DK170732B1 - Insekticid 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-alpha-3-phenoxybenzylester samt insekticidt præparat - Google Patents

Insekticid 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-alpha-3-phenoxybenzylester samt insekticidt præparat Download PDF

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DK170732B1
DK170732B1 DK317589A DK317589A DK170732B1 DK 170732 B1 DK170732 B1 DK 170732B1 DK 317589 A DK317589 A DK 317589A DK 317589 A DK317589 A DK 317589A DK 170732 B1 DK170732 B1 DK 170732B1
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cyclopropane
dichlorovinyl
dimethyl
carboxylic acid
ester
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Julien Warnant
Jacques Prost-Marechal
Philippe Cosquer
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Roussel Uclaf
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Description

DK 170732 B1
Opfindelsen angår den hidtil ukendte forbindelse med insekticid virkning 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-a-cyan-3-phenoxybenzyiester.
Opfindelsen angår tillige insekticide præparater, som er ejendommelige ved et indhold af este-5 ren.
Fra dansk patentansøgning nr. 6287/73 kender man den tilsvarende 2,2-dibromforbindelse med insekticid virkning. I den nævnte patentansøgning er der dog ingen beskrivelse eller anvisning på fremstilling af den tilsvarende 2,2-dichlorforbindelse. Endvidere har 2,2-dichlorforbindelsen 10 ifølge opfindelsen overraskende nok vist sig at have en meget kraftig insekticid virkning, kraftigere end selv nært beslægtede forbindelser, og navnlig meget kraftigere end den tilsvarende 2,2-dibromforbindelse ifølge DK 6287/73.
Dichlorforbindelsen ifølge opfindelsen kan fremstilles ved en epimeriseringsfremgangsmåde,
15 hvor en ester mellem 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre og en optisk aktiv a-cyan-3-phenoxybenzylalkohol med R-struktur eller racemisk R,S-struktur og med formlen B
H _ 20 HO-C—0 (B)
R eller R,S
25 eller en blanding i ikke-ækvimolekylære mængder af en ester mellem 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre og optisk aktiv a-cyan-3-phenoxybenzylalkohol (B) med R-struktur og en tilsvarende ester med S-struktur, hvilken blanding skal betegnes (R+S)-dichlorester til 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre-S-a-cyan-3-phenoxybenzylester med S-struktur, idet man underkaster udgangsmaterialet indvirkning af et 30 basisk middel, som vælges fra en gruppe bestående af ammoniak, primære aminer, sekundære aminer, tertiære aminer, kvatemære ammoniumforbindelser, ionbytterharpikser med basisk karakter, flydende aminer med høj molekylvægt og i katalytisk mængde benyttede stærke baser, i et opløsningsmiddel eller en blanding af opløsningsmidler, hvori S-esteren er uopløselig, medens R-esteren er opløselig, hvorefter man fra reaktionsmiljøet isolerer den så-35 ledes uopløseliggjorte S-ester.
Fremgangsmåden, som kun omfatter et eneste trin og benytter simple manipulationer og lidet bekostelige reagenser, gør det muligt med meget høje udbytter under yderst fordelagtige be- 2 DK 170732 B1 tingeiser at opnå esteren af ovennævnte cyclopropancarboxylsyre omfattende en dichiorvinyi-kæde med optisk aktiv a-cyan-3-phenoxybenzylalkohol med S-struktur, hvilken ester har en usædvanlig høj insekticid aktivitet.
5 2,2-dimethyl-3R-(2,2-dichlorvinyI)-cyclopropan-1R-carboxylsyre-S-a-cyan-3-phenoxybenzyIes-ter og 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre-R-a-cyan-3-phenoxy-benzylester er ikke beskrevet i litteraturen.
Den første af disse forbindelser, dvs. esteren af S-alkohoi, egner sig særlig godt til anvendelse 10 til bekæmpelse af insekter i landbruget.
F.eks. gør den det muligt effektivt at bekæmmpe bladlus, larver af lepidoptera og coieoptera.
Den kan ligeledes anvendes som insekticid i husholdningen (fluer og myg). De i den eksperimentelle dei anførte forsøg viser den insekticide aktivitet af denne forbindelse på husfluen og 15 på larver af Spodoptera l'rttoralis.
2.2- dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-R-a-cyan-3-phenoxybenzyles-ter har en mindre intens insekticid aktivitet end aktiviteten af den tilsvarende ester af S-alko-holen.
20 2.2- dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-a-cyan-3-phenoxybenzyles-ter kan anvendes til fremstilling af insekticide produkter, der som aktiv bestanddel indeholder den nævnte forbindelse.
25 I disse produkter kan den aktive bestanddel være tilsat et eller flere andre pesticide midler.
Disse produkter kan foreligge i form af puddere, granulater, suspensioner, emulsioner, opløsninger, opløsninger til aerosoler, brændbare bånd, lokkemad eller andre præparater, som normalt benyttes til udnyttelse af forbindelser af denne art.
30 Foruden den aktive bestanddel indeholder disse produkter normalt et bærestof og/eller et ikke-ionisk overfladeaktivt stof, der desuden sikrer en ensartet dispersion af stofferne i blandingen.
Det benyttede bærestof kan være en væske såsom vand, ethanol, carbonhydrider eller andre organiske opløsningsmidler, en mineralolie eller en animalsk eller vegetabilsk olie, et pudder * såsom talkum, ler, silicater eller kiselgur eller et brændbart fast stof såsom pyrethrumpulver.
Til forøgelse af den insekticide aktivitet af den omhandlede forbindelse kan man tilsætte klassiske synergistisk virkende stoffer, som benyttes i sådanne tilfælde, såsom 1-(2,5,8-trioxadode-cyl-2-propyl-4,5-methylendioxy)-benzen (eller piperonylbutoxid), N-(2-(2-ethylheptyl)-bicy- 35 3 DK 170732 B1 cfo(2,2,1)-5-hepten-2,3-dicarboximid og piperonyf-bis-2-(2’-n-butoxyethoxy)-ethylacetat (eller tropital).
Disse insekticide produkter indeholder fortrinsvis 0,005-10 vægtprocent aktivt stof.
5
Nedenstående eksempler illustrerer opfindelsen.
Eksempel 1
Omdannelse af 2,2-dimethyl-3R-{2,2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre-R-<x-cy-10 an-3-phenoxybenzylester til 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxyl-syre-S-a-cyan-3-phenoxybenzylester a) Fremstilling af esteren af alkohol med R-struktur 10 g ester af racemisk R.S-alkohol, a20p = +16,5 ° (c = 10%, benzen), chromatograferes på 15 silicagel under eluering med en blanding af petroleumsether (kp. 40-70 °C) og isopropylether (85:15), og man får 3 g 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-R-a-cyan-3-phenoxybenzylester, α20ρ = -31 0 (c= 1%, benzen) og α20ρ = -21,50 (c= 1%, chloroform).
20 b) Omdannelse til ester af alkohol med S-struktur
Til 60 g 2,2-dimethyl-3R-(2,2-dlchlorvinyl)-cyclopropan-1R-carboxylsyre, ot20p = -31 0 (c= 1%, benzen) og a20p = -21,5 0 (c = 1%, chloroform), fremstillet i afsnit a), sætter man 120 ml iso-propanol og derefter 9 ml 22 °Bé ammoniakvand, afkøler til 0 °C, omrører i 48 timer ved 0 °C, isolerer den dannede udfældning ved frasugning, vasker den med 30 ml isopropanol ved -25 20 °C, tørrer den og får 48,5 g 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre- S-a-cyan-3-phenoxybenzylester, smp. 60 °C, a20p = +66 0 (c = 1%, benzen) og a20p = +340 (c= 1%, chloroform).
Eksempel 2 30 Omdannelse af 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-R,S-a-cyan-3-phenoxybenzylester tii 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carbox-ylsyre-S-a-cyan-3-phenoxybenzylester
Til 600 g ester af racemisk R,S-alkohol, a20p = +16,50 (c = 1%, benzen), sætter man 1200 ml 35 isopropanol, hvorefter man i den opnåede opløsning indfører 90 ml 22 ° Bé ammoniakvand, afkøler til 0 °C, omrører i 48 timer ved denne temperatur, isolerer den dannede udfældning ved frasugning, vasker den med 300 ml isopropanol ved -20 °C, tørrer den og får 485 g 2,2-di- 4 DK 170732 B1 methyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-a-cyan-3-phenoxybenzylester, smp. 60 °C, a20D = +66e (c = 1%, benzen) og a20D = +340 (c = 1%, chloroform).
Analyse: C22H19O3NCI2 (416,28) beregnet: C%63,48 H% 4,60 N% 3,36 Cl% 17,03 5 fundet: 63,7 4,6 3,4 17,1 i
Eksempel 3
Produkt på basis af 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre-S-a-cyan-3-phenoxybenzylester 10
Man blander: 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-a-cyan-3--phenoxybenzylester 25 g/liter 2,6-ditert.-butyl-p-cresol 10 g/liter EMCOL H 300 B* 50 g/liter EMCOL H 500 B* 20 g/liter
Supersol ** 786 g/liter * Disse overfladeaktive stoffer er blandinger af calciumsalte af alkylbenzensulfonater 15 (anionisk del) og polyoxyethylenerede ethere (ikke-ionisk del), som forhandles af firmaet WITE ® ** Supersol er en blanding af aromatiske opløsningsmidler fra firmaet B.P. (Shell ®).
20 Undersøgelse af insekticid aktivitet af 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre-S-a-cyan-3-phenoxybenzylester (forbindelse A) A) Undersøgelse af insekticid aktivitet over for stuefluer
Forsøgsinsekteme er stuefluer af blandet køn. Man arbejder ved topisk påføring af 1 μΙ aceto-25 neopløsning på insekternes dorsale thorax. Man benytter 50 individer for hver behandling. Man s foretager kontrol af dødeligheden 24 timer efter behandlingen og bestemmer den dødelige dosis 50, DL50, af forbindelsen.
5 DK 170732 B1
De opnåede forsøgsresultater fremgår af følgende tabel:
Doser_Procent dødelighed ved 24 timer DLsn 5 93,3 3,75 83,2 2,5 68,0 1,6 nanogram pr. insekt 1.25 34,5 0,625 10,0
Konklusion 5 Forbindelse A har en meget høj insekticid aktivitet over for stuefluer.
B Undersøgelse af den insekticide aktivitet over for larver af Spodootera littoralis
Forsøgene udføres ved topisk applikation. Man anbringer 1 μΙ acetoneopløsning af det produkt, som skal undersøges, på den dorsale thorax af hvert individ. Man benytter 15 larver af 10 Spodoptera littoralis i fjerde larvestadie for hver benyttet dosis. Efter behandlingen anbringes individerne i et kunstigt næringsmiljø (Poitot's miljø). Man foretager kontrol for effektivitet (procent dødelighed i forhold til en ikke-behandlet kontrol) 24 timer og 48 timer efter behandlingen, og man bestemmer den letale dosis 50, DL5Q, i nanogram pr. larve.
% dødelighed
Doser 24 timer 48 timer_DLsn ved 48 timer_ 1.25 95,6 97,8 0,625 80,0 82,2 0,3 nanogram pr. larve 0,3125 48,9 62,2 0,1562 20,5 27,3 15
Eksempel 4 I dette eksempel sammenlignes den insekticide aktivitet af (1R,cis)-2,2-dimethyl-3-(2,2-di-chlorvinyl)-cyclopropancarboxylatet af (S)-a-cyano-3-phenoxybenzyl (i det følgende betegnet 20 forbindelse A) med aktiviteten af den tilsvarende dibromvinylforbindelse (i det følgende betegnet forbindelse B). 1
Undersøgelse af letal virkning på stuefluer
Der benyttes 4 dage gamle stuefluer af hunkøn. Ved topisk applikation anbringes 1 μΙ acetone-25 opløsning af den forbindelse, som skal undersøges, på insekternes dorsale thorax ved hjælp af 6 DK 170732 B1 en Arnold ® mikromanipulator. Ved hver behandling anvendes 50 individer. Dødeligheden kontrolleres 24 timer efter behandlingen.
Der udføres 2 forsøgsserier med forskellige insektpopulationer.
5
De opnåede resultater udtrykkes som DL5Q, dvs. som den dosis (i nanogram), der er nødven- 1 dig for at dræbe 50% af insekterne; se den følgende tabel:
Forbindelse__DLsn (ng/individ)_ A 0,77 0,93 B 1,78 1,78 10 Forbindelsen A er altså henholdsvis 2,3 og 1,9 gange kraftigere end forbindelsen B.
2) Undersøgelse af letal virkning på larver af Spodoptera littoralis Ved topisk applikation anbringes en acetoneopløsning af den forbindelse, som skal undersøges, på larvernes dorsale thorax ved hjælp af en Arnold ® mikromanipulator. Der benyttes ΙΟΙ 5 15 larver for hver dosis af den forbindelse, som skal undersøges. Larverne er i fjerde larvesta dium, dvs. omkring 10 dage gamle ved opvækst ved 24 °C og 65% relativ fugtighed. Efter behandlingen anbringes individerne på et kunstigt næringsmedium (Poitout's medium).
48 timer efter behandlingen kontrolleres dødeligehden.
20
Der udføres tre forsøgsserier med forskellige larvepopulationer.
De opnåede resultater er vist i nedenstående tabel:
Forbindelse__DLsn (ng/individ)_ A 0,77 0,13 2,8 B 0,94 0,19 4,7 25
Forholdet mellem DL50 for forbindelsen B og forbindelsen A er henholdsvis 1,22; 1,53 og 1,65; til gunst for forbindelsen A.
7 DK 170732 B1 3) Undersøgelse af forbindelsernes virkning på larver af Eoilachna varivestris
Man anvender topisk applikation som beskrevet ovenfor for larverne af Spodoptera. Der benyttes larver på et stadium før det sidste larvestadium, og efter behandlingen fordres larverne med bønneplanter. 72 timer efter behandlingen kontrolleres dødeligheden.
5
Der foretages fire serier af forsøg med forskellige insektpopulationer.
Følgende resultater opnås:
Forbindelse DLun (ng/individ) A 1,18 2,11 1,99 0,52 B 2,42 7,74 2,85 1,11 10
Forholdet er her henholdsvis 2,04; 3,67; 1,44 og 1,66 til gunst for forbindelsen A.
4) Undersøgelse af chokvirknino oå stuefluer
Der anvendes 4 dage gamle stuefluer. Der fonstøves direkte ind i et kammer ifølge Keams og 15 March, idet der som opløsningsmiddel anvendes en blanding af acetone (5%) og IsoparL® (olie-opløsningsmiddel) i en mængde på 2 ml/sek. Ved hver behandling anvendes 50 insekter.
Der kontrolleres hvert minut de første 10 minutter, efter 15 minutter, og KT50 bestemmes på sædvanlig måde.
20 Der udføres to forsøgsserier med forskellige insektpopulationer.
Følgende resultater opnås:
Forbindelse__KTsn (mn kone. 0,25 g/l)_ A 3,27 4,03 B 5,29 7,67 25 Forholdet er henholdsvis 1,6 og 1,9 til gunst for forbindelsen A.
5) Undersøgelse af virkning på Blatella germanica
Undersøgelserne foretages ved kontakt med en film på en glasplade, idet acetoneopløsninger af forskellige koncentrationer med pipette anbringes i bunden af en glaspetriskål, hvis kanter 30 forinden er drysset med talkum for at forhindre insekterne i at flygte. CL50 bestemmes (CL = letal koncentration).
DK 170732 B1 s
Der udføres to forsøgsserier med forskellige insektpopulationer.
Følgende resultater opnås: 5
Forbindelse _CL«;n (mg/m^)_ A 0,022 0,008 B 0,068 0,021
Forholdet er henholdsvis 3,13 og 2,69 til gunst for forbindelsen A.
Konklusion 10 (1 R,cis)-2,2-dimethyl-3-(2,2-dichlorvinyl)-cyclopropancarboxylatet af S-a-cyan-3-phenoxyben-zylester er i besiddelse af en meget bemærkelsesværdig insekticid virkning, som klart er bedre end virkningen af den tilsvarende dibromvinylforbindelse.

Claims (2)

1. Insekticid 2,2-dimethyl-3R-(2l2-dichlorvinyl)-cyclopropan-1 R-carboxylsyre-S-a-cyan-3-5 phenoxybenzylester.
2. Insekticidt præparat, kendetegnet ved, at det indeholder esteren ifølge krav 1. 10
DK317589A 1976-04-23 1989-06-27 Insekticid 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-alpha-3-phenoxybenzylester samt insekticidt præparat DK170732B1 (da)

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FR7612094A FR2375161A1 (fr) 1976-04-23 1976-04-23 Procede de transformation d'un ester d'acide chiral d'alcool secondaire a-cyane optiquement actif de structure (r) en ester d'acide chiral d'alcool secondaire a-cyane de structure (s)
FR7612094 1976-04-23

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DK317589A DK317589A (da) 1989-06-27
DK170732B1 true DK170732B1 (da) 1995-12-27

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DK177077A DK171573B1 (da) 1976-04-23 1977-04-22 Fremgangsmåde til omdannelse af en chiral ester mellem en dihalogeneret cyclopropancarboxylsyre med to asymmetriske carbonatomer i ringen og en optisk aktiv alfa-cyaneret sekundær alkohol med R-struktur eller en racemisk alkohol med R,S-struktur eller den chirale ester er en blanding af estere af alkohol med R-struktur og alkohol med S-struktur til ester mellem nævnte syre og alkohol med S-struktu
DK317589A DK170732B1 (da) 1976-04-23 1989-06-27 Insekticid 2,2-dimethyl-3R-(2,2-dichlorvinyl)-cyclopropan-1R-carboxylsyre-S-alpha-3-phenoxybenzylester samt insekticidt præparat

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