DK142985B - Pyrazolinforbindelser til anvendelse som insekticider - Google Patents
Pyrazolinforbindelser til anvendelse som insekticider Download PDFInfo
- Publication number
- DK142985B DK142985B DK5377AA DK5377A DK142985B DK 142985 B DK142985 B DK 142985B DK 5377A A DK5377A A DK 5377AA DK 5377 A DK5377 A DK 5377A DK 142985 B DK142985 B DK 142985B
- Authority
- DK
- Denmark
- Prior art keywords
- pyrazoline
- chlorophenyl
- compounds
- chlorophenylcarbamoyl
- diethylaminoethyl
- Prior art date
Links
- 150000003219 pyrazolines Chemical class 0.000 title description 10
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- 235000019359 magnesium stearate Nutrition 0.000 description 1
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- 150000002731 mercury compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CYPNBACJQNTDIB-UHFFFAOYSA-N n,5-bis(4-chlorophenyl)-4-(2-piperidin-1-ylethyl)-3,4-dihydropyrazole-2-carboxamide Chemical compound C1=CC(Cl)=CC=C1NC(=O)N1N=C(C=2C=CC(Cl)=CC=2)C(CCN2CCCCC2)C1 CYPNBACJQNTDIB-UHFFFAOYSA-N 0.000 description 1
- HZYQMNISHOHZDO-UHFFFAOYSA-N n,5-bis(4-chlorophenyl)-4-[2-(diethylamino)ethyl]-3,4-dihydropyrazole-2-carboxamide Chemical compound CCN(CC)CCC1CN(C(=O)NC=2C=CC(Cl)=CC=2)N=C1C1=CC=C(Cl)C=C1 HZYQMNISHOHZDO-UHFFFAOYSA-N 0.000 description 1
- MAGVJLLHDZWQFM-UHFFFAOYSA-N n-chloro-n-methylmethanamine Chemical compound CN(C)Cl MAGVJLLHDZWQFM-UHFFFAOYSA-N 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 210000002787 omasum Anatomy 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- MLGCXEBRWGEOQX-UHFFFAOYSA-N tetradifon Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl MLGCXEBRWGEOQX-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/98—Nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
fås'
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.
fremlaeggelaesskriftet offentliggjort den 9· ®®^*· ' 9° DIREKTORATET FOR . .
PATENT-OG VAREMÆRKEVÆSENET (30) Pnontet begæret fra den
9. Jan. 1976, 7600178, 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.
(74) Fuldmægtig under sagens behandling:
Internationalt Patent-Bureau._ (64) Pyrazolinforbindelser til anvendelse som insekticider.
Opfindelsen angår hidtil ukendte pyrazolinforbindelser til anvendelse som insekticider.
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.
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.
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.
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.
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.
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 .
142985 4
Udover den stærke insekticide virkning, har det vist sig, at forbindelserne ifølge opfindelsen også udviser fungicide egenskaber.
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 .
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.
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.
Befugtelige pulvere, pastaer og blandbare olier er præparater i koncentreret form, der fortyndes med vand,inden eller når de skal anvendes.
Inverte emulsioner anvendes sædvanligvis ved påførsler i luft, nemlig når store arealer skal behandles med forholdsvis små mængder af præparatet.
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.
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) .
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,
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.
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.
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.
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.
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.
Udover de ovenfor nævnte bestanddele kan de omhandlede præparater også indeholde andre substanser der anvendes inden for denne art af præparater.
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.
Kendte pesticide forbindelser kan også inkorporeres i de omhandlede præparater. Herved udvides det aktive spektrum af præparaterne, og der kan opstå synergisme.
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.
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.
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.
De omhandlede forbindelser kan fremstilles ved fremgangsmåder, der er velkendte som sådan til fremstilling af lignende forbindelser# eller ved fremgangsmåder, der er analoge hermed.
F.eks. kan forbindelserne fremstilles ved at omsætte en forbindelse med formlen
Y-0—n—Γ R
N ..
I <
H
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.:
Reaktionen udføres ved stuetemperatur og i nærværelse af et opløsningsmiddel f.eks. en ether, f.eks. diethylether eller petroleumsether.
8 142985
Opfindelsen beskrives nærmere med henvisning til følgende eksempler.
Eksempel 1 1-(4-Chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(3-cyanopropyl)-2-pyrazolin.
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.
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.
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.
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.
9 142985
Eksempel 2 1-(p-chlorphenylcarbamoyl)-3-(4-chlorphenyl)-4-(2-piperidinoethyl)-2 Δ -pyrazolin.
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.
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.
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.
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.
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)-
O
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.
5 Eksempel 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).
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 ro
Ο 1 1 I
Φ — ' ~ ~-—
φ g Η I I +1 + J ι ι I I -Η ι I
O Q.
•Η S Φ-----—- Μ Φ
ιο 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 Η
•Η PQ
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- "
G GO
•Η Ο Ο + + + + + + + + + + + + + + + + + + + Η <44 Π ,·· £ tn φ G £ υ -η ο-----------------—1- Φ G W ro <α λ μ
G G Ο I II
Φ τ-Ι ·Η W > > ----—------—
G
Φ 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
Dj .Μ----1- I—1 Φ Φ <G GGIO +| + + + + + + + +| II ++Ι+ + + +1 + +1
fQ -G I
Φ +4 <Ό Φ IH φ 3 r+---—-------- Ο G GUO +1+ + + + + + + + ++| + ++ + + + + + Φ Ο ro
> -G
G +>--------——-——- Φ Φ
<-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 W
α: -η ·η J-1 ι—1 •Η £ > Ο Φ Μ +1 <α g
•Η G
ο φ +1 ο g α.
Η g ο '
ffl 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 Ό
G -H
•H + Λ
G C
O Φ fo <d .
' ' ................ . '......... . 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 13
Sammenligningsforsøg
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 \ ^
r-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
o m φ >—'J
><|
<U
«J II
0 L il MG ^ tn (U S , , G tn t \ 2 + +
s 1 Λ H 1 "S
^ .g /<a
s g W
•H O / ft Ή >/
'd <D
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 3^ O CM CM
BBS g S
I l » S’ βΓβΓ o° u° o * ddu d ddddd * ggggggddu
CD
ω r—1 $ *0 · ' H 00 3 Ώ H , I <* ___ 15 142980 --1- ><! 7 --Η,-,-—i 1 ,.
Hl MU
d) 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) tn
pL, *H ti} / M< g rH
>4 HS g O) 1 · ta >
Q) 03 tn -H
Id I λ; εη u I] tu ·ιο c h -, xs^ · ft fd 10 h ^ T 44
03 0) -J M * <D
id to ·τ^ \ s co tn
54 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) _ , ^
O -P Sj. ° H
g 174 'S Od) b c 1 m c -σ
tn 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 -j
o 1 s-U P · -P
44 A / A Η 44 — ,/ χΑ ° N > Cn
fSS\ rH ΤΓΊ O
H^/) > w 0) V 7 XI /—‘ rt g g id / ni a a E4 >< a a a
Ch
------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 -
Sj >1 Η O
4-) O
d) tn h Λ 0
Η 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 >
Pd r-4 i—I i—I r-4 i—I C
U U U (JO c - = d) P + d) * ° =
0) M
Η H 4-1 aj ό <o 3 t! Q)
Hg m cm μ* ο n > = _Q C r4 a H CM + _a 1___ =+ ?
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7600178 | 1976-01-09 | ||
| NLAANVRAGE7600178,A NL183400C (nl) | 1976-01-09 | 1976-01-09 | Werkwijze ter bereiding van een insecticide preparaat dat een pyrazoline-verbinding bevat en werkwijze ter bereiding van een pyrazoline-verbinding met insecticide werking. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK5377A DK5377A (da) | 1977-07-10 |
| DK142985B true DK142985B (da) | 1981-03-09 |
| DK142985C DK142985C (da) | 1981-10-12 |
Family
ID=19825416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK5377A DK142985C (da) | 1976-01-09 | 1977-01-06 | Pyrazolinforbindelser til anvendelse som insekticider |
Country Status (28)
| Country | Link |
|---|---|
| JP (1) | JPS5287166A (da) |
| AT (1) | AT353260B (da) |
| AU (1) | AU510358B2 (da) |
| BE (1) | BE850220A (da) |
| BR (1) | BR7700133A (da) |
| CA (1) | CA1111048A (da) |
| CH (1) | CH631870A5 (da) |
| CS (1) | CS205031B2 (da) |
| DD (1) | DD129396A5 (da) |
| DE (1) | DE2700258A1 (da) |
| DK (1) | DK142985C (da) |
| EG (1) | EG13910A (da) |
| ES (1) | ES454857A1 (da) |
| FR (1) | FR2337715A1 (da) |
| GB (1) | GB1570635A (da) |
| GR (1) | GR63086B (da) |
| HU (1) | HU180915B (da) |
| IE (1) | IE45012B1 (da) |
| IL (1) | IL51225A (da) |
| IT (1) | IT1076002B (da) |
| NL (1) | NL183400C (da) |
| NZ (1) | NZ183006A (da) |
| OA (1) | OA05550A (da) |
| PL (2) | PL109512B1 (da) |
| PT (1) | PT66039B (da) |
| SE (1) | SE435176B (da) |
| YU (1) | YU1877A (da) |
| ZA (1) | ZA7714B (da) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0014810A3 (en) | 1979-01-18 | 1980-11-26 | Fbc Limited | Pesticidal pyrazoles, their production, compositions and uses, as well as intermediates and their preparation |
| DE3064749D1 (en) * | 1979-07-03 | 1983-10-13 | Duphar Int Res | New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal composition on the basis of these new compounds |
| JPS57209275A (en) * | 1981-06-19 | 1982-12-22 | Nissan Chem Ind Ltd | Novel pyrazoline derivative, its preparation, and vermin-controlling agent containing said derivative as active component |
| GB2093836B (en) * | 1981-02-17 | 1984-09-05 | Nissan Chemical Ind Ltd | Insecticidal pyrazoline derivatives |
| ATE14309T1 (de) * | 1981-05-12 | 1985-08-15 | Duphar Int Res | Pyrazolinderivate, verfahren zu ihrer herstellung und diese enthaltende insektizide praeparate. |
| ZA858002B (en) * | 1984-10-25 | 1987-04-29 | Fmc Corp | Pyrazoline insecticides |
| AU556949B2 (en) * | 1984-10-25 | 1986-11-27 | Fmc Corporation | Pyrozoline insecticides |
| EP0182746A3 (de) * | 1984-11-16 | 1988-10-12 | Ciba-Geigy Ag | Pyrazolinderivate |
| DE3545786A1 (de) * | 1985-12-21 | 1987-06-25 | Schering Ag | Pyrazolinderivate, ihre herstellung und ihre verwendung als mittel mit insektizider wirkung |
| DE3638631A1 (de) * | 1986-11-11 | 1988-05-26 | Schering Ag | Pyrazoline, ihre herstellung und ihre verwendung als mittel mit insektizider und akarizider wirkung |
| DE4032089A1 (de) * | 1990-01-24 | 1991-07-25 | Bayer Ag | Substituierte pyrazolinderivate |
| DE4217862A1 (de) * | 1991-08-28 | 1993-03-04 | Bayer Ag | Substituierte pyrazoline |
| DE4217863A1 (de) * | 1991-08-28 | 1993-03-04 | Bayer Ag | Substituierte pyrazoline |
| JPH07504658A (ja) * | 1992-03-02 | 1995-05-25 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | 殺節足動物性アミド類 |
| DE4218745A1 (de) * | 1992-06-04 | 1993-12-09 | Schering Ag | 1-(4-Cyanophenyl-carbamoyl)-pyrazoline |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE795264A (fr) * | 1972-02-09 | 1973-08-09 | Philips Nv | Nouveaux composes de pyrazoline a activite insecticide |
| NL158178B (nl) * | 1974-07-12 | 1978-10-16 | Philips Nv | Werkwijze ter bereiding van insekticide preparaten die een pyrazolinederivaat bevatten, aldus verkregen gevormde preparaten, en werkwijze ter bereiding van pyrazolinederivaten met insekticide werking. |
| DE2700289A1 (de) * | 1977-01-05 | 1978-07-06 | Bayer Ag | Substituierte phenylcarbamoyl-2- pyrazoline, verfahren zu ihrer herstellung und ihre verwendung als insektizide |
| DE2700288A1 (de) * | 1977-01-05 | 1978-07-13 | Bayer Ag | Phenylcarbamoyl-pyrazoline, verfahren zu ihrer herstellung und ihre verwendung als insektizide |
-
1976
- 1976-01-09 NL NLAANVRAGE7600178,A patent/NL183400C/xx not_active IP Right Cessation
-
1977
- 1977-01-03 ZA ZA00770014A patent/ZA7714B/xx unknown
- 1977-01-04 SE SE7700067A patent/SE435176B/xx unknown
- 1977-01-05 IT IT19085/77A patent/IT1076002B/it active
- 1977-01-05 DE DE19772700258 patent/DE2700258A1/de not_active Ceased
- 1977-01-06 IL IL51225A patent/IL51225A/xx unknown
- 1977-01-06 CH CH12977A patent/CH631870A5/de not_active IP Right Cessation
- 1977-01-06 IE IE24/77A patent/IE45012B1/en unknown
- 1977-01-06 DD DD7700196841A patent/DD129396A5/xx unknown
- 1977-01-06 DK DK5377A patent/DK142985C/da active
- 1977-01-06 NZ NZ183006A patent/NZ183006A/xx unknown
- 1977-01-06 HU HU77PI557A patent/HU180915B/hu not_active IP Right Cessation
- 1977-01-06 YU YU00018/77A patent/YU1877A/xx unknown
- 1977-01-06 GB GB356/77A patent/GB1570635A/en not_active Expired
- 1977-01-07 ES ES454857A patent/ES454857A1/es not_active Expired
- 1977-01-07 GR GR52531A patent/GR63086B/el unknown
- 1977-01-07 AT AT5177A patent/AT353260B/de not_active IP Right Cessation
- 1977-01-07 BE BE173949A patent/BE850220A/xx unknown
- 1977-01-07 PL PL1977212934A patent/PL109512B1/pl unknown
- 1977-01-07 FR FR7700371A patent/FR2337715A1/fr active Granted
- 1977-01-07 PL PL1977195195A patent/PL110077B1/pl unknown
- 1977-01-07 PT PT66039A patent/PT66039B/pt unknown
- 1977-01-07 CS CS77116A patent/CS205031B2/cs unknown
- 1977-01-08 JP JP110777A patent/JPS5287166A/ja active Granted
- 1977-01-09 EG EG15/77A patent/EG13910A/xx active
- 1977-01-10 BR BR7700133A patent/BR7700133A/pt unknown
- 1977-01-10 CA CA269,399A patent/CA1111048A/en not_active Expired
- 1977-01-10 AU AU21188/77A patent/AU510358B2/en not_active Expired
- 1977-01-21 OA OA56052A patent/OA05550A/xx unknown
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