DE2730620A1 - NEW N-ARYL-N'-ALKYL-S-ALKYL-ISOTHIOHARN SUBSTANCES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AN AGENT FOR CONTROLLING ANIMAL AND VEGETABLE PEST - Google Patents

Description

New N-Aryl-N'-alkyl-S-alkyl-isot hiohai : \\ tpjjjc, _ Verfah ren for their production and their advantages. ι r <q a ₁ I S el Mitt for controlling animal un d pt "LAN / borrowed pests

The present invention relates to new N-aryl-N'-alkyl-S- alkyl-isothioureas, processes for their preparation and their use as agents for combating animal and plant pests, in particular as ectoparasiticides, insecticides and Akari :: ide.

It has already become known that N-aryl-N ', N'-di- alkyl-thioureas are effective as ectoparasiticides, in particular as tickicides against ticks of the genus Boophilus (see German Offenlequngsschrift 2 337 122)

Compared with the known and chemically related compounds, the novel N-aryl-N'-alkyl-S-alkyl-isothioura fe show a better action against phosphoric ester-resistant ticks of the genus Boophilus and also a strong insecticidal action

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ORIGINAL INSPECTED

the comparison products from the German Offenlegungsschrift 2 337 122 is missing. The compounds of the invention can also be used in agriculture against insects which are harmful to plants and against acarids will.

It has been found that the new N-aryl-N ¹ -alkyl-S-alkylisothioureas of the general formula

-N = C-NH-R ⁴ (I)

in which

R ¹ for alkyl or cycloalkyl,

2
R for alkyl with at least two carbon atoms or for cycloalkyl,

the radicals R can be identical or different and R represents alkyl, cycloalkyl or halogen, η stands for an integer from 0 to 2

4th
and R for optionally substituted alkyl,

optionally substituted alkenyl or optionally substituted cycloalkyl and R stands for alkyl, alkenyl or cycloalkyl, and their salts »have a strong effect on animals and plant pests, especially an ectoparasiticide, have insecticidal and acaricidal effects.

Compounds of the formula are particularly preferred

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N = C-NH-R ^IV (Ia)

in which

R ^{1 is} alkyl (C ₁ -C 6) or cycloalkyl (C ₄ -C ₇ ), R ^{11 is} alkyl (C ₃ -C ₆ ) or cycloalkyl (C ₄ -C ₇ ),

the radicals R can be identical or different and are alkyl (C ₁ -C ₇ ), halogen, cycloalkyl (C ₄ -C ₇ )

and η is 0, 1 or 2,

R for alkyl (C ₁ -C ₁₄ ) which is optionally substituted by halogen, cycloalkyl (C ₄ -C ₇ ), cycloalkenyl (C ₅ -C ₇ ) or trifluoromethyl or for alkyl (C 1 -C 14) which is optionally substituted by halogen and / or CF-, mono- or polysubstituted alkenyl (C ₃ ^- C ₁₃₎ or one is optionally substituted by alkyl (C ₁ -C _4), halogen and / or CF ₃ or multiply substituted cycloalkyl (C ₃ -C _10),

and R ^{V stands} for alkyl (C ₁ -Cg), alkenyl (C ₃ -Cg) or cycloalkyl (C ₃ -C ₆ ),
and their salts

a strong effect against animal and vegetable pests, especially an ectoparacitic, insecticidal and have acaricidal effects.

It has also been found that the new N-aryl-N'-alkyl-S-alkyl-isothioureas of the formula (I) are obtained when thioureas of the formula

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.4

NH-C-NH-R (II)

12 3 4 in which R , R , R , R and η have the meaning given above, with a compound of the general formula

R ⁵ -X (III) converts,

where R has the meaning given above and X is a radical which can be removed anionically.

The thioureas of the formula (II) to be used as starting materials and likewise new can be obtained if one

a) Aryl isothiocyanates of the formula

(IV)

R "with alkylamines of the formula

H ₂ NR ⁴ (V)

or, alternatively, b) alkyl isothiocyanates of the formula

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H ₂ NR * (VI)

with arylamines of the formula

(VII)

implements, whereby

R ¹ , R ² , R ³ , R ⁴ and η in the formulas (IV) to (VII)

each have the meaning given above.

Surprisingly, the new N-aryl-N'-alkyl-S-alkyl-isothioureas according to the invention show a more pronounced ectoparasiticidal effect than the N-aryl-N ¹ , N ¹ -dialkyl-thioureas from German Offenlegungsschrift 2 337 122 and also a insecticidal action and an action against mites, which the compounds from German Offenlegungsschrift 2 337 lack.

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

Using N- (2,6-diisopropyl-phenyl) -N ¹ -tert-butylthiourea and methyl iodide as starting materials, the reaction can be represented by the following equation:

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CH, CH- \ 3/3

^X CH

NS,

«Ι J

-NH-C-NH-C-CH CH,

3 - HJ

SCH ₃ CH ₃ HC-NH-C-CH.

CH.,

As can be seen by comparing formula (Ia) with formula (I) , alkyl R is preferably alkyl having 1 to 6, in particular 1 to 4, carbon atoms. White

1 2

Furthermore, cycloalkyl R and R preferably represent cycloalkyl having 4 to 7 carbon atoms. At alkyl radicals R ¹

1 2 and cycloalkyl radicals R and R are mentioned by way of example: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl , tert-butyl, pentyl- (2), pentyl- (3), tert.- Pentyl, cyclopentyl, hexyl- (2), hexyl- (3), cyclohexyl, cycloheptyl,

Alkyl R preferably represents alkyl having 2 to 6, in particular 2 to 4 carbon atoms, the following may be mentioned by way of example: ethyl, propyl, isopropyl, butyl, sec.-butyl, isobutyl , tert.-butyl.

Alkyl R preferably represents straight-chain or branched alkyl having 1 to 7 carbon atoms.

Cycloalkyl R preferably represents cycloalkyl having 3 to 7 carbon atoms.

individual alkyl radicals R "are mentioned by way of example:

as well as cycloalkyl radicals

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Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Isobutyl, tert-butyl, n-pentyl, pentyl- (2), pentyl- (3), 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethylpropyl, tert-pentyl, n-hexyl, hexyl- (2), hexyl- (3), 2,3-dimethyl-butyl, 2-methylpentyl, 2,3-dimethyl-butyl- (2), n-heptyl, 1,1-diethylpropyl, cyclobutyl, cyclopentyl, 1-methyl-cyclopentyl, cycloheptyl, cyclohexyl, 1-methyl-cyclohexyl. The following may be mentioned as halogen R: fluorine, chlorine and bromine.

The radical R ⁴ can represent optionally substituted alkyl and preferably contains 1 to 14, in particular 1 to 1, carbon atoms. The following optionally substituted radicals may be mentioned as examples:

Methyl, ethyl, propyl,

Butyl, pentyl, hexyl, heptyl, octyl, decyl, 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-propy1- (1), 2-methyl-butyl- (2), 4,4-dimethyl-pentyl- (2), 2,4,4-trimethyl-pentyl- (2), hexyl- (2), hexyl- (3).

Optionally substituted alkenyl R preferably contains 2 to 12, in particular 2 to 10, carbon atoms. The following radicals, which may be further substituted, may be mentioned as examples:

Vinyl, 1-methyl-vinyl, 2-methyl-vinyl, 2,2-dimethyl-vinyl, 1,2-dimethyl-vinyl, 1,2,2-trimethyl-vinyl, allyl,

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Crotyl, 1-methyl-allyl, 1,1-dimethyl-ally1, 2-isopropylvinyl, 2-tert-butyl-vinyl, 2-butyl-vinyl, 3,3-dimethylallyl, 3-hexyl-allyl.

4 Optionally substituted cycloalkyl R preferably contains 3 to 10 carbon atoms. Exemplary the following radicals, which may be further substituted, may be mentioned:

Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methyl-cyclopropy ^ Cyclopenten- (1) -yl- (3), Cyclopenten- (1) -yl- (4), Cyclohexen- (1) -yl- (3), 1-methyl-cyclopentyl- (1), 1-methyl-cyclohexy1- (1), 2-methyl-cyclohexy1, 3-methyl-cyclohexyl, 4-methyl-cyclohexyl, 2,3-, 2,6-, 2, 5- or 3,5-dimethyl-cyclohexyl, 3,5-bis-trifluoromethyl-cyclohexyl, 2-, 3- or 4-trifluoromethyl-cyclohexyl, 4-methyl-3-trifluoromethyl-cyclohexyl, 4-ethyl-cyclohexy1, 2 Ethyl-cyclohexyl, 4-isopropyl-cyclohexyl, 2-sec-butylcyclohexyl, norbornyl, 3,3,5-trimethy1-cyclohexy1, bornyl, isobornyl, decahydronaphthyl-d), adamantyl, cycloheptyl, cyclooctyl.

The radical R preferably represents alkyl (C ₁ -C ₆ ), alkenyl (C ₃ -C 6) or cycloalkyl (C ₃ -C ₆ ). Examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, allyl, crotyl, methallyl, butene- (3) -yl- (1), cyclopropyl, cyclopentyl, cyclohexyl.

η is preferably 0, 1 or 2.

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The anionically removable radical X of the general formula (III) is preferably halogen, in particular chlorine, Bromine or iodine or an alkylsulfonyloxy group or an arylsulfonyloxy group of the formulas

θ θ

R ¹ -SO, or R "-SO,

in which

R ^{1 represents} alkyl with preferably 1 to 6 carbon atoms

and
R "represents aryl with preferably 6 or 10 carbon atoms.

Furthermore, X preferably stands for an alkyl sulfuric acid residue the formula

° 2 ^S \ ^{1 X} OR '

for an alkyl sulphate radical of the formula

or for a phosphoric acid alkyl ester radical of the formula

0 ^θ

OR ¹

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where the radicals R 'preferably have the meaning given above.

The following are examples of N- (2,6- ^{dialkylphenyl) -N 1} -alkyl-thioureas of the general formula (II) which are used as starting compounds for the process according to the invention:

N- (2,6-diethyl-phenyl) -N'-methyl-thiourea; F: 103-105 ° C 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'-buty1-thiourea; F: 41-43 ° C N- (2,6-diethyl-phenyl) -N'-isobutyl-thiourea; F: 68-70 ° C N- (2,6-diethyl-phenyl) -N ^l -neopentyl-thiourea; F: 87-89 ° C N- (2,6-diethylphenyl) -N • -penty1-thiourea; (F <30 ° C) N- (2,6-diethyl-phenyl) -N'-hexyl-thiourea; F: 102-105 ° C N- (2,6-diethylphenyl) -N ¹ -hepty1-thiourea; (F <^ 30 ^o C)

N- (2,6-diethyl-phenyl) -N'-octy1-thiourea N- (2,6-diethyl-phenyl) -N'-decy1-thiourea N- (2,6-diethyl-phenyl) -N'-dodecy1-thiourea N- (4-Methy1-2,6-diethy1-pheny1) -N • -methy1-thiourea;

F: 97-1OO ° C

N- (4-methyl-2,6-diethyl-phenyl) -N'-ethyl-thiourea N- (4-methyl-2,6-diethy1-phenyl) -N ¹ -propy1-thiourea N- (4-methyl -2,6-diethyl-phenyl) -N'-buty1-thiourea; F: oil

(F <3O ° C)

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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: 106-1O7 ° 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-Methy1-2,6-diethyl-phenyl) -N * - (2,3-dimethyl-butyl) -

thiourea N- (4-Methy1-2,6-diethyl-phenyl) -N '- (2,2,3-trimethyl-butyl) -

thiourea N- (4-Methy1-2,6-diethyl-phenyl) -N '- (2,3,3-trimethyl-butyl) -

thiourea N- (4-Methy1-2,6-diethyl-phenyl) -N '- (2,2,3,3-tetramethyl-butyl) -

thiourea

N- (4-methyl-2,6-diethyl-phenyl) -N '- (3-methyl-penty1) -thiourea N- (4-methyl-2,6-diethyl-phenyl) -N ¹ - (2- isopropyl-butyl) -

thiourea N- (4-methyl-2,6-diethyl-phenyl) -N '- (2,4,4-trimethyl-pentyl) -

thiourea N- (4-methy 1-2,6-diethyl-phenyl ) -N ■ - ( 2 , 2 , 4 , 4- tetramethy 1-penty 1) -

thiourea

N- (4-Methy1-2,6-diethyl-phenyl) -N'-allyl-thiourea N- (4-Methy1-2,6-diethyl-phenyl) -N'-methallyl-thiourea

F: 86-88 ° C

N- (4-methyl-2,6-diethyl-phenyl) -N'-croty1-thiourea N- (4-Methy1-2,6-diethyl-phenyl) -N - (3,3-dimethyl-allyl) -

thiourea N- (4-methyl-2,6-diethyl-phenyl) -N - (2,3-dimethyl-allyl) -

thiourea N- (4-Methy1-2,6-diethyl-phenyl) -N '- ^ butene- (3) -y1- (1 ) J-

thiourea

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N- <4-methyl-2,6-diethy 1-phenyl) -N ¹ - / 2, 2-dimethyl-buten- (3) -yl-

(1J-thiourea f

N- (4-methyl-2,6-diethy1-phenyl) -N '- (3-isopropyl-allyl) -

thiourea

N- (4-methyl-2,6-diethy1-phenyl) -N · - (3-tert-buty1-ally1) -

thiourea

N- (4-methyl-2,6-diethy1-phenyl) -N ¹ - (3-hexyl-allyl) -thiourea

N- (4-methyl-2,6-diethyl-phenyl) -N'-cyclopropyl-methyl-

thiourea

N- (4-methyl-2,6-diethyl-phenyl) -N ¹ - (cyclopentyl-methyl) -

thiourea

N- (4-Methy 1-2,6-diethy 1-phenyl) -N - ^ yclopenten- (1) -y1- (1) -

methy17-thiourea

N- (4-methyl-2,6-diethy1-phenyl) -N • -cyclohexyl-thiourea N- (4-Methy1-2,6-diethy1-oheny1) -N '- / cyclohexen- (3) -y1- (1) -

methy ij- thiourea

N- (2,6-diethyl-pheny1) -N '- (2,3-dimethy1-buty1) -thiourea N- (2,6-diethyl-phenyl) -N ¹ - (2,2,3-trimethyl- butyl) thiourea

N- (2,6-diethy1-phenyl) -N '- (3-methy1-penty1) -thiourea N- (2,6-diethy1-phenyl) -N '- (2,2,4,4-tetramethy1-penty1) -

thiourea

N- (2,6-diethy1-phenyl) -N '- (3,3-dimethy1-ally1) -thiourea N- (2,6-diethy1-phenyl) -N · - (2,3-dimethy1-ally1) thiourea N- (2,6-Diäthy1-phenyl) -N · -methally1-thiourea N- (2,6-Diäthy1-phenyl) -N * - (cyclopentyl-methyl) thiourea N- (2, 6-Diäthy1 -phenyl) -N - (cyclohexyl-methyl) -thiourea N- (3-methyl-2,6-diethy1-phenyl) -N * -propyl-thiourea

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N- (3-methyl-2,6-diethyl-phenyl) -N · isobutyl-thiourea N- (3-methyl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea

F: 1O2-1O4 ° C

N- (3-methyl-2,6-diethyl-phenyl) -N'-pentyl-thiourea N- (3-methyl-2,6-diethyl-phenyl) -N · -methallyl-thiourea

F: 105-1O6 ° C

N- (3-methyl-2,6-diethyl-phenyl) -N ¹ - (3-methyl-butyl) -thiourea N- (3-methyl-2,6-diethyl-phenyl) -N ¹ - (2- ethyl-butyI) -

thiourea N- (3,5-dimethyl-2,6-diethyl-phenyl) -N'-butyl-thiourea

Q: 108-110 ⁰ C

N- (3,5-Dimethyl-2,6-diethyl-phenyl) -N'-penty1-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) -y1- (1) -

thiourea N- (3,5-dimethyl-2,6-diethyl-phenyl) -N * -cyclopenty1-methyl-

thiourea

N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-neopenty1-thiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-isobuty1-thiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N ¹ -pentyl-thiourea N- (3,4-Dimethyl-2,6-diethyl-phenyl) -N'-methallyl-thiourea N- (3 -Chlor-2,6-diethyl-phenyl) -N-propy1-thiourea N- (3-chloro-2,6-diethyl-phenyl) -N'-butyl-thiourea

F: 108: 111 ° C

N- (3-chloro-2,6-diethyl-phenyl) -N'-neopentyl-thiourea

F: 106-110 ° C

N- (3-chloro-2,6-diethyl-phenyl) -N · - (3-methy1-penty1) -

thiourea

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N- (3-chloro-4-methyl-2,6-diethyl-pheny1) -N'-isobutyl-thiourine-

material

N- (3-chloro-4-methyl-2,6-diethyl-pheny1) -N ¹ -neopenty1-thiourea f

N- (3-chloro-4-methyl-2,6-diethy1-phenyl) -N'-methallyl-thio-

urea

N- (2,4,6-trimethyl-phenyl) -N'-neopenty1-thiourea N- (2,4,6-trimethyl-phenyl) -N · -methalyly1-thiourea

N- (2,3,4,6-tetramethyl-phenyl) -N'-butyl-thiourea N- (2,3,4,6-tetramethy1-phenyl) -N'-methally1-thiourea

N- (2,6-diisopropyl-phenyl) -N ^l -methyl-thiourea F: 167-168 ° C N- (2,6-diisopropyl-phenyl) -N'-ethy1-thiourea N- (2,6- Diisopropy1-phenyl) -N'-propyl-thiourea F: 1O6-1O7 ° C N- (2,6-diisopropyl-phenyl) -N-buty1-thiourea F: 99-1O3 ° C N- (2.6- Diisopropyl-phenyl) -N ¹ -isobuty1-thiourea

F: 108-112 ° C N- (2,6-diisopropyl-phenyl) -N '- (3-methy1-buty1) -thiourea

F: 64-68 ° C, N- (2 _f 6-Diisopropyl-phenyl) -N'-pentyl-thiourea F: 76-83 ° C

P: 150-155 ° C

N- (2,6-Diisopropy1-phenyl) -N'-neopenty1-thiourea

F: 150-1 N- (2,6-diisopropyl-pheny1) -N • -methallyl-thiourea

F: 93-95 ° C

N- (2,6-Diisopropyl-phenyl) -N'-hexyl-thiourea N- (2,6-diisopropyl-phenyl) -N'-dodecyl-thiourea N- (2,6-Diisopropy1-phenyl) -N '- (2-ethy1-buty1) -thiourea N- (2,6-Diisopropyl-phenyl) -N '- (3,3-dimethy1-buty1) -thiourea

N- (2, 6-Diisopropy1-phenyl) -N '- (2,3-dimethyl-butyl) thiourea

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N- (2,6-Diisopropyl-phenyl) -N '- (2,2,3-trimethy1-buty1) -thiourea

N- (2,6-Diisopropyl-phenyl) -N • - (2,4,4-trimethyl-pentyl) -thiourea

N- (2,6-Diisopropyl-phenyl) -N ¹ - (2,3,3-trimethyl-allyI) -thiourea

N- (2,6-Diisopropyl-phenyl) -N ¹ - (cyclopentyl-methyl) -thiourea

N- (2-ethyl-6-isobutyl-phenyl) -N'-methallyl-thiourea

F: 105-1O6 ° 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-isopropy1 -pheny1) -N'-neopenty1-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 ^f - (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 ¹ -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: 83-85 ° C

N- (2,6-Di-sec-butyl-phenyl) -N'-allyl-thiourea F: 83-86 ° C N- (2,6-Di-sec-butyl-phenyl) -N ¹ -methallyl- thiourea

F: 69-72 ° C N- (2,6-Di-sec-butyl-phenyl) -N-neopentyl-thiourea

F: 88-90 ° C

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N- (2,6-di-sec-buty1-pheny1) -N'-pentyl-thiourea N- (2,6-di-sec-buty1-pheny1) -N'-hexy1-thiourea N- (2,6-di-sec-buty1-pheny1) -N'-octyl-thiourea N- (2,6-di-sec-buty1-pheny1) -N'-decy1-thiourea N- (2,6-di-sec-buty1-pheny1) -N '- (2-ethy1-butyl) -thiourea N- (2,6-di-sec-buty1-pheny1) -N '- (3,3-dimethy1-butyl) -thiourea

N- (2,6-di-sec-buty1-pheny1) -N '- (2-methyl-penty1) -thiourea N- (2,6-di-sec-butyl-phenyl) -N '- (2,3,3-trimethyl) -allyl-

thiourea

N- (2-methyl-6-sec-buty1-pheny1) -N'-propy1-thiourea N- (2-ethyl-6-sec-buty1-pheny1) -N ¹ -methally1-thiourea NU-isopropyl- ö-sec-butyl-phenyl) -N ¹ -isobutyl-thiourea N- (4-methyl-2,6-di-sec-butyl-phenyl) -N'-isobutyl-thio-

urea F: 98-1O2 ° C

N- (4.Methyl-2 _f 6-di-sec-butyl-phenyl) -N ^t -butyl-thiourea

F: 97-1OO ° C

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 ¹ -isobutyl-thiourea N- (2,6-di-cyclopentyl-phenyl) -N'-neopentyl-thiourea N- (2,6-di-cyclopentyl-phenyl) -N'-methally1-thiourea N- (2,6-Di-cyclopentyl-phenyl) -N '- (cyclopropyl-methyl) -

thiourea N- (2,6-di-cyclopentyl-phenyl) -N'-penty1-thiourea

N- (2-ethyl-6-cyclopentyl-phenyl) -N ¹ -isobutyl-thiourea

N- (2-methyl 1-6-t-buty1-pheny1) -N ^{1-isobutyl-thiourea} N- (2-methyl-6-t-buty1-pheny1) -N'-neopenty! Thiourea

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N-U-methyl-δ-tert-butyl-phenyl) -N'-methallyl-thiourea N- (2-Methy1-6-tert-buty1-pheny1) -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-thio-

urea N- (2-methyl-4,6-di-tert-butyl-phenyl) -N'-methally1-thio-

urea

N- (4-Methyl-2,6-diisopropyl-phenyl) -N ¹ -methyl-thiourea, N- (4-Methyl-2,6-diisopropyl-phenyl) -N'-propyl-thiourea

F: 125-127 ° C N- (4-Methy1-2,6-diisopropyi-phenyl) -N'-buty1-thiourea

F: 126-129 ° C N- (4-Methy1-2,6-diisopro> y1-pheny1) -N'-isobutyl-thiourea

F: 150-153 ° C

N- (4-Methy1-2,6-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-phenyl) -N'-methyl-thiourea N- (2,4,6-triisopropyl-phenyl) -N'-butyl-thiourea N- (2,4,6-triisopropyl -pheny1) -N ^f -allyl-thiourea N- (2,4,6-triisopropyl-phenyl) -N'-methallyl-thiourea

F: 115-118 ° C

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-Dimethy1-pheny1) -N • -buty! -Thiourea

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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: 65-67 ° C N- (2,4-Dimethyl-6-ethy1-phenyl) -N'-methyl-thiourea

F: 125-126 ° C

N- (2,4-6-triethyl-phenyl) -N'-propyl-thiourea N- (2,4,6-triethyl-phenyl) -N-butyl-thiourea, oil (F <3O ° C) N- (2,4,6-triethyl-phenyl) -N'-isobutyl-thiourea F: 74-76 ° C N- (2,4,6-triethyl-phenyl) -N'-methallyl-thiourea N- (2,4,6-triethyl-phenyl) -N-neophentyl-thiourea F: 78-80 ° C N- (4-Buty1-2,6-diethy1-phenyl) -N'-isobutyl-thiourea,

oil (F <30 ° C) N- (4-Buty1-2,6-diethy1-phenyl) -N ¹ -neopentyl-thiourea

F: 52-54 ° C

N- (4-Buty1-2,6-diethyl-phenyl) -N'-crotyl-thiourea N- (4-butyl-2,6-diethyl-phenyl) -N · -heptyl-thiourea N- (4-Cyclohexyl-2,6-diethyl-phenyl) -N'-buty1-thiourea

F: 63-66 ° C N- (4-Cyclohexyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea

F: 118-120 °

N- (4-Cyclopentyl-2,6-diethyl-phenyl) -N '-isobuty? .- thiourea f N- (4-Cyclopenty1-2,6-diethyl-phenyl) -N ¹ -methaiIyI-thiourea N- ( 4-Cyclopentyl-2,6-diethyl-phenyl) -N · neopentyl-thiourine-

substance N- (4-propyl-2,6-diethyl-phenyl) -N · -n-pentyl-thiourea; oil

(F <30 ° C) N- (4-isobutyl-2,6-diethyl-phenyl) -N · -methy1-thiourea

F: 123-126 ° C

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N- (4-isobutyl-2,6-diethyl-phenyl) -N * -n-hexyl-thiourea;

Oil (F <r3O ° C)

N- (4-tert-butyl-2,6-diethyl-phenyl) -N'-isobutyl-thiourea

F: 121-122 ° C

N- (4-tert-butyl-2,6-diethyl-phenyl) -N ¹ -butyl-thiourea

F: 81-83 ° C

N- (4-tert-butyl-2,6-diethyl-phenyl) -N'-n-penty1-thiourea, Ö1 (F <3O ° C)

N- (2-methyl-4,6-di-tert-butyl-phenyI) -N ¹ -isobutyl-thiourea F: 157-16O ° C

N- (2-methyl-4,6-di-tert-butyl-phenyI) -N ¹ -neopentyl-thiourea F: 157-159 ° C

N- (4-methyl-2,6-di-cyclopentyl-phenyI) -N'-butyl-thiourea

F: 151-153 ° C

N- (2,6-Diisopropyl-phenyl) -N'-tert-butyl-thiourea

Q: ⁰

N- (2,6-Diisopropyl-phenyl) -N'-tert-penty1-thiourea

Q:

N- (2,6-Diisopropyl-phenyl) -N ¹ - (1,1,2,2-tetramethyl-propyl) thiourea F: 161-162 ° C

N- (2,6-diethyl-phenyl) - Ni-tert-butyl-thiourea

F: 98-100 ° C

N- (2,6-diethyl-phenyl) -N'-tert-pentyl-thiourea

F: 85 to 87 ⁰ C.

N- (2,6-di-sec-butyl-phen> 1) -N'-tert-penty1-thiourea

F: 116-118 ° C

N- (2,6-di-sec-butyl-phenyl) -N ¹ -tert-butyl-thiourea

F: 115-117 ° C

N- (2,6-diethyl-phenyl) -N'-isopropyl-thiourea

F: 108-110 ⁰ C.

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2 ζ '

273Ü62Q

N- (2,6-diethyl-phenyl) -N'-sec-butyl-thiourea

F: 78 - 8O ⁰ C

N- (2,6-di-sec-butyl-phenyl) -N ¹ -isopropyl-thiourea

F: 108-111 ° C

N- (2,6-di-sec-butyl-phenyl) -N'-sec-butyl-thiourea

F: 103-105 ° C

N- (2,4-Diroethyl-6-ethyl-phenyl) -N'-tert-butyl-thiourea

F: DO - lj52 ° C

N- (2, ^ - diethyl-6-ethyl-pheny]) - N ^I -tert-pentyl-thiourea

F: 105-107 ° C N- (4-methyl-2,6-diethyl-phenyl) -N ^l -tert-butyl-thiourea

F: 121-123 ° C N- (4-methyl-2,6-diethyl-phenyl) -N'-tert-pentyl-thiourea

F: 98-101 ⁰ C N- (2-methyl-6-ethyl-phenyl) -N'-tert-butyl-thiourea

F: 94-96 ° C N- (2-methyl-6-ethyl-phenyl) -N'-tert-pentyl-thiourea

F: 78 - 8l ° C

N- (2,4,6-trimethyl 1-pheny 1) -N '-tert. -penty 1-thiourea f N- (2,6-diethyl-3-methyl-phenyl) -N ^f -tert-butyl-thiourea N- (2,6-diethyl-3,5-dimethyl-phenyl) -N '-tert-butyl-thiourea N- (2,6-diethyl-3,5-climethyl-phenyl) -N'-pentyl- (2) -thiourea N- (2,6-di-isopropyl-phenyl) - N '-p-methyl-butyl- (2)] -thiourea N- (2,6-di-sec-butyl-phenyl) -N' - [pentyl- (2I-thiourea N- (2,6-di -sec. -butyl-phenyl) -N ¹ - (hexyl- (2 ^ thiourea N- (2,6-di-8ek.-butyl-phenyl) -N'- | pentyl- (3) f-thiourea

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N- (2,6-di-sec-butyl-phenyl) -N'-L4-methy1-penty1- (2 O-thiourea

N- (2,6-Di-sec.-butyl-phenyl) -N'-r2-methyl-pentyl - (^) l-thiourine-

- material

N- (2,6-diisopropyl-phenyl) -N '- | pentyl- (2) j-thiourea N- (2,6-diisopropyl-phenyl) -N'-ßiexyl- (2) J-thiourea N- ( 2,6-diisopropyl-phenyl) -N'-Ij3-methyl-pentyl- (2) J-thiourea N- (2,6-diisopropyl-phenyl) -N'-ipentyl- (3j-thiourea N- (2, 6-diisopropyl-phenyl) -N ¹ - [2,2-dimethyl-pentyl- (3)] -

thiourea

N- (2 -> 'thyl-6-sec-butyl-phenyl) -N' -tert. -butyl thiourea

F: 96-99 C

N- (2-Isopropyl-6-sec-butyl-phenyl) -N'-tert-butyl-thiourea

F: 121-123 ° C

N- (2-Isopropyl-6-sec -butyl-phenyl) -N'-tert-butyl-thiourea

F: 51-53 ° C

N- (2,6-Diisopropyl-phenyl) -N '- [1-cyclopentyl-ethyl-thiourea

N- (2 _f 6-Di-sec-butyl-phenyl) -N ¹ - [2-diethyl-pentyl- (2) j | -thiourea

N- (2,6-Dl-sec-butyl-phenyl) -N ¹ - £ 2-ethyl-pentyl- (2) I-thiourea

N- (2,6-Di-sec-butyl-phenyl) -N ¹ -l_2-methyl-hexyl- (2 Ϊ] -thiourea

N- (2,6-diethyl-phenyl) -N'-r2-raethyl-octyl- (2) I-thiourea

N- (2,6-Diisopropyl-phenyl) -N ¹ - [_ 2-methyl-pentyl- (2)] -thiourea N- (2,6-diisopropyl-phenyl) -N '- [2-ethyl-pentyl- (2i] -thiourea N- (2,6-diethyl-3-chloro-phenyl) -N'-tert-butyl-thiourea

N- (2-ethyl-6-sec-butyl-pheny ^ -N ^l -tert-pentyl-thiourea

F: 74-76 ° C

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273Ü62Ü

N- (2,6-Di-cyclopentyl-phenyl) -N'-tert-butyl-thiourea N- (S-ethyl - ^ - methyl-o-sec.-buty1-phenyl) -N ¹ -tert.-butyl-thio-

urea

N- (2,4-dimethyl-6-tert.-buty1-phenyl) -N'-tert.-penty1-thio-

urea

N- [2,6-di-pentyl- (2) -pheny] | -N'-tert.-butyl-thiourea N- (2, ^ - dimethyl-o-cyclohexy1-phenyl) -N'-tert.- buty1-thiourea N- (2,6-diisopropyl-4-chlorophenyI) -N ¹ -tert.-buty1-thiourea N- (2,5-dimethyl-6-ethyl-phenyl) -N ¹ -tert.-pentyl- thiourea N- (2,5-diraethyl-6-isopropyl-phenyl) -N ¹ -tert-pentyl-thiourea N- (2,6-diethyl-phenyl) -N '- [J2-methyl-pentyl- (2 ) 3-thiourea N- (2,6-diethyl-phenyl) -N '- [2-ethyl-pentyl- (2l | -thiourea N- (2,6-diethy 1-phenyl) -N ¹ -l_2-methyl -hexyl- (2)] -thiourea N- (2,6-diethyl-phenyl) -N '- [decyl- (5r | -thiourea

N- (2,6-diethyl-phenyl) -N'-ri, l # 2,2-tetramethyl-propyri-thionarn-

- material

N- (2,6-diethyl-phenyl) -N '- [2,4-diniethyl-pentyl- (3 0-thiourea N- (2,6-dimethyl-phenyl) -N ¹ - £, 2-dimethyl- pentyl- (3) J -thiourea N- (2-methyl-6-ethyl-pheny1) -N'-cyclopropy1-thiourea ""-N'-cyclopentyl-thiourea

"" -N'-cyclohexyl thiourea

"" -N'-cycloheptyl thiourea

N- (2,4-dimethyl-6-ethyl-phenyl) -N '-) 3-methyl-cyclohexyl) -

thiourea N- (2,6-diethy1-phenyl) -N'-cyclopropy1-thiourea;

F: 111-113 ° C

"" -N'-cyclobutyl thiourea

"" -N'-cyclopentyl thiourea

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2t -

N- (2,6-diethyl-phenyl) -N ¹ - (1-methyl-cyclopentyl) -thiourea; F: 86-88 ⁰ C

"" -N'-cyclohexyl thiourea

"" -N '- (2-methy1-cyclohexy1) -thiourine

material; oil

"" -N'-cycloheptyl thiourea

"" -N'-cyclooctyl thiourea

N- (4-methyl-2,6-diethyl-phenyI) -N ¹ -cyclopropyl-thiourea; F: 113-115 ° C

"" -N'-cyclopentyl thiourea

"" -N'-cyclohexyl thiourea

"" -N ¹ - (4-methy1-cyclohexy1) -

thiourea "" -N '- (3,3,5-trimethyl-cyclo-

hexyl) thiourea -N '- (2,6-diethyl-cyclohexyl) -

thiourea

N- (2,4,6-Triethy1-pheny1) -N'-cyclopropyl-thiourea "" -N'-cyclopentyl thiourea

"" -N'-cyclohexyl thiourea;

F: 97 - 99 ° C "" -N '- (3-trifluoromethyl-cyclohexyl) -

thiourea; F: 52 - 55 ° C "" -N '- (4-trifluoromethyl-cyclohexyl) -

thiourea " "-N'-O ^ -bis-trifluoromethyl-cyclo-

hexyl) thiourea

"" -N'-cyclopentyl thiourea

"" -N'-cyclooctyl thiourea

"" -N '- (2-norbornyl) thiourea

"" -N ¹ - (1-adamantyl) thiourea

Le A 18 232 - 23 -

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N- (4-n-propyl- 2,6-diethyl-phenyl) -N'-cyclopenty1-thiourea ""-N'-cyclohexyl-thiourea

"" -N '- (3-methyl-cyclohexyl) -

thiourea "" -N '- (4-methyl-cyclohexyl) -

thiourea " ^H -N'-O-trifluoromethyl-cyclo-

hexyl) thiourea; Oil " ^H -N '- (4-trifluoromethyl-cyclo-

hexyl) thiourea; oil "" -N '- (2,4-dimethyl-cyclohexyl) -

thiourea "" -N '- (4-ethyl-cyclohexyl) -

thiourea

"" -N ¹ -cyclopentyl thiourea

N- (4-isopropyl- 2,6-diethyl-phenyl) -N ¹ -cyclopentyl-thiourine-

substance "" -N'-cyclohexyl-thiourea;

F: 120-123 ° C

"" -N'-O-trifluoromethyl-cyclo-

hexyl) thiourea;

F: 127-140 ° C

"" -N '- (2-norborny1) -thiourea "" -N '- (decahydronaphthyl-1) -

thiourea

N- (4-n-butyl- 2,6-diethyl-phenyl) -N · -cyclopentyl-thiourea ""-N'-cyclohexyl-thiourea;

oil "" -N'-P-methyl-cyclohexyl) -

thiourea; oil

Le A 18 232 - 24 -

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N- (4-n-butyl-2,6-diethy1-pheny1) -N '- (4-methy1-cyclohexy1) -

thiourea -N ¹ - (4-ethyl-cyclohexyl) -

thiourea "" -N'-O-trifluoromethyl-cyclo-

hexyl) thiourea; oil

^M "-N ¹ -cycloheptyl thiourea

N- (4-n-Penty1-2,6-diethy1-pheny1) -N ¹ -eyelopentyl-thiourea ""-N'-cyclohexyl-thiourea

"" -N'-cycloheptyl-thiourineff

N- (4-pentyl- (3) -2,6-diethy1-pheny1-N '-cyclopenty1-thiourea "" -N'-cyclohexyl thiourea

¹¹ "-N ¹ - (3-trifluoromethyl-cyclo-

hexyl) thiourea

¹¹ "-N'-cycloheptyl thiourea

N- (4-n-hexyl-2,6-diethy1-pheny1) -N'-cyclopentyl-thiourea

"" -N'-cyclohexyl thiourea

N- (4-Cyclohexy1-2,6-diethy1-pheny1) -N * -cyclopenty1-thiourea "" -N'-cyclopropyl-thiourea

"" -N ¹ - (3-trifluoromethyl-cyclo-

hexyl) thiourea;

F: 118 - 125 ° C N- (4- (1-methyl-cyclohexyl) -2,6-diethyl) -N'-cyclopenty1-

thiourea N- (4-cyclopentyl-2,6-diethy1-phenyl) -N ¹ -cyclopentyl-thiour-

material

"" -N'-cyclohexyl-thiourine

material

"" -N '- (cyclohexene 2) -yl-

thiourea

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273U620

N- (4-sec-butyl-2,6-diethyl-phenyl) -N ¹ -eyelopenty1-thiourea
"-N'-cyclohexyl-thiourine-

material; F: 140 ° C "" -N '- (2-methyl-cyclohexyl) -

thiourea; oil "" -N ¹ - (3-methyl-cyclohexyl) -

thiourea; oil "-N '- (4-methyl-cyclohexyl) -

thiourea; F: 88 - 123 ° C "" -N'-O-trifluoromethyl-cyclo-

hexyl-thiourea "" -N'-cycloheptyl-thiourea-

material

-N '- (3,3,5-trimethyl-cyclohexyl-thiourea;

F: 58-80 ° C

N- (Isobutyl-2,6-diethyl-phenyl) -N'-cyclopropyl-thiourea "" -N'-cyclobutyl thiourea

"" -N'-cyclopentyl thiourea;

oil

-N'-cyclohexyl thiourea;

F: 41 - 44 ° C -N ¹ - (1-methyl-cyclopentyl) -

thiourea; F: 73 - 74 ° C -N ¹ - (2-methyl-cyclohexyl) -

thiourea; resin
-N ¹ - (3-methyl-cyclohexyl) -

thiourea; F: 57-85 ° C

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N- (4-isobutyl-2,6-diethyl-phenyl) -N '- (4-methy1-cyclohexyl) -

thiourea; F: 70-165 ° C

^H "-N '- (3-trifluoromethyl-cyclo

hexyl) thiourea;

F: 50-55 ° C

¹¹ "-N ¹ - (4-trifluoromethyl 1-cyclo

hexyl) thiourea;

F: 52 - 60 ° C "" -N ^I - (2,6-dimethyl-cyclohexyl) -

thiourea

¹¹ "-N ¹ - (2-norbornyl) thiourine

material

"" -N '- (1-adamantyI) -thiourea "" -N'-cycloheptyl-thiourine-

substance N- (4-Cycloheptyl-2,6-diethyl-phenyl) -N'-cyclopenty1-thiourine-

substance N- (2,6-diisopropyl-phenyl) -N ¹ -cyclopropyl-thiourea;

F: 166-168 ° C

"" -N'-cyclopenty1-thiourea;

F: 140-142 ° C

"" -N '-d-methyl-cyclopentyl) -thio

urea; F: 149-150 ° C

"" -N'-cyclohexyl thiourea;

F: 120 - 122 ° C

"" -N '- (2-methyl-cyclohexyl) -thio

urea; F: 128-145 ° C

"" -N ¹ - (3-methy1-cyclohexyl) -thio

urea; F: 62-76 ° C

Le A 18 232 - 27 -

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N- (2,6-Diisopropyl-phenyD-N ¹ - (4-methyl-cyclohexyl) -thiourea; F: 155-167 ° C "" -N '- (2-trifluoromethyl-cyclohexyl) -

thiourea; F: 187 ° C

"" -N'-O-trifluoromethyl-cyclohexyD-

thiourea; F: 67 - 75 ° C "" -N '- (4-trifluoromethyl-cyclohexyl) -

thiourea; F: 142-165 ° C N- ( 2,4,6-triisopropy- 1-pheny1) -N'-cyclopropy1-thiourea;

F: 158-160 ° C

N- (2, 6-Diisopropy 1-phenyl 1) -N '- (4-äthy1-cyclohexy1) thiourea

"" -N ¹ - (eyelohexen- (2) -yl) -thiourea " ^H -N '- (3,3,5-trimethyl-cyclohexyl) -

thiourea; F: 84-12O ° C

"" -N'-O ^ -bis-trifluoromethylcyclo-

hexyl) thiourea;

F: 180 - 181 ° C "" -N '- (2,4-dimethyl-cyclohexyl) -

thiourea "" -N ^l - (3-trifluoromethyl-4-methyl-

cyclohexyl) thiourea;

F 145 - 165 ° C "" N '- (2-norbornyl) thiourea

-N '- (2-bornyl) -thiourea

"" -N ¹ - (1-adamantyl) -thiourea ""-N'-cycloheptyl-thiourea N- (2-Ethy1-6-isopropy1-pheny 1) -N ¹ -cyclohexyl-thiourea

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2730020

N- (4-Methy 1-2,6-diisopropyl-phenyI) -N'-cyclopentyl-thiourea
N- (2-isopropyl-6-sec-butyl-phenyl) -N'-cyclopentyl-thio-

urea
N- (2,6-di-sec-butyl-phenyl) -N'-cyclopropy1-thiourea;

F: 151-153 ° C "" -N ¹ -cyclopentyl-thiourea;

F: 140-14 2 ° C

"" -N ¹ -d-ynethyl-cyclopentyl) -thio

urea

"" -N ¹ -cyclohexyl thiourea

"" -N ¹ -O-methyl-cyclohexyl) -thiourea
"-N'-O-trifluoromethyl-cyclohexyl) -

thiourea; F: 58 - 67 ° C "-N'-O / S-bis-trifluoromethyl-cyclo-

hexyl) thiourea; oil

"" -N '- (2-norbornyl) thiourea

"" -N'-cycloheptyl thiourea

N- (2-ethyl-6-sec-butyl-phenyl) -N'-cyclopropy1-thiourea;

F: 122-123 ° C N- (2,6-di-cyclopentyl) -phenyl) -N ¹ -cyclopenty1-thiourea;

F: 168-170 ° C

"" -N'-cyclohexyl thiourea

N- (2,6-di-pentyl- (2) -phenyl) -N'-cyclopentyl-thiourea

"" -N'-cyclohexy1-thiourea

N- (3-chloro-2,6-diethyl-phenyl) -N'-cyclopropy1-thiourea;

F: 130-131 ° C

N- (3-methyl- 2,6-diethyl-phenyl) -N'-cyclopropy1-thiourea;

F: 145-146 ° C

Le Ά 18 232 - 29 -

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N- (4-methyl- (2,6-di-sec-buty1-pheny1) -N • -cyclopropyl-thiourea; F: 154-156 ° C

N- (2,4,6-diethyl-phenyl) -N'-cycloheptyl-thiourea;

F: 84-86 ° C

N- (4-n-propyl-2,6-diethyl-phenyl) -N'-cycloheptyl-thiourea; oil

N- (4-isopropyl-2,6-diethyl-phenyl) -N'-cycloheptyl-thiourea f; F: 89-92 ° C

N- (4-n-butyl-2,6-diethyl-phenyl) -N -cycloheptyl-thiourine-

material; oil

The N- (2,6-dialkyl-phenyl) -N'-alkyl-thioureas of the general formula II are reacted according to the invention with compounds of the general formula III. Examples of compounds III include alkylating, alkenylating or cycloalkylating agents: methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, methyl methanesulfonate , methyl toluenesulfonate, trimethyl phosphate, methyl fluorosulfonate, ethyl chloride, ethyl bromide, ethyl bromide, propyl bromide, propyl bromide, butyl bromide, butyl bromide, triethyl bromide, butyl bromide, triethyl fluoride, methyl iodide, dimethyl sulfate, methyl methanesulfonate, butyl bromide, propyl bromide, butyl bromide, butyl bromide, butyl bromide, butyl bromide, butyl bromide, butyl bromide. Butyl iodide, hexyl iodide, allyl bromide, methallyl chloride, methallyl bromide, crotyl bromide, butene- (3) -yl- (1) -bromide, 3-methyl-butylbromide, isobutylbromide , cyclopropyl bromide, cyclopentyl bromide, cyclohexyl iodide.

The reaction of the thioureas II with the compounds of the formula III is generally carried out in solvents at about 10 ° C to about 120 ° C, preferably at about 20 ° C to about 80 ° C. Suitable solvents are, for example, hydrocarbons

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273G62Q

substances or halogenated hydrocarbons such as hexane, cyclohexane, Methylcyclohexane, octane, methylene chloride, chloroform, 1,2-dichloroethylene, also aromatics such as benzene, Toluene, xylene or polar solvents e.g. ethers and carboxylic acid derivatives such as diethyl ether, diisopropyl ether, Tetrahydrofuran, dioxane, 1,2-dimethoxyethane, acetonitrile, Ethyl acetate, dimethylformamide, N-methyl-pyrrolidone, Phosphoric acid trisdimethylamide, dimethyl sulfoxide, acetone, butanone, methanol, ethanol, isopropanol.

The concentration of thiourea II in the used It is advisable to keep the solvent as high as possible, e.g. a concentration of 10 70 is used Percent thiourea II in the solvent.

In the case of volatile compounds of the formula III such as methyl chloride or ethyl chloride, can also be used in the closed Vessel can be worked under pressure.

You work with at least equimolar amounts of compound of the formula III, based on the thiourea II used, but preferably with an excess of 5 to 50 mole percent, preferably 5-30 mole percent of the component III. If the alkylation, alkenylation or cycloalkylation is difficult, a higher excess can also be used used and the compound of formula III can then be recovered. But it is also possible without Solvent in excess alkylating, alkenylating or cycloalkylating agents as solvents and diluents to work.

Le A 18 232 - 31 -

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.31-

The isothioureas of the general formula I according to the invention fall in the specified processes primarily in the form of their salts, depending on the particular compound of the formula III used for example as hydrochloride, hydrobromide, hydroiodide, methanesulfonate, p-toluenesulfonate, methosulfate, Sulfate etc.

In general, the work-up is neutralized with an aqueous base, for example soda solution, Potassium carbonate solution, dilute sodium hydroxide solution or other bases, the isothioureas according to the invention either as a solution in a water-insoluble solvent or solvent-free as viscous oils incurred under the aqueous phase. The rest of the work-up to the pure substances takes place according to the usual in methods well known in preparative organic chemistry.

Examples of isothioureas of the general formula I that can be prepared according to the invention are:

N-fa-Kethyl-o-fithyl-phonyiy-N ^ -tert.-butyl-S-uethyl-iaοthiourea

N- (2-methyl-6-ethyl-phcr.yl) -N ¹ -isopropyl-S-allyl-isothiourea

N- (2-methyl-6-th7l-phcnyl) -N "-cyclohoxyl-S-crotyl-isothiourea

N- (2-Methy1-6-Hthy1-phenyl) -N • -norbornyl-S-methyl-isothiourea

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N- (2 _f 6-diethyl-phenyl) -N ¹ -ieopropyl-

S-ricthyl-is ο thiourea N- (2,6-diethyl-phenyl) -N ¹ -butyl-Sr.ie thy 1-

isothiourea N- (2,6-diethyl-phenyl) -N ¹ -ock.-butyl-S-ethylisothiourea N- (2,6-diethyl-phony I) -N «-ic obu tyl -S-nc tliyl i isothiourea N- (2,6-diethylphenyl} -N ¹ -tert.-butyl-S-ne thy I- icοthiourea

N- (2,6-diethy1-phenyl) -N-penty1- (2) -S-ma thyI-

isothiourea

N- (2,6-diethylphenyl) -N'-pGntyl- (3) -S-nethyl-

ioothiourea K- (2,6-diethyl-phenyl) -N «-hoptyl- (2) -S-riethy 1-isothiohc \ rn3tof f N- (2,6-diethylphenyl) -N'-octyl- (2 ) -S-methy1-isothiourea N- (2,6-diethyl-phonyl) -N -cyclopropyl-S-alIyI-isothiourea N- (2,6-diethyl-phonyI) -N ¹ -cyclopentyl-S- Tnethylioothiohimstof f K- (2 _f 6-diethylphenyl) -N '- cyclohexyl -S -r.ethyli3othiour3toff N- (2, o-diethylphcr.yl) -N' - (3-trifluoroethyl cyclohexyl) - Sr. ethyl isothiourea

N- (2,6-diethyl-p: -. Onyl) ->; ^l ^ -ethyl-cyclohoxyl) -

S-tno thyl-iso thiourea * N- (2 _l 6-diethyl-phcnyl) -N ^l -cycloheptyl-S-ynethyl isothiourea

N- (2 _t 6-diethyl-phonyl) -N ^l -norbornyl-S-uethyl-

ieothiourea

Le A 18 232 - 33 -

809884/0112

N- (2 _f 6-diethyl-phenyl) -N ^l -bomyl-Sr.ethylisothiohamotoff N- (2,6-diethyl-phenyl) -N ^l -methyl-S-cyclohoxylieothiourea, N- (2-ethyl-6- ioopropyl-pher.yl) -N'-tort.-butyl-S-we thy l-isothioharii3t off N- (2-At ⁷ IyI-O-IcOPrOPyI-PhCHyI) -N'-pentyl- (2) -S- racthyl-isothiourea>! - (2-ethyl-6-isopropyl-phenyl) -N ^l -cyclohexyl-S-ethyl-isothiourea N- (2,6-diisopropyl-phenyl) -N »-ethyl-S-ethyli3 © thiourea N- (2,6-Diioopropyl-phei-Lyl) -N '-isopropyl-S-ricthyl-i3othiour.stoff f K- (2 _t 6-DiisoprOPyI-PhCiXyI) -N'-butyl-S-nethy 1 -isοthiourea: T- (2,6-diisopropyl-phc -.-. yl) -N ^l -sck.-butyl-S-riethyl-isothiourea N- (2,6-diisopropyl-phc-yl) -N '- isobutyl-S-methylisothiourea N- (2,6-DÜ3opropyl-phonyl) -K'-tert. -butyl-S-nethyl-ioοthiourea N- (2,6-diioopropyl-pher.yl) -N ¹ -pentyl-S-ncthylisothiourea K- (2,6-diisopropyl-phenyl) -N'-pentyl- (2) -S-ethyl-isothiourea N- ^ jo-diisopropyl-phcr yl) -N ¹ -pentyl- (3) S-ethyl-isothiourea IT- (2,6-diioopropyl-phcr.yl) -N «- (2- nothyl-butyl) -S-nothy1-isothiourea N- (2,6-diioopropyl-phenyl) -N • - (2,2-dinethyl-propyl) -S-n-ethyl-isothiourea

Le A 18 232 - 34 -

80988W0112

N- (2,6-diisopropyl-phenyl) -N ¹ -tcrt.-S -: - ι · ϊΐΐlyl_iΓ.othioll: ιrr.sto: ff N- (2,6-diioopropyl-phcnyl) -li ^l -hexyl- (2) -S-riothyl-isothioha-nstof f K- (2,6-diisooropyl-p'.isnyl) -N · -heptyl- (3) S-methy1.isothiourea N- (2,6-diieopropyl-phcr .yl) *. N "- (2,2,3, 3-totranethylbutylJ-S-methyl-isothiourea N- (2 _f 6-diioopropyl-phe: -. yl) -N '-cyclopropyl-S-crοty1-isothiourea N- (2,6-Diioopropyl-phcnyl) -N '-cyclopentyl-Sr: ethyl -is ο thiourea N- (2,6-diisopropyl-phosphor.yl) -N ¹ -cyclohoxyl-S-ethyl-i3Otliiohari'. otorf N- (2,6-diisopropyl-phoryl) -N «- (3-trifluoronothylcyclohoxyl) -Sr: nthyl-isothiourr.stoff f IT- (2,6-diisopropyl-phoryl) -N · - (3, 5-bis-trif luorne thy I-cyclohexyl) -S - ::: ethyl-ioothiohar: istoff K- (2,6-diisopropyl-phor.yl) -N '-cycloheptyl-6-r.iot] iyl-i3othiohc > .rr.otof f lI- (2,6-Diir.opropyl-phcny ^ -N '-norbornyl-S-nethylinothioharr.c fcof f

M- (2,5-diisopropyl-ph3: iyl) -N ^l -r'.othyl-S-cyclohoxylir · ο thiourea

N- (2-ioopropyl-6-scl: .- butyl-phonyl) -N '-tert, -bvityl-S-nothyl-icothiourea M- (2-ioopropyl-6-aelc.-butyl-phenyl) -N' -pcntyl- (2) -S-methyl-isothiourea Ϊ; - (2, 6 -Dis ek -buty 1-pheny 1) -K -is opropyl-Sr: et'nyl-isothiohar: istof f II- (2,6-di-sec-butyl-phenyl) - K «-propyl-S-nothyl-isothiourea

Le A 18 232 - 35 -

809884/0112

OR ₁ QiNAL INSPECTED

-fr -

N- (2,6-di-sec.-buty1-pheny1) -N'-see.-buty1-S-methy1-isothiourea N- (2,6-di-sec.-buty1-pheny1) -N'- tert-buty1-S-methy1-isothiourea N- (2,6-di-sec.-buty1-pheny1) -N'-penty1- (2) -S-methy1-isothiourea N- (2,6-di- sec-butyl-phenyl) -N'-hepty1- (3) -S-methylisothiourea N- (2,6-di-sec-butyl-phenyl) -N'-cyclopentyl-S-methylisothiourea N- (2, 6-di-sec.-butyl-phenyl) -N ¹ -cyclohexyl-S-methylisothiourea N- (2,6-di-sec.-butyl-phenyl) -N'-norborny1-S-methy1-isothiourea N- / 2,6-bis-pentyl- (2) -phenyl7 ^{l-N-isopropyl-S-methylisothiourea} N-Z2,6-bis-penty1- (2) JJ -phenyl-N'-see.-buty1-S-methy1 -isothiourea N- D., 6-bis-pentyl- (2) -pheny17-N'-tert-buty1-S-methy1-isothiourea N- (2-ethyl-6-sec-butyl-phenyl) -N '-tert.-buty1-S-methy1-isothiourea N- (2,6-dicyclopentyl-phenyl) -N'-isopropyl-S-methylisothiourea N- (2,6-dicyclopenty1-pheny1) -N'-tert.- butyl-S-methy1-isothiourea N- (2-Xthyl-6-cyclohexy1-pheny1) -N'-tert-buty1-S-methy1-isothiourea N- (4-methyl-2,6-diet hy1-pheny1) -N'-isopropy1-S-methy1-isothiourea

Le A 18 232 - 36 -

R,? q P P '. / 0 1 1

273062Ü

N- (4-methyl-2,6-diethyl-phenyl) -N-tert-butyl-S-methy1-isothiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-methy1- S-penty1-isothiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-propy1-S-cyclopentylisothiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-see. -buty1-S-methylisothiourea N- (4-methyl-2,6-diethyl-phenyl) -N ¹ -pentyl- (2) -S-methylisothiourea N- (4-methyl-2,6-diethyl-phenyl) - N'-heptyl- (3) -S-methylisothiourea N- (methyl-2,6-diethyl-phenyl) -N'-octyl- (2) -S-methylisothiourea N- (4-methyl-2,6-diethyl -phenyl) -N'-cyclopentyl-S-methylisothiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-cyclohexyl-S-methylisothiourea N- (4-methyl-2,6-diethyl-phenyl ) -N'-norbronyl-S-methylisothiourea N- (4-methyl-2,6-diethyl-phenyl) -N'-decahydronaphthy1- (1) -S-raethyl-isothiourea N- (4-methyl-2,6 -diisopropy1-phenyl) -N'-tert-butyl-S-methy 1-isothiourea N- (4-methy1-2,6-diisopropyl-phenyl) -N ¹ -pentyl- (2) -S-methyl-isothiourea N- (4-Methy1-2,6-diisopropyl-phenyl) -N'-isopropyl- S-methyl-isothiourea, N- (4-methyl-2,6-diisopropyl-phenyl) -N'-cyclohexyl-S-methyl-isothiourea

Le A 18 232 - 37 -

a η q? · ^R. 'ο ι ι

2V3U620

N- (4-Methy1-2,6-di-sec-buty1-pheny1) -N • -tert-butyl-S-methyl-isothiourea N- (2,4,6-triethyl-phenyl) -N'-methyl-S-crotyl-isothiourea

N- (2,4,6-triethyl-phenyl) -N'-methy1-S-cyclopenty1-isothiourea N- (2,4,6-triethyl-phenyl-N'-isopropy1-S-methy1-isothiourea N- ( 2,4,6-triisopropyl-phenyl) -N * -isopropy1-S-methy1-isothiourea N- (2,4,6-triethyl-phenyl) -N'-sec.-buty1-S-methy1-isothiourea N- (2,4,6-triethyl-phenyl) -N-isobuty1-S-methy1-isothiourea N- (2,4,6-triethyl-phenyl) -N'-tert-buty1-S-methy1-isothiourea N - (2,4,6-triethyl-phenyl) -N'-pentyl- (2) -S-methylisothiourea N- (2,4,6-triethyl-phenyl) -N -heptyl- (3) -S- methylisothiourea N- (2,4,6-triethyl-phenyl) -N ¹ -cyclohexyl-S-methylisothiourea N- (2,4,6-triethyl-phenyl) -N'-cyclohepty1-S-methy1-isothiourea N- ( 2,4,6-triethyl-phenyl) -N'-cycloocty1-S-methy1-isothiourea N- (2,4,6-triethyl-phenyl) -N '- (trifluoromethyl-cyclohexyl) -S-methyl-isothiourea N - (2,4,6-Triethyl-phenyl) -N-norborny1-S-methy1-isothiourea N- (2,4,6-triethyl-phenyl) -N'-bornyl-S-methylisothiourea

Le Ά 18 232 - 38 -

N- (4-propyl-2,6-diethyl-phenyl) -N'-ethyl-S-buty1-isothiourea N- (4-propyl-2,6-diethyl-phenyl) -N'-tert.-butyl- S-methylisothiourea N- (4-propyl-2,6-diethyl-phenyl) -N'-tert.-pentyl-S-methylisothiourea N- (4-propyl-2,6-diethyl-phenyl) -N '- ( 1,1-dimethylpropyl) -S-methyl-isothiourea N- (4-propyl-2,6-diethyl-phenyl) -N'-cycloheptyl-S-methylisothiourea N- (4-isopropyl-2,6-diethyl-phenyl ) -N'-tert-butyl-S-methylisothiourea N- (4-isopropyl-2,6-diethyl-phenyl) -N'-isopropyl-S-methylisothiourea N- (4-isopropyl-2,6-diethyl- phenyl) -N'-sec.-butyl-S-methylisothiourea N- (4-isopropyl-2,6-diethyl-phenyl) -N ¹ -cyclohexyl-S-methylisothiourea N- (4-isopropyl-2,6-diethyl -phenyl) -N'-bornyl-S-methylisothiourea N- (4-butyl-2,6-diethyl-phenyl) -N'-isopropyl-S-methylisothiourea N- (4-butyl-2,6-diethyl-phenyl ) -N'-sec.-butyl-S-methylisothiourea N- (4-butyl-2,6-diethyl-phenyl) -N'-tert-butyl-S-methy1-isothiourea N- (4-butyl-2 , 6-diethyl-phenyl) -N-cyclopentyl-S-met hylisothiourea N- (4-butyl-2,6-diethyl-phenyl) -N-norbornyl-S-methylisothiourea N- (4-sec-butyl-2,6-diethyl-phenyl) -N'-sec.- butyl-S-methyl 1-isothiourea

Le A 18 232 - 39 -

809884/01

te 273U62Ü

N- (4-sec-Buty1-2,6-diethy1-phenyl) -N'-tert-buty1-S-methyl-isothiourea N- (4-sec-Buty1-2,6-diethy1-phenyl) -N · -cyclohexy1-S-methy1-isothiourea N- (4-isobutyl-2,6-diethyl-phenyl) -N ^T -tert-butyl-S-methylisothiourea N- (4-isobutyl-2,6-diethy1 -phenyl) -N ¹ -cyclohexy1-S-methy1-isothiourea N- (4-isobutyl-2,6-diethy1-phenyl) -N'-norborny1-S-methy1-isothiourea N- (4-tert-butyl- 2,6-diethy1-phenyl) -N ¹ -isopropy1-S-methy1-isothiourea N- (4-tert-buty1-2,6-diethyl-phenyl) -N'-sec.-buty1-S-methy1- isothiourea N- (4-tert-buty1-2,6-diethy1-phenyl) -N'-tert-buty1-S-methy1-isothiourea N- (4-tert-buty1-2,6-diethy1-phenyl ) -N * -tert.-penty1-S-methy 1-isothiourea N- (4-tert-buty1-2,6-diethyl-pheny1) -N'-heptyl- (3) -S-methylisothiourea N- ( 4-tert-buty1-2,6-diethy1-phenyl) -N'-cyclohexyl-S-methy1-isothiourea N- (4-penty1-2,6-diethy1-phenyl) -N'-tert.-buty1- S-methyl-isothiourea N- (4-pentyl-2,5-diethyl-phenyl) -N ¹ -cyclopenty1-S-methy1-isothiourea N- (4-Pe ntyl-2,6-diethy1-phenyl) -N'-norborny1-S-methy1-isothiourea

Le A 18 232 - 40 -

809884/01 1

N- £ i-Pentyl- (3) -2,6-diethyl-phenyl7 ~ N'-isopropyl-S-methy1-isothiourea N-Z3-pentyl- (3) -2,6-diethylphenyl7 ~ N'- see-butyl-S-methylisothiourea N- / 3-pentyl- (3) -2,6-diethyl-phenyl7-N'-tert-butyl-S-methy1-isothiourea N-Zü-pentyl- (3) - 2,6-diethyl-phenyl7 "N'-pentyl- (3) -S-methylisothiourea N- / 4-pentyl- (3) -2,6-diethy1-pheny1 / -N ^r -cyclohexy1-S-methy1-isothiourea N- (4-Cyclopentyl-2,6-diethy1-pheny1) -N ¹ -tert-buty1-S-methy1-isothiourea N- (2,4,6-triisopropy1-pheny1) -N'-tert-buty1 -S-methyl-isothiourea N- (2,4,6-triisopropyl-phenyl) -N ¹ -pentyl- (2) -S-methylisothiourea N- (2,4,6-triisopropyl-phenyl) -N'-cyclopentyl -S-methylisothiourea N- (2,4,6-triisopropy1-pheny1) -N'-norborny1-S-methy1-isothiourea N- (2-ethyl-4-methyl-6-sec-butyl-phenyl) -N ¹ -tert-butyl-S-methy 1- isothiourea N- (2,6-dicyclohexy1-pheny1) -N ¹ -isopropy1-S-methy1-isothiourea N- (4-n-hexyl-2,6-diethyl- phenyl) -N'-tert-butyl-S-methylisothiourea N- (4-n-hexyl-2,6-diethyl-phe nyl) -N'-see.-butyl-S-methylisothiourea N- (4-cyclohexyl-2,6-diethyl-phenyl) -N ¹ -isopropy1-S-methy1-isothiourea N- (4-cyclohexyl-2,6 -diethyl-phenyl) -N'-see.-butyl-S-methy1-isothiourea

Le A 18 232 - 41 -

809884/0112

η-

273U620

N- (4-Cyclohexyl-2,6-diethyl-phenyl) -N -tert-buty1-S-methy1-isothiourea N- (4-Cyclohexyl-2,6-diethylphenyl) -N'-cyclopentyl- S-methylisothiourea N- (4-cyclohexyl-2,6-diethyl-phenyl) -N'-norborny1-S-methy1-isothiourea N- (4-cycloheptyl-2,6-diethylphenyl) -N · -tert. -buty1-S-methy1-isothiourea N- / 4- (1-methy1-cyclohexy1) -2,6-diethyl-phenyl) -N'-tert-buty 1-S-methy1-isothiourea N- (4-fluoro -2,6-diethyl-phenyl) -N'-tert-buty1-S-methy1-isothiourea N- (4-fluoro-2,6-diethyl-phenyl) -N'-cyclohexy1-S-methylisothiourea N- ( 3-methyl-2,6-diethyl-phenyl) -N'-tert.-butyl-S-methylisothiourea N- (3-chloro-2,6-diethyl-phenyl) -N'-tert.-butyl-S- methyl isothiourea N- (3,5-dimethyl-2,6-diethyl-phenyl) -N'-tert-butyl-S-methylisothiourea f N- (3-bromo-2,6-diethyl-phenyl) -N '-tert-butyl-S-methy1-isothiourea N- (4-fluoro-2,6-diethyl-phenyl) -N · -norborny1-S-methy1-isothiourea N- (3,4-dimethyl-2,6 -diethyl-phenyl) -N -tert.-buty1-S-methy1-isothiourea N- (2,5-dimethyl-6-ethy1- pheny1) -N'-tert-buty1-S-methy1- isothiourea N- ( 4-methyl- 2,6-diethylphenyl) -N'-adamantyl-S-methyl isothiourea

Le A 18 232 - 42 -

809884/0112

The active ingredients are suitable if they are well tolerated by plants and favorable dewblood toxicity, especially for combating animal species Pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector. You are against normally sensitive and resistant species as well as effective against all or individual developmental stages. To the above mentioned Pests include:

From the order of the Isopoda, for. B. Oniscus asellus, Armadilli-

dium vulgare, Porcellio scaber.

From the order of the Diplopoda, for. B. Blaniulus guttulatus. From the order of the Chilopoda, for. B. Geophilus carpophagus, Gcutigera spec. From the order of the Symphyla z. B. Scutigerella Immaculata. Aue of the order of the Thysanure z. B. Lepiama saccharine. From the order of the Collembcla, e.g. B. Onychiurus armatus. From the order of the Orthoptera z. B. leaf orientalis, Periplaneta americane, Leucophaea maderae, Blattella germenica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria

mlgratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, for. B. Forficula auricularie. From the order of the isopters e.g. B. Reticulitermes spp .. From the order of the Anoplure z. B. Phylloxere vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp. From the order of the Mallophaga, e.g. Trichodectes spp., Damalinea From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci. From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralie fabae,

Le A 18 2 32 - 4 3 -

809884/01 12

ff

Doralis pomi, Erdosoma lanigerum, Hyalopterus arundinis, Macroslphum 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 app., Psylla spp ..

From the order of the Lepidoptera, for. B. Pectinophora gosaypiella, Bupalus piniarius, Chelmatobia brumata, Llthocolletia blancardella, Hyponomeuta pad11a, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria βρρ., Bucculatrix thurberiella, Phyllocnistia citrella, Agrotia βρρ., Euxoa spp., Peltia spp., Earias insulana, Hellothis app., Laphygma exigua, Manestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichopluaia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraueta nubilalis, Epheatia kuehniella, Gallerla mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumifarena, CIysla ambiguella, Homona magnanima, Tortrlx vlridana. From the order of the Coleoptera, for. B. Anoblum punctatum, Rhizopertha dominlca, Bruchldlua obtactus, Acanthoscelldes obteetue, Hylotrupes bajulus, Agelastlca alni, Leptinotarsa decemllneata, Phaedon cochlearlae, Diabrotica spp., Psylllodea chrysocephala, Epllachna varlvestla, Atomaria spp., Oryzaephllua surlnamensls, Anthonomus spp., Sitophilus spp., Otiorrhynchua aulcatus, Cosmopolites aordldue, Ceuthorrhynchue assiBllis, Hypera poatica, Dermestes spp., Trogoderma βρρ., Anthrenue spp., Attagenus spp., Lyctus βρρ., Meligethes aeneus, Ptinus βρρ., Niptus hololeucue, Gibbium psylloldes, TriboliuB app., Tenebrio molitor, Agriotes spp., Conoderus βρρ., Melolontha melolontha, Amphimallon aolstitialis, Costelytra zealandica.

Aue of the order of the Hynenoptera e.g. B. Diprion βρρ., Hoplocaepa app., Laeius βρρ., Monomorium pharaonls, Veepa βρρ. From the order of the Dlptera e.g. Aedes spp .. Anopheles app., Culex spp., Drosophila melanogaster, Musca spp., Fannla app., Calliphora erythrocephala, Lucllia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus app., Tannla app ..

Le A 18 232 - 44 -

809884/0112

£ 0

Sibio hortulanus, Osc ^ nella frit, Phorbia sop./ Pego.-yia hyoscyani, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratcphyllus spp. . ' From the order of the Arachnida e.g. Scorpio maurus, Latrodectus nactans. From the order of the Acarina e.g. Acarus siro, Argas spp., Crnithodcros spp., Dermanyssus gallinae, Eriophyes ribis, Fhylloccptruta oleivora, Boophilus spp., Rhiplcephalus spp., Ar-.blyo.-L-a spp., Hyalonr.a spp., Ixodes spp., Psoroptes spp., Choricptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia

praetiosa, Panonychus spp., Tetranychus spp ..

The active ingredients according to the invention are used in Form of their customary formulations and / or the application forms prepared for these formulations.

The active ingredient content of the commercially available formulations prepared application forces can vary within wide ranges. The concentration of active ingredients in the application forms can vary from 0.0000001 up to 100 parts by weight of active ingredient, preferably between 0.01 and 10 wt. 96 are.

The application takes place in a form adapted to the application Usual way.

The active ingredients according to the invention are used Veterinary sector in a known manner, such as by oral application in the form of, for example, tablets, capsules, potions, granules, by dermal application in the form of, for example, the Dipping (dipping), spraying (spraying), pouring on (pour-on and spot-on) and powdering as well as by parenteral use in the form of, for example, injection.

Le A 18 232 _ 45 _

809884/0 1 1 2

ORIGINAL INSPECTED

27 306 2 CJ

The active ingredients can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, Granules, aerosols, suspension emulsion concentrates, seed poppers , Active ingredient-impregnated natural and synthetic materials, finest encapsulation in polymer materials and in coating compounds for Seeds, also in formulations with fuel charges, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.

These formulations are produced in a known manner, ζ.3. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents . The following liquid solvents are essentially : aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers are liquids that are gaseous at normal temperature and under normal pressure , e.g. aerosol propellants such as halogenated hydrocarbons

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hydrogen as well as butane, propane, nitrogen and carbon dioxide; as solid carrier materials: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silica, aluminum oxide and Silicates; as solid carriers for granulates: broken and fractionated natural rocks such as Calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well Granules of organic material such as sawdust, coconut shells, corn on the cob, and tobacco stalks; as emulsifying and / or foam-generating 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 dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose.

There can be adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular in the formulations or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate,

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo-metal phthalocyanine dyes, and Trace amounts of nutrients such as salts of Elsen, manganese, boron, copper, Cobalt, molybdenum and zinc can be used.

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

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SL

Example A Plutella test

Solvent: Emulsifier:

3 parts by weight 1 part by weight

D ime thyIformamide alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient is diluted with the stated amount of solvent and the stated amount of emulsifier the concentrate with water to the desired concentration.

With the preparation of active Cabbage leaves (Brassica oleracea) are sprayed dewy and staffed it with caterpillars of the diamondback moth (Plutella maculipennis).

After the specified times, the destruction is determined in % . 100 % means that all the caterpillars have been killed; 0 % means that none of the caterpillars have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in the following table :

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27 30 6 2 above

Tabel

(plant-damaging insects) Plutella test

Active ingredients

Active substance concentration degree of destruction in concentration in%% after 3 days

-NH-CS-

^ Nth.

CH. 0.1
0.01

80 0

(known)

C ₃ H ₇

C ₂ H ₅

NS.

VN = C-NH-C ₄ H ₉ - (tert.)

C ₂ H ₅

^C 2 ^H 5

NS

-NH-C-NH-C ₄ H ₉ (tert.

2 ^H 5

C ₂ H ₅

NS.

-N = C-NH-C ₃ H ₇ (ISO)

2 ^H 5 C ₂ H ₅

NS.

( HV ^ _ VN = C-NH-C ₄ H ₉ (see.

^: 2 ^H 5 ₃ H ₇ (iso)

SCH ₃ -N = C-NH-C ₃ H ₇ (iso)

C ₃ H ₇ (IsO)

0.1

0.01

0.1

0.01

0.1

0.01

0.1

0.01

0.1

0.01

100 100

100 100

100 100

100

100

100 100

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Table (continued) (insects which are harmful to plants) Plutella test

Active ingredients

Active ingredient concentration in%

Degree of destruction in % after 3 days

^C 3 H ₇ (iso) (tert.) 0 ,1 SCH ₃ 0 , 01 -N = C-NH-C ₄ H ₉

100 100

₄ H ₉ (sec.)

SCH ₃ N = C-NH-C ₄ H ₉ (tert.)

₄ H ₉ (sec.)

0.1 0.01 100 100

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Example B.
Tetranychus test (resistant)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which is strongly influenced by all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are infected, sprayed dripping wet.

After the specified times, the destruction is determined in % . In this case, _100%% means that all the spider mites have been killed; 0 % means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in the table below:

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Tabel

(plant-damaging insects) Tetranychus test

Active ingredients Active ingredient concentration Degree of destruction in concentration in%% after 2 days

- (' V-NH-CS-N

"CH.

CH-

(known)

C ₂ H ₅

SCH, C ₃ H ₇ -C ^ -N = C-NH-C ₄ H ₉ (tert.)

C ₂ H ₅ 0.1

0.01

0.1

0.01

60 0

100 100

C ₂ H ₅

SCH ₃ -N = C-NH-C ₄ H ₉ (tert.)

C ₂ H ₅ 0.01

100

100

2 ^H 5 SCH ₃

^ -N = C-NH-C ₄ H ₉ (see.)

C ₂ H ₅ 0.1

0.01

100 100

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Example C Mosquito larva test test animals: Ae * des aegypti

Solvent: 99 parts by weight of acetone Emulsifier: 1 part by weight of benzylhydroxydiphenyl

polyglycol ethers

To produce an appropriate preparation of active ingredient, 2 parts by weight of active ingredient are dissolved in 1000 parts by volume of solvent, which contains the emulsifier in the amount specified above. The solution obtained in this way is diluted with water to the desired lower concentrations.

The aqueous active ingredient preparations are filled into glasses and about 25 mosquito larvae are then placed in each glass.

The degree of destruction is determined in % after 24 hours. 100% means that all larvae have been killed, 0% means that no larvae have been killed at all.

Active ingredients, active ingredient concentrations, test animals and results are shown in the following table:

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Tabel

Mosquito larva test

Active ingredients Active ingredient concentration of the
Solution in ppm

Degree of destruction in%

Known;

Cl-

• -NH-CS-N

CH.

^ CH.

Erf Indungsgetnäß;

SCH ₃ CH ₃ N = C-NH-C-CH ₃ CH,

CH ₃ CH ₃

S-CH - CH = CH

N * C-NH-C-CH. CH,

CH ₃ CH ₃

CH, N =.

2 ^H 5

SCH-CH ' ³ • -N = C-NH-C-CH

C ₂ H ₅

3 CH, 10

10
1

10
1

100

100 90

100 90

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Table (continued) Mosquito larvae test

Active ingredients

Active ingredient concentration degree of killing concentration in% solution in ppm

CH.

CH.

CH-

C ₂ H ₅

SC ₂ H ₅ CH ₃ N = C-NH-C-CH,

H ^CH 3 2 ^H 5 100

CH.
ν.

CH-CH--

NS

-N = C-NH-C-CH ^CH 3 10 1

100 90

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Example D

Test animals: Sitophilus granarius and Blatta orientalis Solvent: acetone

2 parts by weight of active ingredient are used in 1,000 parts by volume Solvent added. The solution obtained in this way is adjusted to the desired concentrations with further solvent diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. A filter paper with a diameter of about 9.5 cm is located on the bottom of the Petri dish. The Petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m ^{2 of} filter paper is different. Then about 10 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The destruction is determined in%.

Active ingredients, active ingredient concentrations, test animals and results are shown in the table below:

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Table Ii) ₁₀₀ -Test

Active ingredients

Test animals

Active ingredient killing in%

centrations

% solution

Known:

Sitophilus granarius 0.2 Blatta orientalis 0.2

0 0

According to the invention:

SCH, CH, 3/3

: -nh-ch

CH,

SCH- CH. ! -NH-C-CH ₃ CH, Sitophilus granarius

Sitopnilus granarius
Blatta orientalis

0.2 0.02

0.02 0.02

100 90

100 100

SCH, CH, Sitopnilus 0.2 100 , 3/3
-N = C-NH-CH granarius 0.02 90 \
ΓΚ3

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Example E.

Test with parasitic adult beef ticks (Boophilus microplus res.)

Solvent: Cremophor

For the production of an appropriate preparation of the active substance the active substance in question is mixed with the specified solvent in a ratio of 1: 2 and diluted the concentrate thus obtained with water to the desired concentration.

10 adult beef ticks (B. microplus res.) Are immersed for 1 min. In the active compound preparation to be tested. After transferring to plastic beakers and storage in an air-conditioned room, the degree of destruction is determined in percent, with 100% meaning that all ticks and 0% that none of the ticks have been killed.

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Active ingredients

Active ingredient conc.
ppm

Killing effect in% Boophilus microplus res.

SCH ₃ CH ₃
NC-NH-C-CH. CH.,

300

100

30th

100

50

^C 2 ^H 5

SC ₀ H ₁ .

ί / Λ ' ⁵ f / \) -N = C-NH-

CH,, 3

C-CH CH., 1000
100

100 0

^C 2 ^H 5

SCH ₃ CH ₃ / ANC-NH-C-CH. 1000
100

100 0

C ₂ H ₅

SCH CH ₃ -NC-NH-C-CH, CH, 1000
100

100 0

^C , 2 ^H 5 CH ₃ 10OO 4ν f ^C 2 ^H 5 -C-CH ₃ 100 y-N = C-NH- CH ₃ ^ 2 ^H 5

100 0

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philus microplus

res.

C ₂ H ₅ ³ 2 ^H 5
I SCH ₃ CH ₃
^ Vn = C-NH-CH-CH ₂ -CH ₃ 1000
100 100
0 CH ₃ \\ - NC-NH-CC ₂ H ₅
L ^ ^H 3
C ₂ H ₅ = 2 ^H 5 1OOO
100 100
0 / ^CH - (
CH ₃ F2 ^H 5
I SCH _{3 / C} H ₃
VNC-NH-CH ₀ -CH
~] ^CH 3
C ₂ H ₅ 2 ^H 5 10OO
1OO 100
0 CH, (
- Ί C.

CH-,. 1 SCH, CH - CH-,

^ 3 if \ , 3/2 3

> CH-C y-N = C-NH-CH CH, ^ n CH "-CH,

1000 1OO

100 0

^C 2 ^H 5

C ₂ H ₅

SCH, CH.

-N = C-NH-CH-CH ₂ -CH _{2 -CH}

10OO 100

100 0

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Active ingredient conc. Killing effect in ppm% Boophilus micro plus res.

SCH ₃ CH ₃ N = C-NH-C-CH,

CH., 1000
100

1OO 0

SCH ₃ CH N = C-NH-C-CH.

1000
100

100 0

^C 2 ^H 5

SC ₂ H ₅ N = C-NH-

-CH. 1000
100

100 0

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Example F Test with parasitic fly larvae

Emulsifier: 80 parts by weight of Cremophor EL

To produce an appropriate preparation of the active compound, 20 parts by weight of the active substance in question are mixed with the stated amount of the emulsifier and the resulting mixture is diluted with water to the desired concentration.

About 20 fly larvae (Lucilia cuprina) are placed in a test tube filled with a cotton plug of the appropriate size, which contains about 3 ml of a 20% egg yolk powder suspension in water. 0.5 ml of the active ingredient preparation are applied to this egg yolk powder suspension. The degree of destruction is determined in% after 24 hours. 100% means that all and 0% that none of the larvae have been killed.

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Active ingredients

Active ingredient concentration ppm

Killing effect in% Lucilia cuprina

SCH, CH-W. ³ .3 ^ Vn = C-NH-C-CH.

CH. 1000 100

100 0

SCH ₃ CH- -N = C-NH-CC, H ₆ . CH, 1000 100

100 0

C ₄ H,

NS

CNH

-C-CH ₃ CH, 1000 100

100 0

ⁿ Vn = c-nh- ^ η

C ₂ H ₅

SCH ₃ CH ₃

-N = C-NH-C-CH.

C ₂ H ₅

CH. 1000 100

1000 100

100 0

100 0

CH

C ₂ H ₅

SCH ₃ CH ₃ -N = C-NH-C-CH.

C ₂ H ₅

CH. 1000 100

1OO 0

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Active ingredient

Active ingredient conc. Killing effects ^in%

ppm

cuprina

C ₂ H ₅

<Γ ^Η 3

-N = C-NH C-CH ₃

CH,

C ₂ H ₅

1000 100

100 0

C ₂ H ₅

SCH, CH,

N = C-NH-CC ₂ H ₅

CH, 1000 100

100 0

1000 100

100 0

C ₂ H ₅

SCH, CH, \\, 3,3 ^) - N = C-NH-CH-CH ₂ -CH 10O0 100

100 50

CH

CH-

SCH, CH ₀ -CH,, 3/2 3

-N = C-NH-CH

CH ₀ -CH,

C ₂ H ₅

100 10

100 0

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Active ingredient active ingredient conc. Killing effect in ppm in% Lucilia cuprina

2 ^H 5

SCH ₃ CH ₃

N = C-NH-C-CH.

CH.

C ₂ H ₅ 100 100

100

1000 100

100 0

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Example G

Test with parasitic mange mites (Psoroptes cunicull) Solvent: Cremophor

To produce an appropriate preparation of the active substance, the active substance in question is mixed with the specified solvent in a ratio of 1: 2 and the concentrate obtained in this way is diluted with water to the desired concentration.

About 10-25 mange mites (Psoroptes cuniculi) are placed in 1 ml of the active ingredient preparation to be tested, which has been pipetted into tablet nests of a thermoformed packaging. After 24 hours, the degree of destruction is determined in percent. 100% means that all mites and 0 \ that none of the mites have been killed.

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Active ingredients

Active ingredient conc. Killing effect in ppm in% Psorptes cuniculi

SCH ₃ CH ₃

N = C-NH-C-CH ι CH, 1
0.3

100 0

SCH ₃ CH ₃ N = C-NH-CC ₂ H ₅ CH ₃ 1
0.3

100 0

SC ₂ H ₅ CH ₃

N = C-NH C-CH,

CH ₃ 100

C ₂ H ₅

SCH ₃ CH ₃ -N = C-NH-C-CH.

CH.

2 ^H 5

1
0.3

100 0

CH

SC ₀ H,

1 *

CH

ι -N = C-NH C-CH

3 CH,

C ₂ H ₅

SCH ₃ CH ₃ -N = C-NH-CC ₂ H ₅ CH,

C ₂ H ₅

1OO

100

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Active ingredient conc. Killing effect in ppm in% Psoroptes cuniculi

NS.

SCH- CH, \\ .3.3

/ -N = C-NH-CH-100

100

CH-C yN = C-NH- ^ H }

CH, - ^

CH _q
^U 2 ⁵

^C 2 ^H 5

SCH, CH, W, 3, J ^X > -N = C-NH-CC ₂ H ₅

CH,

1OO

100

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2 7 3 υ 6 2 υ

Manufacturing examples example 1

N- (2,6-diisopropy1-pheny1) -N'-tert-buty1-S-methy1-isothiourea;

15.0 g of N- (2,6-diisopropyl-phenyl) -N'-tert-butyl-thiourea are dissolved in 30 ml of dimethylformamide and 10 g of methyl iodide are added at 50.degree. The reaction takes place exothermically with the temperature rising to about 70 ^° C. It is then left to stand for a further 16 hours and stirred with 500 ml of water and 100 ml of 15% strength soda solution. The oily precipitated isothiourea is taken up with methylene chloride, the extract is washed with water, dried over potassium carbonate, concentrated and completely freed from the solvent at 60 ° C./1.0 Torr. Yield 14 g of oil. The elemental analysis, NMR and IR spectrum are in agreement with the assumed constitution.

If you use the equivalent amount of dimethyl sulfate instead of methyl iodide or acetone instead of dimethylformamide Solvent, the same compound is obtained.

From the corresponding thioureas one obtains as in The example above indicated the following isothioureas:

N- (2,6-Diisopropy1-pheny1) -N'-tert-penty1-S-methy1-isothiourea

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N- (3-Isobuty1-2,6-diethy1-pheny1) -N'-tert-buty1-S-methy ΓΙ so thiourea N- (4-Isopropyl-2,6-diethy1-pheny1) -N'-tert-buty1-S-methy1-isothiourea N- (4-Isopropyl-2,6-diethy1-pheny1) -N'-tert-penty1-S-methy1-isothiourea N- (4-propyl-2,6-diethyl-phenyl) -N'-tert-butyl-S-methylisothiourea N- (2,6-diisopropy1-pheny1) -N'-isopropy1-S-methy1-isothiourea N- (2,6-Diisopropy1-pheny1) -N'-propy1-S-methylisothiourea N- (2,4,6-triethyl-phenyI) -N'-isopropy1-S-methy1-isothiourea N- (4-isopropyl-2,6-diethy1-pheny1) -N'-isopropy1-S-methylisothiourea N- (4-propyl-2,6-diethy1-pheny1) -N'-isopropyl-S-methylisothiourea N- (4-Buty1-2,6-diethy1-pheny1) -N'-isopropy1-S-methy1-isothiourea N- (4-pentyl- (3) -2,6-diethyl-phenyl) -N'-isopropyl-S-methyl-isothiourea

The compounds listed represent all non-distillable viscous at 20 ⁰ C liquids whose constitution was confirmed by elemental analysis, NMR and IR Spektrem.

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Example 2

N- (2,6-Diethyl-4-n-buty1-phenyl) -N '- (3,3-dimethyl-butyl) -S-methy! -Isothiourea

21.0 g of N- (2,6-diethyl-4-n-butyl-phenyl) -N ¹ - (3,3-dimethyl-butyl) -thiourea are dissolved in 40 ml of dimethylformamide at 50 ° C. and 10.0 g g methyl iodide added. After the exothermic reaction has subsided, the mixture is stored at 20 ° C. for a further hours. The mixture is then stirred with 500 ml of water and 100 ml of 15% strength sodium carbonate solution, the oily reaction product is extracted with methylene chloride, the extract is washed with water, dried over potassium carbonate, and freed from residual solvent at 60 ° C./1.0 Torr. Yield 18.0 g of oil.

The elemental analysis, NMR and IR spectrum are with in accordance with the adopted constitution.

The following isothioureas can be prepared analogously from the corresponding thioureas:

N- (4-Isopropy1-2,6-diethy1-phenyl) -N'-isobutyl-S-methy1-isothiourea

N- (4-Isopropy1-2,6-diethyl-phenyl) -N'-see-butyl-S-methylisothiourea

N- (4-isopropyl-2,6-diethyl-phenyl) -N'-pentyl- (3) -S-methy I- isothiourea

N- (4-Isopropyl- 2,6-diethy1-phenyl) -N ¹ -pentyl- (2) -S-methylisothiourea

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N- (4-Isopropy1-2,6-diethy1-pheny1) -N'-hepty1- (2) -S-methy1-isothiourea N- (4-propyl-2,6-diethy1-pheny1) -N'-hepty1 (2) -S-methy1-isothiourine tof f N- (2,4,6-triethy1-pheny1) -N-hepty1- (2) -S-methy1-i Sothiourea N- (4-butyl-2,6-diethy1-pheny1) -N'-heptyl- (2) -S-methylisothiourea N- (4-Cyclohexyl-2,6-diethy1-pheny1) -N'-sec.-butyl-S-methylisothiourea N- (4-pentyl- (3) -2,6-diethy1-phenyl) -N'-butyl-S-methylisothiourea N- (4-pentyl- (3) -2,6-diethy1-phenyl) -N'-isobutyl-S-methylisothiourea N- (4-pentyl- (3) -2,6-diethy1-phenyl) -N'-sec-butyl-S-methylisothiourea N- (4-pentyl- (3) -2,6-diethy1-pheny1) -N'-penty1- (2) -S-methy1-isothiourea N- (4-pentyl- (3) -2,6-diethy1-phenyl) -N • -tert.-penty1-S-methy1-i sothioharns tof f

All of the above compounds are non-distillable at 20 ° C, viscous liquids, the constitution of which has been confirmed by elemental analysis, NMR and IR spectra became.

Example 3

N- (2,6-di-sec-buty1-phenyl) -N'-cyclopentyl-S-methylisothiourea

19.0 g of N- (2,6-di-sec.-buty1-phenyl) -N ¹ -cyclopenty1-thio-

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urea are dissolved in 40 ml of dimethylformamide at 50 ° C. and 10.0 g of methyl iodide are added. After subsiding The exothermic reaction is left to stand at 20 ° C. for a further 24 hours. The batch is then mixed with 500 ml of water and 100 ml of 15% sodium carbonate solution and stirred the deposited oily reaction product with methylene chloride recorded. The extract is washed with water, dried over potassium carbonate, concentrated and at 60 ° C./1.0 torr freed from solvent. Yield 16.0 g of oil. The elemental analysis as well as the NMR and IR spectrum are in agreement with the assumed constitution.

If one replaces the methyl iodide by the equivalent amount of methyl bromide and works as indicated, one obtains the same connection.

Analogously, from the corresponding thioureas the following connections are made:

N- (2,6-di-sec-buty1-pheny1) -N'-tert-butyl-S-methy1-isothiourea

N- (4-pentyl- (3) -2,6-diethy1-pheny1) -N'-cyclopentyl-S-methylisothiourea

The listed isothioureas represent viscous liquids whose constitution has been determined by elemental analysis, NMR and IR spectra have been secured.

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Example 4

N- (2,6-Dilsopropy1-pheny1) -N'-tert-buty1-S-ethy1-isothiourea

15.0 g of N- (2,6-diisopropyl-phenyl) -N'-tert-butyl-thiourea are dissolved in 30 ml of dimethylformamide at 50 ° C. and 7.7 g of ethyl bromide are slowly added. Thereafter the batch is held at 50 ° C. for a further 6 hours. The mixture is then stirred with 500 ml of water and 100 ml 15% soda solution and takes up the oily reaction product deposited with methylene chloride. The received Solution is washed with water, dried over potassium carbonate, concentrated and freed from residues of solvent at 60 ° C./1.0 Torr. Yield 12.0 g of UI.

If, in the above example, the equivalent amount of propyl bromide is used instead of ethyl bromide, N- (2,6-diisopropyl-phenyl) -N'-tert-butyl-S-propyl-isothiourea is obtained. Similarly, with allyl bromide, N- (2,6-diisopropy1-phenyl) -N'-tert-buty1-S-allyl-isothiourea is obtained; with crotyl bromide the N- (2,6-diisopropy1-phenyl) N'-tert-butyl-S-crotyl-isothiourea; with methallyl bromide to N- (2,6-Diisopropy1-phenyl) -N'-t-buty1-S-methallyl-isothiourea. The S-alkyl-isothioureas form viscous UIe in all cases. The constitutions were confirmed by elemental analysis, NMR and IR spectra.

The following isothioureas can be prepared analogously from the corresponding thioureas:

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N- (2,4,6-Triäthy1-pheny1) -N'-tert-butyl-S-ethyl isothiourea N- (4-isopropyl -2,6-diethyl-phenyl) -N'-tert-butyl- S-äthyli so thiourea N- ( 4-isopropyl- 2,6-diethyl-phenyl) -N'-tert-pentyl-S-ethylisothiourea N- (4-propyl-2,6-diethyl-phenyl) -N ' -tert.-buty1-S-ethyl isothiourea N- ( 4-methy 1-2,6-diethyl-phenyl) -N * -tert.-buty1-S-allyl isothiourea N- (4-methy1-2 , 6- diethyl-phenyl) -N -tert.-penty1-S-ally1-isothiourea N- (2,6-di-sec.-buty1-pheny1) -N'-tert.-buty1-S-methyl isothiourea N- ( 2,6-diisopropy1 -pheny1) -N'-propy1-S-ethy1- isothiourea

Example 5

N- (2,6-diethy1-pheny1) -N'-tert-buty1-S-methy! -Isothiourea

26.0 g of N- (2,6-diethyl-phenyl) -N'-tert-butyl-thiourea are dissolved in 25 ml of dimethylformamide at 50 ° C. and 17.0 g of methyl iodide are added in proportions. When the exothermic The reaction is complete, the mixture is left to stand at 20 ° C. for a further 16 hours. Then the batch with 5OO ml of water and ml of 15% soda solution stirred, the oily reaction product was taken up with methylene chloride and the extract with Water washed. It is dried over potassium carbonate and concentrated, and the solvent is removed at 60 ° C./1.0 torr.

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Yield 26 g of oil. Elemental analysis, NMR and IR spectrum are in accordance with the adopted constitution.

Analogously, one obtains from the corresponding thioureas the following isothioureas:

N- (4-methyl-2,6-diethyl-phenyl) -N'-tert-butyl-S-methylisothiourea

N- (4-Methy1-2,6-diethy1-pheny1) -N'-tert-penty1-S-methy1-isothiourea

The compounds are viscous liquids, their constitution by elemental analysis and NMR and IR spectrum was secured.

Example 6

N- (2, e-Diethyl-4-pentyl- (3) -phenyl) -N'-cyclohexy1-S-methy1-isothlourea

18.0 g of N- (2,6-diethyl-4-pentyl- (3) -phenyl) -N ^l -cyclohexylthiourea are dissolved in 20 ml of dimethylformamide at 50 ° C. and 8.5 g of methyl iodide are added. After the exothermic reaction has subsided, the mixture is stored at 20 ° C. for a further 20 hours. The batch is then stirred with 500 ml of water and 100 ml of 15% strength sodium carbonate solution, the oily reaction product is taken up with methylene chloride and the extract is washed with water. It is dried over potassium carbonate, and the solvent is removed completely by evaporation at 60 ⁰ C / 1.0 Torr. Yield 16 g of oil.

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The elemental analysis as well as the NMR and IR spectrum correspond of the adopted constitution.

In an analogous manner, from the corresponding thioureas the following isothioureas are produced:

N- (4-isopropyl-2,6-diethyl-phenyl) -N ¹ -cyclohexyl-S-methylisothiourea N- (4-isopropyl-2,6-diethyl-phenyl) -N ¹ - (3-tri fluorine thy 1 -cyclohexyl) -S-methyl-isothiourea N- (4-butyl-2,6-diethyl-phenyl) -N'-cyclohexy1-S-methy1-isothiourea N- (4-butyl-2,6-diethylphenyl) -N'-cycloheptyl-S-methylisothiourea

The compounds are viscous liquids whose constitution is determined by elemental analysis, NMR and IR spectrum was secured.

Example 7

N- (2,4,6-triethyl-phenyl) -N'-norbornyl-S-methyl-isothiourea f

21.0 g of N- (2,4,6-triethyl-phenyl) -N'-norbornyl-thiourea are dissolved at 60 C in 25 ml of dimethylformamide and 11g Methyl iodide added. After the exothermic reaction has subsided, the mixture is stored at 20 ° C. for a further 16 hours. Thereafter

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the mixture is poured into 500 ml of water and 100 ml of 15% strength Soda solution and takes up the oily reaction product in methylene chloride. The extract phase is washed with water, dried over potassium carbonate, concentrated and freed from residues of solvent at 60 ° C./1.0 torr. yield 20.0 g of oil.

Elemental analysis, NMR and IR spectrum are with the assumed Constitution in accordance.

In an analogous manner, the following isothioureas can be prepared from the corresponding thioureas:

N- (4-Isopropy1-2,6-diethyl-pheny1) -N'-norborny1-S-methy1-isothiourea

N- (4-Propy1-2,6-diethy1-phenyl) -N'-norborny1-S-methylisothiourea

N- (4-Butyl-2,6-diethy1-phenyl) -N'-norbornyl-S-methylisothiourea

N- (4-Isobutyl-2,6-diethy1-phenyl) -N • -norbornyl-S-methylisothiourea

N- (4-tert-Buty1-2,6-diethyl-pheny1) -N'-norbornyl-S-methylisothiourea

N- (4-pentyl- (3) -2,6-diethy1-phenyl) -N'-norborny1-S-methy1-isothiourea

Because that used for the synthesis of the thioureas Norbornylamine was a mixture of endo- and exo-forms, the isothioureas obtained as end products are also mixtures. The compounds represent viscous oils the constitution of which was confirmed by elemental analysis, NMR and IR spectrum.

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Production of starting compounds: Example 8 N- (2,6-diethyl-phenyl) -N'-isobutyl-thiourea

15, Og 2,6-diethyl phenyl isothiocyanate are introduced into 20 g of isobutylamine at 20 ° C. and left to stand for 12 hours . Thereafter, the mixture is stirred with excess dilute hydrochloric acid until the reaction product, which initially precipitates as an oily, crystallizes. It is filtered and washed neutral with water. The filter cake is then rubbed evenly with methanol, water is added, suction filtered and dried. From booty 19.0 g; F: 68-70 ° C.

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

Analogously, from the corresponding 2,6-diethylphenyl 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 ^l -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 ' -hepty1-thiourea N- (2,6-diethyl-phenyl) -N -dodecyl-thiourea F: 12O-123 ° C N- (2,6-diethyl-phenyl) -N'-methally! -thiourea F: 65-68 ° C

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The starting product 2,6-diethyl-phenylisothlocyanate can be prepared as follows: 100 g of 2,6-diethylaniline in 200 ml of methylene chloride are stirred at 0-5 ° C to a mixture of 5OO ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 92 g of thiophosgene were added dropwise. The mixture is then heated to reflux until the evolution of _{CO 2 has ended.} The cooled batch is filtered, the methylene chloride layer is separated off, dried with calcium chloride and fractionated. Yield 112 g; Bp 101-103 ° C / 1.4 Torr.

Example 2 N- (4-methyl-2,6-diethyl-phenyl) -N'-neopentyl-thlourea

15.0 g of 4-methyl-2,6-diethyl-phenyl isothiocyanate are introduced into 9.0 g of 2,2-dimethyl-propylamine at 20 ° C., whereby exothermic reaction occurs. After 12 hours, the mixture is stirred with excess dilute hydrochloric acid, filtered and washed with water and dilute methanol and dry. Yield 21 g; F: 106-1O7 ° C.

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

The following can be prepared analogously from 4-methyl-2,6-diethylphenyl isothiocyanate and the corresponding aliphatic amines Thioureas are made:

N- (4-methyl- 2,6-diethyl-phenyl) -N ¹ -butyl-thiourea N- (4-methyl -2,6-diethyl-phenyl) -N-isobutyl-thiourea

F: 60-61 ° C N- (4-methyl -2,6-diethyl-phenyl) -N ¹ -methallyl-thiourea

f: 86-88 ° C

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4-methyl-2,6-dlethyl-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 are added dropwise at 0-5 ° C. to a mixture of 500 ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 92 g of thiophosgene with stirring. It is then heated under reflux until the evolution of CO 2 has ended. After cooling, the batch is filtered off from solids, the methylene chloride layer is separated off, dried over calcium chloride and fractionated.
Yield 110 g; Bp: 113-116 ° C / 1.2 Torr.

Example 10 N- (2,6-diisopropyl-pheny?) -N -isobuty! -Thiourea

15.0 g of 2,6-diisopropyl phenyl isothiocyanate are used in 20 ° C entered in 20.0 g of isobutylamine. The reaction is exothermic; it is left to stand for 12 hours and stirred then with excess dilute hydrochloric acid. The reaction mixture which has precipitated out in crystalline form is filtered off with suction, with water and dilute methanol and dried.

Yield 19.0g; F: 108-112 ° C.

Elemental analysis and NMR spectrum correspond to the assumed constitution.

Similarly, from 2,6-diisopropyl-phenyl isothiocyanate and the corresponding aliphatic amines the following thioureas are produced:

N- (2,6-diisopropyl-pheny1) -N'-propyl-thiourea F: 1O6-1O7 ° C N- (2, 6-diisopropyl-phenyl) -N '-buty1-thiourea N- (2,6- Diisopropyl-phenyl) -N ¹ - (3-methyl-butyl) -thiourea

F: 64-68 ° C, N- (2,6-diisopropyl-phenyl) -N'-pentyl- thiourea F: 76-83 ° C

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N- (2 _r 6-diisopropyl-phenyl) -N'-neopentyl-thiourea

F: 150-155 ° C

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

The starting product 2,6-diisopropyl-phenylisothiocyanate can be prepared as follows:

100 g of 2,6-diisopropyl aniline in 200 ml of methylene chloride are added dropwise at 0-5 ° C. with stirring to a mixture of 300 ml of water, 500 ml of methylene chloride, 120 g of calcium carbonate and 78 g of thiophosgene. It is then heated under reflux until the evolution of CO _{2 has} ended. After cooling, it is filtered, the methylene chloride layer is separated off, dried over calcium chloride and fractionated. Yield 110 g; Bp: 144-148 ° C / 11 torr.

Example 11 N- (2,6-di-sec-butyl-phenyl) -N'-methallyl-thiourea

15.0 g of 2,6-di-sec-butyl-phenyl isothiocyanate are introduced into 12.0 g of methallylamine at -10 ° C. The mixture is allowed slowly to +20 ⁰ C and are kept 12 hours at 20 ° C. The batch is then stirred with excess dilute hydrochloric acid, and the crystalline reaction product is filtered off with suction, washed with water and dilute methanol and dried. Yield 20.0 g; F: 69-72 ° C.

The following thioureas can be prepared analogously from 2,6-di-sec-butyl-phenyl isothiocyanate and the corresponding aliphatic amines:

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N- (2,6-di-sec-buty1-pLenyl) -N • -propy! -Thiourea

F: 85-87 ° C

N- (2,6-Di-sec-butyl-phenyl) -N • -allyl-thiourea

F: 83-86 ° C

N- (2,6-di-sec-butyl-phenyl) -N'-butyl-thiourea

F: wax N- (2,6-di-sec-butyl-phenyl) -N'-isobutyl-thiourea

F: 83-85 ° C

N- (2,6-di-sec-butyl-phenyl) -N-pentyl-thiourea (oily)

N- (2,6-di-sec-butyl-phenyl) -N-neopentyl-thiourea

F: 88-90 ° C N- (2,6-Di-sec-butyl-phenyl) -N'-dodecyl-thiourea (oily)

The starting product 2,6-di-sec-butyl-phenyl isothiocyanate can be prepared as follows:

100 g of 2,6-di-sec-buty1-aniline in 200 ml of methylene chloride are stirred 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 were added dropwise. The mixture is then heated under reflux until the evolution of CO. Has ended. After this Cooling is filtered off from the solids, the methylene chloride layer is separated off and dried over calcium chloride and fractionated: yield 112 g, boiling point: 117-12O ° C / 1.0 torr.

Example 12 N- (4-methyl-2 _f 6-diisopropyl-phenyl) -N'-isobutyl-thlourea

15.0 g of 4-methyl-2,6-diisopropyl-phenyl isothiocyanate are introduced at 20% into 20 g of isobutylamine and the exothermic reaction is moderated by cooling. It is left to stand for 12 hours

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and then stirred with excess dilute hydrochloric acid. The reaction product which has crystallized out is filtered off, washed with water and dilute methanol and dried. Yield 18.0 g; F: 150-153 ° C.

Analogously, from 4-methyl-2,6-diisopropyl-phenyl isothiocyanate and the corresponding aliphatic amines the following thioureas are produced:

N- (4-methyl-2,6-diisopropyl-phenyl) -N ^l -butyl-thiourea

F: 126-129 ° C N- (4-methyl-2,6-diisopropyl-phenyl) -N ¹ -propyl-thiourea

F: 125-127 ° C

From 4-methyl-2,6-di-sec-butyl-phenyl isothiocyanate and Isobutylamine is obtained analogously

N- (4-methyl-2,6-di-sec-buty1-pheny1-N'-isobutyl-thiourea F: 98-1O2 ° C

with n-butylamine

N- (4-methyl-2,6-di-sec-buty1-pheny1) -N • -butyl-thiourea

F: 97-1OO ° C

4-methyl-2,6-disopropyl-phenylisothlocyanate can be prepared as follows:

150 g of 4-methyl-2,6-diisopropyl-aniline in 200 ml of methylene chloride are added dropwise at 20 ° C. to a stirred mixture of 500 ml of methylene chloride, 300 ml of water, 120 g of calcium carbonate and 110 g of thiophosgene. It is then heated under reflux until the _{evolution of CO 2 has} ended. Solids are filtered off from the batch, the methylene chloride layer is separated off, dried over calcium chloride and fractionated. Yield 159 g solidifying oil; Bp: 124-126OC / 1.2 torr.

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Analogously, 4-meth / l-2,6-di-sec-butyl-aniline and Thiophosgene obtained 4-methyl-2,6-di-sec-butyl-phenyl isothiocyanate with a boiling point of 130-132 ° C./1.2 Torr.

Example 13 N- (3-methyl-2,6-diethyl-phenyl) -N'-neopentyl-thiourea

15.0 g of 3-methyl-2,6-diethyl phenyl isothiocyanate will be entered at 20 ° C in 9.0 g of 2,2-dimethyl-propylamine. The mixture is left to stand for 12 hours and then stirred with excess dilute hydrochloric acid. That crystallized out The reaction product is filtered off with suction, washed with water and dilute methanol and dried. Yield 20.0 g; F: 102-104 C. Elemental analysis and NMR spectrum are in agreement with the assumed constitution.

Similarly, from 3-methyl-2,6-diethyl-phenyl isothiocyanate

and MethaiIylamin der

N- (3-methyl-2,6-diethyl-phenyl) -N · -methallyl-thiourea

F: 105-106 ° C;

obtained; from 3,5-Dimethy1-2,6-diethyl-phenylisothiocyanate and n-butylamine der N- (3,5-Dimethyl-2,6-diethyl-phenyl) -N'-butyl-thiourea

F: 108-110 ° C;

from 3-chloro-2,6-diethyl-phenyl isothiocyanate and n-butylamine the N- (3-chloro-2,6-diethyl-phenyl) -N ¹ -butyl-thiourea

F: 108-110 ° C;

with 2,2-dimethyl-propylamine der N- (3-chloro-2,6-diethyl-phenyl) -N'-neopentyl-thiourea

F: 106-110 ° C;

from 2-ethyl-6-isopropyl-phenyl isothiocyanate and methallylamine the N- (2-ethyl-6-isopropyl-phenyl) -N · -methallyl-thioharnetoff

F: 50-55 ° C

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from 2,4,6-triisopropyl-phenyl isothiocyanate and methallylamine the N- (2,4,6-triisopropyl-phenyl) -N'-methallyl-thiourea

F: 115-118 ° C.

The aryl isothiocyanates can be prepared from the arylamines and thiophosgene as indicated in the previous examples:
3-methyl-2,6-diethyl phenyl isothiocyanate; Kp: 110-113 ° /

1.5 Torr 3,5-dimethyl-2,6-diethy1-phenyl isothiocyanate:

Bp: 119-127 ° C / 1.2 Torr [p: 118-1 , 2 torr bp: 104-1.2 torr 130-1.2 torr.

Example 14 N- (2,6-diisopropyl-phenyl) -N'-methyl-thiourea

3-chloro-2,6-diethyl-phenyl: isothiocyanate; Bp: 118-121 ° C / 2-ethyl-6-isopropyl-phenyl isothiocyanate; Bp: 1O4-1O6 ° C / 2,4,6-triisopropyl phenyl isothiocyanate; Bp: 130-132 ° C /

120 g of 2,6-diisopropyl aniline are dissolved in 100 ml of triethylamine and 53 g of methyl isothiocyanate are added. The formation of thiourea is slightly exothermic. The mixture is stirred for 12 hours, excess dilute hydrochloric acid is added, the mixture is filtered, washed with water and dilute methanol and dried. Yield 142 g; F: 167-168 ° C.

The following thioureas are obtained analogously from methyl isothiocyanate and the corresponding aniline derivatives:

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N- (2,6-diethyl-phenyl) -N ¹ -methyl-thiourea F: 103-105 C _N _ (4-methyl-2,6-diethyl-phenyl) -N * -methyl-thiourea

F: _{97-100 ° C N} _ (2-methyl-6-ethyl-phenyl) -N'-methyl-thiourea

F: 65-67 ° C

N- (2,4-Dimethyl-6-ethyl-phenyl) -N ¹ -methyl-thiourea

F: 125-126 ° C

Example 15 N- (2,6-di-sec-butyl-phenyl) -N'-tert-butyl-thlourophene

20.0 g of 2,6-di-sec-butyl-phenyl isothiocyanate are dissolved in 20.0 g of tert-butylamine and the batch is kept at 20 ° C. for 12 hours. It is then poured into dilute hydrochloric acid, the reaction product is filtered off, washed neutral and dried.

Yield 25.0 g; 9-6 % d. . Th P: 115 to 117 ⁰ C

Obtained analogously from 2,6-di-sec-butyl-phenyl isothiocyanate

and tert-pentylamine N- (2,6-di-sec-buty1-pheny1) -N'- tert-pentyl-thiourea with a temperature of 116-118 ° C.

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From 2-ethyl-6-sec-butylphenyl isothiocyanate and tert-butylamine the connection

N- (2-ethyl-6-sec-butyl-phenyl) -N-tert-butyl-thiourea from a melting point of 96-99 ° C;

from 2-ethyl-6-sec-butyl-phenylisothiocyanate and tert. Pentylamine the compound N- (2-ethyl-6-sec-butyl-phenyl) -N-tert-pentyl-thiourea from melting point 74-76 ° C;

from 2-isopropyl-6-sec-butyl-phenyl isothiocyanate and tert-butylamine the compound N- (2-isopropyl-6-sec-butyl-phenyl) -N-tert-butyl-thiourea f from melting point 121-123 ° C;

from 2-isopropyl-6-sec-butyl-phenyl) isothiocyanate and tert. Pentylamine the compound N- (2-isopropyl-6-sec -butyl-phenyl) -N · -tert-pentyl-thiourea with a melting point of 51-53 ° C

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Example 16

N- (2,6-diisopropyl-pheny1) -N'-tert-butyl-thiourea

15 g of 2,6-diisopropyl-phenyl isothiocyanate are introduced into 25 g of tert-butylamine and stored at 20 ° C. for 12 hours. It is then poured into dilute hydrochloric acid, filtered, washed and dried.
Yield 17g, mp: 135-137 ° C.

Example 17 N- (2,6-diisopropyl-phenyl) -N'-tert-pentyl-thiourea

11.0 g of 2,6-diisopropyl-phenyl isothiocyanate and 10 g of tert-pentylamine are heated to 100 ° C. with 5 ml of triethylamine for 10 minutes. After standing for 12 hours, the partially auskristllisierte mixture is stirred with petroleum ether, cooled to -10 ⁰ C, filtered and dried. Yield 14.0 g; F: 134-135 ° C.

By reacting 15.0 g of 2,6-diisopropyl-phenyl isothiocyanate with 9.0 g of 1,1,2,2-tetramethyl-propylamine in 10 ml of triethylamine, as described above, the N- (2,6-diisopropyl- phenyl) -N '- (1,1,2,2-tetramethyl-propyl) -thiourea , m: 161-162 ° C.

Example 18 N- (2,6-diethy1-phenyl) -N'-tert-butyl-thiourea

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20 g of 2,6-diethyl phenyl isothiocyanate are dissolved in 20 g of tert-butylamine registered. It is cooled in such a way that 40 ° C. is not exceeded. After 3 hours it is diluted with Stirred hydrochloric acid, suction filtered the crystalline reaction product, washed neutral and dried. Yield 28.0 g; F: 98-100 ° C.

If the tert-butylamine in the above example is replaced by the same amount of tert-pentylamine and if the procedure is as indicated, N- (2,6-diethylphenyl) -N'-tert-penty! -Thiourea is obtained ; F: 85-87 ° C.

Example 19 N- (2,6-di-sec-butyl-phenyl) -N'-isopropyl-thiourea

15.0 g of 2,6-di-sec-butyl-phenyl isothiocyanate are introduced into 20 g of a 65% strength aqueous solution of isopropylamine with cooling. After stirring for 3 hours at 20 ° C., the batch is stirred into dilute hydrochloric acid, the reaction product which has precipitated in crystalline form is filtered off with suction, washed neutral, the paste is triturated with 50% strength methanol, suctioned off again and dried.
Yield 17.0 g; F: 108-111 ° C.

If you replace the isopropylamine in the above example with 15.0 g of see-butylamine and work as indicated, you get the N- (2,6-di-sec-butyl-phenyl) -N'-see-butylamine thlourea;
F: 103-105 ° C

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By reacting 2,6-diethyl-phenyl isothiocyanate with isopropylamine according to the above process is obtained N- (2,6-diethyl-phenyl) -N'-isopropyl-thiourea from F: 108 to 110 ⁰ C; with see-butylamine the N- (2,6- diethyl-phenyl) -N'-see-butyl-thiourea from F: 98-80 ° C

Example 20 N- (2-methyl-6-ethyl-phenyI) -N ¹ -tert.-penty! -Thioureas

15 * 0 ς 2-methyl-6-ethyl-phenylsothlocyanate are introduced into 20.0 g of tert-pentylamine with cooling. After 2 hours it will the batch is stirred into dilute hydrochloric acid, the reaction product is filtered off with suction, triturated with 50% methanol, filtered off with suction and dried. Yield 19.0g; F: 78 - 8l ° C.

In the above example, the tert-pentylamine by the replacing the same amount of tert-butylamine, the result is N- (2-methyl-6-ethyl-phenyl) -N'-tert-butyl-thiourea; F: 9-4-96 ° C.

2-methyl-6-ethyl-phenyl-sothiocyanate can be prepared as follows:

100 g of 2-methyl-6-ethyl-anlline in 200 ml of methylene chloride are added dropwise at 0-5 ° to a mixture of 500 ml of methylene chloride, 500 ml of water, 120 g of calcium carbonate and 103 g of thiophosgene. The mixture is then refluxed until the evolution of CO _{2 has} ended. Solids are then filtered off, the methylene chloride layer is separated off, dried over calcium chloride and fractionated. Yield 121 g; Bp: 88-91 ° C / 1.0 Torr.

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Example 21

N- (4-Methy1-2.6-diethy1-pheny1) -N'-tert-butyl-thiourea

15 # 0 g of 4-Methy1-2, e-diethyl-phenyl-isothlocyanate are under Cooling registered in 20.0 g of tert-butylamine. The mixture is stirred for 2 hours, poured into dilute hydrochloric acid, filtered, washed and dries. Yield 18.0 g; F: 121-12} ° C.

If you replace the tert-butylamine in the above example with the same amount of tert-pentylamine and work as indicated, you get the N- (4-methyl-2,6-dlethylphenyl) -W-tert-pentyl-thlourea , F: 98-101 ⁰ C.

Similarly, N- (2,4-dimethyl-6-ethyl-phenyl) -N'-tert is obtained from 2, Jt-dimethyl-6-ethy 1-phenylisothiocyanate and tert-butylamine. buty! -thiourea , F: 130 - 132 ° C, and from the same subst. Phenylsothiocyanate and tert-pentylamine N- (2,4-dimethyl-6-ethyl-phenyl) -N * -tert-penty! -Thiourea , temperature: 105-107 ° C.

The 2,4-dimethyl-6-ethy1-phenylsothlocyanate used as the starting compound above can be prepared according to the following procedure:

100 g of 2,4-dimethyl-6-ethylaniline in 200 ml of methylene chloride at 0 - 5 ⁰ C was added dropwise to a mixture of 500 ml methylene chloride, 300 ml water, 120 g of calcium carbonate and 92 g of thiophosgene with stirring. The mixture is then heated to reflux until the evolution of CO _{2 has} ended. After cooling, the batch is filtered off from solids, the methylene chloride layer is separated off, dried over calcium chloride and fractionated; Yield II8 g, boiling point 101-1O4 ° C / 1.5 Torr.

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Example 22

4-cyclohexyl-2,6-dlethyl-phenyl isothiocyanate

231 g of 4-cyclohexyl-2,6-diethyl aniline in 300 ml of methylene chloride are added to a suspension of 600 at 10-15 ° C ml of methylene chloride, 500 ml of water, 200 g of calcium carbonate and 140 g of thiophosgene were added dropwise. Then you heat to the Boil until the evolution of gas has ceased. The cooled batch is filtered off from solids, the methylene chloride layer dried over calcium chloride and fractionated; Bp 175-179 ° C / 1.5 torr; Yield 251g.

The following Arylisothiocyana: e can be prepared analogously from the corresponding aniline derivatives:

2,4,6-triethyl-phenylisothi.ocyanate; Bp 128-130 ° C / 1.3 Torr 4-n-propyl-2,6-diethyl-phenyl isothiocyanate;

Bp 132 4-isopropyl-2,6-diethylphenyl isothiocyanate;

Bp 13C 4-n-butyl-2,6-diethylphenyl isothiocyanate;

Bp 150 4-isobutyl-2,6-diethylphenyl isothiocyanate;

Bp 133 4-tert-butyl-2,6-diethylphenyl isothiocyanate;

Kp 2, e-Di-cyclopentyl-phenyl isothiocyanate;

Bp 4-methyl-2,6-dicyclopenty1-phenyl isothiocyanate;

132-137 ° C / 1.5 Torr

130-132 ° C / 1.3 Torr

Bp 150-155 ° C / 2, O Torr

133-136 ° C / 1.4 Torr

130-133 ° C / 1.8 Torr

Bp 165-158 ° C / 1.3 Torr

Bp 188-195 ° C / 2, O Torr

Le A 18 232 - 93 -

809884/0112

CfQ .

2,6-di-pentyl (2) phenyl isothiocyanate; 148-152 ° C / 1.4 Torr 4-methyl-2,6-di-sec-buty1-phenyl isothiocyanate;

Bp 130-132 ° C / 1.2 torr 2-methyl-4,6-di-tert-butyl-phenyl isothiocyanate;

Bp 135-139 ° C / 1.5 Torr 3-methyl-2,6-diethyl-phenyl isothiocyanate;

Bp 110-113 ° C / 1.0 Torr 3-chloro-2,6-diethyl-phenyl isothiocyanate;

Bp 118-121 ° C / 1.2 Torr 3,4-dimethyl-2,6-diethyl-phenyl isothiocyanate;

Kp 125
3,5-dimethyl-2,6-diethyl-phenyl isothiocyanate;

Bp 119-127 ° C / 1.0 Torr 4-methyl-2-ethyl-6-sec. -but.y 1-phenyl isothiocyanate;

Bp 126-128 ° C / 1.5 Torr 4-methyl-2,6-diisopropyl-phenyl isothiocyanate;

Bp 124-126 ° C / 1.2 Torr 2-isopropyl-6-sec-butyl-phenyl isothiocyanate;

Bp 125-130 ° C / 1.2 Torr

Bp 115-117 ° C / 1.0 Torr 2,4,6-tri-isopropyl-phenyl isothiocyanate;

Bp 130-132 ° C / 1.2 torr of 2-ethyl-6-isopropyl-phenyl isothiocyanate;

Bp 104-1O6 ° C / 1.2 torr 4- / pentyl- (3L7-2,6-diethylphenyl isothiocyanate;

Bp 147-149 ° C / 1.2 Torr

The 2,6-disubstituted aniline derivatives required as starting material for the synthesis of the aryl isothiocyanates
can according to the in Angew. Chemie Vol. 69, p. 124 ff (1957)
described method are produced.

Le A 18 232 - 94 -

809884/01 12

Example 23

4-cyclohexyl-2,6-diethyl aniline

300 g of 4-amino-cyclohexylbenzene, 5.0 g of aluminum granules and 17 g of anhydrous aluminum chloride are heated to 250 ° C. in a steel autoclave and ethylene is injected to an internal pressure of 200 atmospheres. After the pressure has dropped, ethylene is pumped in until the uptake has ended; Duration approx. 7 hours. After cooling, the mixture with 500 ml of benzene, 3OO ml 40% sodium hydroxide solution and 500 ml of water for 15 minutes at 40 - 50 ⁰ C stirred, separated, the benzene phase, washed with water, dried over potassium carbonate and fractionated. Bp 148-150 ° C / 0.8 torr; Yield 318g.

The following aniline derivatives can be prepared in a similar manner:

2,4,6-triethyl aniline; Bp 89-91 ° C / 0.6 torr 4-n-propyl-2,6-diethyl aniline; Bp 10 ° C / 1.4 torr 4-isopropyl-2,6-diethyl aniline; Bp 103-1O5 ° C / 2, O torr 4-n-butyl-2,6-diethyl aniline; Bp 117-118 ° C / 2, O Torr 4-isobutyl-2,6-diethyl aniline; Bp 97-99 ° C / 0.7 torr 4-tert-butyl-2,6-diethyl aniline; Bp 89-91 ° C / 0.6 torr

2-ethyl-6-isopropyl aniline; Bp 127-128 ° C / 16 Torr 2-isopropyl-6-sec-butyl-aniline; 136-143 ° C / 13 torr 3-methyl-2,6-diethyl aniline; Bp 132-133 ° C / 2O Torr 3-chloro-2,6-diethyl aniline; Bp 145-148 ° C / 15 Torr 3,4-dimethyl-2,6-diethyl aniline; Bp 147-148 ° C / 15 Torr

Le A 18 232 - 95 -

809884/011?

40ή '

3,5-dimethyl-2,6-diethyl aniline; Bp 146 - 154 ° C / 15 torr,

F: 47-5O ° C

4-methyl-2,6-diisopropyl aniline; Bp 141-143 ° C / 16 Torr 4- / pentyl- (3) / - 2,6-diethyl aniline; Bp 106-1O7 ° C / 1.2 Torr

Example 24 2,6-Bls- (pentyl- (2)) aniline

170 g of aniline, 5 g of aluminum granulate and 15 g of anhydrous aluminum chloride are heated to 300 ° C. in a steel autoclave and 300 g of pentene (1) are pumped in over a period of about 5 hours to an internal pressure of 300 atmospheres. The batch is then held at 300 ° C. for a further 6 hours, the internal pressure falling to 107 atmospheres. After cooling the autoclave with 500 g of benzene, 250 ml of 40% i <Jer sodium hydroxide solution and 300 ml of water for 15 minutes at 30 - 40 ⁰ C stirred, washing the benzene layer with water, dried over potassium carbonate and fractionated. 113 g of 2-monopentyl- (2) -aniline are obtained. Bp 78-82 ° C / 0.6 torr and 131 g of 2,6-bis-pentyl- (2) -aniline, bp 168-174 ° C / 1.5 torr.

Analogously, 2-cyclopentylaniline is obtained from aniline and cyclopentene; Bp 102-1O9 ° C / 1.7 torr and 2,6-di-cyclopentyl-aniline; Bp 159-165 ° C / 1.5 torr; from p-toluidine and cyclopentene

4-methyl-2-cyclopentyl aniline; Bp 104-1O6 ° C / O, 7 torr and 4-methyl-2,6-dicyclopentyl-aniline; B.p. 157-158 ° C / 0.38 torr; from p-toluidine and butene- (1)
4-methyl-2-sec-butyl aniline; Bp 72 ° C / 1.0 torr and

Le A 18 232

- 96 -

809884/0112

273062U

4-methyl-2,6-di-sec-butyl-aniline; Bp 121-128 ° C / 3.0 O Torr. Aniline and butene- (1) give 2-sec-butyl-aniline analogously; Bp 109-111 ° C / 13 Torr and 2,6-di-sec-butyl-aniline; Bp 145-147 ° C / 13 Torr. Tonsil K is obtained from o-toluidine and isobutene 6-methyl-2,4-di-tert-butyl-aniline as a catalyst at 200 ° C. and 200 atmospheres; Bp 101-103 ° C / 1.1 Torr.

The compounds represented according to the invention of the general Formula (I), all of which are oily substances, can be given by the following NMR and IR data are characterized:

The individual abbreviations in the tables of the NMR values mean

S = singlet
D = doublet
T = triplet
Q = Quaternett
M = multiplet

Le A 18 232 - 97 -

809884/01 12

(α; co

Ι «) (b)

₍ α / (X)

CM _x -CM _{3 C} gj

CO CC)

Shift

ppm NMR in CDCl-

Multiplicity assignment

intensity

0.75

0.15

0.9 - 1.9

2.35

1.9-2.7

3.0-3.5

4.15

6.75

T T M S Q M M S S

IR: 2955, 1615, 1456, 868 cm

-1 bV superimposed 23

c)

d)

eV superimposed 8

g 2

h 1

i 2

te

CM ₃ -CH ₂ ,

/ CW ₃ (J.) -NH CH ₂ -CH

CC)

Shift NMR in CDCl ₃ Multiplicity Assignment intensity 23 ppm 0.8 T ä \ 0.85
1.15 1.9 D.
T Overlaid 8th 0.9 - 2.7 M. dj 1.9 - M. €) 2 2.4 S. fy overlaid 1 2.45 Q ύ 2 3.08 T H 4.25 M. i 6.78 S. j

IR: 2955, 1615, 1455, 868 cm

-1

Le A 18 232

- 98

809884/0112

(f> (b)

(β)

.0 -NH

O)

I »)

(ο pk W) (a;

Shift NMR in CDCl ₃ Multiplicity Assignment intensity 27 ppm 0.75 T ¹ p 1.15
1.4 2.2 T
S. Hüber camps 8th 0.9 - M. el) 2.15 S. e) 1 2.45 2.9 M. f / superimposed 2 2.3 - M. qj 4.0 S. H 6.73 S. i

IR: 2959, 1625, 1455, 1122, 868 cm

(al

-1

CH ₃

NH — Crf — CH ₂ C9; erf)

Shift

ppm NMR in CDCl3.

Multiplicity assignment intensity

0.6 - 2.8

3.5-4.0

T D T M S Q M S a b c d e f

IR: 3370, 1616, 1595, 1456, 1279, 689 cm

approx.

approx.

2 2

Le A 18 232

-

809884/0112

ήθ ζ

C ^: —NH — Crt -

CO

(ccj ca;

Shift

ppm NMR in CDCl3.

Multiplicity assignment intensity

0.77 0.80 1.15 O, 7 to 2.9 2.38 2.42 3.5 6.75

4.1

T D T M 3 Q 3 S

away

c d

e f

IR: 3370, 1610, 1590, 1452, 1280, 1150, 871 cm

" ¹

approx.

approx.

cc) ta)

Cc) 0>) ca)

Shift NMR in CDCl ₃ Multiplicity Assignment intensity ppm 1.2 0.9 - T + D I a 'χ 18 2.6 3.5 M. b ~ 4 2.9 - M + DMF C. "S 6 + DMF 4.2 7.2 wide d 1 7.0 + M. e 3

IR: 3380 (NH, 780, 730 (aromatic 1,2,3-trisubst. Possible).

1670 (-N = C

Le A 18

-

809884/01

^{CH3 ί9)}

Shift
ppm

CH ₁ -Cl ₃

(f) W)

Multiplicity

Assignment

intensity

NMR: (in CDCl,)

1.17 ^J T Ia

2.23 D b

1.0-2.0 M c

2.0 - 2.4 M d

2.38 S e

2.46 Q f

2.6-3.1 M g

3.3 - 3.8 M h

4.0 D i

6.88 S k

IR: 1615 cm "I = C = N band

876 cm = 1,2,3,5-tetrasubst.

(f) (bi

CH ₃ VCc) / f / XH -CH ₁

6 6 8 2 3 4 1 1 1 2

C3) (in CDCl,) 2.0 * · 'CH ₂ -CM ₃ Assignment intensity j 2.4 if) Of) Shift Multiplicity ppm I a 6th NMR: 3.9 b 6th 0.89 D. C. 8 + 1 1.16 T d 2 1.0 - M. e 3 2.1 - M. f 6th 2.38 S. G 1 2.43 Q H 1 3.3 - M. i 2 4.0 D. 6.81 S.

IR: 879 cm "! = 1,2,3,5-tetrasubst.
1615 cm "= C = N band

Le A 18 232

- 101

809884/01 12

AO I *

(9)

Assignment

intensity

HMR:

(CDCl ₃ )

0.78 1.18 1.0-2.2 2.33 2.0-2.7 approx. 2.4-3.1 3.1-4.0

ό, * 73

IH:

871 cn " ¹ 1610 cm-1

ca) cc)

T Ia

T b

M c

S d

M e

ti f J

M g

M h

S i

1,2,3,5-tetrasubst C = N-band Le) (b)

Shift ppm

te) O>

Multiplicity

Assignment

intensity

NMR:

(in CDCl ₃ )

0.78 T Ia

1.16 · T b

1.2-2.0 M x c

2, AO S d

2.1-2.3 Q e

2.4-3.0 M f

3.7-4.3 MS g

6.77 S h

IR:

871 cn " ¹ s 1,2,3,5-tetrasubst.

1610 cn-1 = C = N band

Le A 18

-

809884/0112

-AOg ' 273U62G

C a) O>

CH3 ia \

CH ₃ ^ i

Shift ppm

Multiplicity

Assignment

intensity

(in cdci ₃ )

0.7-1.3

1.2-2.0

2.37

2.45

3.6-4.2

6.66

M S

-1

IR: 1615 cn = C = Ni> other a
b
c

e
f

15 2 3 6 2 2

(«0 ca!

Cc) SCH ₃

■ C- NH

Shift ppm

Multiplicity

Assignment

intensity

NMR: (in CDCl ₃ )

0.8-1.3 M.

1.3-2.0 M.

2.37 S

2.1-2.8 M.

3.5-4.1. M.

4.15 D

6.84 S.

Si

f
β

IR: 868 cm " ¹ = 1,2,3,5-tetrasubst.

1595 cm ~ l or 1615 cm " ¹ = C = N band

25th

1 1 2

Le A 18 232

- 103 -

809884/0112

ic) ta)

CH ₂ -CH ₃

Shift ppm

Multiplicity

Assignment

NMR in CDCI

intensity

0.55-1.4 2.33

2Λ5
2.5-3.1
3.S-4.2
6.69

IR: 874 cn " ¹ cn-1

Q M M S

1,2,3,5-tetrasubst. 'CaM gang a b c d

e f

18 3

(W CH ₃ -CH _x -CH ₂ -CH ₂

CB ₃ CH ₃ GS)

Shift multiplicity

ppm NMR in CDCl, Assignment

intensity

0.7-1.4

l.C-2.0

2.37

2.44

3.7-4.2

6.86

M M S Q M S

-1

a b c d

e f

IR: 1615 cn "* = CsS band

cm " ¹ s 1,2,3,5-tetrasubst.

19th

3 6 2 2

Le A 18 232

- 104 -

809884/0112

-AIO 273U62U

SCH ₃ I.

'C — Μ «·

Shift ppm

Multiplicity

Assignment

intensity

r: (in cdci ₃ )

88 T

17 / 1.18 D / D

C-I, 8 M

A2 p

7-3, A M

C-A, 3 M

9-7.2 M.

755 cn "* u

1612 approx

772 cn

s C = N-Eande away

c d

e f

s 1,2,3-Trisubst.

12 2 3 A 1 3

Shift (in Multiplicity M. ppm , A S. NMR: CDCl ₃ ) Q 0.9-1 M. 2.38 , 3 M. 2, A3 »5 S. 3.7-A 3,9-A 6.88

Assignment

intensity

a b c d

e f

IR: 87A cm " ¹ s 1,2,3,5-tetrasubst. 1615 cn-1 s C = N band

15 3 6

1 2

Le A 18 232

- 105 -

809884/0

Jt / dt

¹ CU ₂ TCHz

Shift Multiplicity ppm NMR: (in CDCl,) 1.2 ³ Q ₊ I 1.4 S. 2.2 s 2.2-2.9 M. 4.1 S. 6.8 S.

CW ₃ CH ₃

Assignment

intensity

away c d e f

12 9 3

> 1 2

IR: 3450 (NH), 875, 895 (aromatic 1,2,3,5-tetrasubst.)

CH ₃ ^ CfI ₃

Shift ppm

Multiplicity

Assignment

Intensity

NMR: (in CDCl ₃ )

1.17 / 1.18 D / D

2.38 S

2.6-3.2 M.

3.6-4.1 M.

3.9 D

6.9-7.2 M.

I a b

c d e f

.

2 1 1 3

IR: 697 ca "1 or 755 cm" 1 and 767 cm " ¹ * 1,2,3-Trisubst. 1580 co" * or 1610 cm " ¹ s CsN band

The compound contains approx. 5% dimethylformamide.

Le A 18 232

- 106 809884/0112

CO ca)

H = G Ν «C-CH ₃ IW

Shift U. approx ? Cl: Multiplicity D. Assignment intensity ppm U. 1.2
1.5 U. +
HCO
X X
CMCM I a
b > 24 2.5 5 , 2 2 χ Q C. V ^ λ 2.9 7th , 0 (2x?) D. d / *** Ö 4.1 8th , 0 2 χ p e ~ 1 6.8 2 χ p f 2 7.5 2 χ p G

IR: 3440, 3360, 3160 (NH), 880 (aromatic 1,2,3,5-tetrasubst. )

These data can be assigned to structure I , which exists in two tautonic structures.

R ₁ -NC-NH-R ₃

f ²
R ₁ - NH - C - N - R ₃ . ,

(b> (ei; i> /

₍ b) C ^ "LT * - ™ * f ^c " 3 fb cc «ι

^N CH-f V-hJ5 =? C-NH C-CH _Z - CHa

Assignment intensity

Ia " 3

b / * Ί7

c 2

d 3

e / w 5

f * Ί

g 2

h <1

IR: 3460, 3370 (NH), 875 (Aronat. 1,2,3,5-Tetraubst.).

The compound contains approx. 3O% dimethylformamide. Le A 18 232 - 107 -

Shift Multiplicity ppm NMR <"* Cl
0.9 T 1,1-1, A S + D + T 1.8 Q 2.2 S. 2.2-2.7 M. 2.9 DMF S. 6 ^ 8 S. 7.9 S DMF

273Q62Ü

t) (9) (β) Cc)

Shift Multiplicity CDCl, Assignment intensity pp-Ti ³ τ NMR in s 1.2 D. I a 12th M. b 9 D. C. Λ * 4 3.0 S. d 2 3.3 M. e 2 4.4 S. f 1 5.6 G 2 7.0 H 3

IR: 3390 (NH), 755 (aromatic 1,2,3-trisubst.).

ta) _CeC;

CH ^ -CIf ₃
Ce) (A) (9; intensity Shift Multiplicity Assignment ppm KKR in CDCl ₃ 6th 0.8 - 1 .2 T I a 6th 1.19 D. b 8th 1.1-2.4 M. C. 3 2.31 S. . d 5 2.0-2.7 M. e 1 2.6-3.1 M ' t 1 3.2-4.0 M. G 1 4.0 D. H 2 6.81 S. i

1615 cnu - C ■ N band

871 cm _V "1,2,3,5-tetrasubst.

3370 cm " ^x o. 4450 cm" ^x - NH gang

Le A 18 232

- 108 -

A4 (j

it) C

Shift ppm

Multiplicity

Assignment

Cä;

intensity

17.3. in CDCl Shift 3 T I a 3 intensity 0.90 ppm T b 6th 1.15 S. C. 6th Q d 2 1.35 S. e 3 2.19 S. ¹ f 3 2.23 Q G 4th 2.43 3 H 1 4.0 S. i 2 6.30 IR . 871 cn »" ¹ - 1,2,3,5-tetrasubst . 555 cm " ¹ o. ■ C = N band 1625 cn-1 » «NK gang 3460 cn " ¹ . Cl _{3 v} / CK ι j (ei ) t $) S S-CH _x - CH = - CiI ₃ c » ^LC} X I .1 * 1 NH-C-CV ₃ Cb; ca) v.aj W CH ₃ Multiplicity Assignment

NHR (in CDCl ₃ )

1.11 / 1.23 D / D 'Ia

1.46 S b

3.02 septet c

3.38 D d

4.4 S e

5.1-5.5 M f

5.70 T (split) g

7.04 M h

IR

12 9 2

2 1 2

1 1

1,2,3-trisubst

605 and 761 cm " ¹ ■ 1625 cn" ¹ »C = N band

3420 ca " ¹ - NH band Le A 18 232 - 109 -

809084/011?

Ui ca? CK ₃ X «3

π «

■ Ν-

-λ 4 S-

co

SCM ₃ I.

• NH CH ₃ (W

Shift ppm

Multiplicity

Assignment

Intensity

1.2 1.5 2.2 3.0 4.1 7.0

S S

Sept. SS a
bcd

e f

~ 12 9 3 2

1 3

IR: 3460, 3370 (NH), 800, 760 (aromatic 1,2,3-trisubst.)

co

Q (Z-CW ₃ (d) ca) Shift Multiple quotation ppm NMR (in CDCl ₃ ) 1.17
1.47
2.18
2.50
4.1
6.94 T
S.
S.
Q
S.
S. IR; • 1620 cm ■ ON band . 3450 ca · NH band Le λ 18 232

CH ₃

NH - C - CH ₃ O) CH ₃

Assignment

lntonsitit

a b

e f

6 9

1 3

- 110 -

809884/0112

273062Ü

Cc)

SCM ₃ ι

Shift
ppm

Multiplicity

CH

I CH ₃

Assignment

intensity

NMR: (in CDCl ₃ ) 1.IS/1.21 T

2.1S 2.48

5.87

Ia b

e f

9 9

1 2

IH:

he. " ¹
cc-1

1,2,3,5-tetrasubst, CsM-bond

CH ₃

Shift
ppm

Multiplicity assignment

intensity NICR: (in CDCl ₃ )

Ö, SO D

1.18 T

1.43 S

1.2-2.0 M.

2.20 S

2, AO D

2.49 Q.

4.1 p

6.80 p

IR:

approx. 660 cm

1620 approx

Le A 18 232

Ia b c

β f

Hi

1,2,3,5-tetrasubate C = N bond

Θ0988 /; 6 6 9

1 3 2

^k l 2

Ä = c— -m - ο —c% -

Cl ₃

Shift ppm

Multiplicity

Assignment

intensity

NMR in CDCl- 0.6-1.5

1.0-2.3

2.2

approx. 2.95

4.0

7.0

Li

lh

SWEET

a) 21

£ j superimposed 5

ά) 2

e) 1

U) 3

-1

13: 3460 (3H), 2955, 1623 (C = N), 1U5, 760 cm 1'Si LI ⁺ 320, 273, 272 (LI-KSCH ^), 187 (bp), 145.

ca) (W (♦) (W

(9) f /> - N

¹ ^ r

(W

Shift Multiplicity Assignment intensity (6) ppm superimposed (18) NMR in CDCI superimposed (5) 0.31 ³ T 1.15
1.0-2.3 D.
K W. 2.35-2.45
approx. 2.5 S ¹ S
LI approx. 4.02 LI 7.0 Li a b J

-1

IR: 3330 (ITH), 2958, 1614, 1582, 1275 cm ' HSj IT 346, 300, 283, 270, 214, 201, 145, 69.

Le A 18 232

0 9

- 112 -

/ 0 11?

273062U

Shift
ppm

<- ³⁾ (et) (f J CW

Multiplicity

Ce? 5C%. CJf ₃

CN «C CiZ ₃ Lc)

C9J CiI ₃

Assignment

intensity

KI-R;

(in CDCl ₃ )

T D S M S M S S

IR: 890 cm ■ 3450 cm " ¹ '"

I a

I b

I c

I d

I e

I f

I g I h

1,2, Γ », 5-tetrasubst, NH band

25th

u) (J) (f; i ^hl r CJ * 2-CH _Z

Cfc)

it. C N «

'C-CUa Cc) 1 * CW ₃

Shift ppm

Multiplicity

Assignment

intensity

1.05
• 1.17 1.4f
1.1 -

2.19
2.47

■, ■ I

1.46
¹ 1-2.9

Q S S

4.06
6.33

IR: 3455 (IiK) ₁ 2958, 1521, 1457, 1125 cm "' ¹ .

b c

d e

g (h

superimposed

9 approx.

3 6

Le A 18 232

- 113

n 9 « / 01

(a)

CH ₃

CK

MH-Of - CH ₁ -C * 2 " ^CH 3 (d) koC) (a) ca) (a;

Shift multiplicity

ppm NMR in CDCl ₃

Assignment IntensitSt I a 22nd b 7th C. r-l d 2 e 2

0.9-1.4 M. 2.4 Q-i-S 2.8 M. 3.9 wide 6.9 S.

IR: 3450, 3370 (NH), 875 (aromatic 1, 2 , 3 , 5-tetrasubst.)

Shift Multiplicity Assignment intent ppm IMR in CDCl i + D 0.9-1.2 Q-i-S I a ν ZQ 2.4 M. b ~ 9 3.8 S. C. ~ 2 6.8 d 2

IR: 3460, 3370 (NH), 875 (aromatic 1,2,3,5-tetrasubst.)

Le A 18 232

- 114 -

109884/0112

-ΛΧΟ -

273Ü620

Cfc

IR: 1620 cm " ¹ - C - N bond

670 cm " ¹ ■ 1,2,3,5-tetrasubst.

Shift multiplicity assignment intensity

ppm

KKR: (in CDCl ₃ )

1.16 T Ia>

1.48 S Ib

2.19 S Ic ..

2.25 S Id> 10

2.45 Q Ie ^

4.1 S If 1

6.8 S Ig 2

IR: 882 cm. 1,2,3 »5-tetrasubst. 3450 cm " ¹ - NH band

Le A 18 232 - 115 -

909884/0 1 12

ie)

{, €) W

-crt

Shift Multiplicity Assignment ppm NMR (in
0.8 CDCl ^ I a 1.2 T b 1.3 O C. 1.9 M. d 2.3 Q + S e 2.6-3.1 M. f 4.2 S. G 6.3 S. H

intensity

1 8 4

1 2

IR: 3390 (NH), 880 (1,2,3,5-aromatic tetrasubst.)

XH ₂ -

Approx

-CH

U)

ti)

Shift
ppm (in CDCl
, 6 Multiplicity Assignment intensity NMR
0.8 ^ P, T, D, M I a * < 21 2.3 S + Q I b <w 9 2.9 M. I c Λ / 2 6.8 S. I d 2

IR: 3460, 3370, (NH), 875 (aromatic 1,2,3,5-tetrasubst.)

Le A 18 232

- 116 -

B09884 / 0112

-AWj -

- ~ ^c " ³

- * C - NH

CM

te) L >>

Multiplicity

Assignment

273062U UJ

intensity

(in CDCl ₃ ) cm " ¹ - T te) (b) Multipticity I a / 26 (b) 0.90 cm - M. CU ₂ -CH ₃ b CH ₃ 0.90 - 1.50 M. (e) ce / * L-4 C. 3 0.90 - 1.50 S. d 4th ifl c «w 2.37 Ca) (c) Q CH ₂ -CH ₃ e 1 2.46 CH ₃ -Cii _: M. C «) (W . £>
X 1 intensity 2.5-3.1 M. G 1 3.5-4.1 S. H 2 3.9 S. i 6.83 IR 1,2,3,5-tetrasubst. 872 ON-end 1612 U) S-CH ₃ C NH- (S) Assignment Shift ppm

KMR Hn CDCl ₃ )

0.8-1.0

1.0-1.4

1.0-2.0

2.37

2.47

3.5-4.1

3.9

6.86

M M M S Q M S S

away

e f β h

27

6 1 1 2

IR 364 cm

1615. C "" - ¹ Le A 18 232

• 1,2,3,5-tetrasubst. ■ C * N band

- 117 -

809884/01 1

S-CH3 CH3

Cl ₃ - CI ₂ T ^ VM- £ NH-CIf - (CHO-CH ₃

Cf) C-O (b) C *)

Shift Multiplicity T
M.
S.
Q
M.
S.
S. Assignment intensity ppm NMR (in CDCl 3) = N band 0.68
1.0-1.5
2.37
2.46
3.5-4.1
3, SO
6.87 , 2,3,5-T «trasubst I a
b
C.
d
e
f
G > 23
6th
1
1
2 IR 1618 cn " ¹ - C. 871 ca " ¹ - 1,

S-CH ₃ C-

(9) (ft ( ^c )

Shift Multiplicity M. - 118 - Assignment intensity ppm M. NMR (in CDCl ₃ ) M. 0.8-1.0 S. I a 1.0-1.4 Q b 1 25 1.0-2.0 M. C. 2.37 S. d 3 2.47 S. e 6th 3.5-4.1 f 1 I ' ⁹ "C" N band £ ■ 1 6.86 H 2 IR 1615 cm " ¹ . Le A 18 232

809884/01 12

Cfc-CH I « ζ / NH- Multiplicity CDCl, J CK) (8th) 2730620 intensity I. 9-Cl \ ³ τ Ka-cH ssCHi it ' S. • S. α / 3 6th (C) j ι CH ₃ -Ci ₃ Q C - GM; 3 I » 9 [d) (Λ) D. CH ₃ 3 S. Assignment> Shift K 2 ppm Vi 1 NIlR in S. I a 2 1.2 b 1 1.4 C. 2 2.5 d 2.4 e 3.3 f 4.3 G 5.2 H 5.8 i 6.3

IR: 3430 (NH), 865 (aromatic 1,2,3,5-tetrasubst.).

(«3 CC? Cc) C ·)

Shift ppm

Muttiplitit

Assignment

NMR (in CDCl ₃ )

T T M S Q M D S

I a b c d

e £ S

IR

1615 cm " ¹ - CN band

.-1

862 ca I, 2,3t5-Tetra3ubet.

Le A 18 232

- 119

809884/0112

Shift WW «
C ₁ HS _s _ _c T U Ib) intensity ppm t \ ·
^f VtJ = C- M. I.
- * N Π "C" * ^ * "iij" "~ t / H ^ M. Ch) U) ^) C * J lO S. _, Multiplicity Q Assignment M. KKR (in CDCl ₃ ) M. 3 0.90 . M. I a 4th 0.95-1.30 S. b 1 1.0-2.2 C. 1 2.33 d 1 2.45 e 2 2.7-3.1 f 3.4-4.0 G 3.9 H 6.87 i

IR:

-1

cm »1,2,3,5-tetrasubst.

1620 cm «C

N band

ti) if)

CIr ₃ -CK ₂ -O-CH ₃ (a) («0 IC) (*)

-C-CH ₃ (b) ^W CK ₃

Shift ppm

Multiplicity

Assignment

intensity

NMR in CDCl,

0.7-1.7 ³ M.

1.4 S.

2.7 M 3.4 D 4.3 S 5.0-5.4 M.

5.8 M 7.0 S.

I a b c d e f g h

25th

2 2 1 2

IR: 3420 (NH), 760 (aromatic 1,2,3-trisubst. Possible) (C »N).

Le λ 18 232

- 120 -

809884/0112

- A16 -

CO CH ₃ -Crt _z -CH _Z -CH _? ,

Shift
ppm

CO i » (<*)

Multiplicity assignment intensity

NMR: (in CDCl ₃ )

0.90 τ

1.15 T

1.0-2.0 M.

2.0-2.4 M.

2.33 S.

2.45 Q

3.3-3.3 M.

4.0 D

6.85 S.

IR: 1615 cm

a
b
c
d
e
f

G
H
i

867 or 882 cm "" ¹

Lf) Ca)

s C = N band

1,2,3,5-tetrasubst

CH ₃ -

IR: 1610 cm "J" = C = N band

877 cm " ¹ = 1,2,3,5-tetrasubst,

Le A 18 232

- 121 -

809884/01 12

Shift Multiplicity T Assignment intensity ppm S. NMR: (in CDCl ₃ ) M. 1.18 M. I a 6th 1.31 S. b 9 " 1.0-2.0 Q C. 8th 2.1-2.4 M. d 2 2.38 M. e 3 2.48 S. f 4th 3.3-3.8 G 1 4.05 H 1 7.05 i 2

CHx-C «3

Shift ppm

Multipticity

Assignment

intensity

WMR: (in CDCl ₃ )

0.8-2.0 M.

2.0-2.4 M.

2.37 S

2.45 Q

3.3-3.8 M.

4.0 D

6.87 S.

a b c d

e f β

17 2 3 6 1 1 2

IR:

873 cn " ¹ = 1,2,3,5-tetrasubst. 1615 era" ¹ = C = N band

Ca) co

Shift Multiplicity T Assignment - 122 - intensity ppm T NMR: (in CDCl ₃ ) M. 0.92 M. I a 3 1.15 S. b 6th 1.0-2.0 Q C. 8 + 2 2.0-2.4 M. d 2 2.37 D. e 3 2.45 S. f 6th 3.3-3.8 : CsN band S. 1 4.0 H 1 6.84 i 2 13:.
1610 cm " ¹ p Le A 18 232

809884/0112

Cf; O)

Shift Multiplicity T Assignment cm " ¹ = 1,2,3,5-tetrasubst. intensity ppm T NMR: (in CDCl ₃ ) M. 0.73. M. I a 6th 1.17 S. b 6th 1.0-2.1 Q C. 12th 2.1-2.4 M. d 2 2.37 M. e 3 2.47 D. f 4th 2.5-3.0 S. G 1 3.3-3.8 cm "" * = C = N band H 1 4.05 i 1 6.80 k 2 IR: 1615 873

Le A 18 232

- 123 -

809884/01 U

Claims (9)

Claims 1.jN-aryl-N'-alkyl-S-alkyl-isothioureas of general ^/ my formula -N = C-NH-R ⁴ (I) in which R ¹ for alkyl or cycloalkyl, R for alkyl of at least two carbon atoms or for cycloalkyl, the radicals R can be identical or different and R represents alkyl, cycloalkyl or halogen, η stands for an integer from 0 to 2 and R represents optionally substituted alkyl, optionally substituted alkenyl or optionally substituted cycloalkyl, and R stands for alkyl, alkenyl or cycloalkyl, and their salts. Le A 18 232 - 124 - θ ο π π δ υ ο 11 ?. ORIGINAL INSPECTED ■ / 7 3 UL? U 2. Compounds according to formula (I) in claim 1, in which R ¹ for alkyl (C ₁ -Cg) or cycloalkyl (C ₄ -C ₇ ), R ^{2 represents} alkyl (C ₂ -Cg) or cycloalkyl (C ₄ -C ₇ ), the radicals R can be identical or different and are alkyl (C ₁ -C ₇ ), halogen, cycloalkyl (C ₄ -C ₇ ) and η is 0, 1 or 2, 4th
_{R for alkyl (C 1} -C ₁₄ ) optionally substituted by halogen, cycloalkyl (C _{4 -C 7} ) cycloalkenyl (C 1 -C 4) or trifluoromethyl or for alkenyl optionally substituted by halogen and / or CF, mono- or polysubstituted (C_-C,) or represents cycloalkyl (C ₃ -C ₁₀ ) which is _{optionally monosubstituted or polysubstituted by alkyl (C 1} -C ₄ ), halogen and / or CF _3, and R ^{5 stands} for alkyl (C ₁ -Cg), alkenyl (C ₂ -Cg) or cycloalkyl (C ₃ -Cg), and their salts. 3. Process for the preparation of N-aryl-N ¹ -alkyl-S-alkylisothioureas of the general formula Le A 18 232 "125 - π η η η π w η ORIGINAL INSPECTED SR ⁵ N = C-NH-R ⁴ (I) in which R ¹ for alkyl or cycloalkyl, R for alkyl with at least two carbon atoms or for cycloalkyl, the radicals R can be identical or different and
R for alkyl, cycloalkyl or halogen, η stands for an integer from 0 to 2 and R represents optionally substituted alkyl, optionally substituted alkenyl or optionally substituted cycloalkyl and R stands for alkyl, alkenyl or cycloalkyl, characterized in that thioureas of the formula n-NH-C-NH-R ⁴ (H) Le A 18 232 - 126 - SnnRRii / 0112 12 3 4
in which R, R, R, R and η have the meaning given above, with a compound of the general formula R ⁵ -X (III) converts, in which R has the meaning given above and X stands for a radical which can be removed anionically. 4. Ectoparasiticidal agents, characterized by a content of N-aryl-N ¹ -alkyl-S-alkyl-isothioureas according to claim 1). 5. Insecticidal and acaricidal agents, characterized by a content of N-aryl-N'-alkyl-S-alkyl-isothiourea fen according to claim 1). 6. A process for the preparation of ectoparasiticidal agents, characterized in that one N-aryl-N'-alkyl-S-alkylisothiourea Fe according to claim 1) mixed with inert, non-toxic auxiliaries and / or carriers. 7. A process for the preparation of insecticidal and acaricidal agents, characterized in that one N-aryl-N'-alkyl-S-alkylthioureas according to claim 1) with inert, non-toxic auxiliaries and / or carriers mixed. Le A 18 232 - 127 - 809884/0112 27.3062Q aadurcn 8. methods of combating ectoparasites, characterized in that animals infected by ectoparasites are treated with N-aryl-N'-alkyl-S-alkyl-isothioureas treated according to claim 1). 9. A method for combating insects and acarids, characterized in that one of insects and / or Acarid-infested plants with N-aryl-N'-alkyl-S-alkylisothioureas treated according to claim 1). Le A 18 232 - 128 - η η η ρ η /, / η 113