DK142985B - PYRAZOLINE COMPOUNDS FOR USE AS INSECTICIDES - Google Patents

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Vpa,/ (11) FREMLÆG6ELSESSKRIFT 142985 DANMARK «’>'"« C|S c o? ysi/os §(21) Ansegning nr. 55/77 (22) Indleveret den 6. Jan· 1977 (24) Lebedag 6. Jan.· 1977 (44) Ansegningen fremlagt og q.Vpa, / (11) PUBLICATION 142985 DENMARK "'>" "" C | S co? Ysi / os § (21) Application No. 55/77 (22) Filed on 6 Jan · 1977 (24) Life day 6 Jan · 1977 (44) The claim presented and q.

fremlaeggelaesskriftet offentliggjort den 9· ®®^*· ' 9° DIREKTORATET FOR . .the notice of publication published on 9 ° ®® ^ * · '9 ° DIRECTORATE FOR. .

PATENT-OG VAREMÆRKEVÆSENET (30) Pnontet begæret fra denPATENT AND TRADE MARKET (30) Pnontet requested from it

9. Jan. 1976, 7600178, NLJan. 9 1976, 7600178, NL

(71) DUPHAR INTERNATIONAL RESEARCH B.V», C.J. van Houtenlaan 56, Weesp, NL.(71) DUPHAR INTERNATIONAL RESEARCH B.V », C.J. van Houtenlaan 56, Weesp, NL.

(72) Opfinder: Jan Johannes van Raalen, van Houtenlaan 56, Weesp, NL: Rudolf Mulder, Molenweg 44, Lunteren, NL.(72) Inventor: Jan Johannes van Raalen, 56 van Houtenlaan, Weesp, NL: Rudolf Mulder, 44 Molenweg 44, Lunteren, NL.

(74) Fuldmægtig under sagens behandling:(74) Plenipotentiary in the proceedings:

Internationalt Patent-Bureau._ (64) Pyrazolinforbindelser til anvendelse som insekticider.International Patent Bureau._ (64) Pyrazoline compounds for use as insecticides.

Opfindelsen angår hidtil ukendte pyrazolinforbindelser til anvendelse som insekticider.This invention relates to novel pyrazoline compounds for use as insecticides.

Fra tysk offentliggørelsesskrift 2.304.584 er det kendt, at pyrazolinforbindelser, der j. 1,3- eller 1,3,5-stillingerne i pyrazolinringen er udstyret med en substituent, er i besiddelse af biocid virkning over for arthropoder, f.eks, mider og insekter.From German publication specification 2,304,584 it is known that pyrazoline compounds which j. The 1,3 or 1,3,5 positions in the pyrazoline ring are equipped with a substituent, have biocidal action against arthropods, for example, mites and insects.

Det har nu vist sig, at pyrazolinforbindelser, der er kendetegnet ved den i patentkravet angivne formel, hvor X betegner et halogenatom eller en alkyl-, alkoxy- eller alkylthiogruppe med 1-4 carbonatomer eller en cyanogruppe, Y er et halogenatom eller en alkoxygruppe med 1-4 carbonatomer, og R er en alkylgruppe med 1-6 carbonatomer, der er substitueret med cyano, piperidino eller 2 142985 dialkylamino, hvis alkylgrupper hver især indeholder fra 1-4 carbon-atomer,er i besiddelse af meget stærk insekticid virkning.It has now been found that pyrazoline compounds characterized by the formula of the claim, wherein X represents a halogen atom or an alkyl, alkoxy or alkylthio group of 1-4 carbon atoms or a cyano group, Y is a halogen atom or an alkoxy group having 1-4 carbon atoms and R is an alkyl group of 1-6 carbon atoms substituted by cyano, piperidino or dialkylamino, each of which alkyl groups contain from 1-4 carbon atoms, possesses very strong insecticidal activity.

Strukturelt beslægtede 1,3,4-substituerede pyrazolinderivater er genstand for den ikke forud offentliggjorte hollandske patentansøgning 74.09433. De der omhandlede forbindelser har også gode insekticide egenskaber.Structurally related 1,3,4-substituted pyrazoline derivatives are the subject of unpublished Dutch patent application 74.09433. The compounds of the invention also have good insecticidal properties.

Ved biologiske undersøgelser har det vist sig, at de omhandlede forbindelser har god insekticid virkning, og at de allerede ved lave doseringer er i stand til at kontrollere f.eks. biller, bille-larver, moskitolarver såvel som larver af kålsommerfuglen.In biological studies it has been found that the compounds of the invention have good insecticidal effect and that they are already able to control e.g. beetles, beetle larvae, mosquito larvae as well as larvae of the cabbage butterfly.

Det har'overraskende vist sig, at den insekticide virkning af de omhandlede forbindelser er betydelig bedre end de kendte 1,3-og 1,3,5-substituerede pyrazoliner. Det har vist, at i mange tilfælde har de omhandlede forbindelser også god virkning over for gulfeber-moskitoen udover en udmærket virkning over for både coloradobillen og kålsommerfuglelarven. De kendte forbindelser af rækken af 1,3,5-substituerede pyrazoliner og 1,3-substituerede forbindelser findes ofte bortset fra en god virkning over for larverne af coloradobillen at udvise en mindre stærk virkning over for larverne af den hvide kålsommerfugl og i almindelighed ingen virkning over for larverne af gulfebermoskitoen.Surprisingly, it has been found that the insecticidal effect of the compounds of the present invention is significantly better than the known 1,3- and 1,3,5-substituted pyrazolines. It has been shown that in many cases, the compounds of the present invention also have a good effect on the yellow fever mosquito in addition to an excellent effect on both the Colorado beetle and the cabbage butterfly larva. The known compounds of the series of 1,3,5-substituted pyrazolines and 1,3-substituted compounds are often found, apart from a good effect on the larvae of the Colorado beetle, to exhibit a less potent effect on the larvae of the white cabbage butterfly and in general no effect on the larvae of the yellow fever mosquito.

Mange af de omhandlede virksomme forbindelser udviser for eksempel en optimal virkning i koncentrationer på 0,3 til 3 ppm over for larverne af coloradobillen, og i koncentrationer på 0,3 til 30 ppm en maksimumvirkning over for kålsommerfuglelarven og yderligere i en koncentration på 0,03 til 0,3 ppm maksimumvirkning over for larverne af gulfebermoskitoen. Som eksempler på pyrazolinforbindel-ser ifølge opfindelsen med biocid virkning kan nævnes: 1) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidino-ethyl)-2-pyrazolin, smp. 148°C, 2) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4- (2-piperidino-ethyl)-2-pyrazolin, smp. 113°C, 3) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidino-ethyl)-2-pyrazolin, smp. 111°C, 4) 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidino-ethyl)-2-pyrazolin, smp. 134°C, 5) 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-diethylamino-ethyl)-2-pyrazolin, smp. 100°C, 3 142985 6) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-diethylamino-ethyl)-2-pyrazolin, 7) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorphenyl) -4-(2-diethyl-aminoethyl)-2-pyrazolin, 8) 1-(4-cyanophenylcarbamoy1)-3-(4-chlorphenyl)-4-(2-diethylamino-ethyl)-2-pyrazolin, 9) 1-(4-chlorphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-B-diethyl-aminoethyl-2-pyrazolin, 10) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4"· 0-diethylaminoethyl-2-pyrazolin, 11) 1-(4-isopropylphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-β-diethylaminoethyl-2-pyrazolin, 12) 1“ (4-chlorphenylcarbamoyl) -3- (4-chlorphenyl) -4>-£-piperidino-propyl)-2-pyrazolin, smp. 107°C, 13) 1- (4-cyanophenylcarbamoy1)-3-(4-chlorphenyl)-4-(3-piperidino-propyl)-2-pyrazolin, smp. 120°C, 14) 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-cyanomethy1-2-pyrazolin, smp. 175°C, 15) 1-(4-cyanophenylcarbamoy1)-3-(4-chlorphenyl)-4-cyanomethyl-2-pyrazolin, smp. 205°C, 16) 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-dimethy1aminoethyl) -2-pyrazolin, smp. 131°C, 17) 1- (4-cyanophenylcarbamoy1)-3-(4-chlorphenyl)-4-(β-dimethylamino-ethyl)-2-pyrazolin, smp. 175°C, 18) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethyl-aminoethyl)-2-pyrazolin , smp. 117°C, 19) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethyl-aminoethyl)-2- pyrazolin, smp. 103°C, 2(5 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethyl-aminoethyl)-2-pyrazolin, smp. 157°C, 21) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4τ(3-cyanopropyl)- 2-pyrazolin, smp. 126 C, 22) 1-(4-methylthiophenylcarbamoyl)-3-(4-cblorphenyl)n4r-(3-cyanopropyl)-2-pyrazolin, smp. 109^0, 23) 1- (4-chlorphenylcarbamoyl) -3- (4-chlorphenyl) -4- (3-cyanopropyl) - 2-pyrazolin, smp. 120 C, 24) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-cyano-propyl)-2-pyrazolin, smp. 154°C .For example, many of the present active compounds exhibit an optimal effect at concentrations of 0.3 to 3 ppm against the larvae of the Colorado beetle, and at concentrations of 0.3 to 30 ppm, a maximum effect against the cabbage butterfly larva and further at a concentration of 0 03 to 0.3 ppm maximum effect on the larvae of the yellow fever mosquito. Examples of pyrazoline compounds of the invention with biocidal activity include: 1) 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidinoethyl) -2-pyrazoline, m.p. 148 ° C, 2) 1- (4-isopropoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidinoethyl) -2-pyrazoline, m.p. 113 ° C, 3) 1- (4-ethylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidino-ethyl) -2-pyrazoline, m.p. 111 ° C, 4) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidino-ethyl) -2-pyrazoline, m.p. 134 ° C, 5) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline, m.p. 100 ° C, 3) 1- (4-ethylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline, 7) 1- (4-isopropoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -2-pyrazoline, 8) 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -2- pyrazoline, 9) 1- (4-chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) -4-B-diethylaminoethyl-2-pyrazoline, 10) 1- (4-isopropoxyphenylcarbamoyl) -3- (4-isopropoxyphenyl) - 4 "-O-diethylaminoethyl-2-pyrazoline, 11) 1- (4-isopropylphenylcarbamoyl) -3- (4-isopropoxyphenyl) -4-β-diethylaminoethyl-2-pyrazoline, 12) 1" (4-chlorophenylcarbamoyl) -3 - (4-chlorophenyl) -4β-piperidino-propyl) -2-pyrazoline, mp 107 ° C, 13) 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3- piperidino-propyl) -2-pyrazoline, mp 120 ° C, 14) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4-cyanomethyl-2-pyrazoline, mp 175 ° C, 15) 1 - (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4-cyanomethyl-2-pyrazoline, mp 205 ° C, 16) 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- ( 3-dimethy1ami noethyl) -2-pyrazoline, m.p. 131 ° C, 17) 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylaminoethyl) -2-pyrazoline, m.p. 175 ° C, 18) 1- (4-methylthiophenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylaminoethyl) -2-pyrazoline, m.p. 117 ° C, 19) 1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylaminoethyl) -2-pyrazoline, m.p. 103 ° C, 2 (5 1- (4-Isopropylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylaminoethyl) -2-pyrazoline, mp 157 ° C, 21) 1- (4- methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4τ (3-cyanopropyl) -2-pyrazoline, m.p. 126 C, 22) 1- (4-methylthiophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p. 109 (23) 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p. 120 C, 24) 1- (4-isopropylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyano-propyl) -2-pyrazoline, m.p. 154 ° C.

142985 4142985 4

Udover den stærke insekticide virkning, har det vist sig, at forbindelserne ifølge opfindelsen også udviser fungicide egenskaber.In addition to the strong insecticidal effect, it has been found that the compounds of the invention also exhibit fungicidal properties.

På grund af deres stærke insekticide virkning, kan de omhandlede forbindelser anvendes i lave doseringer til at kontrollere insekter. Doseringsmængden afhænger af en række faktorer f.eks. den anvendte forbindelse, arten af insekter, den anvendte formulering, tilstanden af den afgrøde, der er inficeret med insekter, og de forhåndenværende vejrbetingelser. Sædvanligvis giver til kontrol af insekter inden for landbruget og gartneribruget en dosering svarende til 0,05 til 1 kg af aktiv forbindelse pr. hektar gode resultater .Because of their strong insecticidal activity, the compounds of this invention can be used in low doses to control insects. The dosage amount depends on a number of factors e.g. the compound used, the nature of the insects, the formulation used, the condition of the crop infected with insects, and the weather conditions at hand. Usually for the control of insects in agriculture and horticulture, a dosage equivalent to 0.05 to 1 kg of active compound per acres of good results.

Til anvendelse i praksis formuleres de omhandlede forbindelser til præparater. I disse præparater, blandes den aktive forbindelse med et fast bærestof eller opløses eller dispergeres i et flydende bærestof om ønsket sammen med hjælpe stoffer f.eks. overfladeaktive forbindelser eller stabilisatorer.For use in practice, the present compounds are formulated into compositions. In these compositions, the active compound is mixed with a solid carrier or dissolved or dispersed in a liquid carrier, if desired, together with adjuvants e.g. surfactants or stabilizers.

Eksempler på de omhandlede præparater er vandige opløsninger og dispersioner, olieholdige opløsninger og oliedispersioner, pastaer, støvformige pulvere, opfugtelige pulvere, blandbare olier, granuUer, invertemulsioner, aerosolpræparater og stænger, der frigør røg.Examples of the present compositions are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes, dusty powders, wettable powders, miscible oils, granules, invert emulsions, aerosol preparations and smoke emitting rods.

Befugtelige pulvere, pastaer og blandbare olier er præparater i koncentreret form, der fortyndes med vand,inden eller når de skal anvendes.Wettable powders, pastes and miscible oils are concentrated form preparations diluted with water before or when to be used.

Inverte emulsioner anvendes sædvanligvis ved påførsler i luft, nemlig når store arealer skal behandles med forholdsvis små mængder af præparatet.Inverted emulsions are usually used for applications in air, namely when large areas are to be treated with relatively small amounts of the preparation.

De inverte emulsioner kan fremstilles kort før eller endog under påsprøjtningen i sprøjteapparatet ved at emulgere vand i en olieholdig opløsning eller en oliedispersion af den aktive forbindelse. Nogle præparattyper vil blive beskrevet nærmere nedenfor i form af eksempler.The inverted emulsions may be prepared shortly before or even during spraying in the sprayer by emulsifying water in an oily solution or an oil dispersion of the active compound. Some types of preparation will be described in more detail below by way of examples.

Granulære præparater fremstilles f.eks. ved at optage den aktive forbindelse i et opløsningsmiddel og påføre den resulterende opløsning, eventuelt i nærværelse af et bindemiddel, på et granulært materiale f.eks. porøse granuller (f.eks. pimpsten og attapulgitler), mineralske ikke porøse granuller (sand eller formalet mergel), or 5 142985 ganiske granuller (f.eks. tørrede kaffeskaller og ituskårne tobaksstængler) .Granular compositions are prepared e.g. by absorbing the active compound in a solvent and applying the resulting solution, optionally in the presence of a binder, to a granular material e.g. porous granules (e.g., pumice and attapulgitles), mineral non-porous granules (sand or ground marl), or granular granules (e.g., dried coffee shells and shredded tobacco stems).

Et granulært præparat kan også fremstilles ved at presse den aktive forbindelse sammen med pulveriserede mineraler i nærværelse af smøremidler og bindemidler, hvorefter det sammenpressede produkt sønderdeles og sigtes til den ønskede kornstørrelse,A granular composition may also be prepared by compressing the active compound with powdered minerals in the presence of lubricants and binders, after which the compressed product is decomposed and sieved to the desired grain size.

Støvformige pulvere kan opnås ved grundig blanding af den aktive forbindelse med et inert fast bærestof f.eks, i én koncentration på 1 til 50 vægt%, Eksempler på velegnede f a£te bærematerialer er f.eks. talkum, kaolin, pibeler, diatoméjord,dolomit, gips, kalk, bentonit, attapulgitler og kolloidt SiO^ eller blandinger af disse og lignende stoffer. Organiske bærematerialer f.eks. formalede val-nøddeskaller kan også anvendes.Dusty powders can be obtained by thoroughly mixing the active compound with an inert solid carrier, for example, in one concentration of 1 to 50% by weight. Examples of suitable solid carriers are e.g. talc, kaolin, bibles, diatomaceous earth, dolomite, plaster, lime, bentonite, attapulgitles and colloidal SiO ^ or mixtures of these and similar substances. Organic carriers e.g. ground walnut shells can also be used.

Befugtelige pulvere fremstilles ved at blande 1 til 80 vægtdele af et fast inert bærestof f.eks. de ovenfor nævnte bærematerialer med 10 til 80 vægt% af den aktive forbindelse, 1 til 5 vægtdele af et dispersionsmiddel f.eks. ligninsulfonat eller alkylnaphthalen-sulfonat, der er velkendt til dette formål, og fprtrtnsyis også 0,5 til 5 vægtdele af et hærdemiddel f.eks. sulfater af alifatiske alkoholer, alkylarylsulfonater eller fede syrekondensationsprodukter.Wettable powders are prepared by mixing 1 to 80 parts by weight of a solid inert carrier e.g. the above-mentioned carriers with 10 to 80% by weight of the active compound, 1 to 5 parts by weight of a dispersant e.g. lignin sulfonate or alkyl naphthalene sulfonate, well known in the art, and also contain 0.5 to 5 parts by weight of a curing agent e.g. sulfates of aliphatic alcohols, alkylarylsulfonates or fatty acid condensation products.

Til fremstilling af blandbare olier opløses den aktive forbindelse eller fordeles fint i et passende opløsningsmiddelr der fortrinsvis er dårligt vandblandbartv og der tilsættes et emulgeringsmiddel til denne opløsning. Velegnede opløsningsmidler er f.eks. xylen, toluen, jordoliedestillater, der er rige på aromatiske forbindelser, f.eks. "solventnaphtha", destilleret tjæreolié og blandinger af disse væsker. Som emulgeringsmidler kan f.eks. anvendes alkylphenoxypolyglycolethere, polyoxyethylensorbitanestere . , af fede syrer eller polyoxyethylensorbitolestere af fede syrer. Koncentrationen af den aktive forbindelse i disse blandbare plier er ikke begrænset inden for et snævert område og kan variere f.eks. mellem 2 og 50 vægt%. Udover en blandbar olie kan også som et flydende og højt koncentreret primært præparat nævnes en opløsning af den aktive forbindelse i en med vand let blandbar væske f.eks. apetone, .hvortil man har sat et dispersionsmiddel og muligvis et befugtnings-middel. En vandig dispersion af den aktive forbindelse opnås ved fortynding med vand lige før end eller under påsprøjtnlngep.For the preparation of miscible oils, the active compound is dissolved or finely distributed in a suitable solvent which is preferably poorly water-miscible and an emulsifier is added to this solution. Suitable solvents are e.g. xylene, toluene, petroleum distillates rich in aromatic compounds, e.g. "solvent naphtha", distilled tar oil and mixtures of these liquids. As emulsifiers, e.g. alkylphenoxypolyglycol ethers, polyoxyethylene sorbitan esters are used. , of fatty acids or polyoxyethylene sorbitol esters of fatty acids. The concentration of the active compound in these miscible plies is not limited within a narrow range and may vary e.g. between 2 and 50% by weight. In addition to a miscible oil, a solution of the active compound in a water-miscible liquid, e.g. apetone, to which a dispersant and possibly a wetting agent has been added. An aqueous dispersion of the active compound is obtained by dilution with water just before or during spraying.

På sædvanlig måde opnås et omhandlet aerosolpræparat ved at inkorporere den aktive forbindelse evehtuelt i et opløsningsmiddel 6 142985 i en flygtig- væske, der anvendes som drivmiddel,f.eks. en blanding af chlor-fluor-derivater af methan og ethan.In the conventional manner, the present aerosol composition is obtained by incorporating the active compound evenly in a solvent 6 in a volatile liquid used as a propellant, e.g. a mixture of chlorofluorine derivatives of methane and ethane.

Røgdesinficerende stænger eller røodesinficerende pulvere, dvs. præparater, der kan udvikle en pesticid røg, når de brænder, opnås ved at optage den aktive substans i en brændbar blanding, der f.eks. som brændstof kan indeholde en stikkerart eller træ fortrinsvis i formalet form, en forbindelse, der opretholder forbrændingen f.eks. ammoniumnitrat eller kaliumchlorat og derudover en forbindelse, der forsinker forbrændingen f.eks. kaolin, bentonit og/eller kolloid-silica.Smoke-disinfecting rods or powder-disinfecting powders, ie. preparations which can develop a pesticide smoke when burning are obtained by incorporating the active substance into a combustible mixture, e.g. as fuel may contain a stick species or wood preferably in ground form, a compound which maintains the combustion e.g. ammonium nitrate or potassium chlorate and additionally a compound which delays the combustion e.g. kaolin, bentonite and / or colloidal silica.

Udover de ovenfor nævnte bestanddele kan de omhandlede præparater også indeholde andre substanser der anvendes inden for denne art af præparater.In addition to the above mentioned ingredients, the present compositions may also contain other substances used within this species of compositions.

F.eks. kan et smøremiddel som calciumstearat eller magnesium-stearat tilsættes til et befugteligt pulver eller en blanding, der skal granuleres. "Klæbemidler" f.eks. polyvinylalkohol og cellulosederivater eller andre kolloide materialer som casein kan også tilsættes for at forbedre vedhæftningen af det pesticide præparat på den overflade, der skal beskyttes.Eg. For example, a lubricant such as calcium stearate or magnesium stearate may be added to a wettable powder or mixture to be granulated. "Adhesives" e.g. polyvinyl alcohol and cellulose derivatives or other colloidal materials such as casein may also be added to improve the adhesion of the pesticidal composition to the surface to be protected.

Kendte pesticide forbindelser kan også inkorporeres i de omhandlede præparater. Herved udvides det aktive spektrum af præparaterne, og der kan opstå synergisme.Known pesticidal compounds can also be incorporated into the present compositions. This broadens the active spectrum of the preparations and synergism can occur.

Følgende insekticide, fungicide og acaricide forbindelser er velegnede i sådanne kombinationspræparateri Insekticider som f.eks.i 1. chlorerede carbonhydrider, f.eks. 2,2-bis-(p-chlorphenyl)-1,1,1-trichlorethan og hexachlorepoxyoctahydrodimetharønaphthalen, 2. carbamater, f.eks. N-methyl-l-naphthyl-carbamat, 3. dinitrophenoler, feks. 2-methyl-4,6-dinitrophenol og 2-(2-butyl- 4,6-dinitrophenyl)-3,3-dimethylacrylat, 4. organiske phosphorforbindelser, f.eks. dimethyl-2-methoxy-carbonyl-2-methylvinylphosphat; 0,0-diethyl-0-p-nitrophe-nylthiophosphat;N-monomethylamid af 0,0-dimethyldithiophosphoryl-eddikesyre.The following insecticidal, fungicidal and acaricidal compounds are suitable in such combination preparations Insecticides as for example in 1. chlorinated hydrocarbons, e.g. 2,2-bis- (p-chlorophenyl) -1,1,1-trichloroethane and hexachloropoxyoctahydrodimetharonaphthalene, 2. carbamates, e.g. N-methyl-1-naphthyl carbamate, 3. dinitrophenols, e.g. 2-methyl-4,6-dinitrophenol and 2- (2-butyl-4,6-dinitrophenyl) -3,3-dimethyl acrylate; 4. organic phosphorus compounds, e.g. dimethyl-2-methoxy-carbonyl-2-methylvinyl phosphate; 0,0-diethyl-O-p-nitrophenylthiophosphate; N-monomethylamide of 0,0-dimethyldithiophosphoryl acetic acid.

Acaricider, f.eks.: 5. diphenylsulfider, f.eks. p-chlorbenzyl-p-chlorphenylsulfid og 2,4,4',5-tetrachlordiphenylsulfid, 6. diphenylsulfonater, f.eks. p-chlorphenylbenzensulfonater, 142985 7 7. methylcarbinoler, f.eks. 4/4,-dichlor-Ci-'fcrichXor)nethylbenz-hydrol, 8. quinoxalinforbindelser f.eks. methylquinoxalindithioparbonat.Acaricides, for example: 5. diphenyl sulfides, e.g. p-chlorobenzyl-p-chlorophenyl sulfide and 2,4,4 ', 5-tetrachlorodiphenyl sulfide; 6. diphenyl sulfonates, e.g. p-chlorophenylbenzenesulfonates, 7. methylcarbinols, e.g. 4/4, -dichloro-C1-6richloro-methylbenzhydrol, 8. quinoxaline compounds e.g. methylquinoxalindithioparbonat.

Fungicider, f.eks.: 9. organiske kviksølvforbindelser, f.eks. phenylmercurieddikesyre og methylmercuricyanoguanid, 10.organiske tinforbindelser, f.eks. triphenyltinhydroxid og tri-phenyltinacetat, ll.alkylen-bis-dithiocarbamater, f.eks. zlnkethylen-rbis-dithio-r carbamat, og 12.2,4-dinitro-6- (2-octyl-phenyl-crotonat;), l^biS"· (dimethylaminP) -phosphoryl-3-phenyl-5-amino-l,2,4-triazol, 6-mefhyl-quinoxalin- 2,3-dithiocarbonat, 1,4-dithia anthraquinon·*· 2,3-dicarbonitril f N-trichlor-methylthiophthalimid, N-trichlor-methylthiotetra-hydrophthalimid, N-(1,1,2,2-tetrachlorethylthio)-tetrahydro-phthalimid, N-dichlor-fluormethylthio-N-phenyl-N'-dimethylsul-fonyldiamid og tetrachlorisophthalonitril.Fungicides, for example: 9. organic mercury compounds, e.g. phenylmercuric acetic acid and methylmercuricyanoguanide, 10. Organic tin compounds, e.g. triphenyltin hydroxide and triphenyltin acetate, II alkylene bis-dithiocarbamates, e.g. zinc ethylene-rbis-dithio-r-carbamate, and 12,2,4-dinitro-6- (2-octyl-phenyl-crotonate;), 2,4-triazole, 6-methyl-quinoxaline-2,3-dithiocarbonate, 1,4-dithia anthraquinone · 2,3-dicarbonitrile for N-trichloro-methylthiophthalimide, N-trichloro-methylthiotetra-hydrophthalimide, N- ( 1,1,2,2-tetrachlorethylthio) -tetrahydro-phthalimide, N-dichlorofluoromethylthio-N-phenyl-N'-dimethylsulfonyl diamide, and tetrachloroisophthalonitrile.

De omhandlede forbindelser kan fremstilles ved fremgangsmåder, der er velkendte som sådan til fremstilling af lignende forbindelser# eller ved fremgangsmåder, der er analoge hermed.The compounds of the present invention may be prepared by methods well known as such for the preparation of similar compounds # or by methods analogous thereto.

F.eks. kan forbindelserne fremstilles ved at omsætte en forbindelse med formlenEg. For example, the compounds may be prepared by reacting a compound of the formula

Y-0—n—Γ RY-0 — n — Γ R

N ..N ..

I <I <

HH

hvor Y og R har den ovenfor anførte betydning, med en forbindelse med formlen X ^—N=C=0 hvori x har den ovenfor anførte betydning.:wherein Y and R have the meaning given above, with a compound of formula X 1 -N = C = 0 wherein x has the meaning given above:

Reaktionen udføres ved stuetemperatur og i nærværelse af et opløsningsmiddel f.eks. en ether, f.eks. diethylether eller petroleumsether.The reaction is carried out at room temperature and in the presence of a solvent e.g. an ether, e.g. diethyl ether or petroleum ether.

8 1429858 142985

Opfindelsen beskrives nærmere med henvisning til følgende eksempler.The invention is further described with reference to the following examples.

Eksempel 1 1-(4-Chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-cyanopropyl)-2-pyrazolin.Example 1 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline.

a) 10,6 g dimethylaminohydrochlorid, 4,2 g paraformaldehyd og 22,1 g 4'-chlor-5-cyanovalerophenon opslæmmedes i 30 ml dioxan. Denne blanding kogtes under tilbagesvaling i 30 timer, hvorefter den afkøledes til stuétemperatur. Herefter afdampedes størstedelen af di-oxanen ved reduceret tryk. Man tilsatte vand og ether til resten, etherlaget fraskiltes, vaskedes med vand og tørredes med natriumsulfat og inddampedes. Udbytte 22,5 g 2-(p-chlorbenzoyl)-5-cyano-penten-1.a) 10.6 g of dimethylamino hydrochloride, 4.2 g of paraformaldehyde and 22.1 g of 4'-chloro-5-cyanovalerophenone were suspended in 30 ml of dioxane. This mixture was refluxed for 30 hours, then cooled to room temperature. Subsequently, most of the dioxane was evaporated under reduced pressure. Water and ether were added to the residue, the ether layer was separated, washed with water and dried over sodium sulfate and evaporated. Yield 22.5 g of 2- (p-chlorobenzoyl) -5-cyano-pentene-1.

b) En opløsning af 22,5 g 2-(p-chlorbenzoyl)-5-cyanopenten-l og 3,5 ml hydrazinhydrat i 50 ml ethanol kogtes i 5 timer. Efter afdampning af opløsningsmidlet opnåedes 23,8 g 3-(p-chlorphenyl)-4-(3-cyanopropyl)-2-pyrazolin. Kogepunkt (0,35 - 0,40 mm Hg): 155-165°C.b) A solution of 22.5 g of 2- (p-chlorobenzoyl) -5-cyanopenten-1 and 3.5 ml of hydrazine hydrate in 50 ml of ethanol was boiled for 5 hours. After evaporation of the solvent, 23.8 g of 3- (p-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline was obtained. Boiling point (0.35 - 0.40 mm Hg): 155-165 ° C.

c) 3,1 g p-chlorphenylisocyanat sattes til en opløsning af 4,95 3-(p-chlorphenyl)-4-(3-cyanopropyl)-2-pyrazolin i 30 ml tør ether. Efter omrøring i 1 time fradestilleredes etheren, og den erstattedes med 50 ml petroleumsether. Omrøringen fortsattes yderligere 5 timer, hvorefter petroleumsetheren frasugedes. Udbytte 4,9 g af titelforbindelsen. Smp. 120°C.c) 3.1 g of p-chlorophenyl isocyanate was added to a solution of 4.95 3- (p-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline in 30 ml of dry ether. After stirring for 1 hour, the ether was distilled off and replaced with 50 ml of petroleum ether. Stirring was continued for another 5 hours, after which the petroleum ether was aspirated. Yield 4.9 g of the title compound. Mp. 120 ° C.

På analog måde fremstilledes følgende forbindelser: ' 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-cyanomethyl-2-pyra-zolin, smp. 175°C, 1-(4-cyanophenylcarbamoyl)-3-(4-chlorphenyl)-4-cyanomethyl-2-pyra-zolin, smp. 205°C, 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-cyanopropyl)-2-pyrazolin, smp. 126°C, 1- (4-methylthiophenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-cyanopropyl)- 2- pyrazolin, smp. 109°C, 1- (4-isopropylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-cyanopropyl)- 2- pyrazolin, smp. 154°C.Analogously, the following compounds were prepared: 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4-cyanomethyl-2-pyrazoline, m.p. 175 ° C, 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4-cyanomethyl-2-pyrazoline, m.p. 205 ° C, 1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p. 126 ° C, 1- (4-methylthiophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p. 109 ° C, 1- (4-isopropylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-cyanopropyl) -2-pyrazoline, m.p. 154 ° C.

9 1429859 142985

Eksempel 2 1-(p-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidinoethyl)-2 Δ -pyrazolin.Example 2 1- (p-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidinoethyl) -2β-pyrazoline.

a) En opslæmning af 26,6 g 4'-chlor-4-piperidinobutyrophenon, 4 g paraformaldehyd og 10 g dimethylaminhydrochlorid i 40 ml dioxan kogtes med tilbagesvaling i 24 timer. Efter inddampning tilsattes vand, og reaktionsblandingen blev gjort alkalisk med 50% natriumhydroxidopløsning. Efter ekstraktion med ether, vask med vand og tørring og inddampning opnåedes 26,7 g 1-(dimethylamino)-2-(p-chlorbenzoyl)-4-piperidinobutan.a) A slurry of 26.6 g of 4'-chloro-4-piperidinobutyrophenone, 4 g of paraformaldehyde and 10 g of dimethylamine hydrochloride in 40 ml of dioxane was refluxed for 24 hours. After evaporation, water was added and the reaction mixture was made alkaline with 50% sodium hydroxide solution. After extraction with ether, washing with water and drying and evaporation, 26.7 g of 1- (dimethylamino) -2- (p-chlorobenzoyl) -4-piperidinobutane were obtained.

b) En opløsning af 26,7 g af forbindelsen opnået i a) og 10 ml hydrazinhydrat kogtes med tilbagesvaling i 35 ml ethanol i 7 timer, hvorefter den destilleredes. Der opnåedes 18,1 g 3-(p-chlorphenyl)- 2 4-(2-piperidinoethyl)-Δ -pyrazolin. Kogepunkt (0,4 - 0,5 mm Hg): 200-208°C.b) A solution of 26.7 g of the compound obtained in a) and 10 ml of hydrazine hydrate was refluxed in 35 ml of ethanol for 7 hours and then distilled. 18.1 g of 3- (p-chlorophenyl) -2 4- (2-piperidinoethyl) -A-pyrazoline were obtained. Boiling point (0.4 - 0.5 mm Hg): 200-208 ° C.

c) 15,4 g p-chlorphenylisocyanat sattes til en opløsning af 29,2 2 g 3-(p-chlorphenyl)-4-(2-piperidinoethyl)-Δ -pyrazolin i 500 ml petroleumsether. Blandingen omrørtes i 12 timer, hvorefter der fra-sugedes.På denne måde opnåedes 36,4 g af forbindelsen nævnt i indledningen. Smp. 134°C.c) 15.4 g of p-chlorophenyl isocyanate was added to a solution of 29.2 2 g of 3- (p-chlorophenyl) -4- (2-piperidinoethyl) -A-pyrazoline in 500 ml of petroleum ether. The mixture was stirred for 12 hours, then suctioned. This gave 36.4 g of the compound mentioned in the introduction. Mp. 134 ° C.

Følgende forbindelser fremstilledes på analog måde.* 1-(p-cyanophenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidinoethyl-Δ^-pyrazolin, smp. 148°C, 1-(p-isopropoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidinoethyl) -Δ^-pyrazolin, smp. 113°C.The following compounds were prepared in an analogous manner. * 1- (p-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidinoethyl-Δ ^ -pyrazoline, mp 148 ° C, 1- (p-isopropoxyphenylcarbamoyl) - 3- (4-Chlorophenyl) -4- (2-piperidinoethyl) -α-pyrazoline, mp 113 ° C.

1-(p-ethylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidinoethyl)-Δ^-pyrazolin, smp. 111°C, 1-(p-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-diethylaminoethyl)-Δ^-pyrazolin, smp. 100°C, 1-(p-ethylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-diethylaminoethyl)-Δ^-pyrazolin, 1-(p-isopropoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-diethylamino-2 ethyl)-Δ -pyrazolin, 1- (p-cyanophenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-diethylaminoethyl)-1- (p-Ethylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-piperidinoethyl) -Aβ-pyrazoline, m.p. 111 ° C, 1- (p-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -ΔΔ -pyrazoline, m.p. 100 ° C, 1- (p-Ethylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -Δ - (2-diethylamino-2-ethyl) -A-pyrazoline, 1- (p-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (2-diethylaminoethyl) -

OISLAND

Δ "-pyrazolin, 1-(4-chlorphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-(β-diethylamino-ethy1)-Δ^-pyrazolin, 1-(4-isopropoxyphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-(β-diethyl-2 aminoethyl)-å -pyrazolin, 142985 ίο 1-(4-isopropylphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-(β-diethyl-2 aminoethyl)-Δ -pyrazolin, 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-piperidinopropyl)-Δ -pyrazolin, smp. 107°C, 1-(4-cyanophenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-piperidinopropyl)-Δ^-pyrazolin, smp. 120°C, 1-(4-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethylamino-ethyl)-Δ-pyrazolin, smp. 131°C, 1-(4-cyanophenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethylamino-ethyl)-Δ^-pyrazolin, smp. 175°C, 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethyl-aminoethyl)-A2-pyrazolin, smp. 117°C, 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethylamino-ethyl)-Δ^-pyrazolin, smp. 103°C, 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorphenyl)-4-(β-dimethylamino-ethyl)-Δ^-pyrazolin, smp. 157°C.Δ "-pyrazoline, 1- (4-chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) -4- (β-diethylaminoethyl) -4-pyrazoline, 1- (4-isopropoxyphenylcarbamoyl) -3- (4-isopropoxyphenyl) ) -4- (β-diethyl-2-aminoethyl) -α-pyrazoline, 1- (4-isopropylphenylcarbamoyl) -3- (4-isopropoxyphenyl) -4- (β-diethyl-2-aminoethyl) -Δ-pyrazoline, 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (3-piperidinopropyl) -Δ-pyrazoline, mp 107 ° C, 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) - 4- (3-piperidinopropyl) -Δβ-pyrazoline, mp 120 ° C, 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylaminoethyl) -Δ-pyrazoline, m.p. 131 ° C, 1- (4-cyanophenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylamino-ethyl) -β-pyrazoline, mp 175 ° C, 1- (4-methylthiophenylcarbamoyl) - 3- (4-chlorophenyl) -4- (β-dimethylaminoethyl) -A2-pyrazoline, mp 117 ° C, 1- (4-methoxyphenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylamino -pyrazoline, mp 103 ° C, 1- (4-isopropylphenylcarbamoyl) -3- (4-chlorophenyl) -4- (β-dimethylamino-ethyl) -Δ ^ -pyrazoline, mp 157 ° C.

5 Eksempel 3Example 3

De omhandlede aktive forbindelser dispergeredes i vand således at der opnåedes koncentrationer på 300, 100, 30, 10, 3, 1 og 0,3 mg aktiv forbindelser pr. liter af den vandige dispersion. De insekti-cide virkninger af disse dispersioner bestemtes på sædvanlig måde over for Leptinotarsa decemlineata (Coloradobillen)og Pieris brassicae (kålorm).The active compounds of this invention were dispersed in water to obtain concentrations of 300, 100, 30, 10, 3, 1 and 0.3 mg of active compounds per ml. liter of the aqueous dispersion. The insecticidal effects of these dispersions were determined in the usual manner against Leptinotarsa decemlineata (Coloradobillen) and Pieris brassicae (cabbage worms).

Resultaterne af disse forsøg er afbildet i den følgende tabel. Betydningen af de i tabellen angivne tegn er følgende: + = 90 til 100% drab + = 50 til 90% drab - = <50% drab 142985 11 roThe results of these experiments are depicted in the following table. The meaning of the characters in the table is as follows: + = 90 to 100% kill + = 50 to 90% kill - = <50% kill 142985 11 ro

Ο 1 1 IΟ 1 1 I

Φ — ' ~ ~-—Φ - '~ ~ -—

φ g Η I I +1 + J ι ι I I -Η ι Iφ g Η I I +1 + J ι ι I I -Η ι I

O Q.O Q.

•Η S Φ-----—- Μ Φ• Η S Φ -----—- Μ Φ

ιο Ογο+| + + + + + +) ι +1 + 1 + + . I I +1 I Iιο Ογο + | + + + + + +) ι +1 + 1 ++. I I + 1 I I

Φ Μ -Η G φ (0---1—1-Γ,- Λ +> m -Η Φ Ο + + + + + + + + + + ++ +| + + J + +1 W Η Μ ΗΦ Μ -Η G φ (0 --- 1—1-Γ, - Λ +> m -Η Φ Ο + + + + + + + + + + ++ ++ | + + J + +1 W Η Μ Η

•Η PQ• Η PQ

U SJ-----—1---1--' ..... .1 --1---- φ φ ω .....U SJ -----— 1 --- 1-- '..... .1 --1 ---- φ φ ω .....

•Η ft -Η Ο + + + + + + 4- + + ++ + + + I + + + + Ρη S-i <ό Φ Φ tn ω -Η ;___- __ ' _ 0 Η (¾ 1 ...... Γ"' 1 Φ Ο Φ <0 ο + + + + + + + ++ + + + + + + + + + + 4J G 1-4 Φ -Η Φ Λ----1- "• Η ft -Η Ο + + + + + + 4- + + ++ +++ + I ++++ Ρη Si <ό Φ Φ tn ω -Η; ___- __ '_ 0 I (¾ 1 ... ... Γ "'1 Φ Ο Φ <0 ο +++++++ +++++++++++ 4J G 1-4 Φ -Η Φ Λ ---- 1-"

G GOG GO

•Η Ο Ο + + + + + + + + + + + + + + + + + + + Η <44 Π ,·· £ tn φ G £ υ -η ο-----------------—1- Φ G W ro <α λ μ• Η Ο Ο + + + + + + + + + + + + + + + + + + + Η <44 Π, ·· £ tn φ G £ υ -η ο ----------- ------— 1- Φ GW ro <α λ μ

G G Ο I IIG G Ο I II

Φ τ-Ι ·Η W > > ----—------—Φ τ-Ι · Η W>> ----—------—

GG

Φ Ό tn 1-4 +1111 44 I +1 IΦ Ό tn 1-4 +1111 44 I +1 I

+> -Η £ _____________>- ο υ --—--- G Ο -Η £ β,μ 01 I I + +1+1 +1 I I I I I Ι+.+Ι+Ι+ΙΙ+> -Η £ _____________> - ο υ --—--- G Ο -Η £ β, µ 01 I I + + 1 + 1 + 1 I I I I I Ι +. + Ι + Ι + ΙΙ

Dj .Μ----1- I—1 Φ Φ <G GGIO +| + + + + + + + +| II ++Ι+ + + +1 + +1Dj .Μ ---- 1- I — 1 Φ Φ <G GGIO + | + + + + + + + + | II ++ Ι ++++ +1 + +1

fQ -G IfQ -G I

Φ +4 <Ό Φ IH φ 3 r+---—-------- Ο G GUO +1+ + + + + + + + ++| + ++ + + + + + Φ Ο roΦ +4 <Ό Φ IH φ 3 r + ---—-------- Ο G GUO +1+ + + + + + + + ++ | + ++ + + + + + Φ Ο ro

> -G> -G

G +>--------——-——- Φ ΦG +> --------——-——- Φ Φ

<-4 GO<-4 GO

-G Ο + ++ + + + + + + + + + + + + + + + + G G r4 Ο Φ___ 44 υ c ο G Ο Ο + ++ + + + + + + + + + + + + + + + + Φ Κ ro > Ο-----------π- tn G Φ -Η +-G Ο ++++++++++++++++++ GG r4 Ο Ο ___ 44 υ c ο G Ο Ο ++ ++ +++++++++++++ + + Φ Κ ro> Ο ----------- π- tn G Φ -Η +

G WG W

α: -η ·η J-1 ι—1 •Η £ > Ο Φ Μ +1 <α gα: -η · η J-1 ι — 1 • Η £> Ο Φ Μ +1 <α g

•Η G• Η G

ο φ +1 ο g α.ο φ +1 ο g α.

Η g ο 'Η g ο '

ffl Gffl G

G Φ .. G HCNrorrinvor-co σ^θι-4Γ4Γθ^ι·ιηνρΓ^οοσ> ΦΦ ρ4γ4ι—Ir4r4r4i—I ι-4 r-4 r4 m tn r4 -r4 φ .-4 Ό ΌG Φ .. G HCNrorrinvor-co σ ^ θι-4Γ4Γθ ^ ι · ιηνρΓ ^ οοσ> ΦΦ ρ4γ4ι — Ir4r4r4i — I ι-4 r-4 r4 m tn r4 -r4 φ.-4 Ό Ό

G -HG -H

•H + Λ• H + Λ

G CG C

O Φ fo <d .O Φ fo <d.

' ' ................ . '......... . I, II, —I'' ................. '.......... I, II, —I

142985 12 ro ο' 1 η +| + +1 ο + ι + + Γ"Ί Ο + I +1 + + ΓΟ ο + + + + + I—1 ο ο + + + + + η η + Ο £ Η 1 1 + ns ------ ω f ^ +ι ι +ι + ι ^ ______— ΙΗ ^ ο + +ι + + +ι γΗ (D----- Λ (0 Ο + + + + + Επ Π g + + + + + γΗ ο ο + + + 4- + ΓΟ Ο Η 03 ΓΟ ^ CM D Μ Μ 142985 13142985 12 ro ο '1 η + | + +1 ο + ι + + Γ "Ί Ο + I +1 + + ΓΟ ο + + + + + I — 1 ο ο + + + + + η η + Ο £ Η 1 1 + ns ----- - ω f ^ + ι ι + ι + ι ^ ______— ΙΗ ^ ο + + ι + + + ι γΗ (D ----- Λ (0 Ο + + + + + Επ Π g ++ + + + + γΗ ο ο + + + 4- + ΓΟ Ο Η 03 ΓΟ ^ CM D Μ 142985 13

Sammenligningsforsøgcomparison Tests

Forbindelserne ifølge opfindelsen sammenlignedes med hensyn til insekticid virkning med de før omtalte, fra tysk offentliggørelsesskrift nr. 2.304.584 kendte 1,3- og 1,3,5-substitueredg pyra-zoliner ved afprøvning over for Pieris brassicae som angivet i eksempel 3. Resultaterne er angivet i efterfølgende tabel: 142985 14 ι—i G G JI + + + + + + tf x d \ ^The compounds according to the invention were compared with respect to insecticidal activity with the previously mentioned 1,3- and 1,3,5-substituted pyrazolines known from German Publication No. 2,304,584 when tested against Pieris brassicae as described in Example 3. The results are given in the following table: 142985 14 ι — in GG JI + + + + + + + tf xd \ ^

r-ί Pk <\ /\ g Η Hr-ί Pk <\ / \ g Η H

(D O Y \ T 10 *ϋ 1 2—O rr -a· ro cm m .s g. *<v s "S s. G \ ff(D O Y \ T 10 * ϋ 1 2 — O rr -a · ro cm m. S g. * <V s "S s. G \ ff

o m φ >—'Jo m φ> - 'J

><|> <|

<U<U

«J II«J II

0 L il MG ^ tn (U S , , G tn t \ 2 + +0 L il MG ^ tn {U S,, G tn t \ 2 ++

s 1 Λ H 1 "Ss 1 Λ H 1 ”S

^ .g /<a^ .g / <a

s g Ws g W

•H O / ft Ή >/• H O / ft Ή> /

'd <D'd <D

O +) Vj e ^ 1 r 0 ,’ Jp* · 0 i 0 i o 2^ 2 13 2 2 ?O +) Vj e ^ 1 r 0, 'Jp * · 0 i 0 i o 2 ^ 2 13 2 2?

^ ‘cm 'cm 'ro CM CM ^_CM^ 'Cm' cm 'ro CM CM ^ _CM

"*CM ""cm 3^ O CM CM"* CM" "cm 3 ^ O CM CM

BBS g SBBS g S

I l » S’ βΓβΓ o° u° o * ddu d ddddd * ggggggdduIn l »S 'βΓβΓ o ° u ° o * ddu d ddddd * ggggggddu

CDCD

ω r—1 $ *0 · ' H 00 3 Ώ H , I <* ___ 15 142980 --1- ><! 7 --Η,-,-—i 1 ,.ω r — 1 $ * 0 · 'H 00 3 Ώ H, I <* ___ 15 142980 --1-> <! 7 --Η, -, -— i 1 ,.

Hl MUHL MU

d) kS^N Q3 0) Ό i li Ό Ό U C >1 >i 0) H 4J +1d) kS ^ N Q3 0) Ό i li Ό Ό U C> 1> i 0) H 4J +1

Hg, I +++ + +ΛΛ il _a * 10 ^ ^ ^ + * h tn /=\ \»/ ° h cm o,d Λ H / \ Z \ g }4 P ^ C \ / H dl o m (u >—y ^ o) tnHg, I +++ + + ΛΛ il _a * 10 ^ ^ ^ + * h tn / = \ \ »/ ° h cm o, d Λ H / \ Z \ g} 4 P ^ C \ / H dl if ( u> —y ^ o) tn

pL, *H ti} / M< g rHpL, * H ti} / M <g rH

>4 HS g O) 1 · ta >> 4 HS g O) 1 · ta>

Q) 03 tn -HQ) 03 tn -H

Id I λ; εη u I] tu ·ιο c h -, xs^ · ft fd 10 h ^ T 44Id I λ; εη u I] tu · ιο c h -, xs ^ · ft fd 10 h ^ T 44

03 0) -J M * <D03 0) -J M * <D

id to ·τ^ \ s co tnid to · τ ^ \ s co tn

54 H I J. C n -H54 H I J. C n -H

° « Λ / 5 « - s 5 S /=0=' ώ 1 I s 54 Λ (v /) 6 0) 0) 54 V II ·* ® Ό •r4 o / * 6 w Οι 44 S-ι CU X 54 ·* a o> o Ό <1) _ , ^° «Λ / 5« - s 5 S / = 0 = 'ώ 1 I s 54 Λ (v /) 6 0) 0) 54 V II · * ® Ό • r4 o / * 6 w Οι 44 S-ι CU X 54 · * ao> o Ό <1) _, ^

O -P Sj. ° HO -P Sj. ° H

g 174 'S Od) b c 1 m c -σg 174 'S Od) b c 1 m c -σ

tn d) 0) Ctn d) 0) C

C W Γ Μ ΌΗ0) -4S -Η |J O) r4 54 -P c IxA > 0) rd id 44 } Λ > 03 u . n4 t n id oi P η r^\ S C -P -jC W Γ Μ ΌΗ0) -4S -Η | J O) r4 54 -P c IxA> 0) rd id 44} Λ> 03 u. n4 t n id oi P η r ^ \ S C -P -j

o 1 s-U P · -Po 1 s-U P · -P

44 A / A Η 44 — ,/ χΑ ° N > Cn44 A / A Η 44 -, / χΑ ° N> Cn

fSS\ rH ΤΓΊ OfSS \ rH ΤΓΊ O

H^/) > w 0) V 7 XI /—‘ rt g g id / ni a a E4 >< a a aH ^ /)> w 0) V 7 XI / - 'rt g g id / ni a a E4> <a a a

ChCh

------1--,—I--— --H n H------ 1 -, - I --— --H n H

/ <N S 0) »£ i I , J- I *" o * a W S, 5 g " n Z Z æ Z m 4-1 = I I u I '-', 0) (ΜΗ CM CM ς· tn o f 5* f § — — v- a o 54 a ^ οι d o -/ <NS 0) »£ i I, J- I *" o * a WS, 5 g "n ZZ æ Z m 4-1 = II u I '-', 0) (ΜΗ CM CM ς · tn of 5 * f § - - v- ao 54 a ^ οι do -

Sj >1 Η OSj> 1 Η O

4-) O4 O

d) tn h Λ 0d) tn h Λ 0

Η P PΗ P P

d) H o pH r-4 r4 h r—ι h ,qh u u u υ o id - -POT! O d) 0) H >d) H o pH r-4 r4 h r — ι h, qh u u u υ o id - -POT! O d) 0) H>

Pd r-4 i—I i—I r-4 i—I CPd r-4 i — I i — I r-4 i — I C

U U U (JO c - = d) P + d) * ° =U U U (JO c - = d) P + d) * ° =

0) M0) M

Η H 4-1 aj ό <o 3 t! Q)Η H 4-1 aj ό <o 3 t! Q)

Hg m cm μ* ο n > = _Q C r4 a H CM + _a 1___ =+ ?Hg m cm μ * ο n> = _Q C r4 and H CM + _a 1___ = +?