SI7611131A8

SI7611131A8 - Process for preparing new thiazoline compounds

Info

Publication number: SI7611131A8
Application number: SI7611131A
Authority: SI
Inventors: Dieter Duerr; Walter Traber
Original assignee: Ciba Geigy Ag
Priority date: 1975-05-07
Filing date: 1976-05-06
Publication date: 1994-12-31

Description

57) Abstrakt: Postopek za pripravo novih spojin tiazolina s formulo // sf57) Abstract: Process for the preparation of novel thiazoline compounds of formula // sf

N va katerih pomenijoN va they mean

Ri in Rj neodvisno drug od drugega klor, metil ali etil, pri čemer se lahko R; nahaja v legi 4 ali 6. z izjemo, da tedaj, ko Ri io R; pi,menita klo;·, R: ne sme stati v legi 4, terR1 and R1 are independently chlorine, methyl or ethyl, wherein R1 can be; is in position 4 or 6. with the exception that when Ri io R; pi, consider chlo; ·, R: shall not stand in position 4, ter

07Ri v danem primc-ru z metoksilom substituiCM rano ravno ali razvejeno alkilno skupino ς— z 1 do 4 atomi ogljika, ravno ali razvejeCO no, v danem primeru s klorom substitui-- rano alkenilno skupino s 3 do 5 atomi ogIjika.07Ri in a given methoxyl substituent substitutes a linear or branched alkyl group ς - with 1 to 4 carbon atoms, straight or branched, optionally substituted by a chlorine alkenyl group of 3 to 5 carbon atoms.

(51) Int CH(51) Int CH

C 07D 277/42 A 01N 9/22 vključno njihovih kislinskih adicijskih soli, zlasti hidrokloridov, pri katerem spojino s formuloC 07D 277/42 A 01N 9/22 Including their acid addition salts, in particular hydrochlorides, wherein the compound of formula

v kateri imajo ostankiin which they have remains

Ri do Rj pod formulo I navedeni pomen, v polarnem topilu pri temperaturi refluksa presnovimo s kloracetaldehidom in, če se kloracetaldehid nahaja v obliki dietilacetala, v razredčeni mineralni kislini pri temperaturi refluksa, — 39 243 —R1 to R1, having the formula indicated in the formula I, is reacted in polar solvent at reflux temperature with chloracetaldehyde and, if chloracetaldehyde is in the form of diethyl acetal, in dilute mineral acid at reflux temperature, - 39 243 -

Predloženi izum se nanaša na postopek za pripravo novih spojin tiazolina s splošno formulo (I)The present invention relates to a process for the preparation of novel thiazoline compounds of general formula (I)

v kateri pomenijoin which they mean

R2 in R2 neodvisno drug od drugega klor, metil ali etil, pri čemer se lahko R2 nahaja v legi ali 6, z izjemo, da tedaj, ko R, in R, pomenita .klor, R2 ne sme stati v legi 4, terR 2 and R 2 are independently chlorine, methyl or ethyl, wherein R 2 may be in position or 6, except that when R 1 and R 2 are .chlorine, R 2 must not be in position 4, and

Rs v danem primeru z alkosilom z 1 do 2 atomoma ogljika substituirano ravno ali razvejeno alkilno skupino z 1 do 4 atomi ogljika, ravno ali razvejeno, v danem primeru s halogenom substituirano alkenilno skupino z 3 do atomi ogljika.R5 optionally with a straight chain or branched alkyl group of 1 to 2 carbon atoms, straight or branched, optionally straight or branched alkyl group of 3 to 3 carbon atoms, optionally.

ki vključujejo kislinske adicijski soli, zlasti hidrokloride.which include acid addition salts, in particular hydrochlorides.

Pod alkalnimi skupinami v smislu formule 1 je treba razumeti metilno, etilno, n-propilno. izopropilno, n-butilno, sek. butilno ali terc. butilno skupino in pod v danem primeru z atomi halogena substituiranimi alkenilnimi skupinami v smislu formule I je treba razumeti alilno, krotonilno. metalilno, 2,2-dimetilvinilno, 2-kloral:lno, 3-kloralilno ali 2,3-dikloralilno skupino.Methyl, ethyl, n-propyl should be understood to mean alkaline groups within the meaning of formula 1. isopropyl, n-butyl, sec. butyl or tert. butyl group and, optionally, halogen atoms substituted alkenyl groups within the meaning of formula I should be understood to be allyl, crotonyl. a methyl, 2,2-dimethylvinyl, 2-chloro: linear, 3-chloroallyl or 2,3-dichloroallyl group.

Kot soli spojin s formulo I pridejo razen hidrokloridov v poštev še sulfati, fosfati, perklorati, acetati, laktati, sukcinati, citrati. ali naftilindisulfonati.In addition to the hydrochlorides, salts of the compounds of formula I include sulphates, phosphates, perchlorates, acetates, lactates, succinate, citrates. or naphthylindisulfonates.

Obstoja stalna potreba po postopkih za pripravo novih spojin z akaricidnim učinkom, ki po svojih lastnosti prekašajo spojine iz znanega stanja tehnike, pri tem pa ne kažejo hib znanih spojin.There is an ongoing need for processes for the preparation of novel acaricidal compounds which, by their properties, exceed those of the prior art without exhibiting known compounds.

Biološko aktivne spojine tizolina so že znane. Tako spojine s formulo I pripadajo k skupini tiazolinov. ki so v švicarskem patentnem spisu št. 439 858 opisani kot sredstva za zatiranje škodljivcev. Spojine s formulo I v smislu izuma pa niso v navedanem patentnem spisu niti opisane glede njihovega načina učinka niti so sploh eksplicitne naSedaj smo presenetljivo ugotovili, da imajo svojih lastnosti pruekašajo spojine iz znanega stakovitost proti akaridom, zlasti pri odlaganju jajčec pri klopih, in pri tem daleč prekašajo doslej znane spojine enake smeri učinka.The biologically active compounds of tizoline are already known. Thus, the compounds of formula I belong to the group of thiazolines. which are in Swiss patent file no. 439 858 described as pest control agents. The compounds of the formula I of the invention are neither described in the said patent file nor described in terms of their mode of action, nor explicit at all. far surpass the hitherto known compounds of the same direction of effect.

2-(2-metil-4-klor-fenilimino)-3-metil-tiazolin in 2-(2,4-dimetil-fenilimino)-3-metil-tiazolin.2- (2-methyl-4-chloro-phenylimino) -3-methyl-thiazoline and 2- (2,4-dimethyl-phenylimino) -3-methyl-thiazoline.

Za pripravo tiazolinov tiosečnine v prisotnosti polarnih topil pri višji temperaturi presnovimo z a-halogenkarbonil'nimi spojinami.To prepare thiazolines, thiourea is reacted with α-halogencarbonyl compounds in the presence of polar solvents at a higher temperature.

Tako lahko spojine s formulo I pripravimo na tak način, da spojino s formuloThus, the compounds of formula I can be prepared in such a way that the compound of formula

v kateri imajo ostanki 1in which the remains have 1

Ri do Rj po formulo I navedeni pomen, v polarnem topilu pri višji temperaturi presnovimo s kloracetaldehidom in, če se kloracetaldehid nahaja v obliki dietilacetala, kot reakcijski medij uporabimo razredčeno mineralno kislino.R 1 to R 1 according to the formula I having the above meaning, in a polar solvent at higher temperature is reacted with chloracetaldehyde and, if the chloracetaldehyde is in the form of diethyl acetal, dilute mineral acid is used as the reaction medium.

Kot polarno topilo uporabimo npr. vodo ali alkohol.As a polar solvent, e.g. water or alcohol.

Kot izhodne spojine uporabljene tiosečnine s formulo II so znane in jih lahko pripravimo po že znanih metodah. Dobimo jih lahko npr. bodisi s presnovo fenilizotiocianatov z amini ali fenilaminov z izotiocianati po nasalednjih formulskih shemah:The thioureas of formula II used as starting compounds are known and can be prepared by known methods. They can be obtained e.g. either by metabolizing phenylisothiocyanates with amines or phenylamines with isothiocyanates according to the following formulas:

; 'v s; 'in s

S. < L·.' ·SS. <L ·. ' · S

Primer 1Example 1

2-(2,4-ksililimino)-3-metil-tiazolin2- (2,4-xylylimino) -3-methyl-thiazoline

19,4 g (0,1 mol) N-2,4-ksilil-N’-metil-tiosečnine in 15,2 g (0,1 mol) kloracetaldehid-dietilacetala v 150 ml 2 n vodne solne kisline pod refluksom 1 uro segrevamo do vrenja. Kato bistro, svetlorumeno raztopino ohladimo na sobno temperaturo, s 30%-nim vodnim natrijevim lugom uravnamo lahke alkalno in ekstrahiramo z etrom. Etrni ekstrakt izperemo z vodo, posušimo z natrijevim sulfatom, odfiltriramo in eter oddestiliramo. Oljnati ostanek destiliramo.19.4 g (0.1 mol) of N-2,4-xylyl-N'-methyl-thiourea and 15.2 g (0.1 mol) of chloroacetaldehyde-diethylacetal in 150 ml of 2 n aqueous hydrochloric acid under reflux for 1 hour heat to a boil. As a clear, light yellow solution was cooled to room temperature, light alkaline was adjusted with 30% aqueous sodium hydroxide solution and extracted with ether. The ether extract was washed with water, dried with sodium sulfate, filtered and the ether distilled off. Distill the oily residue.

Pri tem se s posebno velikima aktivnostima odlikujeta zlasti spojiniIn particular, the compounds exhibit particularly high activity

Dobimo 20,2 g oz. 92% teoretskega naslovne spojine z vrel. 132 do 134°C/0,4 mbar.20.2 g oz. 92% of the theoretical title compound by boiling. 132 to 134 ° C / 0.4 mbar.

—. 39 243 —-. 39 243 -

Primer 2Example 2

2-(2,6-diklor-fenil)-3-metil-tiazolin g (0,12 molov) N-(2,4-diklor-fenil)-N’-metiltiosečnine in 32 g (0,12 molov) 30%-ne vodne raztopine kloracetaldehida ob mehanskem mešanju pod refluksom v 100 ml vode 3 ure segrevamo do vrenja. Bistro raztopino ohladimo na sobno temperaturo in uravnamo lahno alkalno s 30%-nim vodnim natrijevim lugom. Nato ekstrahiramo z etrom, etrno fazo izperemo z vodo, posušimo z natrijevim sulfatom in eter oddestiliramo. Oljnati ostanek destiliramo v krogelni cevi.2- (2,6-Dichloro-phenyl) -3-methyl-thiazoline g (0.12 mol) of N- (2,4-dichloro-phenyl) -N'-methylthiourea and 32 g (0.12 mol) 30 With a mechanical stirring under reflux of 100% water in 100 ml of water, the chloracetaldehyde aqueous solution is heated to boiling for 3 hours. The clear solution was cooled to room temperature and light alkaline was adjusted with 30% aqueous sodium hydroxide solution. It is then extracted with ether, the ether phase is washed with water, dried with sodium sulfate and the ether distilled off. Distill the oily residue in a ball tube.

Dobimo 21,7 g oz. 70% teoretskega· belih kristalov naslovne spojine s tal. 88 do 90’C in vrel. 140°C/0,0066 mbar. . % 'Na analogen način dobimo naslednje tiazo)i^ ne s formulo I21.7 g oz. 70% of theory · white crystals of the title compound from the ground. 88 to 90'C and boiling. 140 ° C / 0.0066 mbar. . % 'The following thiazole and formula I are obtained in an analogous manner

Spojina št. Compound no. Rt Rt R? R? Rj Rj Fizikalni podatki 1 ·, Physical Information 1 ·, 1 1 Cl Cl ' 6-C1 '6-C1 CH} CH} 88'do 90°, 14070,0066 mbar 88 'to 90 °, 14070,0066 mbar 2 2 Cl Cl 6-CH} 6-CH} CH} CH} 86 do 88’ 9- 86 to 88 '9- 3 3 CH} CH} 6-CH} ' 6-CH} ' CIN CIN 83 'do 85’ 83 'to 85' 4 4 C₂H₅ C ₂ H ₅ 6-C2H5 6-C2H5 CH} CH} 58 do 59’ 58 to 59 ' 5 5 ch₃ ch ₃ 4-C1 4-C1 CH} CH} 66° 66 ° 6 6 CHj CHj 4-CH} 4-CH} CH} CH} 132 do .13470,4 mbar 156 do 1570,53 rpbar 132 to .13470.4 mbar 156 to 1570.53 rpbar 7 7 CH} CH} 4-CH} 4-CH} CiH₉ CiH ₉ γΛ = 1,5919 γΛ = 1.5919 8 8 CH} CH} 4-CH} 4-CH} (CH})₂CH(CH}) ₂ CH 49 do 51° 49 to 51 ° 9 9 CH} CH} 4-CH} 4-CH} (CH})}-C (CH})} - C 53’ ' 53 '' 10 10 CH} CH} 4-CH} 4-CH} CHj=CH-CH2 CH2 = CH-CH2 n^MD = 1,6149n ^M D = 1.6149 11 11 C Ih C Ih 4-CH} 4-CH} C}H7 C} H7 nV= 1,6023 nV = 1.6023 12 12 CIN CIN 4-CHi 4-CHi CH}-CH = CH-CHj CH} -CH = CH-CH2 13 13 CH₃ CH ₃ 4-CHt 4-CHt (CHO2CH.-CH2 (CHO2CH.-CH2 n-.:· - 1,5913 9 n-.:· - 1.5913 9 14 14 CH} CH} 4-CH} 4-CH} C2H5 C2H5 65° ; . 65 °; . 15 15 Cl Cl l-Clh l-Clh CH} CH} 92 do 94’ 92 to 94 ' 10 10 C H} C H} G--C2H5 G - C2H5 CH} CH} 16070,4 mbar 16070.4 mbar 17 17 C Hi C Hi 4-C1 ·. 4-C1 ·. CHj CH} 1 CHj CH} 1 85 do 88’ {.- 85 to 88 '{.- 18 18 CH} CH} 4-CII} 4-CII} CH₂ = C-CH}CH ₂ = C-CH} 120 do 12770,0013 mbar 120 to 12770,0013 mbar 19 19 C H} C H} 4-CH} 4-CH} CH₂=CC1-CH’CH ₂ = CC 1 -CH ' 20 20 • CH} • CH} 4-CH} ' 4-CH} ' C1CH = CH-CH’ C1CH = CH-CH ' 21 21 ČHj ČHj 4-CHi 4-CHi CiCH = CCl-CH’ CiCH = CCl-CH ' 97 97 Ci Ci 6-C1 6-C1 C2II5 Cii, C2II5 Cii, 149 do 15270,0013 mbar 149 to 15270,0013 mbar -COCMTC -COCMTC 138 do 14070,04 mbar 138 to 14070.04 mbar 2-1 2-1 Ci Ci ••-i γ •• -i γ C3H7 C3H7 15070,'0013 mbar·-' i · 15070, '0013 mbar · -' and · 25 25 Ci Ci 6-CI 6-CI C4H5 C4H5 14070,0013 mbar - - i 14070,0013 mbar - - i 26 26 Cl Cl 0-Cl 0-Cl (CH}):CH (CH): CH 130 do 13570,0013 mbar 130 to 13570,0013 mbar 27 27 Cl Cl 6-Ci . .. 6-Ci. .. (CH})iC (CH}) iC 28 28 Cl Cl , 6-Ci , 6-Ci CH2-CH-CK2 CH2-CH-CK2 150 do 15570,0013 mbar 150 to 15570,0013 mbar

— 39 243 —- 39 243 -

29 29 Cl Cl 6-C1 6-C1 (CHj)2CH-CH2 (CH2) 2CH-CH2 147 do 15270,0013 mbar 147 to 15270,0013 mbar 30 30 Cl- Cl- 6-C1 6-C1 CH2=CC1-CH₂ CH 2 = CC1-CH ₂ 31 31 Cl Cl 6-C1 6-C1 C1CH=CH-CH2 C1CH = CH-CH2 32 32 Cl Cl 6-C1 6-C1 C1CH = CC1-CH2 C1CH = CC1-CH2 33 33 Cl Cl 6-C1 6-C1 CHj-CH = CH-CH2 CH2-CH = CH-CH2 34 34 Cl Cl 6-C1 6-C1 CH2=C-CH₂ 1CH2 = C-CH ₂ 1 1 CHj 1 CHj 35 35 CHj CHj 6-CjHs 6-CjHs C₂H_s C ₂ H _s 13070,04 mbar 13070,04 mbar 36 36 CHj CHj 6-C2H5 6-C2H5 CjHj CjHj 11970,0013 mbar 11970,0013 mbar 37 37 CHj CHj 6-C2HJ 6-C2HJ C<H9 C <H9 129 do 13570,0013 mbar 129 to 13570,0013 mbar 38 38 CHj CHj 6-C2H5 6-C2H5 (CHj)2CH (CH2) 2CH 13070,0013 mbar 13070,0013 mbar 39 39 CHj CHj 6-C2H3 6-C2H3 (CHj)jC (CH2) jC 13470,0066 mbar 13470,0066 mbar 40 40 CHj CHj 6-CjHs 6-CjHs CH2=CH-CH2 CH2 = CH-CH2 14070,013 mbar 14070,013 mbar 41 41 CHj CHj 6-C2H5 6-C2H5 (CHj)2-CH-CH2 (CH2) 2-CH-CH2 12870,0060 mbar 12870,0060 mbar 42 42 CHj CHj 6-C2H5 6-C2H5 CH2=CC1-CH₂ CH 2 = CC1-CH ₂ 43 43 CHj CHj e-CzHs e-CzHs C1CH=CH-CH2 C1CH = CH-CH2 44 44 CHj CHj 6-C2H5 6-C2H5 C1CH = CC1-CH₂ C1CH = CC1-CH ₂ 45 45 CHj CHj 6-C2H5 6-C2H5 CHj-CH = CH-CH2 CH2-CH = CH-CH2 46 46 CHj CHj 6-C2H5 6-C2H5 CH₂=C-CH2CH ₂ = C-CH 2 120 do 12770,0013 mbar 120 to 12770,0013 mbar

II

CHjCHj

47 47 C) C) 4-CHj 4-CHj C2H5 C2H5 145 do 15070,0033 mbar 145 to 15070.0033 mbar 48 48 Cl Cl 4-CHj 4-CHj CjHj CjHj 15070,0066 mbar 15070,0066 mbar 49 49 Cl Cl 4-CHj 4-CHj CjH» CjH » 15570,0066 mbar 15570,0066 mbar 50 50 Cl Cl 4-CHj 4-CHj (CHj)2CH (CH2) 2CH 13570,0066 mbar 13570,0066 mbar 51 51 Cl Cl 4-CHj 4-CHj (CHj)jC (CH2) jC 155 do 16070,00013 mbar 155 to 16070.00013 mbar 52 52 Cl Cl 4-CHj 4-CHj CHi=CH-CH2 CH1 = CH-CH2 16570,00013 mbar 16570,00013 mbar 53 53 Cl Cl 4-CHj 4-CHj (CHj)2-CH-CH₂ (CHZ) 2-CH-CH ₂ 54 54 Cl Cl 4-CHj 4-CHj CH2 = CC1-CH2 CH2 = CC1-CH2 55 55 Cl Cl 4-CHj 4-CHj CICH-CH-CH: CICH-CH-CH: 56 56 Cl Cl 4-CHj 4-CHj CHj-CH = CH-CH₂ CHj-CH = CH-CH ₂ 57 57 Cl Cl 4-CHj 4-CHj CH; = C-CH2 CH; = C-CH2

CHjCHj

58 58 CHj CHj 4-C1 4-C1 C2H5 C2H5 14870,013 mbar 14870,013 mbar 39 39 CHj CHj 4-C1 4-C1 CjHj CjHj 122 do 13070,0107 mbar 122 to 13070.0107 mbar 60 60 CHj CHj 4-C1 4-C1 14570,0066 mbar 14570,0066 mbar 61 61 CHj CHj 4-C1 4-C1 (CHjJzCH (CHjJzCH 139 do 14570,013 mbar 139 to 14570,013 mbar 62 62 CHj CHj 4-C1 4-C1 (CHj)jC (CH2) jC 135 do 14070,0093 mbar 135 to 14070.0093 mbar 63 63 CHj CHj 4-C1 4-C1 CH₂=CH-CHjCH ₂ = CH-CH ₂ 135 do 14070,013 mbar 135 to 14070,013 mbar 64 64 CHj CHj 4-C1 4-C1 (CHj)2-CH-CH₂ (CHZ) 2-CH-CH ₂ 14770,013 mbar 14770,013 mbar 65 65 CHj CHj 4-C1 4-C1 CH₂ = CC1-CH2CH ₂ = CC 1 -CH 2 66 66 CHj CHj 4-C1 4-C1 C1CH = CH-CH₂ C1CH = CH-CH ₂ 67 67 ru, ru, 4-C1 4-C1 C1CH = CC1-CH2 C1CH = CC1-CH2 68 68 CHj CHj 4-C1 4-C1 CHj-CH = CH-CHz CH2-CH = CH-CH2 69 69 CHj CHj 4-C1 4-C1 CH₂=C-CH2 ! CHjCH ₂ = C-CH 2! CHj 135 do 13970,0013 mbar 135 to 13970,0013 mbar 70 70 Cl Cl 6-CHj 6-CHj CjHs CjHs 15370,013 mbar 15370,013 mbar 71 71 Cl Cl 6-CHj 6-CHj C3H7 C3H7 14170,013 mbar 14170,013 mbar

— 39 243- 39 243

72 72 Cl Cl 6-CHj 6-CHj CjHj CjHj 14070,0013 mbar 14070,0013 mbar 73 73 Cl Cl 6-CHj 6-CHj (CHj)zCH (CH3) zCH 15570,013 mbar 15570,013 mbar 74 74 Cl Cl 6-CHj 6-CHj (CHj)jC (CH2) jC 75 75 Cl Cl 6-CHj 6-CHj CH2=CH-CH₂ CH 2 = CH-CH ₂ 14670,013 mbar 14670,013 mbar 76 76 Cl Cl 6-CHj 6-CHj (CHj)2CH-CH2 (CH2) 2CH-CH2 14070,0066 mbar 14070,0066 mbar 77 77 Cl Cl 6-CHj 6-CHj CH₂=CC1-CH2CH ₂ = CC 1 -CH 2 78 78 Cl Cl 6-CHj 6-CHj C1CH-CH-CH2 C1CH-CH-CH2 79 79 Cl Cl 6-CHj 6-CHj C1CH-CC1-CH2 C1CH-CC1-CH2 80 80 Cl Cl 6-CHj 6-CHj CHj-CH=CH-CH2 CH2-CH = CH-CH2 81 81 Cl Cl 6-CHj 6-CHj CH2=C-CH2 1 CH2 = C-CH2 1 130 do 13570,0013 mbar 130 to 13570,0013 mbar 1 CHj 1 CHj 82 82 CjHj CjHj 6-C2H5 6-C2H5 C₂H₅ C ₂ H ₅ 119 do 12370,0013 mbar 119 to 12370,0013 mbar 83 83 C2H5 C2H5 6-C2H5 6-C2H5 CjHj CjHj 84 84 C2H5 C2H5 6-C2H5 6-C2H5 C4H5 C4H5 85 85 C2H5 C2H5 6-C2H5 6-C2H5 (CHj)2CH (CH2) 2CH 86 86 C2H5 C2H5 6-C2H5 6-C2H5 (CHj)jC (CH2) jC 87 87 C2H5 C2H5 6-C2H5 6-C2H5 CH2=CH-CH2 CH2 = CH-CH2 112 do 11870,0013 mbar 112 to 11870.0013 mbar 88 88 CjHs CjHs 6-C2H5 6-C2H5 (CHj)2CH-CHi (CH2) 2CH-CH1 129 do 13270,0013 mbar 129 to 13270,0013 mbar 89 89 C2H5 C2H5 6-C2H5 6-C2H5 CH2=CC1-CH2 CH2 = CC1-CH2 90 90 C2H5 C2H5 6-C2H5 6-C2H5 C1CH=CH-CHj C1CH = CH-CH2 91 91 CjHj CjHj 6-C2H5 6-C2H5 C1CH-CC1-CH2 C1CH-CC1-CH2 92 92 CjHj. CjHj. 6-C2H5 6-C2H5 CH)-CH = CH-CH2 CH) -CH = CH-CH2 93 93 CjHs CjHs 6-C2H5 6-C2H5 CH2=C-CH2 I CH2 = C-CH2 I 1 CHj 1 CHj 94 94 CHj CHj 6-CHj 6-CHj CzHj CzHj 135 do 14070,0013 mbar 135 to 14070.0013 mbar 95 95 CHj CHj 6-CHj 6-CHj CjH₇ CjH ₇ 14070,0013 mbar 14070,0013 mbar 96 96 CHj CHj 6-CHj 6-CHj (CHj)2CH (CH2) 2CH 14570,0013 mbar 14570,0013 mbar 97 97 CHj CHj 6-CHj 6-CHj C4H» C4H » 14870,0013 mbar 14870,0013 mbar 98 98 CHj CHj 6-CHj 6-CHj (CHj)2CH-CHj (CH3) 2CH-CH3 12870,0013 mbar 12870,0013 mbar 99 99 CHj CHj 6-CHj 6-CHj (CHj)j-C (CH3) j-C 13570,0013 mbar 13570,0013 mbar 100 100 CHj CHj 6-CHj 6-CHj CH2 = CH-CH₂ CH 2 = CH-CH ₂ 14670,0013 mbar 14670,0013 mbar 101 101 CHj CHj 6-CHj 6-CHj CH2=C-CHj i CH2 = C-CH2 i 122 do 12770,0013 mbar 122 to 12770,0013 mbar 1 CHj 1 CHj

Tiazolini s formulo 1 imajo odlične lastnosti zatiranja akaridov, zlasti klopov (Ixodidae), kot npr, Amblyomma, Rhipicephalus in Boophilus. To velja zlasti za zatiranje odlaganja fertilnih jajčec. Poleg tega kažejo te spojine intenzivni detaširni učinek, kar je posebnega pomena za obdelavo že okuženih živali gostiteljic (npr. goveda ali kuncev). Detašimi učinek se prične neposredno po aplikaciji učinkovite snovi, s čemer se klopi ovirajo pri tem, da nadaljujejo privzem hrane iz gostiteljice, t.j. krvi. V teku obdelave se odločijo od živali gostiteljice, pri čemer je ta v končnem učinku popolnoma prosta škodljivcev.Thiazolines of formula I have excellent acarid suppression properties, especially ticks (Ixodidae), such as Amblyomma, Rhipicephalus and Boophilus. This is especially true for suppressing the laying of fertile eggs. In addition, these compounds show an intense detachment effect, which is of particular importance for the treatment of already infected host animals (eg cattle or rabbits). The detachment effect begins immediately after the administration of the effective substance, thereby preventing the ticks from continuing to retrieve food from the host, i.e. blood. In the course of processing, they are decided by the host animal, which in the final effect is completely free from pests.

Primer 3Example 3

Test učinka pri klopih: zaviranje odlaganja jajčecBench effect test: inhibiting egg deposition

Kot testne živali uporabimo polno napite samice govejega klopa Boophilus microplus. Za vsako koncentracijo obdelamo po 10 klopov odpornega in normalno občutljivega soja. Klope za kratek čas potopimo v vodne emulzije oz. vodne raztopine soli spojin, ki jih preiskujemo. Fiksiramo jih na ploščah, prevlečenih z dvojnim lepilnim trakom, in ob konstantnih pogojih hranimo v klimatiziranem prostoru. Vrednotimo po teh tednih. Ugotovimo totalno zaviranje odlaganja fertilnih jajčec.As test animals, we use Boophilus microplus fully drunk female bovine ticks. For each concentration, 10 ticks of resistant and normally sensitive soybeans are treated. Immerse the ticks for a short time in water emulsions. aqueous solutions of the salts of the compounds under investigation. They are fixed on panels coated with double adhesive tape and kept in an air-conditioned room under constant conditions. We value after these weeks. We determine the total inhibition of the laying of fertile eggs.

Zaviralni učinek snovi izrazimo kot koncentracijo snovi v ppm pri 100%-nem učinku proti normalno občutljivim in odpornim odraslim klopovim samicam.The inhibitory effect of the substance is expressed as the concentration of the substance in ppm at 100% effect against normally sensitive and resistant adult tick females.

— 39 243 —- 39 243 -

Rezultati so naslednji:The results are as follows:

Minimalna koncentracija v ppm pri 100%-nem zavir. učinkuMinimum concentration in ppm at 100% inhibition. effect

Spojina Compound občutljive sensitive otporne resistant 1) 2-(2,6-diklorfenilimino)-3-metil-tiazolin 1) 2- (2,6-Dichlorophenylimino) -3-methyl-thiazoline 10 10 10 10 2) 2-(2-klor-6-metilfenilimino)-3-metil-tiazolin 2) 2- (2-Chloro-6-methylphenylimino) -3-methyl-thiazoline <50 <50 <50 <50 3) 2-(2,6-dietilfenilimino)-3-metil-tiazolin 3) 2- (2,6-Diethylphenylimino) -3-methyl-thiazoline <50 <50 <50 <50 4) 2-(2-metil-4-klorfenilimino)-3-metil-tiazolin 4) 2- (2-methyl-4-chlorophenylimino) -3-methyl-thiazoline 10 10 5 5 5) 2-(2,4-dimetilfenilimino)-3-metil-tiazolin 5) 2- (2,4-dimethylphenylimino) -3-methyl-thiazoline 10 10 10 10 6) 2-(2-metil-6-etilfenilimino)-3-metil-tiazolin 6) 2- (2-methyl-6-ethylphenylimino) -3-methyl-thiazoline <50 <50 <50 <50

Preizkus toksičnosti: DL» pri podgani p.o. spojina št. 4 2500 mg/kg)Toxicity test: DL »in rat p.o. compound no. 4 2500 mg / kg)

Primerjalni rezultati znanih spojinComparative results of known compounds

Minimalna koncentracija v ppm pri 100%-nem zaviralnem učinkuMinimum concentration in ppm at 100% inhibitory effect

Spojina Compound občutljive sensitive odporne resistant 2-(3,4-diklorfenilimino)-N-n-butil-pirolidin (Bimarit) 2- (3,4-Dichlorophenylimino) -N-n-butyl-pyrrolidine (Bimarite) 1000 1000 1000 1000 2-(3,4-diklorfenilimino)-3-metil-tiazolin .(švicarski patentni spis Št. 439 858) 2- (3,4-Dichlorophenylimino) -3-methyl-thiazoline (Swiss Patent File No. 439 858) >1000 > 1000 >1000 > 1000 2-(3,4-diklorfenilimino)-3-metil-tiazolin.HCl (švicarski patentni spis št. 439 858) 2- (3,4-Dichlorophenylimino) -3-methyl-thiazoline.HCl (Swiss Patent File No. 439 858) > 1000 > 1000 >1000 > 1000 2-(4-klorfenilimino)-3-metil-tiazolin.HCl (švicarski patentni spis št. .439 858) 2- (4-chlorophenylimino) -3-methyl-thiazoline.HCl (Swiss Patent File No. 439 858) > 1000 > 1000 >1000 > 1000

Primer 4Example 4

Test učinka pri klopih: detaširni učinekBench impact test: detachment effect

Odrasle klope in nimfe namestimo na kunčja ušesa, pri čemer ušesa s tekstilno tkanino v obliki vrečke obdamo tako, da škodljivci ne morejo pobegniti. Pred obdelavo ovoj odstranimo in .uoeiežimo okužbo. Okužena ušesa za okoli 2 minuti potopimo v 0,05%-no raztopino preizkušane snovi. Pri testni raztopini gre za vodno razredčino emulzijskega koncentrata zadevne snovi. Nato ovoj ponovno namestimo. Vrednotimo po 24 urah. Učinkovitost preizkušane snovi izrazimo v % odločenih klopov v odnosu na število klopov, ki so bili pred obdelavo pritrjeni na kunčjem ušesu.Adult ticks and nymphs are placed on rabbit ears, with bag-shaped ears wrapped around the fabric so that the pests cannot escape. Before treating the wrapping, remove and clean the infection. Immerse the infected ears for about 2 minutes in a 0.05% solution of the test substance. The test solution is an aqueous dilution of the emulsion concentrate of the substance in question. Then reinstall the wrap. Valued after 24 hours. The effectiveness of the test substance is expressed in% of ticks determined relative to the number of ticks that were attached to the rabbit ear prior to treatment.

Rezultati so naslednji:The results are as follows:

Spojina Compound Detaširni učinek v % odločenih klopov Detachment effect in% of ticks determined Amblyomma hebraeum Amblyomma hebraeum Rhipice- phalus bursa Rhipice- phalus bursa odrasle samice in samci adult females and males nimfe nymphs 2-(2-metil-4-klorfenil- 2- (2-methyl-4-chlorophenyl- imino)-3-metil-tiazolin imino) -3-methyl-thiazoline 100 100 100 100 100 100 2-(2,4-dimetilfenilimino)- 2- (2,4-dimethylphenylimino) - -3-metil-tiazolin -3-methyl-thiazoline 100 100 100 100 100 100

Primerjalni poizkus z znano spojino (Comparison with known compound (

Govedo okužimo s samicami Amblyomma in, ko se klopi v teku 1 do 2 dni trdno nasesajo, napršimo z raztopino emulzijskega koncentrata, razredčeno z vodo, pri čemer znaša koncentracija učinkovite snovi 0,05%.The cattle are infected with Amblyomma females and, when the ticks are firmly inoculated for 1 to 2 days, sprayed with a solution of the emulsion concentrate diluted with water at a concentration of 0,05%.

Rezultati so naslednji:The results are as follows:

Detaširni učinek, šte-Detachment effect, count-

vilo fiksirnih villa of fixers klopov ticks Spojina Compound pred obdelavo before processing Po obdelavi Po processing 2-(2-metil-4-klorfenil-imino) -3-metil-tiazolin 2- (2-methyl-4-chlorophenyl-imino) -3-methyl-thiazoline 60 60 0 0 2-(2,4-dimetilfenilimino)- -3-metil-tiazolin 2- (2,4-dimethylphenylimino) - -3-methyl-thiazoline 60 60 0 0 BIMARIT BIMARIT 75 75 73 73

Spojine s formulo I lahko uporabimo same ali skupaj s primernimi nosilci in/ali dodatnimi snovmi. Primerni nosilci in dodatne snovi so lahko trdni ali tekoči ter ustrezajo v formulirni tehniki običajnim snovem, kot npr. naravnim ali regeneriranim snovem, topilom, dispergirnim sredstvom, omočilnim, oprijemnim sredstvom, zagostilom in/ali vezivom.The compounds of formula I can be used alone or together with suitable carriers and / or additional substances. Suitable carriers and excipients can be solid or liquid and are suitable for formulation techniques with conventional substances such as e.g. natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners and / or binders.

Za aplikacijo lahko spojine s formulo I predelamo v oprašilna sredstva, emulzijske koncentrate, granulate, disperzije, spreje, v raztopine ali naplavine z običajno sestavo, ki v aplikacijski tehniki spadajo v splošno znanje. Nadalje naj omenim- kopeli za živali in napršilne prehode kakor tudi metodo »pour-on«, pri katerih uporabimo vodne pripravke ali koncentrate.For application, the compounds of formula I can be converted into pollinators, emulsifiable concentrates, granulates, dispersions, sprays, solutions or debris of a conventional composition, which are common in the application technique. Furthermore, mention should be made of animal baths and spray passageways as well as a pour-on method using aqueous preparations or concentrates.

Sredstva v smislu izuma pripravimo na sam po sebi znan način z dobrim mešanjem in/ali mletjem uičnkovitih snovi s formulo I s primernimi nosilci, v danem primeru ob dodatku proti učinkovitim snovem inertnih ^?dispe'rgirnih sredstev aliThe agents of the invention are prepared in a manner known per se by good mixing and / or milling of the Formula I active ingredients with suitable carriers, optionally when added against effective inert substances ^? dispensing agents or

243 —243 -

7· top:!. Učinkovite snovi se lahko nahajajo in jih uporabimo v predelanih oblikah, opisanih v nadaljevanju.7 · top:!. The active substances can be found and used in the recovered formulations described below.

Trdne predelane oblike so oprašilna sredstva, posipalna sredstva, granulati, ovojnični granulati, inpregnirani granulati in homogeni granulati.Solid reclaimed forms are pollinating agents, spreading agents, granules, envelope granules, inpregnated granules and homogeneous granules.

Tekoče predelane oblike soThey are liquid processed forms

a) v vodi dispergirni koncentrati učinkovitih snovi, t.j. razpršilni praški (wettable powders), paste, emulzije,a) dispersible concentrates of active substances in water, i.e. wettable powders, pastes, emulsions,

b) raztopine.b) solutions.

Vsebnost učinkovite snovi v zgoraj opisanih sredstvih znaša 1 do 80%.The content of the active substance in the agents described above ranges from 1 to 80%.

Primer 4Example 4

Emulzijski koncentrat utež. delov zgoraj navedene učinkovite snovi raztopimo v utež delih ksilola in dodamo utež. delov emulgirnega sredstva, ki obstaja iz mešanice arilfenilpoliglikoletra in kalcijeve soli dodecilbenzolsulfonske kisline. Emulzijskemu koncentratu lahko dodamo vodo v poljubnem razmerju in pri tem tvori mlečnato emulzijo.Emulsion concentrate by weight. parts of the above-mentioned active substance are dissolved in a weight of parts of xylene and a weight is added. parts of an emulsifying agent consisting of a mixture of arylphenylpolyglycol ether and the calcium salt of dodecylbenzenesulfonic acid. Water can be added to the emulsion concentrate in any proportion, forming a milky emulsion.

Primer 5Example 5

Emulzijski koncentrat do največ 30 utež. delov učinkovite snovi ob nvšanju pri sobni temperaturi raztopimo vEmulsion concentrate up to a maximum of 30 weights. dissolve parts of the active substance at room temperature by dissolving in

211 utež. delih dibutilftalata,211 weight. parts of dibutyl phthalate,

IG utež. delih Solvent 200 (visokoaromatskega naftnega destilata z majhno viskoznostjo) in do 35 utež. delih Dutrcx 238 FC (viskoznega visokoaromatskega naftnega destilata) ter dodamo utež. delov cmulgatorskc mešanice, ki obstaja iz poliglikoletra ricinusovega olja in kalcijeve >oli dodecilbenzolsulfonske kisline. Tako dobljeni emulzijski koncentrat daje v vodi mlečnate emulzije.IG weight. parts of Solvent 200 (high-aromatic low-viscosity petroleum distillate) and up to 35 weights. parts of Dutrcx 238 FC (viscous high-aromatic petroleum distillate) and added weight. parts of a cmulgator mixture consisting of castor oil polyglycoleter and calcium or dodecylbenzenesulfonic acid. The emulsion concentrate thus obtained gives milky emulsions in water.

Pia mer 0Pia mer 0

Razpršilni prašek uo 30 utež. delov učinkovite snovi v mešalni aparaturi dobro pomešamo s utež. deli nosilčne snovi, ki sesa (kremenica K 320 ali Wessalon S).Spray powder at 30 weights. parts of the active substance in the mixing apparatus are well mixed with the weight. parts of the carrier substance to be sucked in (silica K 320 or Wessalon S).

do 80 utež. deli nosilčne snovi (Bolus alba al! Paola; B 24) ter mešanice dispergirnega Kredeva, ki obstaja iz utež. delov natrijevega lavrilusfonata in 5 utež. delov, alkilarilpoliglikoletra. To mešanico zmeljemo v miinu s čepi ali mlinu z zračnim curkom. Tako dobljeni razpršilni prašek daje v vodi dobro suspenzijo.up to 80 weights. parts of the carrier substance (Bolus alba al! Paola; B 24) and mixtures of dispersing Cretaceous existing from weights. portions of sodium lauryl sulfonate and 5 weights. parts, alkylaryl polyglycol ether. Grind this mixture in a mine with plugs or an air jet mill. The spray powder thus obtained gives a good suspension in water.

Primer 7 ..Example 7..

Oprašilno sredstvo utež. delov drobno zmlete učinkovite snovi dobro pomešamo z .Pollinator weight. parts of finely ground active substance are well mixed with.

utež. deloma oborjene kremenice in .weight. partly precipitated quartz and.

utež. deli smukca.weight. parts of talc.

19,4 g (0,1 mol) N-2,4-ksilil-N’-metil-tiosečnine in 15,2 g (0,1 mol) kloracetaldehid-dietilacetala v 150 ml 2 n vodne solne kisline pod refluksom 1 uro segrevamo do vrenja. Nato bistro, svetlorumeno raztopino ohladimo na sobno temperaturo, s 30%-nim vodnim natrijevim lugom uravnamo lahno alkalno in ekstrahiramo z etrom. Etrni ekstrakt izperemo z vodo, posušimo z natrijevim sulfatom, odfiltriramo in eter oddestiliramo. Oljnati ostanek destiliramo.19.4 g (0.1 mol) of N-2,4-xylyl-N'-methyl-thiourea and 15.2 g (0.1 mol) of chloroacetaldehyde-diethylacetal in 150 ml of 2 n aqueous hydrochloric acid under reflux for 1 hour heat to a boil. The clear, light yellow solution was then cooled to room temperature, the aqueous sodium hydroxide solution was adjusted with a light alkaline solution and extracted with ether. The ether extract was washed with water, dried with sodium sulfate, filtered and the ether distilled off. Distill the oily residue.

Najpomembnejši tehnološki parametri, do katerih je prišel prijavitelj v teku razvijanja prijavljenega postopka, so naslednji:The most important technological parameters encountered by the applicant in the course of developing the notified procedure are the following:

Pri uporabi dietilacetala kloracetaldehida kot reaktanta je treba delati v prisotnosti razredčene mineralne kisline.When using diethyl acetal chloracetaldehyde as a reactant, it must be worked in the presence of dilute mineral acid.

Najboljše dobitke dosežemo, če teče presnova pri temperaturi refluksa uporabljenega topila.The best results are obtained if the reaction is carried out at the reflux temperature of the solvent used.

Kot reakcijski medij so uporabna polarna topila.Polar solvents are useful as the reaction medium.

Claims

A process for the preparation of novel thiazoline compounds of formula ^R 1

3-;

J in which they mean

Ri and R? independently of one another chlorine, methyl or ethyl, wherein R: may be in the 4 or 6 position, except that when R1 and R3 are; mean chlorine, R? may not stand in position 4, and - 39 243 - in which the remains have

R 1 to R _{3 of} the formula I having the above meaning, in a polar solvent at reflux temperature, is reacted with chloroethaldehyde and, if the chloroacetaldehyde is in the form of diethyl acetal, in dilute mineral acid at reflux temperature.

Process according to claim 1, characterized in that water is used as a polar solvent.

Process according to claim 1, characterized in that dilute aqueous hydrochloric acid is used as the diluted acid.

Rj optionally substituted by straight or branched alkyl group of 1 to 4 carbon atoms with methoxyl, straight or branched alkenyl group optionally substituted with 3 to 5 carbon atoms, including their acid addition salts, in particular hydrochlorides, characterized by , to give a compound of formula