DE2017969A1 - 2-Arylimino-thiazolidines and process for their preparation - Google Patents

Description

FARBENFABRIKEN BAYER AG _2017969

LEVERKU S EN-Bayerwerk Patent department

Hu / Wed

, ΐ.ΑΗΪ.1970

2-Α ^ γ11τηΐηο-ΐοΐ3ζοϋάίη6 and process for their preparation

The present invention relates to new 2-arylimino-thiazolidines as well as processes for their preparation and their use as ectoparasiticides.

2-Arylimino-3-aryl-thiazolidines have been known for a long time (e.g. FB Dains and coworkers, J.Am.Chera.Soc. 44, 2637 (1922); J. Am.Chem.Soc. £ 7, 1981 (1925) ; 0. Mitsunobo et al., Bull. Chem. Soc. Japan J59, 708 (1966)). 2-Phenyl-3-methyl- (and ethyl) -thiazolidine have also already been described (P-B. Dains and coworkers, J. Am. Chem. Soc. 47 , 1981 (1925); E. Cherbuliez and coworkers, Helv . Chim. Acta 49 , 807 (1966)). However, so far nothing is known about an effect of these compounds against ectoparasites.

It has now been found that the new 2-arylimino-thiazolidines of the formula (I),

N '

S.
(D

in which R is a phenyl radical substituted in the 2- or 2,6-position, which can be further substituted by lower alkyl groups »and / or halogen atoms, the 1-Napntnyl- or 5» 6 »7,8-Te- ' ■ denotes trahydro-1-naphthyl radical, and R ^{1 stands} for a straight-chain or branched alkyl group with 1 to 4 or a straight-chain or branched alkylene group with 3 to 5 carbon atoms, optionally substituted by halogen atoms,

Le A 12901 - 1 -

209812/174 3

or their salts for combating animal ectoparasites, i ~ ^ns particular from the classes of acarids, are eminently suitable.

In the case of the phenyl radical R which is substituted in the 2- or 2,6-position it is preferably 2-tolyl, 2-trifluoromethylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl and 2-metboxyphenyl-, 2,6-xyIyI-, 2-chloro-6-methylphenyl, 2,6-dichlorophenyl, 2,6-dibromo-4-methylphenyl-, 2-chloro-6-methoxyphenyl-, 2-methoxy-6-methylphenyl-, 2,6-dimethoxyphenyl-, 2-chloro-6-trifluoromethylphenyl-, 2-methyl-6-trifluoromethylphet nyl and 2-methoxy-6-trifluoromethylphenyl radical.

R ¹ preferably represents methyl, ethyl, n-propyl, η-butyl, isopropyl, isobutyl, sec-butyl and tert-butyl, allyl, crotonyl, methallyl, 2 , 2-dimethylvinyl, 2-GhIoT ^: allyl, 3-chloroallyl and 2,3-dichloroallyl.

It has also been found that 2-arylimino-thiazolidines of the formula (I) are obtained if thioureas of the formula (II), _Rl

(II)

HO-CH ₂ -CH ₂ -N-CS-NH-R

in which R and R ^{1 have} the meaning given above, cyclized under the action of strong acids.

Instead of the aforementioned thioureas, it is also possible to use those of the formula (III),

in which R and R ^{1 have} the abovementioned meaning and X is a halogen atom or a sulfonic acid radical, e.g. B. is the p-toluenesulfönyloxy radical,

use.

Le A 12901 - 2 -

209812/1743

R «

X-CH ₂ -CH ₂ -N-CS-NH-R
(III)

In this case, the cyclization takes place immediately afterwards to their production without the addition of acids.

The new compounds of the formula (I) can also be prepared by adding thioureas of the formula (IV)

R'-NH-CS-NH-R
(IV)

in which R and R 'have the meaning given above, reacts with 1,2-dihaloethanes, or arylamines of formula (V)

R-NH ₂

(V)

with 2-thiono- or 2-imino-thiazolidines of the formulas (VI) and (VIa) ■■■ * ■ - ■■

(VI) (VIa)

or 2-arylamino-thiazolines of the formula (VII) with reactive ones Esters, such as halides or sulfuric acid esters, of alcohols of the formula (VIII)

NH-R R-OH

(VII) (VIII)

in which R and R * have the meaning given above.

The 2-aryliminothiazolidines according to the invention surprisingly have a strong ectoparasiticidal effect, in particular against phosphoric acid ester-resistant tick strains. About that

Le A 12 901 . - 3 -

209812/1743

In addition, they are stable and when used in beef dip also highly effective against mange mites. The substances according to the invention thus represent an enrichment of technology.

The thioureas to be used as starting materials of Formula (II) can be prepared by reacting aryl isothiocyanates of the formula (IX) or arylthiocarbamic acid chlorides of the formula (X) with 2-aminoethanols of the formula (XI)

R-NCS R-NH-CS-Cl HO-CH ₂ -CH ₂ -NH-R '

(IX) (X) (XI)

The starting materials of the formula (III) are obtained, for example by reacting isothiocyanates (IX) or thiocarbamic acid chlorides (X) with amines of the formula (XII)

X-CH ₂ -CH ₂ -NH-R ¹
(XII)

or by reacting thiocarbamic acid chlorides of the Formula (XIII) with amines of the formula (¥).

E ⁸
X-CH ₂ -GH ₂ -I-GS-Cl

The starting materials of the formula (IT) are generally better known Way aura example by converting isothiocyanates' the Formula (XIY) with the amines (V) or by reacting isothiocyanates (IX) or Tfaiocartoamideauueetaloriden (X) with Amines of formula (XV).

R '-VCS R'-HH ₂

(XIV) (IV)

In the formulas (IX) there are (IV) R ₉ R ⁸ and X you

above meaning.

Le A 12g01 "- 4 -"

209812/1743

The amines (XII) are obtained, for example, by reaction Hydrochlorides of the compounds (XI) with thionyl chloride or p-toluenesulphonic acid chloride. From them, in turn, the compound of the formula (XIII) is accessible by reaction with thiophosgene. The amines (XII) are obtained as salts during their production. They become before or during the reaction with the isothiocyanates or thiocarbamic acid chlorides or with thiophosgene by adding basic substances, for example Alkali or alkaline earth hydroxides, carbonates, hydrogencarbo natural or tertiary amines, the corresponding amines are released.

For example, 2-chlorophenyl isothiocyanate and 2-Metbylaminoäthanol as starting materials, the reaction can can be represented by the following equation.

HO-CH ₂ -OH ₂ -NH-CH ₃ + SCN-

HO-CH ₂ -

Im EaHe the implementation of 2-methylaminoethanol and 2,6-dichloro phenyl-thiocarbamic acid chloride, the reaction proceeds as follows Scheme: Cl

2 HO-CH ₉ -CHo-NH-CH, + Cl-CS-NH-f ^

HO-CH ₂ -CH ₂ -N-CS-NH- / η

Cl

+ HO-CH ₂ -CH ₂ -NH-CH ₃ -HCi

LA 12901

- 5 -209812/1743

η! "

/ ^CH 3 Cl

If 2-tert-butylaminoethanol and 2-tolylisotniocyanate are used as starting materials, the reaction proceeds according to the following scheme:

HO-OHo-CH ₉ -HH-C-CH *. HCl
CH,

CH ₃
Cl-CH ₂ -CH ₂ -NH-C-CH ₅ + SCN- ^ '

CH,

CH, ι ■> Oü, -0 "" Gii γ

Cl-OH ₂ -OH ₂ -H-OS-NH-

OH

/ c

C-GH •;

CH,

GH

Suitable solvents or diluents for carrying out the reaction are hydrocarbons such as benzene or ligroin, ethers, see, for example, dietary ether or dioxane, halogenated hydrocarbons such as methylene chloride, ethylene chloride, ethylene chloride. ibromide or chlorobeazole, esters such as ethyl acetate, but also alcohols such as ethanol and even water. D ₃ at la is the selection of suitable solvents or diluents are determined in known manner by the stability and responsiveness of the respective reaction components. · It is the use of solvents or diluents, in most cases

Ic A 12901

200812/174

2017369

useful, but not absolutely necessary.

Suitable acids for the cyclization of the thioureas of the formula (II) are aqueous or anhydrous strong ones Acids such as Example hydrochloric acid, hydrobromic acid, Phosphoric acid, polyphosphoric acids, sulfuric acid, benzenesulfonic acid or methanesulfonic acid.

The reaction temperatures can be varied over a wide range. In general, the reaction is preferably carried out at between O and 15O ⁰ C, at the reflux temperature of the mixture. It is often advantageous to carry out the reaction with cooling at the beginning.

When carrying out the reactions, one can in general Use stoichiometric amounts of the starting components. In some cases, however, it is beneficial to use the more accessible ones Use reactants in a slight excess.

As examples of usable Arylisothiocyanate (IX) may be mentioned are: 2-tolyl isothiocyanate, 2-methoxyphenyl isothiocyanate, 2-trifluoromethylphenyl, 2-Fluorphenylieothiocyanat, 2-chlorophenyl isothiocyanate, 2-Bromphenylisottaiocyanat, 2,6-Xylylisothiocyanat, 2-methoxy-6-methylphenylisotfaioeyanat , 2-chloro-6-methylphenylisothiocyanat, 2-chloro-6-methoxyphenyl isothiocyanate, 2,6-Dimethoxyphenylisothiocyanat, 2-Ohlor-6-trifluoromethylphenyl, 2-methyl-6-trifluoro! aethylphenylisothiocyanat _f 2-methoxy-6-trifiuormetbylphenylisothiocyanat, 1 -Naphthyl isothiocyanate,

All examples of the arylthiocarbamic acid chlorides (X) may be mentioned; aje-bichlorophenylthiocarbamic acid chloride and 2 , e-dibromo ^ -methylphenylthiocarbamic acid chloride.

Le A 12901 - 7 -

209812/1743

Examples of the 2-aminoethanols (XI) are:

2-mettaylaminoethanol, 2-ethylaminoethanol, 2-n-propylaminoethanol, 2-n-butylaminoethanol, 2-isopropylaminoethanol, 2-isobutylaminoethanol, 2-sec-butylaminoethanol, 2-tert-butylaminoethanol, 2-allylaminoethanol, 2-crotonylaminoethanol, 2-methallylaminoethanol, 2- (3-chloroallylamino) -ethanol, 2- (2, 3-DichlorallylaTDino) -ethanol »2- (2-Chlorallylamino) -ethanol, 2- (2,2-dimethyl vinylamine) ethanol.

Examples of the 2-aryliraino-thiazolidines according to the invention

2- (2-Tolylimino) -3-methyl-thiazolidine 2- (2-methoxyphenylimino) -3-raethyl-thiazolidine 2- (2-trifluoromethylphenylimino) -3-methyl-thiazolidine 2- (2-pluophenylimino) -3 -methyl-thiazolidine 2- (2-chlorophenylimino) -3-methyl-thiazolidine 2- (2-bromophenylimino) -3-methyl-thiazolidine 2- (2,6-xylylimino ') -3-methyl-thiazolidine 2- (2 -Methoxy-6-methylphenylimino) -3-methyl-thiazolidine 2 «(2-chloro-6-methylphenylimino) -3-taethyl-thiazolidine 2- (2-chloro-6-methoxyphenylimino)" 3-methyl-thiazolidine 2- (2,6-Dimethoxyphenyliiaino) -3-methyl-thiazolidine 2- (2 ~ Ohlor - 6- ^< Irifluorraethylphenylitnino) -3-methyl-thiazolidine "2- (2-methyl-6-trifluoromethylpbenylimino) ~ 3 - niethyl- thiazolidine 2- (2-Metho3cy-6-trifluoromethylpbenylimino) "- 3-methyl-thiazolidine 2- (2, 5-dichlorophenylimino) -3-3ietbyl-tlaiazolidine 2- (l-naphthylimino) -3-raethyl thiasolidine 2- ( 5 * 6,75 8-Tetrahydro ~ l-iaaphthylimino) -3-Biethyl-thiezolidine 2- (2,6-Dibromo-4-methylphenylimiao) -3 ~ methyl- "thiazolidine 2- (2-Tolylimino) -3- ethyl thiazolidine

2- (2-methoxyphenylimino) -3-ethyl-thiazolidine 2- (2-trifluoromethylphenylimino) -3-ethyl-thia! Bolidine 2- (2-fluorophenylitnino) -3-ethyl-thiazolidine 2- (2-chlorophenylimino) -3 -ethyl-tbiaeolidine 2- (2-bromobbenylimino) -3-ethyl-thiazolidine 2- (2,6-xylylimino) -3 "ethyl-tbiaeolidine

Le A 12901 - 8 -,

209812/1743

2- (2-Methoxy-6-methylphenyliminQ) -3-ethyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3-ethyl-thiazolidine 2- (2-chloro-6-methoxyphenylimino) -3-ethyl- thiazolidine 2- (2,6-l) imethoxyphenylimino) -3 - ethyl-thiazQlidin 2- (2-chloro-6-trifluoromethy Ipheny lixnino-3-ethyl-thiazoXidin 2- (2 ~ methyl-6-trifluorotethylphenylimino) - 3-ethyl · ■ thiazolidine 2- (2-methoxy-6-trifluoromethylphenylimino} -3-ethyl-thiazolidine 2- (2,6-dichlorophenylimino) -3-ethyl-thiazolide | .n 2- (l-naphthylimino) -3 -äthyl-thiazolidine 2 "(5,6,7,8-tetrahydro-l-naphthylimino) -3-ethyl-thiazolidine 2- (2-tolylimino) -3-n-propyl-thiazolidine 2- (2-methoxyphenylimino) - 3-n-propyl-t ¹ hiazolidine 2- (2-trifluoromethylphenylimino) -3-n-propyl-thiasolidine 2- (2-fluorophenylimino) -3-n-propyl-thiazolidine 2- (2-chlorophenylimino) -3-n -propyl-thiazolidine 2- (2-bromophenylimino) -3-n-propyl-thiazolidine 2- (2,6-xylylimino) -3-n-propyl-thiazolidine 2- (2-methoxy-6-methylphenylimino) - 3-n-propyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3-n-propyl-thiazolidine 2- (2-chloro-6-m ethoxyphenylimino) -3-n-propyl-thiazolidine 2- (2,6-dimethoxyphenylimino) -3-n-propyl-thiazolidine 2- (2-chloro-6-trifluoromethylphenylimino) -3-n-propyl-thiazolidine 2- (2 -Methyl-6-trifluoromethylphenylimino) -3-n-propyl-thiazolidine 2- (2-methoxy-6-trifluoromethylphenylimino) -3-n-propyl-thiazolidine 2- (2,6-dichlorophenylimino) -3-n-propyl- thiazolidine 2- (1-naphthylimine) -3-n-propyl-thiazolidine 2- (5,6,7,8-tetrahydro-1-naphthyliraino) -3-n-propyl-thiazolidine 2- (2-tolylimino) -3 -n-butyl-thiazolidine 2- (2-methoxyphenylimino) -3-n-tiutyl-thiazolidine 2- (2-G? rifluoromethylphenylimino) -3-n-butyl-thiazolidine 2- (2-fluorophenylimino) -3-n -butyl-thiazolidine 2- (2-chlorophenylimino) -3-n-butyl-thiazolidine 2- (2-bromophenylimino) -3-n-butyl-thiazolidine

It A 12901 - 9 - ■

209812/1743

2- (2,6-Xylylimino) -3-n-butyl-thiazolidine 2- (2-Metboxy-6-methylphenylimino) -3 ~ n-butyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3- n-butyl-thiazolidine 2- (2-chloro-6-methoxyphenylimino) -3-n-butyl-thiazolidine 2- (2,6-dimethoxyphenylimino) -3 ~ n-butyl-thiazolidine 2- (2-chloro-6 -trifluoroniethylpheny! imino) -3-n-butyl-thiazolide in 2- (2-methyl-6-trifluoromethylphenylimino) -3-n-butyl-thiazolidine 2- (2-methoxy.-6-trifluoromethylphenylimino) -3-n- butyl-thiazolidine 2- (2,6-dichlorophenylimino) -3-n-butyl-thiazolidine 2- (l-naphthylimino) -3-n-butyl-thiazolidine 2- (5,6,7,8-tetrahyro ~ l- naphthylimino) -3-ß-13utyl-thiazolidine 2- (2-tolyliraino) >> 3-isopropyl-thiazolidine 2- (2-methoxyphenylimino) -3-isopropyl-thiazolidine 2- (2-trifluoromethylphenylimino) -3-isopropyl-thiazolidine 2 - (2-Pluophenylimino) -3-isopropyl-thiazolidine 2- (2-chlorophenylimiao) -3-iBopropyl-thia3olidine 2- (2-bromophenylimino) ~ 3-isopropyl "thiazolidine 2- (2,6-xylylimino) -3- isopropyl-thiazolidine 2- (2-methoxy-6-methylphenylimino) -3-isopropyl »thiazolidine 2- (2-Ch lor-6-methylphenylimino) -3-isopropyl-thiazolidine 2- (2- "chlorine" 6-methoxyphenyliTiiino) -3-isopropyl-thiazolidine 2- (2,6-dimethoxyphenylimino) -3-isopropyl-thiazolidine 2- (2- Chloro-6-trifluoromethylphenylimino) -3-isopropyl-thiazolidine 2- (2-methyl-6-trifluorraethylphenylimino) -3-isopropyl-thiazolidine 2- (2-metboxy-6-trifluoromethylphenylimino) -3-isopropyl-thiazolidine 2- (2 , 6-Dichlorphenylixniiio) -3 ~ @ i opropyl-thiazoliaIn 2- (l-Naphthylimino) -3-isopropyl ~ thiasolidiu 2- (5 »6, 7, 8-tetrahydro-l-naphthyliinino) -3-isopropyl-2 thiazolldin - (2-Tolylimino) -3-isobutyl-tbiazolidine 2- (2-methoxyphenylimiao) ~ 3-isobutyl-thiazolidine 2- (2-trifluoromethylphenylimino) -3-isol) utyl-tert-biazolidine 2- (2-fluorobranylimino ) -3-isol3utyl-thiaaolidia 2- (2-Cblorpbenylimino) -3-isobutyl-thiazolldin 2- (2-bromophenylimiao) -3-iaobutyl-thiasolidine

Le A 129OX - IO -

209812/1743

2- (2,6-xylylimino) -3-isobutyl-thiazolidine 2- (2-methoxy-6-methylphenylimino) -3-isobutyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3 = isobutyl-thiazolidine 2 - (2-Chloro-6-methoxyphenylimino) -3-isobutyl-thiazolidine 2- (2,6-Dimethoxyphenylimino) -3-isobutyl-thiazolidine 2- (2-chloro-6-trifluoromethylpbenylimino) -3-isobutyl-tbiazolidine 2- (2-methyl-6-trifluoromethylphenylimino) -3-isobutyl-thiazolidine 2- (2-methoxy-6-trifluoromethylphenylimino) -3-isobutyl-thiazolidine 2- (2,6-dichlorophenylimino) -3-iBobutyl-thiazolidine ¹ 2- (l-Naphthylimino) -3-isobutyl-thiazolidine 2- ( 5 » 6 , 7 » 8-tetrahydro-l-naphthylimino) -3-isobutyl-thiazolid in 2- (2-tolylimino) -3-sec-butyl- thiazolidine 2- (2-methoxyphenylimino) -3-sec-butyl-thiazolidine 2- (2-trifluoromethylphenylimino) -3-sec-butyl-thiazolidine 2- (2-fluorophenylimino) -3-sec-butyl-thiazolidine 2 - (2-Chlorophenylimino) -3-Bek.-butyl-thiazolidine 2- (2-bromophenylimino) -3-sec-butyl-thiazolidine 2- (2,6-xylylimino) -3-sec-butyl-thiaaolidine - 2- (2-methoxy-6-methylphenylimino) -3-sec-bu tyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3-sec-butyl-thiasolidine 2- (2-chloro-6-methoxyphenylimino) -3-Bek.-butyl-thiazolidine 2 ~ (2,6- Dimethoxyphenylimino) -3-sec-butyl-thiazolidine 2- (2-chloro-6-trifluoromethylphenylimino) -3-eek-butyl-thiazolidine 2- (2 ~ methyl-6-trifluoromethylphenylimino) -3-sec-butyl- thiazolidine -2- (2-methoxy-6-trifluoromethylphenylimino) -3-eek.-t »utyl-thiazolidine 2- (2,6-dichlorophenylimino) -3-sec-butyl-thiazolidine 2- (l-naphthylimino) - 3-eek.-butyl-thiazolidine 2- (5 »6 _t 7« 8-tetrahydro-l-naphthylltBino) -3-Bek.-butyl-> thia8olidln 2- (2-tolylmlno) -3-tert.-butyl- thiazolidine 2- (2-methoxyphenylimino) -3-tert-butyl-thiazolidine 2- (2-trifluoromethylphenyltnino) -3 ~ tert-butyl-thiazolidine 2- (2-fluorophenylimino) -3-tert-butyl-thiazolidine 2 - (2-Chlorophenylimino) -3-tert-butyl-thiazolidine 2- (2-bromophenylimino) -3-tert-butyl-thiazolidine

Le A 12901 - 11 -

20 9812/1743

2- (2,6-XyIy! Imino) -3 ~ tert-butyl-thiazolidine 2- (2-Methoxy-6-methylphenylimino) ~ 3-tert-butyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3-tert-butyl-thiazolidine 2- (2 ~ chloro-6-methoxyphenylimino) -3-tert-butyl-thiazolidine 2- (2,6-Dimethoxyphenyliraino) -3-tert-butyl-thiazolidine

2- (2-chloro-6-trifluoromethylphenylimino) -3-tert-butylthiazolidine

2- (2-methyl-6-trifluoromethylphenylimino) -3-tert. -butylthiazolidine

2- (2-methoxy-6-trifluoromethylpheny! Imino) -3-tert-butylthiazolidine

2- (2, β-Dichlorophenylimino) ™ 3-tert-butyl-thiazolidine 2- (1-naphthyliraino) -3-tert-butyl-thiasolidine 2- (5,6,7 Fe-Setrahydro-l-naphthylimino) -3-tert. »Btityl-

thiazolidine

2- (2-Tolylimino) -3-allyl-thiazolidine 2- (2-Methoxyphenylimino) ~ 3-allyl-thiazolidiia 2 »(2-trifluoromethylphenylimino) -3-allyl-thiazolidine 2 »(2-fluoropheny! Imino) ™ -3-allyl" thia2! Olidine 2- (2-Chlorophenylitßino) -3 ~ allyl-thia ^ olidine 2 ~ (2-bromopheoylimino) ~ 3 ~ allyl-thiaisolidine 2 ~ (2,6-xylylimino) -3-allyl-thiazolidia 2 ~ (2-M © tho3Ey-6 "-methylphenyliiniB.o)" 3-allyl-thia25olidi! I 2- (2-Ch! Or-6-methylphenylimino) -3-allyl- "febiai8olidine 2- (2-chloro-6-methoxypheaylimine) -3-allyl "thiazolidine 2- (2,6-Diinethoxypbenyli®iEo) -3-allyl »ttaia ^ ol £ d.i! I 2- (2-0hloro-6-trifluoromethylpbeBylimino5- "3-allyl-thiaisolidine

2- (2-Methoxy-6-trifluoromethylpbeBylimino) -3-allyl-thiazolidine

2- (5 1 6 s7 je-Tetrabydro-l-naptattaylimino) -3-allyl-thlazolide 2- (2-tolylliaino) -3-crotoayl-

2> (2-Metboxypbenylimiao) -3-c

- 12

209812/1743

2 - (- 2-chlorophenylimino) -3-erotonyl-thiazolidine 2- (2-bromobenzylimino) -3-crotonyl-thiazolidiri 2- (2 ₎ 6-xylylimino) -3-crotonyl * -thiazolidine 2- (2-methoxy- 6-methylphenylimino) -3-cro-tonyl-thiazolidine 2- (2-chloro-6-methylphenylimino) -3-crotonyl-thiazolidine 2- (2-chloro-6-methoxyphenylimino) -3-crotonyl-thiazolidine 2- (2 , 6-Dimethoxyphenylimino) -3-crotonyl-thiazolidine 2- (2-chloro-6-trifluoromethylphenylinino) ~ 3-crptonyl _< -thiazolidine 2- (2-methyl-6-trifluorraettaylphenylimino) -3-crotonyl-thiazolidine 2- (2 -Methoxy-6-trifluoromethylphenylimino) -3-crotonyl-thiazolidine 2- (2,6-dichlorophenylimino) -3-crotonyl-thiazolidine 2- (l-naphthylimino) -3-crotonyl-thiazolidine 2- (5,6,7, 8-Tetrahydro-l-naphthylimino) -3-crotonyl-thiazolidine 2- (2-ToIyI) -3-methallyi-thiazolidine 2- (2-methoxyphenylimino) -3-tethallyl-thiazolidine 2- (2-trifluoromethylphenylitnino) -3- methallyl-thiazolidine 2- (2-pluophenylimino) -3-tethallyl-thiazolidine 2- (2-chlorophenylimino) -3-raethallyl-thiazolidine 2- (2-bromophenylimino) -3-methallyl-thiazolidine 2- ( 2,6-xylylimino) -3-methallyl-thiazolidine 2- (2-methoxy-6-methylphenylimino) -3-methallyl-thiazolidine 2- (2-chloro-6-metbylphenyliTnino) -3-methallyl-thiazolidine 2- (2 -Ctalor-6-mettaoxyphenylimino) -3-raethallyl-tbiazolidine 2- (2,6-DiTnetboxyphenylimino) -3-methallyl-thiazolidine 2- (2-chloro-6-trifluoromethylpbenylit-dino) -3-metballyl-thiazolidine 2- (2- Metbyl-6-trifluoromethylphenylimino) -3-met ha lly1-

thiazolidine

2- (2-methoxy-6-trifluoromethylphenylimino) -3-methally1-

thiazolidine

2- (2,6-Dicblorpbenylimino) -3-tnetballyl-tbiazolidine 2- (2 _t 6-xylylimino) -3- (2-chloroallyl) -thiazoMdin 2- (2-chloro-6-14ethylphenyliinino) -3- (2 chlorallyl) thiazolidine 2- (2-tolylimino) -3- (3-chloroallyl) thiazolidine 2- (2-methoxyphenylimino) -3- (3-chloroallyl) tbiazolidine

Ie A 12901 - 13 -

209812/1743

2- (2-Trifluoromethylphenylimino) -3- (3-ChIo ^ lIyI) -thiazolidine 2- (2-fluorophenyliraino) -3- (3-chloroallyl) thiazolidine 2- (2-chlorophenylimino) -3 - (3-chloroallyl) thiazolidine 2- (2-bromophenylimino) -3- (3-chloroallyl) thiazolidine 2- (2,6-xylylimino) -3- (3-chloroallyl) thiazolidine 2 - ^ - methoxy-δ-methylphenylimino) -3- (3-chlorallyl) thiazolidine 2- (2-Chloro-6 ~ methylphenyliiBino) -3 - (3-chloroallyl) -thiazolidine 2- (2-chloro-6-methoxyphenylimino) -3- (3-chloroallyl) thiazolidine 2- (2,6-Dimethoxyphenylimino) -3- (3-chloroallyl) thiazolidine 2- (2-chloro-6-trifluoromethylphenylimino) -3- (3-chlorallyl) -

thiazolidine

2- (2-methyl-6 "-trifluoromethylphenylimino) -3- (3-chlorallyl) -

thiazolidine

2- (2-methoxy-6-trifluoromethylphenylimino) -3 ~ (3-chlorallyl) -

thiazolidine

2- (2,6 ~ dichlorophenylimino) -3- (3-cblorallyl) -thiazolidine 2- (1-Naphthylimino) -3- (3-chloroallyl) thiazolidine 2- (5,6,7,8-tetrahydro-1-naphthobylamino) -3- (3-chlorallyl) -

thiazolidine

2- (2-Tolylitnino) -3- (2,3-dichloroallyl) thiazolidine 2 ~ (2-Methoxypbenylimino) -3 "(2,3-dichloroallyl) -fcbiazolidine 2- (2-trifluoromethylphenylimiao) -3- (2,3-dichloroallyl) -

thiazolidine

2- (2 ~ fluoropbenylimino) -3- ^ r3-dichloroallyl) thiazolidine 2- (2-chlorophenylimino) -3 "- (2 _i 3-dicbloroallyl) thiazolidine 2- (2-bromobbeny! Imino) -3- ( 2,3-dichloroallyl) thiazolidine 2- (2,6-xylylimino) -3- (2,3-dichloroallyl) -tbiazolidine 2- (2-methoxy »6-metbylphenylimino) -3- (2,3-dichloroallyl) -

thiazolidine

2- ( 2-chloro-6-methylpheny! Imino) -3- (2,3-dicblorallyl) -

thiazolidine

2- (2-chloro-6-methoxyphenylimino) -3- (2,3-dichloroallyl) -

thiazolidine

2- (2,6-Dimetboxyphenylimino) -3- (2,3-dichloroallyl) -tbiazolidine 2- (2-chloro-6-trifluoromethylphenylimino) -3- (2,3-dichloroallyl) -

tbiazolidine

Ie A 129OX - 14 -

209812/1743

2- (2-methyl-6-trifluoromethylphenylimino) -3- (2,3-dichloroallyl) -

thiazolidine

2- (2-methoxy-6 ^ trifluoromethylphenylimino) -3- (2,3-dichlorallyI) -

thiazolidine

2- (2,6-dichlorophenylimino) -3- (2,3-dichloroallyl) thiazolidine 2- (1-naphthylimino) -3- (2,3-dichloroallyl) thiazolidine ? - (5,6,7,8-Tetrahydro-1-naphthylimino) -3- (2,3-dichloroallyl) -

thiazolidine.

The new substances according to the invention have a basic character and are mostly oils that can be distilled, some of which are Crystallize at room temperature. They can be used as free bases or in the form of their salts, for example the hydrochloride, Sulphates, phosphates, nitrates, acetates, lactates, or succinates Naphthalene disulfonates.

The free bases such as the salts of the 2-arylimino-thiazolidines according to the invention «Have strong acaricidal properties, especially against acarids that are considered animal Ectoparasians infest domesticated animals such as cattle and sheep. They are therefore well suited for combating animal ectoparasites from the order of the acarids. As economical important ectoparasl species of this type, which play a particularly important role in tropical and subtropical countries, are for example:

the Australian and South American cattle ticks Boophilus micropluB, the South African cattle ticks Boophilus decoloratus and multi-host cattle and sheep ticks of the Genera Rhipicephalusi, Amblyonma utnd Hyalomma _t all from the family of the Ixodldae.

In the course of time, ticks have been used in various areas against the phosphoric acid esters previously used as a control agent and carbamates have become resistant, so that the control is successful is imprinted in many areas. To ensure economic livestock farming in the

Le A 12901 - 15 -

209812/1743

Infested areas therefore have a need for means with which ticks “also from resistant strains, for example des Genus Boophilus can be controlled safely. To a large extent against the phosphoric acid esters used to date and In Australia, for example, the Ridgeland strain and the Biarra strain of Boophilus have become resistant to carbamates microplus. The active ingredients according to the invention prove to be both against the normal sensitivity as well as against the resistant ones For example, strains of Boophilus are equally effective. They have a strong egg deposition inhibiting effect on the adult forms »

In the same way, representatives from the Sarcoptidae family, such as the Schafsaugmilb® (Faoroptes ovis) and the Rabbit suction mite (Psoroptee eunieuli) can be controlled.

The active ingredients in the usual manner, for example by dusting ^ spraying "watering, misting or as a dip (dip), the formulations or the ready solutions or any other Hilfsetoff®, extenders and / or surface active © agent b _'s agents, wi® insecticides or disinfectants, sugemiecht «,

Ie A 12 901

JI

Application examples

Example A: In-vitro test for egg-deposition-inhibiting effect on ticks

3 parts of active ingredient are 7 parts of a mixture of equal parts by weight of ethylene glycol monomethyl ether and Mixed nonylphenol polyglycol ether. The emulsion concentrate obtained in this way is adjusted to the desired in each case with water Application concentration diluted.

Adult fully sucked female ticks of the species Boophilus mioroplus (resistant) are thawed for one minute in this active compound preparation. After 10 female specimens of each of the different tick strains have been immersed, the individual ticks are transferred to plastic dishes, the bottom of which is covered with a filter paper pad. After 35 days, the effectiveness of the active compound preparation is determined by determining the inhibition of the laying of fertile eggs compared to the laying of untreated control ticks. The effect is stated in #, where 100? Έ meaning that no fertile eggs more were filed and $ 0> means that the ticks have passed in a normal way as the untreated control ticks eggs.

Investigated agents tested concentration tested parasites and results obtained are shown in the following Table 1:

La A 12 901 - 17 -

209812/1743

Table 1

In-vitro test for egg-deposition-inhibiting effect on ticks (Boophilua mioroplua, Biarra strain)

Active ingredient

100

50

Inhibition at an active ingredient concentration in io of

_L -TW *

GH,

CH,

0.1

0.08

(known comparator preparation)

0.1

0.03

—-2Ϊ ·

. HCl

0.1

0.03

0.05

0.02

I A 12

- 18 - ·

209812 / Π43

Table 1 (continued)

Active ingredient

100 1o 50 io

Inhibition in the case of an active ingredient concentrate ion in? £ of

.HCl

0.1

0.03

CH,

0.01

0.008

CHp-CH = CHp ι / ^{2 2}

0.03

0.01

^ CH ₂ -CH-CH ₂

Ql

. HCl

CH,

Le A 12 901 0.01

- 19 209812/1743

0.003

Example B: In vitro tea on Psqroptes cuniculi

3 parts of active ingredient are made with 7 parts of a mixture equal parts by weight of ethylene glycol roriomethyl ether and Mixed nonylphenol polyglycol ether. The emulsion thus obtained concentrate is mixed with water to the desired level Application concentration diluted.

With this active ingredient preparation larvae, nymphs and Adults brought into contact by Psoroptes cuniculi. For this 5 ml of the active compound preparation are placed on filter paper sandwiches pipettiart, dia mites between di® filter paper discs brought and stored in Petri dishes for 24 hours.

After 24 hours, the effectiveness of the active ingredient preparation is determined by determining the number of dead mites. The effect is stated as% , where 100 $> means that all mites have been killed and 0 $ "means that all mites are alive.

Investigated® active ingredientS ₉ tested concentrations, tested parasites and received® "findings® are based on the following table 2 II

α η ιοί

c = 5 , Z II J) C =

Table 2

In-vitro-Teat for railben-killing effect in Paoroptea ounioulit

Active ingredient

100

50

Effect at an active ingredient concentration in $> of

OH,

CH

0.03

0.01

ι

ΟΙ, 03

0.003

. HCl

0.03

0.01

CP,

0.03

0.01

La A 12

- 21 -

209812/1743

Table 2 (continued)

Active ingredient

100

50 ok

Effect at an active ingredient concentration in% τοπ

GH,

O ₉ O3

0.01

CH,

ΟΙ, 03

0.01

0.003

0.001

.CH,

Le A 12 0.03

- 22 -

0.01

209812/1743

Table 2 (port setting) .100 i » 50 fo

Active ingredient Effect with one active ingredient concentration

tion in # of

0.03

0.01

H,

. HCl

CH

0.03

0.01

1

CH

0.03

0.01

0 ₃ H ₇ (n)

. HCl

0.03-23

0.01

209812/1743

Table 2 (continued)

100

50

Active ingredient

Effect at an active ingredient concentration in io of

N '

(n)

GH,

. HGl

CE

0.03

0.01

■ κτ.

^ G ₃ H ₇ (Ii)

Eq 0.03

• HGl

GH 0.01

HGl ■ O ₉ 03 0.01

■ .m ^^ A £, \ VifJtA Ώ ld J

trm

I® A 24 112 /

te

Table 2 (continued)

100

90

Active ingredient

Effect at an active ingredient concentration in io of

0.03

j naphtha- ^^ li15

disulfonic acid

T 1

0.01

0.03

S- - «γ ^. HCl

ch;

0.01

UX. Φ-

, HCl 0.03 0.01

CH

0.003

Naphtha-

Uli — 1.5 -

dieulfonic acid

Lt A 12 901

- 25 -

0.001

209812/1743

Table 2 (continued)

Active ingredient

100 jS

50

Effect at an active ingredient concentration in io of

JT

, CH ₂ -CH = CH ₂

CH:

0.03

0.01

Cl

0.03

0.01

CJ

^ 0H ₂ -CH-OH ₂

0.03

0.01

, H

^ JH ₂ -CH = CH ₂

Cl

_HC1 0.03

0.01

Le A 12 901 - 26 -

209812/1743

Manufacturing examples Example 1:

2- (2-chlorophenylimino) -3-methyl-thiazolidine

135.7 g (0.8 mol) of 2-chlorophenyl isothiocyanate are added in the course of 1/2 hour with stirring to a solution of 60 g (0.8 mol) of 2-methylaminoethanol in 500 ecm of methylene chloride, the mixture for Simmering comes. The mixture is stirred under reflux for a further 1 hour, then evaporated to dryness, the residue is treated with 480 ecm of concentrated hydrochloric acid and the reaction mixture is stirred under reflux for 1 hour. After cooling, the batch with 1 ltr. Diluted water, alkalized with concentrated sodium hydroxide solution while cooling, and the base obtained as an oil was extracted with methylene chloride. The extract is dried over sodium sulfate and evaporated, and the residue is distilled. B.p. _{0 o1:} 135-14O ⁰ C. The yield is 147.1 g (81 i "of theory).

The following connections can be established in an analogous manner:

2- (2-Tolylimino) -3-methyl-thiazolidine, b.p. _{Q Q1.} 120 ⁰ C 2- (2-Hethoxyphenylimino) -3-methyl-thiazolidine Hydrochloride

Mp. 228-229 ° C 2- (2-trifluoromethylphenylimino) -3-methyl-thiazolidine,

Sdp.Q _o1: 119-125 ⁰ C

2- (2-bromophenylimino) -3-methyl-thiazolidine, hydrochloride,

Mp .: 184 to 185 ⁰ C

2- (2,6-xylylimino O ^ -methyl-thiazolidine, hydrochloride,

M.p. 248-253 ° C

2- (2-methoxy-6-methylphenylimino) -3-methyl-thiazolidine,

Hydrochloride m.p .: 217-218 ⁰ C.

La A 12 901 - 27 -

209812/1743

2- (2-chloro-6-methylphenylimino) -3-methyl-thiazolidine,

M.p .: 87-89 ° C 2- (2,6-Mmethoxyphenylimino) -3-methyl-thiazolidine hydrochloride m.p .: 216-217 ⁰ C.

2- (1-naphthylimino) -3-methyl-thiazolidine, m.p .: 80-81 ⁰ O 2- (5,6,7,8-tetrahydro-1-naphthylimino) -3-methyl-thiazolidine,

_Bp . 0f02: ^{192-198 0} C 2- (2-chlorophenylimino) -3-ethyl-thiazolidine,

Bp. _{O o1} : 132 - HO ⁰ C 2- (2,6-xylylimino) -3-ethyl-thiazolidine,

Hydrochloride m.p .: 194-195 ⁰ C 2- (2-chloro-6-methylphenylimino) -3-ethyl-thiazolidine,

.Q _o1 : 144 - 148 ⁰ C 2- (1-naphthylimino) -3-ethyl-thiazolidine,

M.p .: 95-96 ⁰ C 2- (5,6,7,8-tetrahydro-1-naphthylimino) -3-ethyl-thiazolidine,

Q _o1 : 180 - 192 ° C 2- (2-chlorophenylimino) -3-n-propyl-thiazolidine,

Hydrochloride m.p .: 138 - HO ⁰ C 2- (2,6-xylylimino) -3-n-propyl-thiazolidine,

Hydrochloride m.p .: 190-191 ⁰ C 2- (2-chloro-6-methylphenylimino) -3-n-propyl-thiazolidin

Hydrochloride m.p .: 173-174 ° C 2- (2-chloro-6-methoxyphenylimino) -3-n-propyl-thiazoldine,

M.p .: 146-150 ⁰ C 2- (2-methoxy-6-methylphenylimino) -3-n-propyl-thiazolidine, ^b.p. -o, or ^{U3 "U7} ° ^c

2- (1-naphthylimino) -3-n-propyl-thiazolidine,

.Q _02: 178-182 ⁰ C 2- (5,6,7 1 8-tetrahydro-1-naphthylimino) -3-n-propyl-thiazolidine,

Bp _{o. 01:} 184-187 ⁰ C 2- (2-Tolylimino) -3-isopropyl-thiazolidin, bp _{o.. o1:} 134-136 ⁰ C

Le A 12 901 - 28 -

209812/1743

2- (2-Chlorophenylimino) -3-isopropyl-thiazoMin _t

neutral naphthalene-1,5-diaulfonate m.p .: 254-256 ⁰ C. 2- (2-bromophenylimino) -3-isopropyl-thiazolidine,

Bp Q ₀₁ : 137 - H2 ° C 2- (2-methoxyphenylimino) -3-isopropyl-thiiazolidine,

Hydrochloride Sohmp. 184 - 187 ⁰ C. 2- (2,6-xylylimino) -3-isopropyl-thiazolidine,

Hydrochloride Schinp. 240 ⁰ C 2- (2-chloro-6-methylphenylimino) -3-isopropyl-thiazolidine,

Hydrochloride m.p. 207-209 ° C 2- (2-chloro-6-methoxyphenylimino) -3-isopropyl-thiazolidine,

Bp. _{O o1} : ^{148-153 0} C 2- (2-methoxy-6-methylphenylimino) -3-isopropylthiazolidine,

. Sdp _{0) 02:} 156-160 ⁰ C 2- (1-Naphthylimino) -3-isopropyl-thiazolidine,

M.p. 97-99 ⁰ C 2- (516.7 , 8-tetrahydro-1-naphthylimino) -3-isopropyl-thiazoli-

din, bp _{Q Q1} : ^{179-184 0} C 2- (2-tolylimino5-3-n-'butyl-thiazolidine, ■

. Sdp _{0> 01:} 147-149 ⁰ C 2- (2-chlorophenylimino) -3-n-butyl-thiazolidine, Sdp.Q _01: 146-156 ⁰ C.

2- (2-bromopnenylimino) -3-n-butyl-thiazoldine, bp. " 2- (2,6-xylylimino) -3-n-butyl-thiazolidine,

neutral naphthalene-1,5-disulfonate m.p .: 250-253 ⁰ C 2- (2-chloro-6-me thy lphenyl imino) -3-n-l3utyl-thiazolidine

Hydrochloride m.p .: 143-144 ⁰ C 2- (2-chloro-6-methoxyphenylimino) -3-n-butyl-thiazolidine,

_OiOi: 161-165 ⁰ C 2- (2-methoxy-6-methylphenylimino) -3- "n-butyl-thiazolidine _t

Q ₀₁ : 158 - 164 ⁰ C 2- (1-Naphthyliraino) -3-n-butyl-thiazoUäin,

Hydrochloride Sohmp .: 197-199 ° C 2-C 5,6,7 1 8-Tetrahydro-1-naphthylimino) -3 "- n-butyl-thiazolidine _f

^Sdp 0.02 ^{s 193} * ¹⁹⁷ ° ^C Le A 12 901 - 29 -

209812/1743

Example 2;

2- (2 _t 6-Dic] aIophenyl imi ^ oJ-3 -methyl "thiazolidine

A solution of 24.3 g (0.15 mol) of 2,6-bichloroaniline and 25.8 g (150 mol- ^) of thiophosgene in 150 ecm of dry ethylene chloride is stirred under reflux overnight. The mixture is then evaporated to dryness under reduced pressure, the crude 2,6-dichlorophenyl-thiocarbamic acid chloride is taken up in 100 ecm of absolute benzene, the impurities are filtered off with suction and the impurities are washed with absolute benzene. The piltrate is slowly added dropwise at room temperature to a solution of 24.8 g (0.33 mol) of 2-methylaminoethanol in 100 ecm of absolute benzene, the mixture is stirred under reflux for 4 hours and evaporated to dryness again. The residue, consisting of N- (2,6-dichlorophenyl) -Ii'-2-hydroxyethyl-N ^{l-methyl-thiourea} and 2-methylaminoethanol hydrochloride is stirred with 90 cc of concentrated hydrochloric acid for 1 hour under reflux. After cooling, the batch is diluted with 200 ecm of water, alkalized with concentrated sodium hydroxide solution while cooling, and the product recrystallized from benzene-ligroin. M.p .: 110-113 ⁰ C. The yield is 25.6 g (65.6 i "of theory).

The following compounds are obtained in an analogous manner:

2- (2,6-dichlorophenylimino) -3-ethyl-thiazolidine,

Hydrochloride m.p .: 191-193 ⁰ C 2- (2,6-dichlorophenylimino) -3-n-propyl-thiazolidine,

Hydrochloride m.p .: 188-190 ⁰ C 2- (2,6-dichlorophenylimino) -3-isopropyl-thiazolidine,

Hydrochloride m.p .: 211-213 ⁰ C 2- (2,6-dichlorophenylimino) -3-n-butyl-thiazolidine,

F: - * 'Oc-.lo.riÄ S? / Rr / p .: 16C - ^{1 <} 2 ° C

Ie A 12 901 - 30 -

209812/1743

2- (2,6-dichlorophenylimino) -3-sec-butyl-thiazolidine,

156 - 16O ⁰ C

Q ₀₁
2- (2,6-dichlorophenylimino) -3-isobutyl-thiazolidine,

Bp. _{O 02} : 161-166 ⁰ C
2- (2,6-Dibromo-4-methylphenylinino) -3-methyl-thiazolidine, m.p .: 137-138 ° C

Example 3t

2- (2-Tolylimino) -3-tert-butyl-thiazolidine

A solution of 11.7 g (0.1 mol) of 2-tert-butylaminoethanol in 50 ecm of dry benzene is saturated with dry hydrogen chloride. Are then added dropwise 11.4 g (0.105 mol) of thionyl chloride to the mixture, stirring it for 2 hours at room temperature, then until completion of development at 40 to 45 ⁰ C and attenuates them under reduced pressure to dryness. The crude 2-tert-butylaminoethyl chloride hydrochloride is taken up in 100 ml of dry chloroform and mixed with 14.9 g (0.1 mol) of 2-tolyl isothiocyanate. A solution of 10.1 g (0.1 mol) of dry triethylamine in 25 ecm of dry chloroform is then added dropwise to the reaction mixture, it is stirred for 2 hours at room temperature and 3 hours under reflux, it is evaporated to dryness under reduced pressure and the residue is taken in water, alkalize it with concentrated sodium hydroxide solution and ether out the product. The extract is dried over sodium sulfate and evaporated, and the residue is distilled. Bp. _{Q Q1} : 145 148 ⁰ C. The yield is 16.4 g (66 # of theory).

The following connections can be made in the same way:

2- (2-Chlorophenylimino) -3-tert-butyl-thiazolidine ₀₀₂ : 151-155 ° C

Le A 12 901 - 31 -

209812/1743

.? - (2-Broraphenylimino) -3-tert. -butyl-thiazolidine

Sdp. _{N ΛΟ} : 158 - 16O ⁰ C
2- (2-methoxyphenylimino) -3-tert-butyl-thiazolidine

Bp Q _o1 : 152-155 ° C
2- (2,6-xylylimino) -3-tert-butyl-thiazolidine

^Bp '0.02 ^{: 153} " ¹⁵⁵ ° ^C
2- (2-chloro-6-methylphenylimino) -3-tert-butyl-thiazolidine

^Bp '0.02 ^{: 159} " ¹⁶³ ° ^C
2- (2-chloro-6-methoxyphenylimino) -3-tert-butyl-thiazolidine bp _0t02. 154-157 ⁰ C.

2- (2-methoxy-6-methylphenylimino) -3-tert-butyl-thiazolidine

Bp Q ₀₂ : 152-158 ° C
2- (1-Naphthylimino) -3-tert-butyl-thiazolidine, b.p. _{Λ no.:} 167-171 ⁰ C.

U, K) C.

2- (5,6,7,8-tetrahydro-1-naphthylimino) -3-tert-butyl-thiazolidine b.p. ~ _AO. 177-181 ⁰ C.

Example 4:

2- (2-Tolylimino) -3-allyl-thiazolidine

11.9 g of 2-tolylisothipcyanate are added in the course of 1/2 hour with stirring to a solution of 8.1 g (0.08 mol) of 2-allylaminoethanol in 35 ecm of methylene chloride. The mixture is stirred under reflux for a further 1 hour, then evaporated to dryness under reduced pressure, 120 g of polyphosphoric acid are added to the residue and the reaction mixture is stirred for 5 hours at 80 ^° C. After cooling, the batch is taken up in ice water concentrated potassium hydroxide solution made alkaline, the base extracted with methylene chloride, the extract dried over sodium sulfate, evaporated and the residue distilled. Sdp " _{0 Q2} % 130 - 138 °. The yield is 7.7 g (41.5 ° / ° of theory).

Le A 12 901 - 32 -

209812/1743

The following are obtained analogously:

2- (2-chlorophenylimino) -3-allyl-thiazolidine,

.Q _o1 : ^{138-142 0} C 2- (2-trifluoromethylphenylimino) -3-allyl-thiazolidine,

Bp.Q ₀₁ : ^{128-132 0} C 2- (2,6-xylylimino) -3-allyl-thiazolidine,

_OfO1 : 135 - 139 ° C 2- (2-chloro-6-methylphenylimino) -3-allyl-thiazolidine,

Hydrochloride m.p .: 165 - 166 ⁰ C 2- (1-naphthylimino) -3-allyl-thiazolidine,

^Bp -0.01 ^{s 138} ~ ^U3 ° ^G 2- (2-tolylimino) -3-crotonyi-thlazolidine,

_Bp . 0j02: 137 - 141 ⁰ G 2- (2-chlorophenylimino) -3-crotonyl-thiazolidine,

_OjO1 : 135 - 137 ° C 2- (2-trifluoromethylphenylimino) -3-crotonyl-thiazolidine,

Bp. _{0> 01} : ^{133-137 0} C 2- (2,6-xylylimino) -3-crotonyl-thiazolidine,

^{Bp #} 0.02 ^{: U3} " ^H5 ° ^C 2- (2-chloro-6-methylphenylimino) -3-crotonyl-thiazolidine _>

^Sdp 'O, O1 ^{: H1} " ^H4 ° ^G 2- (1-naphthylimino) -3-crotonyl-thiazolidine,

Bp. _{O 01} : 145-15O ⁰ C 2- (2-tolylimino) -3-methallyl-thiazolidine,

Bp. _{0> 01} : 125 - 13O ⁰ C 2- (2-chlorophenylimino) -3-methallyl-thiazolidine,

Bp. _{O 02} : ^{131-134 0} C 2- (2-trifluoromethylphenylimino) -3-methallyl-thiazolidine,

Bp. _{0> 01} : ^{132-136 0} C 2- (2,6-xylylimino) -3-methallyl-thiazolidine,

Bp.Q ₀₁ : 139 - HI ⁰ C 2- (2-chloro-6-methylphenylimino) -3-methallyl-thiazolidine,

: 143 - H7 ° C

2- (2-Chlorophenylimino) -3- (2-chloroallyl) -thiazolidine, bp _{Q o1} s -155-16O ⁰ C

Le A 12 901 - 33 -

209812/1743

2- (2-trifluoroethylphenylimino) -3- (2-chloroallyl) thiazolidine

Bp.Q ₀₁ s ^{157-161 0} C 2- (2,6-xylylindno 5-3- (2-chloroallyl) thiazolidine

Bp Q ₀₂ s 160-167 ° C 2- (2-chloro-6-methylphenylimino) -3- (2-chloroallyl) thiazolidine

Sdp.Q ₀₁ s 161-164 ⁰ C 2- (2-Tolylimino) -3- (2, 3-dichloroallyl) -thlazolldin

_{Bp OsO1} s 172-176 ° C 2- (2-chlorophenylimino) -3- (2,3-dichloroallyl) thiazolidine

Bp Q ₀₁ s ^{175-178 0} C 2- (2 , 6-xylylimino 5-3- = (2, 3-dichloroallyl) thiazolidine

SdpoQ ₀₁ i 178-182 ⁰ C 2- (2-chloro »6-methylphenylimino) -3- (2, 3-dichloroallyl) -thiazolidine

Bp QQ ₁ S 180-185 ° C 2- (2,6-xylylimino) -3- (3-chloroallyl) thiazolidine

Bp. _0>01; 158-163 ⁰ C 2- (2-chloro-6-methylphenylimino) -3- (3 = chloroallyl) -thiazolidine Sdp.Q ₀₁ s 165-168 ⁰ C.

Example 5i

2- ( ^ Chlorophen yMminoJ ^ ^

20.0 g (0.1 mol) 1- (2-chlorophenyl) -3-methylthiourea who stirred the reflux for 8 hours together with 100 g of 1,2 ~ dibromopropane. After cooling, the crystals separated out are filtered off with suction and washed they with ether, dissolve the crystals in warm water and alkalize the mixture with concentrated sodium hydroxide solution. The oily base is extracted with methylene chloride, the extract is dried over sodium sulfate, evaporated and the residue is distilled. Bp _{Q Q2} s 138 - 145 ° C. The yield is 13.2 g (58% of theory)

Example 6 ;

2- (2-Chl or-6- "methylphe ny_limi no) -g- ethyl-» thiazolidi n

A solution of 8.9 g (0.1 mol) of 2-ethylaminoethanol in 50 ecm dry benzene is saturated with hydrogen chloride.

Le A 12 901 - 34 -

209812/1743

IS

11.4 g (0.105 mol) of thionyl chloride are then added dropwise to the mixture, the mixture is stirred for 2 hours at room temperature, then under reflux until the evolution of gas has ceased, and the mixture is evaporated to dryness under reduced pressure. The crude 2-ethylaminoethyl chloride hydrochloride is taken up in 50 ecm v / water and mixed with a solution of 13.0 g (0.115 mol) thiophosgene in 50 ecm ethylene chloride, then 19 g pulverized calcium carbonate are added in portions over the course of about 4 hours with vigorous stirring Mix at room temperature until there is no more gas evolution (approx. 6 hours), separate the organic phase, dry it over sodium sulfate, add a solution of 14.1 g (0.1 mol) of 2- Chlor-6-methylaniline and 10.1 g (0.1 mol) of triethylamine in 20 ecm of ethylene chloride and the reaction mixture is stirred for 2 hours at room temperature, then for 4 hours under reflux the mixture twice with dilute sodium hydroxide solution, the organic phase is dried over sodium sulfate, evaporated and the residue is distilled. B.p. _{Q Q1.} 145-148 ⁰ C. The yield is I5 _f 8 g (62 <f o of theory).

Example 7 t

2- (2-chlorophenylimino) -3-methyl-thiazolidine

2-thiono-3-methyl-thiazolidine heating a mixture of 13 "3 g (0.1 mol), 12.8 g (0.1 mol) of 2-chloroaniline and 50 cc chlorobenzene is stirred for 2 hours at 140 ⁰ C. . The solution is then evaporated under reduced pressure and the residue is distilled. B.p. _{Q Q1.} 138-141 ⁰ C. The yield is 12.2 g (54% of theory).

Le A 12 901 - 35 -

209812/1743

Example 8 : 3C

2- (2-chloro-6-methylphenyl imino) -3-allyl-thiazolidine

18.4 g (0.1 mol) of 2-chloro-6-methylphenyl isothiocyanate are added in the course of 1/2 hour with stirring to a solution of 6.8 g (0.1 mol) of 90 percent. 2-aminoethanol added in 50 ecm methylpnchloride. The mixture is stirred under reflux for 1 hour, then evaporated to dryness under reduced pressure, 40 ecm of concentrated hydrochloric acid are added to the residue and the reaction mixture is stirred under reflux for 1 hour. After cooling, the mixture is diluted with 120 cc of water, alkalized under cooling with concentrated sodium hydroxide and 2- (2-chloro-6-methylphenylamino) -thiazoline sucked off the resulting crystalline 141-143 ⁰ C of melting point. After drying, it is dissolved in 150 ecm of dry benzene and 12.1 g (0.1 mol) of allyl bromide are added over the course of 1/2 hour. The reaction mixture is stirred for 1 hour at 50 C and 2 hours under reflux, after cooling with 50 ecm 10 percent. Sodium hydroxide solution shaken until the crystals have dissolved. After the phases have been separated, <% le aqueous layer is extracted twice with benzene. The combined benzene phases are dried over sodium sulfate and then saturated with dry hydrogen chloride. The precipitating hydrochloride is filtered off with suction, recrystallized from ethanol-ether and melts at 165-166 ° C. The yield is 24.9 g (8296 of theory)

Le A 12 901 - 36 -

2Q9812 / 1743

Claims (6)

Claims;
/ 1) / 2-Arylimino-thiazolidines of the general formula -R ¹
-R in which R is a phenyl radical substituted in the 2- or 2,6-position, which can be further substituted by lower alkyl groups and / or halogen atoms, the 1-naphuyl- or 5,6,7,8-tetrahydro-1- denotes naphthyl radical, and R ¹ denotes a straight-chain or branched alkyl group with 1 to 4 or a straight-chain or branched alkylene group with 3 to 5 carbon atoms, optionally substituted by halogen atoms. 2) Process for the preparation of 2-arylimino-thiazolidines, characterized in that one a) Thioureas of the general formula R
Y-CHo-CH ₂ -N-GS-NH-R in which R and R ^{1 have} the meaning given in claim 1, while Y stands for the hydroxyl group, a halogen atom or a Sμlfonsäurerest, optionally cyclized in the presence of strong acids, or b) thioureas of the general formula R ¹ -NH-CS-NH-R BATH ORIGINAL Le A 12 901 - 37 - 209812/1743 reacts with 1,2-dihaloethanes, or
c) Arylamines of the general formula R-NH ₂ with 2-thiono- or 2-imonothiazolidines of the general formula M-R ' reacted, where R and R 'in the last-mentioned formulas have the meaning given in claim 1, and Z stands for a sulfur atom or the imino group or
d) 2-Arylamine- 2_thiazoline of the general formula * N3 J -NH- NH-R with reactive esters such as halides or sulfuric acid esters, of alcohols of the general formula RAW
converts, where R and R 'have the meaning given in claim 1 "own tung 3) Ectoparasiticidal agent characterized by a content of 2-AryliHäino-thiazolidinen according to Claim 1 or their Salt. 4) Methods of combating won ectopes ^ asite: ", ii from the class of the acarids, characterized in that Le A 12 901 - 38 - 209812/1743 one 2-arylamino-thiazolidines according to claim. 1 or their Let salts act on ectoparasites or their habitat. 5) Use of 2-Aryljmino-thiazolidinen according to claim 1 or their salts for combating ectoparasites. 6) processes for the preparation of ectoparasiticidal agents, characterized in that 2-arylimino-thiazolidines according to claim 1 or their salts with auxiliaries, Mixing extenders and / or surface-active agents, optionally with admixture of other active ingredients. BAD ORIGNAL Le A 12 901 - 39 - 209812/1743