für die Herstellung der Verbindung der allgemeinen Formel (I) gemäß Reaktionsgleichung B verwendet werden.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.
An Alkylisothiocyanaten der allgemeinen Formel IV seien beispielsweise genannt: 2"cthylisothiocyanat Ät:wlisothiocyanflt Propylicothiocyanat Butylisothiocyanat Isobutylisothiocyanat Pentylisothiocyanat Neopentylisothiocyanat 3-Methyl-butylisothiocyanat 2,3-Dimethyl-butylisothiocyanat 2,2,3-Trimethyl-butylisothiocyanat 2,2,3,3-Tetramethyl-butylisothiocyanat 3,3-Dimethyl-butylisothiocyanat 2-Äthyl-butylisothiocyanat 2-Isopropyl-butylisothiocyanat 2,2-Dimethyl-butylisothiocyanat Hexylisothiocyanat Heptylisothiocyanat Oc tylisothiocyanat Decylisothiocyanat Dodccylidothiocyanat 2,4,4-Trimethyl-pentylisothiocyanat 2,2,4,-Tetramethyl-pentylisothiocyanat Allylisothiocyanat 2-::cthyl-allylisothiocyanat Crotylisothiocyanat 2, 3-Dimcthyl-allylisothiocyanat 2,3,3-Trimethyl-allylisothiocyanat Buten-(3)-yl(1)-isothiocanat 2,2-Dimethyl-buten-(3)-yl-(1)-isothiocyanat 3-Isopropyl-allyl-isothiocyanat 3-tert.-Butyl-allyl-isothiocyanat 3-Hexyl-allyl-isothiocyanat Cyclopropyl-methylisothiocyanat Cyclopentyl-methylisothiocyanat Cyclopenten-(1)-yl-(1)-methylisothiocyanat Cyclopenten-(2)-yl-(1)-methylisothiocyanat Cyclohexyl-nethylisothiocyanat Cyclohexen-(1)-yl-(1)-methylisothiocyanat Die den vorgenannten Alkylisothiocyanaten zugrundeliegenden Alkylamine der allgemeinen Formel (III) können alternativ für die Herstellung von Verbindungen der allgemeinen rornel (I) in Analogie zu Reaktionsgleichung A verwendet werden.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.
Erfindungsgemäß werden wie bereits oben erwähnt a) d.e substituierten Arylisothiocyanate der allgemeinen Formel (11) mit den Alkylaminen der allgemeinen Formel (III) oder alternativ b) Alkylisothiocyanate der allgemeinen Formel (IV) mit Arylaminen der allgemeinen Formel (V) umgesetzt.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).
De Umsetzung erfolgt in molaren oder annähernd molaren Verhältnissen, wobei die leichter flüchtige oder weniger wertvolle Komponente im Überschuß, eingesetzt werden kann, beispielsweise mit 5-50 % Überschuß. Es ist jedoch in einer bevorzugten Ausführungsform auch möglich, beispielsweise die Alkylamine der allgemeinen Formel (III) in einem großen L'berschuß, nämlich 2-20 Mol, bezogen auf 1 Mol an Arylisothiocyanat II, einzusetzen. Sie dienen somit gleichzeitig als Lösungsmittel für die entstehenden Thioharnstoffe der allgemeinen Formel (I) und können nach erfolgter Umsetzung durch Destillation weitgehend zurückgewonnen werden.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.
Bei der Durchführung der Umsetzung nach Gleichung A oder B können zur Reaktionsbeschleunigung tertiäre organische Basen zugesetzt werden. Man arbeitet beispielsweise bei Temperaturen von 10 bis 1200C, insbesondere bei 20 bis 60°C. Die Umsetzung der substituierten Arylisothiocyanate der allg. Formel (II) it den Alkylaminen der allgemeinen Formel III oder alternativ der Alkylisothiocyanate IV mit den Arylaminen der Formel V an ohne Lösungsmittel in der Schmelze oder unter Zusatz eines Lösungs- und Verduflflungsmittels erfolgen. Als solche können teispielsweise verwendet werden: Kohlenwasserstoffe oder Halogenkohlenwasserstoffe wie Petroläther, Waschbenzin, Ligroin, Cyclohexan, Benzol, Toluol, Chlorbenzol, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, wasserlösliche lösungsmittel wie Methanol, Äthanol, Aceton, Acetonitril, Dimethylformamid, Falls erforderlich, können den Ansätzen weiter anorganische oder wie bereits vorne erwähnt, organische Basen als Beschleuniger zugesetzt werden, beispielsweise Triäthylamin, 1,4-Daizabicyclo-[2,2,2]-octan (DABCO) 1,5-Diaza-bicyclo-[4,3,9]-nonen-(5) (DBN) 1,8-Diaza-bicyclo-[5,4,0]-undecen-(7) (DBU), Kaliumhydroxid, Natriumhydroxid, Natriumhydrid, Natrlumoxid.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.
Die Umsetzungen können Je nach den Ausgangsverbindungen exother verlaufen und müssen Je nach Größe und Anwesenheit von Verdünnungsmittel durch kühlung unter Kontrolle gehalten werden oder die Unsetzungen müssen durch Erhitzen, beispielsweise auf Temperaturen von 40-1500C, vorzugsweise 50-1000C, beschleunigt werden. Die Urdsetzungsbedingungen sind also individuell verschieden und hängen von der Art und Menge der eingesetzten Ausgangsmaterialien sowie von dem verwendeten Lösungsmittel ab.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.
Die kafarbeitung erfolgt entweder durch Abdestillieren von Lösungsmitteln und Umkristallisieren des Reaktionsproduktes oder durch Eingießen in Wasser oder verdünnte wäßrige Mineralsäuren, Filtration und Trocknung.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.
Als neue N-Aryl-N'-alkyl-thioharnstoffe der allgemeinen Formel (I) seien die folgenden Verbindungen aufgeführt: N- (2,6-Diäthyl-phenyl)-N'-methyl-thioharnstoff; F: 103-1050C N-(2,6-Diäthyl-phenyl)-N'-äthyl-thioharnstoff; F: 72-73°C N-(2,6-Diäthyl-phenyl)-N'-propyl-thioharnstoff; F:58-60°C N-(2,6-Diäthyl-phenyl)-N'-butyl-thioharnstoff; F:41-43°C N-(2,6-Diäthyl-phenyl)-N'-isobutyl-thioharnstoff; F:68-70°C N-(2,6-Diäthyl-phenyl)-N'-neopentyl-thioharnstoff; F: 87-890C N-(2,6-Diäthyl-phenyl)-N'-pentyl-thioharnstoff; (F<30°C) N-(2,6-Diäthyl-phenyl)-N'-hexyl-thioharnstoff; F: 102-105°C N-(2,6-Diäthyl-phenyl)-N'-heptyl-thioharnstoff; (F<30°C) N-(2,6-Diäthyl-phenyl)-N'-oktyl-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-decyl-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-dedecyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-methyl-thioharnstoff; F: 97-1000C N- (4-Methyl-2, 6-diäthyl-phenyl) -N' äthyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-propyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-butyl-thioharnstoff; F: öl (F <30°C) N-(4-Methyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff; F: 60-61 0C N-(4-Methyl-2,6-diäthyl-phenyl)-N'-neopentyl-thioharnstoff; F: 106-1070C N-(4-Methyl-2,6-diäthyl-phenyl)-N'-pentyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-hexyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,2-dimethyl-butyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,3-dimethyl-butyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,2,3-trimethyl-butyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,3,3-trimethyl-butyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,2,3-tetramethyl-butyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(3-Methyl-pentyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2-isopropyl-butyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,4,4-trimethyl-pentyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,2,4,4-trimethyl-pentyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-allyl-thioharstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-methallyl-thioharstoff F: 86-88°C N-(4-Methyl-2,6-diäthyl-phenyl)-N'-crotyl-thioharstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(3,3-dimethyl-allyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(2,3-dimethyl-allyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-[buten-(3)-yl-(1)]-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-[2,2-dimethyl-buten-(3)-yl-(1)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(3-isopropyl-allyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(3-tert.-butyl-allyl)-thioharbstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-(3-hexyl-allyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'cyclopropyl-methylthioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'(cyclopentyl-methyl)-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-[cyclopenten-(1)-yl-(1)-methyl]-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-cyclohexyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-ohenyl)-N'-[cyclohexen-(3)-yl-(1)-methyl]-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(2,3-dimethyl-butyl)-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(2,2,3-trimethyl-butyl)-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(3-methyl-pentyl)thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(2,2,4,4-tetramethyl-pentyl)-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(3,3-dimethyl-allyl)-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(2,3-dimethyl-allyl)-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-methallyl-thioharstoff N-(2,6-Diäthyl-phenyl)-N'-(cyclopentyl-methyl)-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-(cyclohexyl-methyl)-thioharnstoff N-(3-Methyl-2,6-diäthyl-phenyl)-N'-propyl-thioharnstoff N-(3-Met}lyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff N- (3-Methyl-2, 6-diäthyl-plieny L) -N' -neopenty-thioharnstoff F: 102-104 0C N-(3-Methyl-2,6-diäthyl-phenyl)-N'-pentyl-thioharnstoff N-(3-Methyl-2,6-diäthyl-phenyL)-N'-methaLlyl-tliioharnstoff F: 105-1060C N-(3-Methyl-2,6-diäthyl-phenyl)-N'-(3-methyl-butyl)-thioharnstoff N-(3-Methyl-2,6-diäthyl-phenyl)-N'-(2-äthyl-butyl)-thioharnstoff N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-butyl-thioharnstoff F: 108-1100C N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-pentyl-thioharnstoff N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-neopentyl-thioharnstoff N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-metallyl-thioharnstoff N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-penten-(4)-yl-(l)-thioharnstoff N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-cyclopentyl-methylthioharnstoff N-(3,4-Dimethyl-2,6-diäthyl-phenyl)-N'-neopentyl-thioharnstoff N-(3,4-Dimethyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff N-(3,4-Dimethyl-2,6-diäthyl-phenyl)-N'-pentyl-thioharnstoff N-(3,4-Dimethyl-2,6-diäthyl-phenyl)-N'-methallyl-thioharnstoff N-(3-Chlor-2,6-diäthyl-phenyl)-N'-propyl-thioharnstoff N-(3-Chlor-2,6-diäthyl-phenyl)-N'-butyl-thioharnstoff F: 108:1110C N-(3-Chlor-2,6-diäthyl-phenyl)-N'-neopentyl-thioharnstoff F: 106-1100C N-(3-Chlor-2,6-diäthyl-phenyl)-N'-(3-methyl-pentyl)-thioharnstoff N-(3-Chlor-4-methyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff N- (3-Ch Ior-4-methyl-2, 6-diäthyl-phenyl) -N' -neopentyl-thioharnstoff N-(3-Chlor-4-methyl-2,6-diäthyl-phenyl)-N'-methallyl-thioharnstoff N-(2,4,6-Trimethyl-phenyl) -N ' -neopentyl-thioharnstoff N-(2,q,6-Trimethyl-phenyl)-N'-methallyl-thioharnstoff N-(2,3,4,6-Tetramethyl-phenyl)-N'-butyl-thioharstoff N-(2,3,4,6-Tetramethyl-phenyl)-N'-methallyl-thioharstoff N-(2,6-Diisopropyl-phenyl)-N'-methyl-thioharnstoff F: 167-1680C N-(2,6-Diisopropyl-phenyl)-N'-äthyl-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-propyl-thioharnstoff F: 106-1070C N-(2,6-Diisopropyl-phenyl)-N'-butyl-thioharnstoff F: 99-1030C N-(2,6-Diisopropyl-phenyl)-N'-isobutyl-thioharnstoff F: 108-1120C N-(2,6-Diisopropyl-phenyl)-N'-(3-methyl-butyl)-thioharnstoff F: 64-680C N-(2,6-Diisopropyl-phenyl)-N'-pentyl-thioharnstoff F: 76-830C N-(2,6-Diisopropyl-phenyl)-N'-neopentyl-thioharnstoff F: 150-1550C N-(2,6-Diisopropyl-phenyl)-N'-methallyl-thioharnstoff F: 93-950C N-(2,6-Diisopropyl-phenyl)-N'-hexyl-thioharnstoff N- (2, 6-Di 1 sopropyl-phenyl)-N'-dodecyl-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-(2-äthyl-butyl)-thioharnstoff N-(2,6-Diisopropyl-pl1enyl)-N'-(3,3-dimethyl-butyl)-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-(2,3-dimethyl-butyl)-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-(2,2,3-trimethyl-butyl)-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-(2,2,4-trimethyl-pentyl)-thioharnstoff N-(2,6-Diisopropyl-l)llenyl)-N'-(2,3,3-trimethyl-allyl)-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-(cyclopentyl-methyl)-thioharnstoff N-(2-Äthyl-6-isobutyl-phenyl)-N'-methallyl-thioharnstoff F: 105-1060C N-(2-Äthyl-6-isobutyl-phenyl)-N'-butyl-thioharnstoff N- (2-Äthyl-6-isobutyl-phenyi) -N'-neopentyl-thloharnstoff N-(2-Athyl-6-isobutyl-phenyl)-N-isobutyl-thioharnstoff N-(2-Methyl-6-isopropyl-phenyl)-N'-butyl-thioharnstoff N-(2-Methyl-6-isopropyl-phenyl)-N'-isobutyl-thioharnstoff ?- (2-Methyl -6-lsoproj)yi-phenyl) -N'-neopentyl-thloharnstoff N- (2-Methyl-6-äthyl-phenyl) -N' -isobutyl-thioharnstoff N- (2-Methyl-6-äthyl-phenyl) -N' -neopentyl-thioharnstoff N-(2-Methyl-6-äthyl-phenyl)-N'-(3,3-dimethyl-butyl)-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-methyl-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-äthyl-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-propyl-thioharnstoff F: 85-87°C N-(2,6-Di-sek-butyl-phenyl)-N'-butyl-thioharnstoff N- (2, 6-Di-sek-butyl-phenyl) -N' -isobutyl-thioharnstoff F: 83-850C N-(2,6-Di-sek-butyl-phenyl)-N'-allyl-thioharnstoff F: 83-86°C N- (2, 6-Di-sek-butyl-phenyl) -N'-methallyi-thioharnstoff F: 69-720C N- (2, 6-Di-sek-butyl-phenyl) -N' -neopentyl-thioharnstoff F: 88-900C N-(2,6-Di-sek-butyl-phenyl)-N'-pentyl-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-hexyl-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-octyl-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-decyl-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-(2-äthyl-butyl)-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-(3,3-dimethyl-butyl)-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-(2-methyl-pentyl)-thioharnstoff N-(2,6-Di-sek-butyl-phenyl)-N'-(2,3,3-trimethyl)-allylthioharnstoff N-(2-Methyl-6-sek.-butyl-phenyl)-N'-propyl-thioharnstoff N-(2-Athyl-6-sek.-butyl-phenyl)-N'-methallyl-thioharnstoff N-(2-Isopropyl-6-sek.-butyl-phenyl)-N'-isobutyl-thioharnstoff N-(2-Methyl-2,6-di-sek.-phenyl)-N'-isobutyl-thioharnstoff F: 98-1020C N-(4.Methyl-2,6-di-sek.-butyl-phenyl)-N'-butyl-thioharnstoff F: 97-1000C N-(2,6-Di-cyclopentyl-phenyl)-N'-methyl-thioharnstoff N-(2,6-Di-cyclopentyl-phenyl)-N'-butyl-thioharnstoff N-(2,6-Di-cyclopentyl-phenyl)-N'-isobutyl-thioharnstoff N- (2, 6-Di-cyclopentyl-phenyl) -N'-neopentyi-thioharnstoff N-(2,6-Di-cyclopentyl-phenyl)-N'-methallyl-thioharnstoff N-(2,6-Di-cyclopentyl-phenyl)-N'-(cyclopropyl-methyl)-thioharnstoff N-(2,6-Di-cyclopentyl-phenyl)-N'-pentyl-thioharnstoff N- (2-Äthyl-6-cyclopentyl-phenyl) -N' -isobutyl-thioharnstoff N-(2-Methyl-6-tert.-butyl-phenyl)-N'-isobutyl-thioharnstoff N- (2-Methyl-6-tert.-butyl-phenyl) -N' -neopentyl-thioharnstoff N-(2-Methyl-6-tert.-butyl-phenyl)-N'-methallyl-thioharnstoff N- (2-Methyl-6-tert.-butyl-phenyl) -N'-pentyl-thioharnstoff N-(2-Methyl-4,6-di-tert.-butyl-phenyl)-N'-methyl-thioharnstoff N-(2-Methyl-4,6-di-tert.-butyl-phenyl)-N'-isobutyl-thioharnstoff N-(2-Methyl-4,6-di-tert.-butyl-phenyl)-N'-methallyl-thioharnstoff N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-methyl-thioharnstoff N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-propyl-thioharnstoff F: 125-1270C N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-butyl-thioharnstoff F: 126-1290C N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-isobutyl-thioharnstoff F: 150-1530C N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-neopentyl-thioharnstoff N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-methallyl-thioharnstoff N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-hexyl-thioharnstoff N-(4-Äthyl-2,6-diisopropyl-phenyl)-N'-isobutyl-thioharnstoff N-(4-Äthyl-2,6-diisopropyl-phenyl)-N'-neopentyl-thioharnstoff N-(2,4,6-triisopropyl)-N'-methyl-thioharnstoff N-(2,4,6-triisopropyl-phenyl)-N'-butyl-thioharnstoff N-(2,4,6-triisopropyl-phenyl)-N'-allyl-thioharnstoff N-(2,4,6-triisopropyl)-N'-methallyl-thioharnstoff F: 115-1180C N-(2,4,6-triisopropyl-phenyl)-N'-(3-methyl-pentyl)-thioharnstoff N-(2,4,6-triisopropyl-phenyl)-N#-(2-äthyl-pentyl)-thioharnstoff N-(2,6-Dimethyl-phenyl)-N'-butyl-thioharnstoff N-(2,6-Dimethyl-phenyl)-N'-neopentyl-thioharnstoff N- (2, 6-Dimethyl-phenyl) -N' -methallyl-thioharnstoff N-(2,6-Dimethyl-phenyl)-N'-isobutyl-thioharnstoff N-(2,6-Dimethyl-phenyl)-N'-hexyl-thioharnstoff N- (2-Methyl-6-äthyl-phenyl) -N'-methyl-thioharnstoff F: 65-670C N- (2, 4-Dimethyl-6-äthyl-phenyl) -N' -methyl-thioharnstoff F: 125-1260C N-(2,4,6-Träthyl-phenyl)-N'-propyl-thioharnstoff N-(2,4,6-Träthyl-phenyl)-N'-butyl-thioharnstoff, Öl (F<30°C) N-(2,4,6-Träthyl-phenyl)-N'-isobutyl-thioharnstoff F: 74-76°C N-(2,4,6-Triäthyl-phenyl)-N'-methallyl-thioharnstoff N-(2,4,6-Träthyl-phenyl)-N'-neophentyl-thioharnstoff F: 78-80°C N-(4-Butyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff, Öl (F<30°C) N-(4-Butyl-2,6-diäthyl-phenyl)-N'-neopentyl-thioharnstoff F:52-540C N-(4-Butyl-2,6-diäthyl-phenyl)-N'-crotyl-thioharnstoff N-(4-Butyl-2,6-diäthyl-phenyl)-N'-heptyl-thioharnstoff N- (4-Cyclohexyl-2 ,6-diäthyl-phenyl) -N' -butyl-thioharnstoff F:63-660C N-(4-Cyclohexyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff F:118-12O0 N-(4-Cyclohexyl-2,6-diäthyl-phenyl)-N'isobutyl-thioharnstoff N-(4-Cyclohexyl-2,6-diäthyl-phenyl)-N'-methallyl-thioharnstoff N- (4-Cyclopentyl-2 ,6-diäthyl-phenyl) -N'-neopentyl-thioharnstoff N-(4-Propyl-2,6-diäthyl-phenyl)-N'-n-pentyl-thioharnstoff; Öl (Fs30°C) N- (4-Isobutyl-2,6-diäthyl-phenyl)-N'-methyl-thioharnstoff F:123-1260C N-(4-Isobutyl-2,6-diäthyl-phenyl)-N'-n-hexyl-thioharnstoff; öl (F<30°C) N-(4-tert.-Butyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff F:121-1220C N-(4-tert.-Butyl-2,6-diäthyl-phenyl)-N'-butyl-thioharnstoff F:81-830C N-(4-tert.-Butyl-2,6-diäthyl-phenyl)-N'-n-pentyl-thioharnstoff, Öl (F<30°C) N-(2-Methyl-4,6-di-tert.-butyl-phenyl)-N'-isobutyl-thioharnstoff F:157-16O0C N-(2-Methyl-4,6-di-tert.-butyl-phenyl)-N'-neopentyl-thioharnstoff F: 157-159°C N-(4-Methyl-2,6-di-cyclopentyl-phenyl)-N'-butyl-thioharnstoff F:151-1530C Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören: Aus der Ordnung der Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.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.
Aus der Ordnung der Diplopoda z. B. Blaniulus guttulatus.From the order of the Diplopoda, for. B. Blaniulus guttulatus.
Aus der Ordnung der Chilopoda z. B. Geophilus carpophagus, Scutigera spec.From the order of the Chilopoda, for. B. Geophilus carpophagus, Scutigera spec.
Aus der Ordnung der Symphyla z. B. Scutigerella immaculata.From the order of the Symphyla z. B. Scutigerella immaculata.
Aus der Ordnung der Thysanura z. B. Lepisma saccharina.From the order of the Thysanura z. B. Lepisma saccharina.
Aus der Ordnung der Collembola z. B. Onychiurus armatus.From the order of the Collembola, for. B. Onychiurus armatus.
Aus der Ordnung der 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 Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorloides, Melanoplus differentialis, Schistocerca gregaria.
Aus der Ordnung der Dermaptera z. B. Forficula auricularia.From the order of the Dermaptera, for. B. Forficula auricularia.
Aus der Ordnung der Isoptera z. B. Reticulitermes spp..From the order of the Isoptera, for. B. Reticulitermes spp ..
Aus der Ordnung der Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.From the order of the Anoplura, e.g. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.
Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci.
Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
Aus der Ordnung der Homoptera z.B. 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 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 ..
Aus der Ordnung der Lepidoptera z. 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 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.
Aus der Ordnung der Coleoptera z. 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 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.
Aus der Ordnung der Hymenoptera z. B. Diprion spp.. Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the Hymenoptera, for. B. Diprion spp. Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Diptera z.B. 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.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 der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ceratophyllus spp., Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans.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.
Aus der Ordnung der Acarina z.B. 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., Die Anwendung der erfindungsgemäßen Wirkstoffe erfolgt in Form ihrer handelsüblichen Formulierungen und/oder den.aus diesen Formulierungen bereiteten Ansendungsfornen.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.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren.The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges.
Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Cew.-% Wirkstoff vorzugsweise zwischen 0,01 und 10 Gew.-% liegen.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.
Die Anwendung geschieht in einer den Anwendungstormen angepaßten Ublichen Weise.The application takes place in a customary adapted to the application norms Way.
Die Anwendung der erfindungsgemäßen Wirkstoffe geschieht i Veterinärsektor in bekannter Weise, wie durch orale Anwendung in Fofl. von beispielsweise Tabletten, Kapseln, Tränken, Granulaten, durch dermale Anwendung in Form beispielsweise des Tauchens (Dippen), Sprühens (Sprayen), Aufgießens (puor-on and spot-on) und des Einpuderns sowie durch parenterale Anwendung in Form beispielsweise der Injektion.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.
Die Wirkstoffe können in die üblichen Formulierungen Ubergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Schäume, Pasten, lösliche Pulver, Granulate, Aerosole, Suspensions-Emulsionskonzentrate, Saatgutucer, Wirkstoff-imprägnierte Natur- und synthetische Stoffe, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, ferner in Formulierungen mit Brennsätzen, wie Räucherpatronen, -dosen, -spiralen u.ä. sowie ULV-Kalt- und Warmnebel-Formulierungen.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.
Diese Formulierungen werden in bekannter Weise hergestellt, z.3. durch Vermischen der Wirkstoffe mit Streckmitteln, also ilussigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen urd/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln.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.
Im Falle der Benutzung von Wasser als Streckmittel können z.B.In the case of using water as an extender, e.g.
auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, Chlor vierte Aromaten oder chlorierte aliphatische K«blenwasseratoff , wie Chlorbenzole, ChlorEthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Parafeine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Clycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark pore e Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streck-Mitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasr förmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gerste in mehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate: gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehle, Kokosnußschalen, Maiskolben und Tabakstengel; als Emulgier-und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglykol-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z.B. Lignin, Sulfitablaugen und Methylcellulose.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.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat.Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo-Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.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.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.
Beispiel Test mit parasitierenden adulten Rinderzecken (Boophilus microplus res.) Lösungsmittel: Cremophor Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man die betreffende aktive Substanz mit dem angegebenen Lösungsmittel im Verhältnis 1:2 und verdünnt das so erhaltene Konzentrat mit Wasser auf die gewünschte Konzentration.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 adulte Rinderzecken (B. microplus res.) werden in der zu testenden
Wirkstoffzubereitung 1 Min. getaucht. Nach Überführung in Plastikbecher und Aufbewahrung
in einem klimatisierten Raum wird der Abtötungsgrad in Prozent bestimmt, wobei 100
% bedeuten, daß alle und 0 %, daß keine Zecken abgetötet worden sind.
Etwa 20 Fliegenlarven (Lucilia cuprina) werden in ein mit Wattestopfen
entsprechender Größe beschicktes Teströhrchen gebracht, welches ca. 3 ml einer 20
%igen Eigelbpulver-Suspension in Wasser enthält. Auf diese Eigelbpulver-Suspension
werden 0,5 ml der Wirkstoffzubereitung gebracht. Nach 24 Stunden wird der Abtötungsgrad
in % bestimmt. Dabei bedeuten 100 %, daß alle und O %,daß keine Larven abgetötet
worden sind.
Etwa 10-25 Räudemilben (Psoroptes cuniculi) werden in 1 ml der zu testenden Wirkstoffzubereitung gebracht, die in Tablettennester einer Tiefziehverpackung pipettiert wurden.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.
Nach 24 Stunden wird der Abtötungsgrad in Prozent bestimmt.After 24 hours, the degree of destruction is determined in percent.
Dabei bedeuten 100 %, daß alle und 0 %, daß keine Milben abgetötet
worden sind.
Mit der Wirkstoffzubereitung werden Bohnenpflanzen (Phaseolue vulgaris), die stark von allen Entwicklungsstadien der gemeinen Spinnmilbe oder Bohnenspinnmilbe (Tetranychus urticae) befallen sind, tropfnaß besprüht.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.
Nach den angegebenen Zeiten wird die Abtötung in X bestimmt.After the specified times, the destruction in X is determined.
Dabei bedeutet 100 %, daß alle Spinnmilben abgetötet wurden; 0 , bedeutet, daß keine Spinnmilben abgetötet wurden.100% means that all spider mites have been killed; 0, means that no spider mites have been killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate
gehen aus der nachfolgenden Tabelle hervor:
Tabelle (pflanzenschädigende
Milben) Tetranychus-Test
Mit der Wirkstoffzubereitung besprüht man Kohlblätter (Brassica oleracea) taufeucht und besetzt sie mit Raupen der Kohlschabe (Plutella maculipennis).Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound dewy and populated with caterpillars of the cabbage moth (Plutella maculipennis).
Nach den angegebenen Zeiten wird die Abtötung in % bestimmt.After the specified times, the destruction is determined in%.
Dabei bedeutet 100 %, daß alle Raupen abgetötet wurden; 0 % bedeutet, daß keine Raupen abgetötet wurden.100% means that all the caterpillars have been killed; 0% means that no caterpillars were killed.
Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate
gehen aus der nachfolgenden Tabelle hervor:
Tabelle (pflanzenschädigende
Insekten) Plutella-Test
Die so erhaltene Flüssigkeit wird in der gewünschten Aufwandmenge in Untersetzer gegeben, auf denen am Boden durchlöcherte Töpfe mit 30 ca. 2 Wochen alten Reispflanzen stehen.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.
Die Aufnahme der Versuchspräparate erfolgt über die Wurzel.The test preparations are absorbed through the roots.
Nach 3 Tagen, während der die Pflanzen in einem Gewächso haus bei 22 - 24 C und ca. 70 % relativer Luftfeuchtigkeit verbleiben, werden die Pflanzen mit einer wäßrigen Suspension von 100 000 bis 200 000 Sporen / ml Pyricularia oryzae inokuliert und in einem Raum bei 24 - 26 0C und 100 % relativer Luftfeuchtigkeit aufgestellt.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.
Etwa 4 Tage nach der Inokulation wird der Befall bei allen zur Zeit der Inokulation vorhandenen Blättern im Vergleich zu unbehandelten, aber ebenfalls inokulierten Kontrollpflanzen bestimmt.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.
Die Auswertung erfolgt in Wertzahlen von 1 - 9. 1 bedeutet 100 % Wirkung, 3 = gute Wirkung, 5 = mäßige Wirkung und 9 = keine Wirkung.The evaluation takes place in numbers from 1 to 9. 1 means 100% effect, 3 = good effect, 5 = moderate effect and 9 = no effect.
Wirkstoffe, Aufwandmengen und Resultate gehen aus der nachfolgenden
Tabelle hervor:
Tabelle Pyricularia-Test / Reis / systemisch
Mit der Spritzflüssigkeit bespritzt man 30 etwa 14 Tage alte Reispflanzen bis zur Tropfnässe. Die Pflanzen verbleiben bis zum Abtrocknen in einem Gewächshaus bei Temperaturen von 22 bis 240C und einer relativen Luftfeuchtigkeit von etwa 70 %. Danach werden sie mit einer wäßrigen Suspension von 100 000 bis 200 000 Sporen/ml von Pyricularia oryzae inokuliert und in einem Raum bei 24 - 260C und 100 % relativer Luftfeuchtigkeit aufgestellt.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 Tage nach der Inokulation wird der Befall bei allen zur Zeit der Inokulation vorhandenen Blättern in Prozent der unbehandelten, aber ebenfalls inokulierten Kontrollpflanzen bestimmt. Die Auswertung erfolgt in Wertzahlen von 1 - 9. 1 bedeutet 100 %ige Wirkung, 3 = gute Wirkung, 5 = mäßige Wirkung und 9 = keine Wirkung.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.
Wirkstoffe, Wirkstoffkonzentrationen und Resultate gehen aus der nachfolgenden
Tabelle hervor:
Tabelle Pyricularia-Test / flüssige Wirkstoffzubereitung
Danach wird der Nutschkuchen mit Methanol gleichmäßig verrieben, Wasser zugesetzt, abgesaugt und getrocknet. Ausbeute 19,0 g; F: 68-70°C.Then the filter cake is rubbed evenly with methanol, water added, suctioned off and dried. Yield 19.0g; F: 68-70 ° C.
Elementaranalyse und NMR-Spektrum stehen mit der angenommenen Konstitution in Übereinstimmung.Elemental analysis and NMR spectrum are with the assumed constitution in accordance.
Analog können aus dem entsprechenden 2,6-Diäthyl-phenylisothiocyanat und den entsprechenden aliphatischen Aminen die folgenden N-Aryl-N'-alkyl-thioharnstoffe hergestellt werden: N-(2,6-Diäthyl-phenyl)-N'-äthyl-thioharnstoff F: 72-73°C N-(2,6-Diäthyl-phenyl)-N'-propyl-thioharnstoff F: 58-60°C N-(2,6-Diäthyl-phenyl)-N'-butyl-thioharnstoff F: 41-43°C N-(2,6-Diäthyl-phenyl)-N'-pentyl-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-neopentyl-thioharnstoff F: 87-89°C N-(2,6-Diäthyl-phenyl)-N'-hexyl-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-heptyl-thioharnstoff N-(2,6-Diäthyl-phenyl)-N'-dodecyl-thioharnstoff F: 120-1230C N-(2,6-Diäthyl-phenyl)-N'-methallyl-thioharnstoff F: 65-68°C Das Ausgangsprodukt 2,6-Diäthyl-phenylisothiocyanat kann folgendermaßen hergestellt werden: 100 g 2,6-Diäthylanilin in 200 ml Methylenchlorid werden bei 0 - SOC unter Rühren zu einem Gemisch von 500 ml Methylenchlorid, 300 ml Wasser, 120 g Calciumcarbonat und 92 g Thiophosgen zugetropft. Danach erhitzt man zum Rückfluß, bis die C02-Entwicklung beendet ist. Der abgekühlte Ansatz wird filtriert, die Methylenchloridschicht abgetrennt, mit Calciumchlorid getrocknet und fraktioniert.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.
Ausbeute 112 g; Kp. 101 - 103°C/ 1,4 Torr Beispiel 2 N-(4-MethYl-2,6-diäthYl-Phenol)-N'-neopentel-thioharnstoff 15,0 g 4-Methyl-2,6-diäthyl-phenylisothiocyanat werden bei 200C in 9,0 g 2,2-Dimethyl-propylamin eingetragen, wobei exotherme Reaktion eintritt. Nach 12 Stunden verrührt man mit überschüssiger verdünnter Salzsäure, filtriert, wäscht mit Wasser und verdünntem Methanol und trocknet.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.
Ausbeute 21 g; F: 106-107°C.Yield 21 g; F: 106-107 ° C.
Elementaranalyse und NMR-Spektrum stehen mit der angenommenen Konstitution in Übereinstimmung.Elemental analysis and NMR spectrum are with the assumed constitution in accordance.
Analog können aus 4-Methyl-2 , 6-diäthyl-phenylisothiocyanat und den entsprechenden aliphatischen Aminen die folgenden Thioharnstoffe hergestellt werden: N- (4-Methyl-2, 6-diäthyl-phenyl) -N' -butyl-thioharnstoff N-(4-Methyl-2,6-diäthyl-phenyl)-N'-isobutyl-thioharnstoff F: 60-61 0C N-(4-Methyl-2,6-diäthyl-phenyl)-N'-methallyl-thioharnstoff f: 86-880C 4-Methyl-2,6-diäthyl-phenylisothiocyanat kann nach folgender Vorschrift hergestellt werden: 100 g 4-Methyl-2,6-diäthyl-anilin in 200 ml Methylenchlorid werden bei O - 5 0C zu einem Gemisch von 500 ml Methylenchlorid, 300 ml Wasser, 120 g Calciumcarbonat und 92 g Thiophosgen unter Rühren zugetropft. Danach wird unter RUckfluß erwärmt, bis die C02-Entwicklung beendet ist. Nach dem Abkühlen wird der Ansatz von Feststoffen abfiltriert, die Methylenchloridschicht abgetrennt, über Calciumchlorid getrocknet und fraktioniert.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.
Ausbeute 110 g; Kp: 113-116°C/1,2 Torr.Yield 110 g; Bp: 113-116 ° C / 1.2 Torr.
Beispiel 3 15,0 g 2,6-Diisopropyl-phenylisothiocyanat werden bei 20°C in 20,0 g Isobutylamin eingetragen. Die Reaktion verläuft exotherm; man läßt 12 Stunden stehen und verrührt dann mit überschüssiger verdünnter Salzsäure. Das kristallin ausgefallene Reaktionsgemisch wird abgesaugt, mit Wasser und verdünntem Methanol gewaschen und getrocknet.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.
Ausbeute 19,0 g; 108-112°C.Yield 19.0g; 108-112 ° C.
Elementaranalyse und NMR-Spektrum entsprechen der angenommenen Konstitution.Elemental analysis and NMR spectrum correspond to the assumed constitution.
Analog können aus 2,6-Diisopropyl-phenylisothiocyanat und den entsprechenden aliphatischen Aminen die folgenden Thioharnstoffe hergestellt werden: N-(2,6-Diisopropyl-phenyl)-N'-propyl-thioharnstoff F: 106-107°C N-(2,6-Diisopropyl-phenyl)-N'-butyl-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-(3-methyl-butyl)-thioharnstoff F: 64-680C N- (2,6-Diisopropyl-phenyl) -N'-pentyl-thioharnstoff F: 76-830C N- (2, 6-Diisopropyl-phenyl) -N' -neopentyl-thioharnstoff F: 150-1550C N-(2,6-Diisopropyl-phenyl)-N'-hexyl-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-dodecyl-thioharnstoff N-(2,6-Diisopropyl-phenyl)-N'-methallyl-thioharnstoff F: 93-95°C 2,6-Diisopropyl-phenylisothiocyanat kann folgendermaßen hergestellt werden: 100 g 2,6-Diisopropyl-anilin in 200 ml Methylenchlorid werden bei 0 - 5°C unter Rühren zu einem Gemisch aus 300 ml Wasser, 500 ml Methylenchlorid, 120 g Calciumcarbonat und 78 g Thiophosgen zugetropft. Danach erwärmt man unter Rückfluß, bis die CO2-Entwicklung beendet ist.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.
Nach dem Abkühlen wird filtriert, die Methylenchloridschicht abgetrennt, über Calciumchlorid getrocknet und fraktioniert.After cooling, it is filtered, the methylene chloride layer is separated off, dried over calcium chloride and fractionated.
Ausbeute 110 g; Kp: 144-1480C/11 Torr.Yield 110 g; Bp: 144-1480C / 11 torr.
Beispiel 4 N- (2, 6-Di-sek-butyl-phenyl) -N -methallyl-thioharnstoff 15,0 g 2,6-Di-sek-butyl-phenylisothiocyanat werden bei -100C in 12,0 g Methallylamin eingetragen. Man läßt langsam auf +200C kommen und bewahrt 12 Stunden bei 200C auf. Danach wird der Ansatz mit überschüssiger verdünnter Salzsäure verrührt, das kristalline Reaktionsprodukt abgesaugt, mit Wasser und verdünntem Methanol gewaschen und getrocknet.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.
Ausbeute 20,0 g; F: 69-720C.Yield 20.0 g; F: 69-720C.
Analog können aus 2,6-Di-sek-butyl-phenylisothiocyanat und den entsprechenden aliphatischen Aminen die folgenden Thioharnstoffe hergestellt werden: N-(2,6-Di-sek.-butyl-phenyl)-N'-propyl-thioharnstoff F: 85-870C N-(2,6-Di-sek.-butyl-phenyl)-N'-allyl-thioharnstoff F: 83-860C N-(2,6-Di-sek.-butyl-phenyl)-N'-butyl-thioharnstoff F: Wachs N-(2,6-Di-sek.-butyl-phenyl)-N'-isobutyl-thioharnstoff F: 83-850C N-(2,6-Di-sek.-butyl-phenyl)-N'-pentyl-thioharnstoff (ölig) N-(2,6-Di-sek.-butyl-phenyl)-N'-neopentyl-thioharnstoff F: 88-900C N-(2,6-Di-sek.-butyl-phenyl)-n'-dodecyl-thioharnstoff (älig) 2,6-Di-sek.-butyl-phenylisothiocyanat kann folgendermaßen hergestellt werden: 100 g 2,6-Di-sek.-butyl-anilin in 200 ml Methylenchlorid werden bei O - 50C unter Rühren zu einem Gemisch aus 300 ml Wasser, 500 ml Methylenchlorid, 100 g Calciumcarbonat und 68 g Thiophosgen zugetropft. Danach erwärmt man unter Rückfluß bis die C02-Entwicklung beendet ist. Nach dem Abkühlen wird von den Feststoffen abfiltriert, die Methylenchloridschicht abgetrennt, über Calciumchlorid getrocknet und fraktioniert: Ausbeute 112 g, Kp: 117-1200C/1,0 Torr.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.
Beispiel 5 N- (4-Methyl-2 ,6-diisopropyl-phenyl) -N' -isobutyl-thioharnstoff 15,0 g 4-Methyl-2 , 6-diisopropyl-phenylisothiocyanat werden bei 209tin 20 g Isobutylamin eingetragen und die exotherme Reaktion durch Kühlung gemäßigt. Man läßt 12 Stunden stehen und verrührt dann mit überschüssiger verdünnter Salzsäure.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.
Das auskristallisierte Reaktionsprodukt wird abfiltriert, mit Wasser und verdünntem Methanol gewaschen und getrocknet.The reaction product which has crystallized out is filtered off with water and dilute methanol and dried.
Ausbeute 18,0 g; F: 150-1530C.Yield 18.0 g; F: 150-1530C.
Analog können aus 4-Methyl-2,6-diisopropyl-phenylisothiocyanat und den entsprechenden aliphatischen Aminen die folgenden Thioharnstoffe hergestellt werden: N- (4-Methyl-2 ,6-diisopropyl-phenyl) -N' -butyl-thioharnstoff F: 126-1290C N-(4-Methyl-2,6-diispropyl-phenyl)-N'-propyl-thioharnstoff F: 125-127°C Aus 4-Methyl-2,6-di-sek.-butyl-phenylisothiocyanat und Isobutylamin erhält man analog N-(4-Methyl-2,6-di-sek.-butyl-phenyl-N'-isobutyl-thioharnstoff F: 98-1020C mit n-Butylamin N-(4-Methyl-2,6-di-sek.-butyl-phenyl)-N'-butyl-thioharnstoff F: 97-100°C 4-Methyl-2 , 6-diisopropyl-phenylisothiocyanat kan folgendermaßen hergestellt werden: 150 g 4-Methyl-2,6-diisopropyl-anilin in 200 ml Methylenchlorid werden bei 200C zu einem gerührten Gemisch aus 500 ml Methylenchlorid, 300 ml Wasser, 120 g Calciumcarbonat und 110 g Thiophosgen zugetropft. Danach erwärmt man unter Rückfluß bis die C02-Entwicklung beendet ist. Der Ansatz wird von Feststoffen abfiltriert, die Methylenchloridschicht abgetrennt, über Calciumchlorid getrocknet und fraktioniert.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.
Ausbeute 159 g erstarrendes öl; Kp: 124-1260C/1,2 Torr.Yield 159 g solidifying oil; Bp: 124-1260C / 1.2 Torr.
Analog wird aus 4-Methyl-2,6-di-sek.-butyl-anilin und Thiophosgen das 4-Methyl-2 , 6-di-sek.-butyl-phenylisothiocyanat vom Kp: 130-1320C/1,2 Torr erhalten.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.
Beispiel 6 N-(3-MethYl-2,6-diäthyl-phenyl)-N'-neopentyl-thioharnstoff 15,0 g 3-Methyl-2 ,6-diäthyl-phenylisothiocyanat werden bei 200C in 9,0 g 2,2-Dimethyl-propylamin eingetragen.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.
Man läßt 12 Stunden stehen und verrührt dann mit überschüssiger verdünnter Salzsäure. Das auskristallisierte Reaktionsprodukt wird abgesaugt, mit Wasser und verdünntem Methanol gewaschen und getrocknet. Ausbeute 20,0 g; F: 102-1040C. Elementaranalyse und NMR-Spektrum stehen mit der angenommenen Konstitution in Ubereinstimmung.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.
Analog kann aus 3-Methyl-2 , 6-diäthyl-phenylisothiocyanat und Methallylamin der N-(3-Methyl-2,6-diäthyl-phenyl)-N'-methallyl-thioharnstoff F: 105-106°C; erhalten werden; aus 3,5-Dimethyl-2,6-diäthyl-phenylisothiocyanat und n-Butylamin der N-(3,5-Dimethyl-2,6-diäthyl-phenyl)-N'-butyl-thioharnstoff F: 108-1100C; aus 3-Chlor-2,6-diäthyl-phenylisothiocyanat und n-Butylamin der N-(Chlor-2,6-diäthyl-phenyl)-N'-butyl-thioharnstoff F: 108-11°C; mit 2,2-Dimethyl-propylamin der N- (3-Chlor-2, 6-diäthyl-phenyl) -N' -neopentyl-thioharnstoff F: 106-1100C; aus 2-Äthyl-6-isopropyl-phenylisothiocyanat und Methallylamin der N- (2-Äthyl-6-isopropyl-phenyl) -N' -methallyl-thioharnstoff F: 50-550C aus 2,4,6-Triisopropyl-phenylisothiocyanat und Methallylamin der N-(2,4,6-Triisopropyl-phenyl)-N'-methallyl-thioharnstoff F: 115-1180C.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.
Die Arylisothiocyanate können aus den Arylaminen und Thiophosgen wie in den vorhergehenden Beispielen angegeben hergestellt werden: 3-Methyl-2,6-diäthyl-phenylisothiocyanat; Kp: 110-113°/ 1,5 Torr 3, 5-Dimethyl-2, 6-diäthyl-phenylisothiocyanat: Kp: 119-1270C/ 1,2 Torr 3-Chlor-2,6-diäthyl-phenylisothiocyanat; Kp: 118-121°C/ 1,2 Torr 2-Äthyl-6-isopropyl-phenylisothiocyanat; Kp 104-106°C/ 1,2-Torr 2,4,6-Triisopropyl-phenylisothiocyanat; Kp: 130-1320C/ 1,2 Torr.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.
Beispiel 7 N- (2, 6-Diisopropyl-phenyl) -N' -methyl-thioharnstoff 120 g 2,6-Diisopropyl-anilin werden in 100 ml Triäthylamin gelöst und 53 g Methylisothiocyanat zugegeben. Die Thioharnstoffbildung verläuft schwach exotherm. Man rührt 12 Stunden, versetzt mit überschüssiger verdünnter Salzsäure, filtriert, wäscht mit Wasser und verdünntem Methanol und trocknet.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.
Ausbeute 142 g; F: 167-1680C.Yield 142 g; F: 167-1680C.
Analog erhält man aus Methylisothiocyanat und den entsprechenden Anilin-derivaten die folgenden Thioharnstoffe: N-(2,6-Diäthyl-phenyl)-N'-methyl-thioharnstoff F: 103-105°C N-(4-Methyl-2,6-diäthyl-phenyl)-N'-methyl-thioharnstoff F: 97-1000C N-(2-Methyl-6-äthyl-phenyl)-N'-methyl-thioharnstoff F: 65-670C N-(2,4-Dimethyl)-6-äthyl-phenyl)-N'-methyl-thioharnstoff F: 125-1260C.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)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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DE19772702235 DE2702235A1 (en) | 1977-01-20 | 1977-01-20 | 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites |
NZ186237A NZ186237A (en) | 1977-01-20 | 1978-01-17 | N-aryl-n'-alkyl-thioureas and pesticidal compositions for both plant and animal use |
GB1815/78A GB1571970A (en) | 1977-01-20 | 1978-01-17 | Use of n-aryl-n'-alkyl-thioureas as agents for combating animal and plant pests |
FR7801519A FR2392970A1 (en) | 1977-01-20 | 1978-01-19 | NEWS N-ARYL-N'-ALKYL-THIOUREES, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO THE CONTROL AGAINST ANIMAL AND PLANT PARASITES |
NL7800674A NL7800674A (en) | 1977-01-20 | 1978-01-19 | NEW N-ARYL-N'-ALKYLTHIOUREA, METHOD FOR PREPARING IT AND ITS USE AS MEANS FOR CONTROL OF ANIMAL AND VEGETABLE HARMFUL ORGANISMS. |
BE184449A BE863078A (en) | 1977-01-20 | 1978-01-19 | NEWS N-ARYL-N'-ALKYL-THIOUREES, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO THE CONTROL AGAINST ANIMAL AND PLANT PARASITES |
ZA00780356A ZA78356B (en) | 1977-01-20 | 1978-01-19 | Novel n-aryl-n'-alkyl-thioureas and their use as agents for combating animal and plant pests |
ES466151A ES466151A1 (en) | 1977-01-20 | 1978-01-19 | 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites |
AU32584/78A AU3258478A (en) | 1977-01-20 | 1978-01-20 | N-aryl-n'-alkyl-thioureas |
ES78475478A ES475478A1 (en) | 1977-01-20 | 1978-11-28 | 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites |
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---|---|---|---|
DE19772702235 DE2702235A1 (en) | 1977-01-20 | 1977-01-20 | 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2702235A1 true DE2702235A1 (en) | 1978-07-27 |
Family
ID=5999125
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19772702235 Pending DE2702235A1 (en) | 1977-01-20 | 1977-01-20 | 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites |
Country Status (4)
Country | Link |
---|---|
BE (1) | BE863078A (en) |
DE (1) | DE2702235A1 (en) |
ES (2) | ES466151A1 (en) |
ZA (1) | ZA78356B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0210487A1 (en) * | 1985-07-12 | 1987-02-04 | Ciba-Geigy Ag | Use of N-(4-phenoxy-2,6-diisopropylphenyl)-N'-tert.butylthiourea in the control of white flies |
EP0392802A2 (en) * | 1989-04-11 | 1990-10-17 | Beecham Group p.l.c. | Preparation of urea analogues and their use in bronchial, cerebrovascular and neuronal disorders |
-
1977
- 1977-01-20 DE DE19772702235 patent/DE2702235A1/en active Pending
-
1978
- 1978-01-19 BE BE184449A patent/BE863078A/en unknown
- 1978-01-19 ZA ZA00780356A patent/ZA78356B/en unknown
- 1978-01-19 ES ES466151A patent/ES466151A1/en not_active Expired
- 1978-11-28 ES ES78475478A patent/ES475478A1/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0210487A1 (en) * | 1985-07-12 | 1987-02-04 | Ciba-Geigy Ag | Use of N-(4-phenoxy-2,6-diisopropylphenyl)-N'-tert.butylthiourea in the control of white flies |
EP0392802A2 (en) * | 1989-04-11 | 1990-10-17 | Beecham Group p.l.c. | Preparation of urea analogues and their use in bronchial, cerebrovascular and neuronal disorders |
EP0392802A3 (en) * | 1989-04-11 | 1992-06-03 | Beecham Group p.l.c. | Preparation of urea analogues and their use in bronchial, cerebrovascular and neuronal disorders |
Also Published As
Publication number | Publication date |
---|---|
BE863078A (en) | 1978-07-19 |
ES475478A1 (en) | 1979-04-16 |
ES466151A1 (en) | 1979-05-01 |
ZA78356B (en) | 1979-01-31 |
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OHN | Withdrawal |