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GB1571970A - Use of n-aryl-n'-alkyl-thioureas as agents for combating animal and plant pests - Google Patents

Use of n-aryl-n'-alkyl-thioureas as agents for combating animal and plant pests Download PDF

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Publication number
GB1571970A
GB1571970A GB1815/78A GB181578A GB1571970A GB 1571970 A GB1571970 A GB 1571970A GB 1815/78 A GB1815/78 A GB 1815/78A GB 181578 A GB181578 A GB 181578A GB 1571970 A GB1571970 A GB 1571970A
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phenyl
methyl
thiourea
butyl
isothiocyanate
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Bayer AG
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Bayer AG
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Priority claimed from DE19772702235 external-priority patent/DE2702235A1/en
Priority claimed from DE19772727529 external-priority patent/DE2727529A1/en
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates
    • C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
    • 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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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Description

(54) THE USE OF N-ARYL-N'-ALKYL-THIOUREAS AS AGENTS FOR COMBATING ANIMAL AND PLANT PESTS (71) We, BAYER AKTIENGESELLSCHAFT, a body corporate, organised under the laws of Germany, of Leverkusen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to the use of certain N-aryl-N'-alkylthioureas as agents for combating animal and plant pests, especially as arthropodicides and fungicides.
It has already been disclosed that N-aryl-N', N'-di-alkyl-thioureas have an action as ectoparasiticides, in particular as tickicides againt ticks of the genus Boophilus (see DT-OS (German Published Specification 2,337,122).
It has now been found that the N-aryl-N'-alkyl-thioureas of the general formula
in which R' represents alkyl or cycloalkyl, R2 represents alkyl with at least 2 carbon atoms or cycloalkyl, R3 represents alkyl, cycloalkyl or halogen, n represents 0, 1 or 2, it being possible, if n represents 2, for the substituents R3 to be identical or different, and R4 represents hydrogen, alkyl, alkenyl, optionally methyl-substituted cycloalkyl or cycloalkenyl, have a powerful action against animal and plant pests, in particular an arthropodicidal and fungicidal action.
Accordingly, the present invention now provides an arthropodicial or fungicidal composition containing as active ingredient a compound of the formula (I), in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The invention also provides a method of combating arthropods or fungi which comprises applying to the arthropods or fungi, or to a habitat thereof (other than on on animal's body), a compound of the formula (I) alone or in the form of a composition containing as active ingredient a compound of the formula (I) in admixture with a diluent or carrier.
Preferably, R1 represents alkyl (C1-C6) or cycloalkyl (C3-C7) [for example, methyl, ethyl, propyl, isopropyl, butyl, sec. - butyl, isobutyl, tert. - butyl, pent 2 - yl, pent - 3 - yl, tert. - pentyl, cyclopentyl, hex - 2 - yl, hex - 3 - yl or cyclohexyl], R2 represents alkyl (C2-C6) or cycloalkyl (C3-C7) [for example, ethyl, propyl, isopropyl, butyl, sec. - butyl, iso - butyl, tert. - butyl, pent - 2 - yl, pent - 3 - yl, tert. - pentyl, cyclopentyl, hex - 2 - yl, hex - 3 - yl or cyclohexyl], R3 represents alkyl (C1-C6) [especially alkyl (C1-C4)] [for example, methyl, ethyl, propyl, isopropyl, butyl, sec. - butyl, iso-butyl, tert. - butyl or n - hexyl], chlorine, bromine or cycloalkyl (C3-C7) [for example cyclopentyl or cyclohexyl], and R4 represents hydrogen, straight-chain alkyl (C1-C12) [for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl or dodecyl], branched alkyl (C3-C12) or alkenyl (C2-C12) [for example, isopropyl, sec. - butyl, isobutyl, tert. butyl, 2 - methyl - butyl, 3 - methyl - butyl, tert.-pentyl, pent-2-yl, 3-methyl-but2 - yl, 2,3 - dimethyl - but -2 - yl, 2,3,3 - trimethyl - but -2 - yl, 2,2 - dimethyl - prop - 1 - yl, 2 - methyl - but - 2 - yl, 4,4 - dimethyl - pent - 2 - yl, 2,4,4 trimethyl - pent - 2 - yl, hex - 2 - yl, hex - 3 - yl, vinyl, 1 - methylvinyl, 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 - isopropyl - vinyl, 2 - tert. - butyl - vinyl, 2 - butyl - vinyl, 3,3 - dimethyl - allyl or 3 - hexyl - allyl], cycloalkyl (C3-C7) or cycloalkenyl (C3-C7) [for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloprop - 1 - en - 1 - yl, cyclobut - 1 - en - 3 - yl, cyclopent - 1 - en - 3 - yl, cyclohex - 1 - en - 3 - yl or 1 - methyl cyclopent - 1 - yl].
Compounds in which n is 0 or 1 are especially preferred.
The preparation of an N-aryl-N'-alkyl-thiourea of the formula (I) may be effected by a process in which (a) an aryl isothiocyanate of the general formula
is reacted with an alkylamine of the general formula H2N-CH2-R (III) or (b) an alkyl isothiocyanate of the general formula R4-CH2-NCS (IV) is reacted with an arylamine of the general formula
in which R1, R2, R3, R4 and n in the formulae (II) to (V) each have the meaning stated above in the respect of the formula (I).
Surprisingly, the N-aryl-N'-alkyl-thioureas to be used according to the invention exhibit a more strongly pronounced ectoparasiticidal action, especially against phosphorus-ester resistant ticks of the genus Boophilus, than the N-aryl N',N'-dialkyl-thioureas known from DT-OS (German Published Specification) 2,337,122, which are closely related chemically, and additionally exhibit an insecticidal action as well as an action against mites, which the compounds known from DT-OS (German Published Specification) 2,337,122 lack.
The use of the compounds according to the invention thus represents an enrichment of the art.
If, according to process 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:
If, according to process 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:
The aryl isothiocyanates of the general formula (II) and alkyl isothiocyanates of the general formula (IV) used as starting compounds are known or can be prepared by known methods, for example by reacting arylamines of the general formula (V) or alkylamines of the general formula (III) with thiophosgene, by reacting the salts of N-aryl-dithiocarboxylic or N-alkyl-dithiocarboxylic acids with phosgene or oxidising agents, or from alkyl halides and alkyl thiocyanates or from olefins and thiocyanic acid (see, inter alia, Houben-Weyl, "Methoden der organischen Chemie" ("Methods of Organic Chemistry"), volume IX, pages 867-878).
Examples of the aryl isothiocyanates of the general formula (II), which are to be employed in process variant (a) as starting compounds are: 2 - methyl - 6 - ethyl - phenyl isothiocyanate, 2,6 - diethyl - phenyl isothiocyanate, 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 isothiocyanate, 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 - cyclopentyl - 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, 2,6 - diethyl - 4 - methylphenyl 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, 4methyl - 2,6 - di - sec. - butyl - 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, 4chloro - 3 - methyl - 2,6 - diethyl - phenyl isothiocyanate, 4 - methyl - 2,6 dicyclopentyl- phenyl isothiocyanate, 4 - n - butyl - 2,6 - diethylphenyl isothiocyanate, 4 - isobutyl - 2,6 - diethyl - phenyl isothiocyanate, 3 - tert. - butyl 2,6 - diethyl - phenyl isothiocyanate, 4 - n - propyl - 2,6 - diethyl - phenyl isothiocyanate, 4 - cyclohexyl - 2,6 - diethyl - phenyl isothiocyanate, 2 - methyl - 4,6 - di - tert. - butyl - phenyl isothiocyanate, 4 - pent - 3 - yl - 2,6 - diethylphenyl isothiocyanate and 4 - n - nexyl - n-exyl - 2,6 - diethyl - phenyl isothiocyanate.
Examples of the arylamines of the general formula (V) to be used in process variant (b) are those from which the above-mentioned aryl isothiocyanates are derived.
Examples of alkyl isothiocyanates of the general formula (IV) are: methyl iso thiocyanate, ethyl isothiocyanate, propyl isothiocyanate, 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 iso thiocyanate, 2-ethyl-butyl isothiocyanate, 2-isopropyl-butyl isothiocyanate, 2,2 dimethyl-butyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate, decyl isothiocyanate, dodecyl isothiocyanate, 2,4,4-trimethyl pentyl isothiocyanate, 2,2,4,4-tetramethyl-pentyl isothiocyanate, allyl isothio cyanate, 2-methyl-allyl isothiocyanate, crotyl isothiocyanate, 2,3-dimethyl-allyl iso thiocyanate, 2,3 ,3-trimethyl-allyl isothiocyanate, but-3-en- 1 -yl isothiocyanate, 2,2 dimethyl-but-3-en-1-yl isothiocyanate, 3-isopropyl-allyl isothiocyanate, 3-tert. butyl-allyl isothiocyanate, 3-hexyl-allyl isothiocyanate, cyclopropyl-methyl iso thiocyanate, cyclopentyl-methyl isothiocyanate, cyclopent- 1-en-I -yl-methyl iso thiocyanate, cyclopent-2-en-1-yl-methyl isothiocyanate, cyclohexyl-methyl isothio cyanate and cyclohex-2-en- l-yl-methyl isothiocyanate.
Examples of the alkylamines of the general formula (III) to be used in process variant (a) are those from which the above-mentioned alkyl isothiocyanates are derived.
The reactants, whether in process variant (a) or (b), are generally employed in equimolar or approximately equimolar amounts, it being possible, however, to employ the more volatile or less expensive reactant in excess, for example in a 550% excess. However, in a preferred embodiment of process variant (a) it is also possible, for example, to employ the alkylamine of the general formula (III) in a large excess, for example 2-20 moles, relative to 1 mole of aryl isothiocyanate (II).
The amine thus simultaneously serves as a solvent for the thiourea of the general formula (I) so formed and, after the reaction has been carried out, can be substantially recovered by distillation.
In carrying out the reaction according to process variant (a) or (b), tertiary organic bases can be added in order to accelerate the reaction.
The reaction in both process variants may be carried out, for example, at temperatures of from 20 to 150"C preferably at from 500 to 100 C.
The reaction of the substituted aryl isothiocyanates (II) with the alkylamines (III) or, alternatively, of the alkyl isothiocyanates (IV) with the arylamines (V) can be carried out without a solvent in the melt or with the addition of a solvent or diluent.
Examples of solvents and diluents which can be used are: hydrocarbons or halogenohydrocarbons, such as petroleum ether, wash benzine, ligroin, cyclohexane, benzene, toluene, chlorobenzene, methylene chloride, chloroform or carbon tetrachioride, and water-soluble solvents, such as methanol, ethanol, acetone, acetonitrile and dimethylformamide.
If necessary, further inorganic or, as already mentioned above, organic bases, for example triethylamine, 1,4 - diaza - bicyclo - [2,2,2] - octane (DABCO), 1,5 diaza - bicyclo - [4,3,0] - non - 5 - ene (DBN), 1,9 - diaza - bicyclo - [5,4,0] - undec - 7 - ene (BDU), potassium hydroxide, sodium hydroxide, sodium hydride and sodium oxide, can be added to the reaction mixtures as accelerators.
Depending on the starting compounds, the reactions can proceed exothermically and, depending on the quantity and presence of diluents, must be kept under control by cooling, or the reactions must be accelerated by heating, for example to temperatures of 40--150"C, preferably 50--100"C. The reaction conditions are thus different in individual cases and depend on the nature and amount of the starting materials employed and on the solvent used. The reaction mixture generally is worked up either by distilling off solvents and recrystallising the reaction product, or by pouring it into water or dilute aqueous mineral acids and filtering off and drying the product.
Examples of the N - aryl - N' - alkyl - thioureas of the general formula (I) are: N - (2,6 - diethyl - phenyl) - N' - methyl- thiourea (melting point: 103-105 C), N -(2,6 - diethyl - phenyl) - N' - ethyl - thiourea (melting point: 72--73"C), N - (2,6 - diethyl - phenyl) - N' - propyl - thiourea (melting point: 58600 C), N - (2,6 - diethyl - phenyl) - N' - butyl - thiourea (melting point: 41--43"C), N - (2,6 - diethyl - phenyl) - N' - isobutyl - thiourea (melting point: 68--70"C), N - (2,6 - diethylphenyl) - N' - neopentyl - thiourea (melting point: 87--89"C), N - (2,6 - diethyl - phenyl) - N' - pentyl - thiourea (melting point < 30 C), N - (2,6 - diethyl - phenyl) - N' - hexyl - thiourea (melting point: 102--105"C), N - (2,6 - diethyl - phenyl) - N' - heptyl - thiourea (melting point < 30 C), N - (2,6 - diethyl - phenyl) - N' - octyl - thiourea, N - (2,6 - diethyl phenyl) - N' - decyl - thiourea, N - (2,6 - diethyl - phenyl) - N' - dodecyl thiourea, N-(4-methyl- 2,6 - diethyl - phenyl) - N' - methyl- thiourea (melting point: 97-100 C), 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 (oil, melting point: t30 C), N - (4 - methyl - 2,6 - diethyl - phenyl) - N' - isobutyl - thiourea (melting point: 606l0C), N - (4 - methyl - 2,6 - diethyl - phenyl) - N' neopentyl - thiourea (melting point: 106--107"C), 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) - thi6urea, N - (4 - methyl - 2,6 - diethyl - phenyl) - N' (2,3,3 - trimethyl - butyl) - thiourea, N -(4 - methyl - 2,6 r diethyl - phenyl) N' - (2,2,3,3 - tetramethyl - butyl) - thi6urea, N - (4 - methyl - 2,6 - diethyl phenyl) - N' - (3 - methyl - pentyl) - thiourea, N - (4 - methyl - 2,6 - diethyl phenyl) - N' - (2 - isopropyl - butyl) - thiourea, N - (4 - methyl - 2,6 - diethyl phenyl) - N' - (2,4,4 - trimethyl - pentyl) - thiourea, N - (4 - methyl - 2,6 diethyl - phenyl) - N' - (2,2,4,4 - tetramethyl - pentyl) - thiourea, N- (4- methyl - 2,6 - diethyl - phenyl) - N' - allyl - thiourea, N - (4 - methyl - 2,6 diethyl - phenyl) - N' - methallyl - thiourea (melting point: 86-880C), 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' - [but - 3 - en - I - yl] - thiourea, N - (4 - methyl - 2,6 diethyl - phenyl) - N' - [2,2 - dimethyl - but - 3 - en - I - yl] - 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) - thiourea, N - (4 methyl - 2,6 - diethyl - phenyl) - N' -(3-hexyl- allyl) - thiourea, N - (4 methyl - 2,6 - diethyl - phenyl) - N' - cyclopropyl - methyl - thiourea, N - (4 methyl - 2,6 - diethyl - phenyl) - N' - (cyclopentyl - methyl) - thiourea, N - (4 methyl - 2,6 - diethyl - phenyl) - N' - [cyclopent - 1 - en - 1 - yl - methyl] - thiourea, N - (4 - methyl - 2,6 - diethyl - phenyl) - N' - cyclohexylmethyl thiourea, N - (4 - methyl - 2,6 - diethyl - phenyl) - N' - [cyclohex - 3 - en - I yl - methyl] - thiourea, N - (2,6 - diethylphenyl) - 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 diethylphenyl)- 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 - diethylphenyl) - N' - propyl - thiourea, N - (3 methyl - 2,6 - diethyl - phenyl) - N' - isobutyl - thiourea, N - (3 - methyl - 2,6 diethyl - phenyl) - N' - neopentyl - thiourea (melting point: 102--104"C), N - (3 methyl - 2,6 - diethyl - phenyl) - N' - pentyl - thiourea, N - (3 - methyl - 2,6 diethyl - phenyl) - N' - methallyl - thiourea (melting point: 105--106"C), 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 (melting point: l08-ll00C), 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 - diethylphenyl) - N' - methallyl - thiourea, N - (3,5 - dimethyl - 2,6 - diethylphenyl) - N' - pent - 4 - en - 1 - yl - thiourea, N - (3,5 - dimethyl - 2,6 - diethylphenyl) - N' - cyclopentyl - methyl - thiourea, N - (3,4 - dimethyl - 2,6 - diethylphenyl) - 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 - diethvl phenyl) - N' - methallyl - thi6urea, N - (3 - chloro - 2,6 - diethyl - phenyl) - N' - propyl - thiourea, N - (3, - chloro - 2,6 - diethyl - phenyl) - N' - butyl thiourea (melting point: 108-111 0C), N - (3 - chloro - 2,6 - diethyl -phenyl) - N' - neopentyl - thiourea (melting point: 106-1 l00C), N - (3 chloro - 2,6 - diethylphenyl) - 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 - (2,6 diisopropylphenyl) - N' - methyl - thiourea (melting point: 167--168"C), N (2,6 - diisopropyl - phenyl) - N' - ethyl - thiourea, N - (2,6 - diisopropyl - phenyl) - N' - propyl - thiourea (melting point: 106--107"C), N - (2,6 - diisopropyl - phenyl) - N' - butyl - thiourea (melting point: 99--1030C), N - (2,6 diisopropyl - phenyl) - N' - isobutyl - thiourea (melting point: 108--112"C), N (2,6 - diisopropyl - phenyl) - N' - (3 - methyl - butyl) - thiourea (melting point: 63--68"C), N - (2,6 - diisopropyl - phenyl) - N' - pentyl - thiourea (melting point: 76--83"C), N - (2,6 - diisopropyl - phenyl) - N' - neopentyl - thiourea (melting point: 150155 C), N - (2,6 - diisopropyl - phenyl) - N' - methallyl - thiourea (melting point: 93-950C), N - (2,6 - diisopropyl - phenyl) - N' - hexyl - thiourea, N - (2,6 - diisopropyl - phenyl) - N' - dodecyl - thiourea, N - (2,6 - diisopropyl phenyl) - N' - (2 - ethyl - butyl) - thiourea, N - (2,6 - diisopropyl - phenvl) 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' - (2,4,4 trimethyl - pentyl) - thiourea, N - (2,6 - diisopropyl - phenyl) - N' - (2,3,3 trimethyl - allyl) - thiourea, N - (2,6 - diisopropyl - phenyl) - N' - cyclopentyl methyl) - thiourea, N - (2 - ethyl - 6 - isobutylphenyl) - N' - methallyl - thiourea (melting point: 105--106"C), 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, N - (2 - methyl - 6 - isopropyl - phenyl) - N' neopentyl - thiourea, 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 (melting point: 85--87"C), N - (2,6 - di - sec. - butyl - phenyl) N' - butyl - thiourea, N-(2,6 - di - sec. - butyl - phenyl) - N' - isobutyl thiourea (melting point: 83--85"C), N - (2,6 - di - sec. - butyl - phenyl) - N' allyl - thiourea (melting point: 83--86"C), N - (2,6 - di - sec. - butyl - phenyl) N' - methallyl - thiourea (melting point: 69--72"C), N - (2,6 - di - sec. butylphenyl) - N' - neopentyl - thiourea (melting point: 88--90"C), 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) - allyl - thiourea, 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. - butvl phenyl) - N' - isobutyl - thiourea, N - (4 - methyl - 2,6 - di - sec. butylphenyl)- N' - isobutyl - thiourea (melting point: 98--1020C), N - (4 - methyl - 2,6 - di - sec. - butylphenyl) - N' - isobutyl - thiourea (melting point: 97--1000C), N - (2,6 - di - cyclopentyl - phenyl) - N' - methyl - thiourea, N - (2,6 - dicyclopentyl - phenyl) - N' - butyl - thiourea, N - (2,6 - di - cyclopentyl - phenyl) N' - isobutyl - thiourea, N - (2,6 - dicyclopentyl - phenyl) - N' - neopentyl thiourea, N - (2,6 - dicyclopentyl - phenyl) - N' - methallyl - thiourea, N - (2,6 - di cyclopentyl - phenyl) - N' - (cyclopropyl - methyl) - thiourea, N - (2,6 - di - cyclo pentyl - 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 (melting point: 125-127 C), N - (4 - methyl - 2,6 - diisopropyl - phenyl) - N' - butyl thiourea (melting point: 126--1290C), N -(4 - methyl - 2,6 - diisopropyl - phenyl) N' - isobutyl - thiourea (melting point: 150-153 C), N -(4 - methyl - 2,6 - diiso propyl 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 - pheny 2,6 - diethyl - phenyl) - N' - butyl - thiourea (melting point: 81--83dC).
N - (4 - tert. - butyl - 2,6 - diethylphenyl) - N' - n - pentyl - thiourea (oil, melting point < 30 C), N - (2 - methyl - 4,6 - di - tert. - butyl - phenyl) - N' isobutyl - thiourea (melting point: 157--160"C), N - (2 - methyl - 4,6 - di - tert. butyl - phenyl) - N' - neopentyl - thiourea (melting point: 157--159"C) and N (4 - methyl - 2,6 - di - cyclopentyl - phenyl) - N' - butyl - thiourea (melting point: 151--153"C).
The active compounds of the formula (I) are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, especially insects and acarids, and nematode pests which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pest include: from the class of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber; from the class of the Diplopoda, for example Blaniulus guttulatus; from the class of the Chilopoda, for example Geophilus carpophagus and Scutigera spec.; from the class of the Symphyla, for example Scutigerella immaculata from the order of the Thysanura, for example Lepisma saccharina; from the order of the Collembola, for example Onychiurus armatus; from the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattela germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria; from the order of the Dermaptera, for example Forficula auricularia; from the order of the Isoptera, for example Reticuliltermes spp.; from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp.; Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.; from the order of the Mallophaga, for example Trichodectes spp. and Damalinea spp.; from the order of the Thvsanoptera, for example Hercinothrips femoralis and Thrips tabaci; from the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypit, Brevicoryne 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 aurantit, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.; from the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius. Cheimatobia brumata, Lithocolletis blancardella, Hypomeuta patella Plutella maculipennis. Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicue, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Ho mona magnanima and Tortrix viridana; from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylo trupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus 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, Triboliunt spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica; from the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.; from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., kvppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophvllus spp.; from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans; from the order of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus 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.
and Tetranvchus spp.
The active compounds of the formula (I), as mentioned above, also exhibit a fungicidal action. For this reason, they are suitable for use as plant protection agents for combating fungi and bacteria. Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes Chytridiomvcetes.
Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The active compounds can be converted into tile customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used-with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid solvents diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid estes, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention may be used in the form of their formulations of the types that are commercially available- or in the use forms prepared from these formulations.
The active compound content of the use forms prepared from the formulations of the types that are commercially available can vary within wide ranges. The active compound concentration of the use forms can be from 0.0000001 to 100% by weight of active compound, preferably from 0.01 to 10% by weight.
The compounds may be employed in a customary manner appropriate for the particular use forms.
In the veterinary field, the active compounds according to the invention may be used in a known manner, such as orally in the form of, for example, tablets, capsules, drenches and granules; dermally by means of, for example, dipping, spraying, pouring-on, spotting-on and powdering and parenterally, for example by means of injections.
The present invention also provides a method- of freeing of protecting domesticated animals from ectoparasitical insects or acarids (especially ticks) which comprises applying to said animals a compound of the formula (I) in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by arthropods or fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the formula (I) was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The present invention further provides domesticated animals whenever freed or protected from ectoparasitical insects or acarids by the application to said animals of a compound of the formula (I) in admixture with a diluent or carrier.
The insecticidal, acaracidal and fungicidal activity of the compounds of the formula (I) is illustrated by the following biotest Examples.
In these Examples, the compounds of the formula (I) are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
The compounds of the formula (I) mentioned in these biotest Examples are all novel.
The known comparison compound identified as follows:
Example A.
Test with parasitic adult cattle ticks (Boophilus microplus res.) Solvent: Cremophor (trade Mark) To produce a suitable preparation of active compound, the active substance in question was mixed with the stated solvents in the ratio of 1:2 and the concentrate thus obtained was diluted with water to the desired concentration.
10 adult cattle ticks (B.microplus, Biarra strain, res.) were dipped for 1 minute into the active compound preparation to be tested. After transfer into plastic beakers and storage in a climatically controlled room, the degree of destruction in percent was determined. 100% meant that all of the ticks had been killed and 0% meant that none of the ticks had been killed.
The results are shown in the following table.
Table A Active compound Active concentration Destructive compound in ppm action in % (25) 10,000 100 1,000 > 50 (27) 10,000 100 1,000 > 50 (28) 10,000 100 1,000 > 50 (35) 10,000 100 1,000 > 50 Example B.
Test with parasitic fly larvae Emulsifier: 80 parts by weight of Cremophor EL To produce a suitable preparation of active compound, 20 parts by weight of the active substance in question were mixed with the stated amount of the emulsifier and the mixture thus obtained was diluted with water to the desired concentration.
About 20 fly larvae (Lucilia cuprina, res.) were introduced into a test tube which contained about 3 ml of a 20% strength suspension of egg yolk powder in water and which was fitted with a cottonwool plug of appropriate size. 0.5 ml of the active compound preparation was placed on this egg yolk powder suspension. After 24 hours, the degree of destruction in % was determined. 100% meant that all of the larvae had been killed and 0% meant that none of the larvae had been killed.
The results are shown in the following table.
Table B Active compound Active concentration Destructive compound in ppm action in % (25) 1,000 100 100 100 (30) 1,000 100 100 100 (35) 1,000 100 100 100 10 0 Example C Test with parasitic scab mites (Psoroptes cuniculi) Solvent: Cremophor To produce a suitablepreparation of active compound, the active substance in question was mixed with the stated solvent in the ratio of 1:2 and the concentrate thus obtained was diluted with water to the desired concentration.
About 10--25 scab mites (Psorptes cuniculi) were introduced into 1 ml portions of the active compound preparation to be tested, which had been pipetted into the tablet nests of a blister pack. After 24 hours, the degree of destruction in percent was determined. 100% meant that all of the mites had been killed and 0% meant that none of the mites had been killed.
Active compounds, active compound concentrations and results can be seen from the table which follows: Table C Active compound Active concentration Destructive compound in ppm action in % (27) 10 100 3 100 100 0.3 0 (18) 100 100 30 100 10 100 3 100 O Example D Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, I part by weight of the active compound was mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris) which were heavily infested with the twospotted spider mite (Tetranychus urticae) in all stages of development were sprayed with the preparation of the active compound until dripping wet.
After the specified periods of time, the degree of destruction was determined as a percentage: 100% meant that all of the spider mites were killed whereas 0% meant that none of the spider mites were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: Table D (Mites which damage plants) Tetranychus test Active compound Degree of destruction Active concentration in % after compounds in % 2 days (A) 0.1 60 0.01 0 (16) 0.1 100 0.01 98 (34) 0.1 100 0.01 95 (25) 0.1 98 0.01 95 (33) 0.1 100 0.01 99 (36) 0.1 100 0.01 100 (19) 0.1 100 0.01 99 (29) 0.1 100 0.01 100 (21) 0.1 100 0.01 100 (35) 0.1 100 0.01 100 Example E Plutella test Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether.
To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella maculipennis).
After the specified periods of time, the degree of destruction was determined as a percentage: 100% meant that all of the caterpillars were killed whereas 0% meant that none of the caterpillars were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: Table E (Insects which damage plants) Plutella test Active compound Degree of destruction Active concentration in % after compound in % 3 days (A) 0.1 80 0.01 0 (34) 0.1 100 0.01 100 (27) 0.1 100 0.01 100 (28) 0.1 100 0.01 100 (35) 0.1 100 0.01 100 (30) 0.1 100 0.01 100 Example F Pyricularia test/rice/systemic Solvent: 11.75 parts by weight of acetone Dispersing agent: 0.75 part by weight of alkylaryl polyglycol ether Water: 987.50 parts by weight The amount of active compound required for the desired concentration of active compound in the watering liquid was mixed with the stated amount of the solvent and dispersing agent and the concentrate was diluted with the stated amount of water.
The amount it was desired to use of the liquor thus obtained was placed in saucers on which stood pots, with perforated bottoms, containing 30 rice plants which were about 2 weeks old. The test preparations were taken up through the root.
After 3 days, during which the plants remained in a greenhouse at 22 to 24 deg.C and about 70% relative atmospheric humidity, the plants were inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Pyricularia oryzae and were set up in a room at 24 to 26 deg.C and 100% relative atmospheric humidity.
About 4 days after the inoculation, the infection of all leaves present at the time of the inoculation was determined in comparison with the untreated, but also inoculated, control plants.
The evaluation was made in terms of a scale of 1--9. 1 meant a 100% action, 3 denoted a good action, 5 denoted a moderate action, and 9 denoted no action.
The active compounds, the amounts used and the results can be seen from the table which follows: Table F Pyricularia test/rice/systemic Amount Active used, compound 10 kg/ha Action Control (untreated) 9 (12) 3 (13) 3 (2) 2 (3) 3 (4) 2 (1) 3 Example G Pyricularia test/liquid preparation of active compound Solvent: 11.75 parts by weight of acetone Dispersing agent: 0.75 parts by weight of alkylaryl polyglycol ether Water: 987.50 parts by weight The amount of active compound required for the desired concentration of active compound in the spray liquid was mixed with the stated amount of the solvent and of the dispersing agent and the concentrate was diluted with the stated amount of water.
30 rice plants about 14 days old were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse at temperatures of 22 to 24 deg.C and a relative atmospheric humidity of about 70% until they were dry.
Thereafter, the plants were inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Pyricularia oryzae and placed in a chamber at 24 to 26 deg.C and 100% relative atmospheric humidity.
5 days after the inoculation, the infection of all the leaves present at the time of inoculation was determined as a percentage of the untreated, but also inoculated, control plants.
The evaluation was made on a scale of from 1 to 9. 1 denoted 100% action, 3 denoted good action, 5 denoted moderate action and 9 denoted no action.
The active compounds, the concentrations of the active compounds and the results can be seen from the table which follows.
Table G Pyricularia test/liquid preparation of active compound Active Action at an active compound concentration compound of 0.025 percent: (A) 9 (28) 3 (2) 3 (1) 3 Example H Pellicularia test Solvent: 11.75 parts by weight of acetone Dispersing agent: 0.75 parts by weight of alkylaryl polyglycol ether Water: 987.50 parts by weight The amount of active compound required for the desired concentration of active compound in the spray liquid was mixed with the stated amount of the solvent and of the dispersing agent and the concentrate was diluted with the stated amount of water.
2 x 30 rice plants about 2--4 weeks old were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse at temperatures of 22 to 24 deg.C and a relative atmospheric humidity of about 70% until they were dry.
The plants were infected with a culture of Pellicularia sasakii grown on malt agar and were set up at 28 to 300C and 100% relative atmospheric humidity.
The infection in the leaf sheaths was determined after 5-8 days, in relation to the untreated but infected control.
The evaluation was made on a scale of from 1 to 9. 1 denoted 100% action, 3 denoted good action, 5 denoted moderate action and 9 denoted no action.
The active compounds, the concentrations of the active compounds and the results can be seen from the table which follows.
Table H Pellicularia test Active Action at an active compound compound concentration (in %) of 0.025 (A) 9 (70) 3 (100) 3 (68) 3 (83) 3 PREPARATIVE EXAMPLES Example 1.
N-(2,6-Diethyl-phenyl)-N'-isobutyl-thiourea 15.0 g of 2,6-diethylphenyl isothiocyanate were introduced, at 200 C, into 20 g of isobutylamine and the mixture was left to stand for 12 hours. Thereafter, it was mixed with excess dilute hydrochloric acid until the reaction product, which initially precipitated as an oil, crystallised. The crystals were filtered off and washed with water until neutral. Thereafter, the filter cake was uniformly triturated with methanol, water was added and the product was filtered off and dried. Yield: 19.0 g; melting point: 68--70"C.
The elementary analysis and NMR spectrum were in agreement with the supposed structure.
Analogously to Example 1, the N-aryl-N'-alkyl-thioureas which follow were prepared from 2,6-diethyl-phenyl isothiocyanate and the corresponding aliphatic amines: Example 2.
N-(2,6-Diethylphenyl)-N'-ethyl-thiourea (melting point: 72-730C).
Example 3.
N-(2,6-Diethylphenyl)-N'-propyl-thiourea (melting point: 58600 C).
Example 4.
N-(2,6-Diethyl-phenyl)-N'-butyl-thiourea (melting point: 4130C).
Example 5.
N-(2,6-Diethylphenyl)-N'-pentyl-thiourea.
Example 6.
N-(2,6- Diethyl-phenyl)-N'-neopentyl-thiourea (melting point: 87--89"C).
Example 7.
N-(2,6-Diethyl-phenyl)-N'-hexyl-thiourea.
Example 8.
N-(2,6-Diethyl-phenyl)-N'-heptyl-thiourea.
Example 9.
N-(2,6-Diethyl-phenyl)-N'-dodecyl-thiourea (melting point: 120--123"C).
Example 10.
N-(2,6-Diethyl-phenyl)-N'-methallyl-thiourea (melting point: 65--68"C).
The starting material 2.6-diethyl-phenyl isothiocyanate was prepared as follows: 100 g of 2,6-diethylaniline in 200 ml of methylene chloride were added dropwise, at 0--50C, to a mixture of 500 ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 92 g of thiophosgene, whilst stirring. Thereafter, the mixture was heated under reflux until the evolution of CO2 had ended. The cooled mixture was filtered and the methylene chloride layer was separated off from the filtrate, dried with calcium chloride and fractionated.
Yield 112 g; boiling point 101--103"C/1.4 mm Hg.
Example 11.
N-(4-Methyl-2 ,6-diethylphenyl)-N'-neopentyl-thiourea 15.0 g of 4-methyl-2,6-diethylphenyl isothiocyanate were introduced at 200C, into 9.0 g of 2,2-dimethyl-propylamine, whereupon an exothermic reaction began.
After 12 hours, the mixture was stirred with excess dilute hydrochloric acid and the product was filtered off, washed with water and dilute methanol and dried.
Yield 21 g; melting point: 106--107"C.
The elementary analysis and NMR spectrum were in agreement with the supposed structure.
Analogously to Example 11, the thioureas which follow were prepared from 4methyl-2,6-diethyl-phenyl isothiocyanate and the corresponding aliphatic amines: Example 12.
N-(4-methyl-2,6-diethylphenyl)-N'-butyl-thiourea.
Example 13.
N-(4-Methyl-2,6-diethylphenyl)-N'-isobutyl-thiourea (melting point: 60--61"C).
Example 14.
N-(4-methyl-2,6-diethyl-phenyl)-N'-methallyl-thiourea (melting point: 86--88"C).
4-Methyl-2.6-diethyl-phenyl isothiocyanate was prepared according to the following instruction: 100 g of 4-methyl-2,6-diethyl-aniline in 200 ml of methylene chloride were added dropwise, at 0--50C, to a mixture of 500 ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 92 g of thiophosgene, whilst stirring.
Thereafter, the mixture was warmed under reflux until the evaporation of CO2 had ended. After cooling, the solid materials were filtered off from the mixture and the methylene chloride layer was separated off, dried over calcium chloride and fractionated.
Yield 110 g; boiling point: 113-116 C/1.3 mm Hg.
Example 15.
N-(2,6-diisopropyl-phenyl)-N'-isobutyl-thiourea 15.0 g of 2,6-diisopropyl-phenyl isothiocyanate were introduced, at 200C, into 20.0g of isobutylamine. The reaction proceeded exothermically, the mixture was left to stand for 12 hours and was then stirred with excess dilute hydrochloric acid.
The reaction product, which had precipitated in the crystalline form, was filtered off, washed with water and dilute methanol and dried.
Yield 19.0 g; melting point: 108--1120C.
The elementary analysis and NMR spectrum corresponded to the supposed structure.
Analogously to Example 15, the thiourea which follow were prepared from 2,6-diisopropyl-phenyl isothiocyanate and the corresponding aliphatic amines: Example 16.
N-(2,6-Diisopropylphenyl)-N'-propyl-thiourea (melting point: 106--107"C).
Example 17.
N-(2,6-Diisopropyl-phenyl)-N'-butyl-thiourea.
Example 18.
N-(2,6-Diisopropyl-phenyl)-N'-(3-methyl-butyl)-thiourea (melting point: 64680C).
Example 19.
N-(2,6-Diisopropyl-phenyl)N'-pentyl-thiourea (melting point: 76--83"C).
Example 20.
N-(2,6-Diisopropyl-phenyl)-N'-neopentyl4hiourea (melting point: 15W155 C).
Example 21.
N-(2,6-Diisopropyl-phenyl)-N'-hexyl-thiourea.
Example 22.
N-(2,6-Diisopropyl-phenyl)-N'-dodecyl-thiourea.
Example 23.
N-(2,6-Diisopropyl-phenyl)-N'-methallyl-thiourea (melting point: 93--95"C).
2.6-Dilsopropyl-phenyl isothiocyanate was prepared in the following manner: 100 g of 2,6-diisopropyl-aniline in 200 ml of methylene chloride were added dropwise, at ID cooling, the mixture was filtered and the methylene chloride layer was separated off from the filtrate, dried over calcium chloride and fractionated.
Yield 110 g; boiling point: 144--148"C/11 mm Hg.
Example 24.
N-(2,6-D i-sec. -butyl-phenyl)-N'-methallyl-thiourea 15.0 g of 2,6-di-sec.-butyl-phenyl isothiocyanate were introduced, at --100C, into 12.0 g of methallylamine. The mixture was allowed to come slowly to +20"C and was stored for 12 hours at 200C. Thereafter, the mixture was stirred with excess dilute hydrochloric acid and the crystalline reaction product was filtered off, washed with water and dilute methanol and dried.
Yield 20.0 g; melting point: 69--72"C.
Analogously to Example 24, the thioureas which follow were prepared from 2,6-di-sec.-butyl-phenyl isothiocyanate and the corresponding aliphatic amines: Example 25.
N-(2,6-Di-sec .-butyl-phenyl)-N'-propyl-thiourea (melting point: 85--87"C).
Example 26.
N-(2,6-Di-sec.-butyl-phenyl)-N'-allyl-thiourea (meltling point: 83860 C).
Example 27.
N-(2,6-Di-sec.-butyl-phenyl)-N'-butyl-thiourea (wax).
Example 28.
N-(2,6-Di-sec.-butyl-phenyl)-N'-isobutyl4hiourea (melting point: 83--85"C).
Example 29.
N-(2,6-Di-sec.-butyl-phenyl)-N'-pentyl-thiourea (oil).
Example 30.
N-(2,6-Di-sec.-butyl-phenyl)-N'-neopentyl-thiourea (melting point: 88900 C).
Example 31.
N-(2,6-Di-sec.-butyl-phenyl)-N'-dodecyl-thiourea (oil).
2.6-Di-sec.-butylphenyl isothiocyanate was prepared in the following manner: 100 g of 2,6-di-sec-butyl-aniline in 200 ml of methylene chloride were added dropwise, at 0--5"C, to a mixture of 300 ml of water, 500 ml of methylene chloride, 100 g of calcium carbonate and 68 g of thiophosgene, whilst stirring. Thereafter, the mixture was warmed under reflux until the evolution of CO2 had ended. After cooling, the solid materials were filtered off and the methylene chloride layer was separated off from the filtrate, dried over calcium chloride and fractionated.
Yield 112 g; boiling point: 117--120"C/1.0 mm Hg.
Example 32.
N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-isobutyl-thiourea 15.0 g of 4-methyl-2,6-diisopropylphenyl isothiocyanate were introduced, at 20"C, into 20 g of isobutylamine and the exothermic reaction was moderated by cooling. The mixture was left to stand for 12 hours and then stirred with excess dilute hydrochloride acid. The reaction product which had crystallised out was filtered off, washed with water and dilute methanol and dried.
Yield 18.0 g; melting point: 15Q--153"C.
Analogously to Example 32, the thioureas which follow were prepared from 4methyl-2,6-diisopropylphenyl isothiocyanate and the corresponding aliphatic amines; Example 33.
N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-butyl-thiourea (melting point: 126--129"C).
Example 34.
N-(4-Methyl-2,6-diisopropyl-phenyl)-N'-propyl-thiourea (melting point: 125-1 270 C).
Analogously to Example 32, 4-methyl-2,6-di-sec.-butyl-phenyl-isothiocyanate with isobutylamine or n-butylamine gave, respectively: Example 35.
N-(4-methyl-2,6-di-sec.-butyl-phenyl)-N'-isobutyl-thiourea (melting point: 98--102"C).
Example 36.
N-(4-methyl-2,6-di-sec.-butylphenyl).N'-butyl-thiourea (melting point: 97--1000C).
4-Methyl-2.6-diisopropyl-phenyl isothiocyanate was prepared in the following manner: 150 g of 4-methyl-2,6-diisopropyl-aniline in 200 ml of methylene chloride were added dropwise, at 200 C, to a stirred mixture of 500ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 110 g of thiophosgene. Thereafter, the mixture was warmed under reflux until the evolution of CO2 had ended. The solid materials were filtered off from the mixture and the methylene chloride layer was separated off from the filtrate, dried over calcium chloride and fractionated.
Yield 159 g of a solidifying oil; boiling point: 124--1260C/1.2 mm Hg.
Analogously, 4-methyl-2,6-di-sec.-butylphenyl isothiocyanate of boiling point: 130-1320C/l.2 mm Hg was obtained from 4-methyl-2,6-di-sec.-butyl-aniline and thiophosgene.
Example 37.
N-(3-Methyl-2,6-diethyl-phenyl)-N'-neopentyl.thiourea 15.0 g of 3-methyl-2,6-diethyl-phenyl isothiocyanate were introduced, at 200 C, into 9.0 g of 2,2-dimethylpropylamilie. The mixture was left to stand for 12 hours and then stirred with excess diltite hydrochloric acid. The reaction product which had crystallised out was filtered off, washed with water and dilute ethanol and dried. Yield 20.0 g; melting point: 102--104"C. The elementary analysis and NMR spectrum were in agreement with the supposed structure.
The following were prepared by methods analogous to that of Example 37.
Example 38.
N-(3-Methyl-2,6-diethylphenyl)-N'-methallyl-thiourea (melting point 105--1060C) was obtained from 3-methyl-2,6-diethyl-phenyl isothiocyanate and methallylamine.
Example 39.
N-(3 ,5-dimethyl-2,6-diethylphenyl)-N'-butyl-thiourea (melting point: 108-11 00C) was obtained from 3,5-dimethyl-2,6-diethyl-phenyl-isothiocyanate and n-butylamine.
* Example 40.
N-(3-chloro-2,6-diethylphenyl)-N'-butyl-thiourea (melting point: 108--110"C) was obtained from 3-chloro-2,6-diethyl-phenyl isothiocyanate and n-butylamine.
Example 41.
N-(3-chloro-2,6-diethyl-phenyl)-N'-neopentyl-thiourea (melting point: 106--110"C) was obtained from 3-chloro-2,6-diethylphenyl isothiocyanate and 2,2dimethylpropylamine.
Example 42.
N-(2-ethyl-6-isopropyl-phenyl)-N'-methallyl-thiourea (melting point: 50--55"C) was obtained from 2-ethyl-6-isopropyl-phenyl isothiocyanate and methallylamine.
Example 43.
N-(2,4,6-triisopropyl-phenyl)-N'-methallyl-thiourea (melting point: 115--1180C) was obtained from 2,4,6-tri-isopropylphenyl isothiocyanate and methallylamine.
The following aryl isothiocyanates were prepared from the aryl-amines and thiophosgenes as indicated in the preceding examples: 3-methyl-2,6-diethylphenyl isothiocyanate (boiling point: 110113 C/1.5 mm Hg), 3,5-dimethyl-2,6-diethylphenyl isothiocyanate (boiling point: 119-127 C/1.2 mm Hg), 3-chloro-2,6diethylphenyl-isothiocyanate (boiling point: 118--1210C/1.2 mm Hg), 2-ethyl-6isopropyl-phenyl isothiocyanate (boiling point: 104-106"C/1.2 mm Hg) and 2,4,6triisopropyl-phenyl isothiocyanate (boiling point: 130-132 C/1.2 mm Hg).
Example 44.
N-(2,6-Diisopropyl-phenyl)-N'-methyl-thiourea 120 g of 2,6-diisopropyl-aniline were dissolved in 100 ml of triethylamine and 53 g of methyl isothiocyanate were added. The thiourea formation proceeded weakly exothermically. The mixture was stirred for 12 hours, excess dilute hydrochloric acid was added and the product was filtered off, washed with water and dilute methanol and dried.
Yield 142 g; melting point: 167--168"C.
Analogously to Example 44, the thioureas which follow were obtained from methyl isothiocyanate and the corresponding aniline derivatives: Example 45.
N-(2,6-diethyl-phenyl)-N'-methyl4hiourea (melting point: 103--105"C).
Example 46.
N-(4-methyl-2,6-diethyl-phenyl)-N'-methyl-thiourea (melting point: 97--100"C).
Example 47.
N-(2-methyl-6-ethyl-phenyl)-N'-methyl-thiourea (melting point: 657750C).
Example 48.
N-(2,4-dimethyl-6-ethyl-phenyl)-N'-methyl-thiourea (melting point: 125--126"C).
Analogously to the procedures indicated in Examples 1 to 48, the compounds listed in the table which follows can be prepared by either process variant (a) or process variant (b).
For simplification, the compounds are represented by the following general formula
Table Example Ar Alk Melting No. lRgint:
Ex ample Ar Alk Melting No. point:
Ex- No Melting ample No. Ar Alk point
Ex ample Melting No. Ar Alk point:
cCHHftcHcH 2H5 CH3 3 2H5 -CH2-C1-CH3 Oil CH3 'CHZ'(of H CHC2H5 Oil CH3HCH2 -c6H13(n) Oil C2H5 66 CH3) H-CHi 4 -CH3 123-126 ZH-CHi-(123-126 67 CH3 CH CH2 ,C3H7 (n) CHCHCH2 H Oil 25 CH3\ CH CH 68 CH3cH g -CH2-CH2-CH-CH3 Oil 25 69 CCHHHCH22HS CH3 Oil 3 -2H5 CH3 (solidifies) 70 C4 942 s CH3 Oil C2H5 Ex- Melting ample Ar Alk point: No. cJ
C2H5 -c4H9(n) Oil 7 C4Hg < C2H5 2H5 -cH(n) 72 C4Hs' 511 1 Oil - 2H5 CH 2H5 .3 -CH2-C-CH3 52-54 73 C4H9-- CH3 C2H5 74 C2H5 -C3H7 52-54 C4 9 4 2 5 5 2 - 5 4 75 -cH 75 C4Hg < ; -CH3 106-110 C2H5 C2H5 CH3 Oil 76 c4H9'- -CH2 -CH2 -C-CH3 C2H5 CH3 77 CH -CHZ-CH' 77 CH3 \ -CH2-CH-CH3 182-184 Ex- Melting ample Ar Alk point: No. ~ ~~ ~ C
78 :H3-eS CH4H9(n) 15-153 C 79 CH3 -C5N11 (n) 151-153 CH C1H3 Oil 80 c,H,-g -CH2-CH-CH3 C2H5 81 5 /\Cc2H5 -C5N11(n) Oil 25 82 C3 -c}13 86-90 83 C3 C0N3 CH2-CN2CNCH3 Oil CH 6 6H13 (n) 84 3 7C2H5 Oil Ex- Melting ample Ar Alk point No. [ C]
C2H5 C,H3 103-107 C 3 7 -CH3 103-107 H3 86 -CH,-CH3 -CH2-CH-CH3 118-120 H-CH3 25 87 G C4Hg (n) 63-66 C2N5 88 C2H5 -C5H11(n) Oil C2H5 C2H5 -C3H7(n) 109-110 89 C2H5 90 C 2 5 -CH3 143-1117 C2H5 91 (9 -C6H13(n) Oil C2N5 Ex- Melting ample Ar No . [ C ]
C2H5 CH3 92 - CH2.cN2CHCN3 Oil C Q -C2HS C6H13( Oil CH3- H-C2H5 CH3-CH-C2H5 C,H3 Oil 94 iL CH-CH CII3-H-C2Hg CH3 CN -CN-C2H5 C1N3 95 C2H5 CH2CN2CCOHCN3 117-119 CH > CH-CH3 c,R3 3 CH 96 > -CH2-CH2-C-CH3 135-136 CH3- -CH3 CH3 CH3-lCH-C3H7 CH3 97 2 CH2 3 Oil CE3 C3H7 C g H-C3H7 CSH11(n) Oil 98 < CH3-CH-C3H7 CH3- H-C3H7 -C4N9(n) Oil 99 cH- -C3 N7 Preparation of the starting materials was effected, for example, as follows: (a) 4-Cyclohexyl-2,6-diethyl-phenyl isothiocyanate: 231 g of 4-cyclohexyl-2,6-diethyl-aniline in 300 ml of methylene chloride were added dropwise, at 10--15"C, to a suspension of 600 ml of methylene chloride, 500 ml of water, 200 g of calcium carbonate and 140 g of thiophosgene. Thereafter, the mixture was heated to the boil until the evolution of gas had ended. The solid materials were filtered off from the cooled mixture and the methylene chloride layer was dried over calcium chloride and fractionated; boiling point 175--179"C/1.5 mm Hg; yield 251 g.
Analogously, the aryl isothiocyanates which follow could be prepared from the corresponding aniline derivatives: 2,4,6-triethyl-phenyl isothiocyanate (boiling point 128--130"C/1.3 mm Hg), 4-n-propyl-2,6-diethyl-phenyl isothiocyanate (boiling point 132--137"C/1.5 mm Hg), 4-isopropyl-2,6-diethyl-phenyl isothiocyanate (boiling point 130--132"C/1.3 mm Hg), 4-n-butyl-2,6-diethyl-phenyl isothiocyanate (boiling point 150--155"C/2.0 mm Hg), 4-isobutyl-2,6-diethylphenyl isothiocyanate (boiling point 133--136"C/1.4 mm Hg), 4-tert.-butyl-2,6diethyl-phenyl isothiocyanate (boiling point 13e-133"C/1.8 mm Hg), 2,6-dicyclopentyl-phenyl isothiocyanate (boiling point 165--168"C/1.3 mm Hg), 4methyl-2,6-dicyclopentylphenyl isothiocyanate (boiling point 188-195 C/2.0 mm Hg), 2,6-di-pent-2-yl-phenyl isothiocyanate (boiling point 148--152"C/1.4 mm Hg), 4-methyl-2,6-di-sec.-butyl-phenyl isothiocyanate (boiling point 130-132 C/1.2 mm Hg) and 2-methyl-4,6-di-tert.-butylphenyl isothiocyanate (boiling point 135--139"C/1.5 mm Hg).
(b) 4-Cyclohexyl-2,6-diethyl-aniline;
300 g of 4-amino-cyclohexylbenzene, 5.0 g of aluminium granules and 17 g of anhydrous aluminium chloride were heated to 2500C in a steel autoclave and ethylene was forced in up to an internal pressure of 200 atmospheres gauge. After the pressure had fallen, further ethylene was pumped in until the absorption had ended; this took about 7 hours. After cooling, the mixture was stirred with 500 ml of benzene, 300 ml of 40% strength sodium hydroxide solution and 500 ml of water for 15 minutes at 40--500C and the benzene phase was separated off, washed with water, dried over potassium carbonate and fractionated.
Boiling point 148--150"C/0.8 mm Hg; yield 318 g.
The following aniline derivatives could be prepared in an analogous manner: 2,4,6-triethyl-aniline (boiling point 89-910C/0.6 mm Hg), 4-n-propyl-2,6-diethylaniline (boiling point 102"C/1.4 mm Hg), 4-isopropyl-2,6-diethyl-aniline (boiling point 103--105"C/2.0 mm Hg), 4-n-butyl-2,6-diethyl-aniline (boiling point 117--118"C/2.0 mm Hg), 4-isobutyl-2,6-diethyl-aniline (boiling point 97--99"C/0.7 mm Hg) and 4-tert.-butyl-2,6-diethyl-aniline (boiling point 89--91"C/0.6 mm Hg).
(c) 2,6-Bis-pent-2-yl-aniline:
170 g of aniline, 5 g of aluminium granules and 15 g of anhydrous aluminium chloride were heated to 3000C in a steel autoclave and 300 g of pent-l-ene were pumped in over the course of about 5 hours until the internal pressure was 300 atmospheres gauge. The mixture was then kept at 3000C for a further 6 hours, whereupon the internal pressure fell to 107 atmospheres gauge. After cooling, the contents of the autoclave were stirred with 500 ml of benzene, 250 ml of 40% strength sodium hydroxide solution and 300 ml of water for 15 minutes at 3040"C, and the benzene layer was washed with water, dried over potasisum carbonate and fractionated. This gave 113 g of 2-mono-pent-2-yl-aniline (boiling point 78--82"C/0.6 mm Hg) and 131 g of 2,6-bis-pent-2-yl-aniline (boiling point 168--174"C/1.5 mm Hg).
Analogously, aniline and cyclopentene gave 2-cyclopentylaniline (boiling point 102--109"C/1.7 mm Hg) and 2,6-di-cyclopentyl-aniline (boiling point 159--1650C/1.5 mm Hg); p-toluidine and cyclpentene gave 4-methyl-2cyclopentyl-aniline (boiling point 104--106"C/0.7 mm Hg) and 4-methyl-2,6dicyclopentyl-aniline (boiling point 157--1580C/0.8 mm Hg); and p-toluidine and but-l-ene gave 4-methyl-2-sec.-butyl-aniline (boiling point 720C/1.0 mm Hg) and 4methyl-2,6-di-sec.-butyl-aniline (boiling point 121--128"C/3.0 mm Hg. 6-Methyl2,4-di-tert.-butyl-aniline (boiling point 101-1030C/l .1 mm Hg), was obtained from o-toluidine and isobutene, using Tonsil (trade Mark) K 10 as a catalyst, at 2000C and 200 atmospheres gauge.
Example 100.
N-(4-methyl-2,6-di-sec.-butylphenyl)-N'methyl thiourea was obtained from methyl isothiocyanate and 4-methyl-2,6-di-sec.-butyl-aniline in a manner analogous to that of Example 44.
WHAT WE CLAIM IS: 1. An arthropodicidal or fungicidal composition containing as active ingredient an N-aryl-N'-alkyl-thiourea of the general formula
in which R' represents alkyl or cycloalkyl, R2 represents alkyl with at least 2 carbon atoms or. cycloalkyl, R3 represents alkyl, cycloalkyl or halogen, n represents 0, 1 or 2, it being possible, if n represents 2, for the substituents R3 to be identical or different, and R4 represents hydrogen, alkyl, alkenyl, optionally methyl-substituted cycloalkyl or cycloalkenyl, in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
2. A composition according to claim 1, containing a compound of the formula (I) in which R' represents alkyl (C,C^) or cycloalkyl (C3-C7), R2 represents alkyl (C3-C0) or cycloalkyl (C3-C7), R3 represents alkyl (C,Ce), chlorine, bromine, or cycloalkyl (CS3K',), R4 represents hydrogen,- straight-chain aikyl (C1-C12), branched alkyl (C3-C12), alkenyl (C2-C12), cycloalkyl (C3-C7) or cycloalkenyl (C3C7).
3. A composition according to claim 2, containing a compound of the formula (I) in which n is 0 or 1.
4. A composition according to claim 1 containing a compound of the formula (I) that is disclosed in any one of Examples 1 to 48.
5. A composition according to claim 1 containing a compound of the formula (I) that is disclosed in any one of Examples 49 to 99.
6. A composition according to any of claims I to 5 containing from 0.1 to 95% of the active compound, by weight.
7. A method of combating arthropods or fungi which comprises applying to the arthropods or fungi, or to a habitat thereof, (other than an animal's body), a compound of the formula (I) as specified in any of claims 1 to 5 alone or in the form of a composition containing as active ingredient a compound of the formula (I) as specified in any of claims 1 to 5, in admixture with a diluent or carrier.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (15)

**WARNING** start of CLMS field may overlap end of DESC **. pumped in over the course of about 5 hours until the internal pressure was 300 atmospheres gauge. The mixture was then kept at 3000C for a further 6 hours, whereupon the internal pressure fell to 107 atmospheres gauge. After cooling, the contents of the autoclave were stirred with 500 ml of benzene, 250 ml of 40% strength sodium hydroxide solution and 300 ml of water for 15 minutes at 3040"C, and the benzene layer was washed with water, dried over potasisum carbonate and fractionated. This gave 113 g of 2-mono-pent-2-yl-aniline (boiling point 78--82"C/0.6 mm Hg) and 131 g of 2,6-bis-pent-2-yl-aniline (boiling point 168--174"C/1.5 mm Hg). Analogously, aniline and cyclopentene gave 2-cyclopentylaniline (boiling point 102--109"C/1.7 mm Hg) and 2,6-di-cyclopentyl-aniline (boiling point 159--1650C/1.5 mm Hg); p-toluidine and cyclpentene gave 4-methyl-2cyclopentyl-aniline (boiling point 104--106"C/0.7 mm Hg) and 4-methyl-2,6dicyclopentyl-aniline (boiling point 157--1580C/0.8 mm Hg); and p-toluidine and but-l-ene gave 4-methyl-2-sec.-butyl-aniline (boiling point 720C/1.0 mm Hg) and 4methyl-2,6-di-sec.-butyl-aniline (boiling point 121--128"C/3.0 mm Hg. 6-Methyl2,4-di-tert.-butyl-aniline (boiling point 101-1030C/l .1 mm Hg), was obtained from o-toluidine and isobutene, using Tonsil (trade Mark) K 10 as a catalyst, at 2000C and 200 atmospheres gauge. Example 100. N-(4-methyl-2,6-di-sec.-butylphenyl)-N'methyl thiourea was obtained from methyl isothiocyanate and 4-methyl-2,6-di-sec.-butyl-aniline in a manner analogous to that of Example 44. WHAT WE CLAIM IS:
1. An arthropodicidal or fungicidal composition containing as active ingredient an N-aryl-N'-alkyl-thiourea of the general formula
in which R' represents alkyl or cycloalkyl, R2 represents alkyl with at least 2 carbon atoms or. cycloalkyl, R3 represents alkyl, cycloalkyl or halogen, n represents 0, 1 or 2, it being possible, if n represents 2, for the substituents R3 to be identical or different, and R4 represents hydrogen, alkyl, alkenyl, optionally methyl-substituted cycloalkyl or cycloalkenyl, in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
2. A composition according to claim 1, containing a compound of the formula (I) in which R' represents alkyl (C,C^) or cycloalkyl (C3-C7), R2 represents alkyl (C3-C0) or cycloalkyl (C3-C7), R3 represents alkyl (C,Ce), chlorine, bromine, or cycloalkyl (CS3K',), R4 represents hydrogen,- straight-chain aikyl (C1-C12), branched alkyl (C3-C12), alkenyl (C2-C12), cycloalkyl (C3-C7) or cycloalkenyl (C3C7).
3. A composition according to claim 2, containing a compound of the formula (I) in which n is 0 or 1.
4. A composition according to claim 1 containing a compound of the formula (I) that is disclosed in any one of Examples 1 to 48.
5. A composition according to claim 1 containing a compound of the formula (I) that is disclosed in any one of Examples 49 to 99.
6. A composition according to any of claims I to 5 containing from 0.1 to 95% of the active compound, by weight.
7. A method of combating arthropods or fungi which comprises applying to the arthropods or fungi, or to a habitat thereof, (other than an animal's body), a compound of the formula (I) as specified in any of claims 1 to 5 alone or in the form of a composition containing as active ingredient a compound of the formula (I) as specified in any of claims 1 to 5, in admixture with a diluent or carrier.
8. A method according to claim 7 in which a composition is used containing
from 0.0000001 to 100% of the active compound, by weight.
9. A method according to claim 8 in which a composition is used containing from 0.01 to 10% of the active compound, by weight.
10. A method according to claim 7, 8 or 9 in which the active compound is applied against insects or acarids.
11. A method of freeing or protecting domesticated animals from ectoparasitical insects or acarids which comprises applying to said animals a compound of the formula (I) as specified in any of claims 1 to 5, in admixture with a diluent or carrier.
12. A method according to claim 10 or 11 in which the active compound is as specified in claim 1, 2, 3 or 4.
13. Crops protected from damage by arthropods or fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the formula (I) as specified in any of claims 1 to 5 was applied alone or in admixture with a diluent or carrier.
14. Domesticated animals whenever free or protected from ectoparasitical insects or acarids by the application to said animals of a compound of the formula (I) as specified in any of claims 1 to 5, in admixture with a diluent or carrier.
15. The compound of the formula (I), as given in claim 1, that is disclosed in any one of Examples 1--4, 12, 13, 16, 18, 19, 21, 25, 2730, 3336, 68, 70, 83 and 100.
GB1815/78A 1977-01-20 1978-01-17 Use of n-aryl-n'-alkyl-thioureas as agents for combating animal and plant pests Expired GB1571970A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772702235 DE2702235A1 (en) 1977-01-20 1977-01-20 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites
DE19772727529 DE2727529A1 (en) 1977-06-18 1977-06-18 1-Substd. phenyl-3-alkyl-thiourea derivs. - useful for control of parasites, esp. ectoparasites

Publications (1)

Publication Number Publication Date
GB1571970A true GB1571970A (en) 1980-07-23

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Application Number Title Priority Date Filing Date
GB1815/78A Expired GB1571970A (en) 1977-01-20 1978-01-17 Use of n-aryl-n'-alkyl-thioureas as agents for combating animal and plant pests

Country Status (5)

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AU (1) AU3258478A (en)
FR (1) FR2392970A1 (en)
GB (1) GB1571970A (en)
NL (1) NL7800674A (en)
NZ (1) NZ186237A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4962126A (en) * 1985-07-12 1990-10-09 Ciba-Geigy Corporation Use of N-(4-phenoxy-2,6-diisopropylphenyl)-N'-tertbutylthiourea for controlling white flies
US4965389A (en) * 1987-03-10 1990-10-23 Ciba-Geigy Corporation Phenoxyphenylthioureas phenoxyphenylisothioureas and phenoxyphenylcarbodiimides and use thereof for controlling pests
US7718671B2 (en) 2003-07-10 2010-05-18 Achillion Pharmaceuticals, Inc. Substituted arylthiourea derivatives useful as inhibitors of viral replication

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4962126A (en) * 1985-07-12 1990-10-09 Ciba-Geigy Corporation Use of N-(4-phenoxy-2,6-diisopropylphenyl)-N'-tertbutylthiourea for controlling white flies
US4965389A (en) * 1987-03-10 1990-10-23 Ciba-Geigy Corporation Phenoxyphenylthioureas phenoxyphenylisothioureas and phenoxyphenylcarbodiimides and use thereof for controlling pests
US7718671B2 (en) 2003-07-10 2010-05-18 Achillion Pharmaceuticals, Inc. Substituted arylthiourea derivatives useful as inhibitors of viral replication

Also Published As

Publication number Publication date
NL7800674A (en) 1978-07-24
NZ186237A (en) 1978-12-18
AU3258478A (en) 1979-07-26
FR2392970A1 (en) 1978-12-29

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