FI58774C - SAOSOM INSEKTICIDER ANVAENDBARA 4-HYDROXIKINOLIN- OCH 4-HYDROXITETRAHYDROKINOLINKARBAMATER - Google Patents
SAOSOM INSEKTICIDER ANVAENDBARA 4-HYDROXIKINOLIN- OCH 4-HYDROXITETRAHYDROKINOLINKARBAMATER Download PDFInfo
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- FI58774C FI58774C FI3524/74A FI352474A FI58774C FI 58774 C FI58774 C FI 58774C FI 3524/74 A FI3524/74 A FI 3524/74A FI 352474 A FI352474 A FI 352474A FI 58774 C FI58774 C FI 58774C
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- hydroxitetrahydrokinolinkarbamater
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/20—Oxygen atoms
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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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- C07D213/63—One oxygen atom
- C07D213/68—One oxygen atom attached in position 4
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/20—Oxygen atoms
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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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- C07D215/36—Sulfur atoms
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/38—Nitrogen atoms
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/38—Nitrogen atoms
- C07D215/40—Nitrogen atoms attached in position 8
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/38—Nitrogen atoms
- C07D215/42—Nitrogen atoms attached in position 4
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/50—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 4
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
- C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
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- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
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- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
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- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Description
U^TJ Γοΐ (11) KUULUTUfJULKAISU p - -U ^ TJ Γοΐ (11) ANNOUNCEMENT p - -
JgTtt l J (11) utlAggningsskmft 58774 C Patentti nyonnetty 10 04 1901 • ·ί1\ί (45) ' Patent meddelat pi, K»*.Wa3 ^0? OT^f/io221'06JgTtt l J (11) utlAggningsskmft 58774 C Patent granted 10 04 1901 • · ί1 \ ί (45) 'Patent meddelat pi, K »*. Wa3 ^ 0? OT ^ f / io221'06
SUOMI—FINLAND (21) λμ·*«»»λ·ι»κι·—ρκ·ΜΜ*ΐ(ΐιΐηι 352U/7UFINLAND — FINLAND (21) λμ · * «» »λ · ι» κι · —ρκ · ΜΜ * ΐ (ΐιΐηι 352U / 7U
(22) Hftkemiipilvt — Antttknlngtdt| 05 · 12.?U(22) Hftkemiipilvt - Antttknlngtdt 05 · 12.?U
(23) AlkupUvt—Gikl|h«t*d«f 05.12.7U(23) AlkupUvt — Gikl | h «t * d« f 05.12.7U
(41) Tullut Julkiseksi — Bllvlt oftatlif 11.06. 75(41) Became Public - Bllvlt oftatlif 11.06. 75
Patentti· J» rekisterihallitut „ Nihttviksip»*,). kuutjuiksiMn pvm.-Patent · J »register-controlled„ Nihttviksip »*,). monthsMn date-
Patent- och registerstyrelaen ' AmOkan utlagd och utl.skrtftsn publtc*rad 31 · 12.80 (32)(33)(31) Pyy*·»/ •tuoik.u*—Begird priority 10.12.73Patent and registration authorities' AmOkan utlagd och utl.skrtftsn publtc * rad 31 · 12.80 (32) (33) (31) Ask * · »/ • Tuoik.u * —Begird priority 10.12.73
Saksan Liittotasavalta-Förbundsrepubliken Tyskland(DE) P 2361U38.2 (71) Hoechst Aktiengesellschaft, 6230 Frankfurt/Main 80, Saksan Liittotasa- valta-F8rhundsrepubliken Tyskland(DE) (72) Adolf Studeneer, Kelkheim/Taunus, Gerhard SaTbeck, Kelkheim/Taunus,Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 2361U38.2 (71) Hoechst Aktiengesellschaft, 6230 Frankfurt / Main 80, Federal Republic of Germany F8rhundsrepubliken Tyskland (DE) (72) Adolf Studeneer, Kelkheim / Taunus, Kelhardk Saitbeck, Gerhard SaTbeck ,
Ludwig Emmel, Bergen-Enkheim, Werner Knauf, Eschborn/Taunus, Saksan Liittotasavalta-Forbundsrepubliken Tyskland(DE) (7*0 Oy Roister Ab (5*0 Insektisideinäkäytettävät U-hydroksikinoliini- ja U-hydroksitetrahydro-kinoliinikarbamaatit - S&som insekticider användbara U-hydroxikinol in -oc h U-hydro xit et rahydrokin o 1 inkarb amat erLudwig Emmel, Bergen-Enkheim, Werner Knauf, Eschborn / Taunus, Federal Republic of Germany-Forbundsrepubliken Germany (DE) (7 * 0 Oy Roister Ab (5 * 0 U-hydroxyquinoline and U-hydroxytetrahydroquinoline carbamates for insecticide use hydroxyquinol in -oc h U-hydroxy and rhydroquin o 1 incarbate er
Esillä olevan keksinnön kohteena ovat uudet, insektisideinä käytettävät U-hydroksikinoliini- ja U-hydroksitetrahydrokinoliinikarbarnaatit, joilla on yleinen kaava IThe present invention relates to novel U-hydroxyquinoline and U-hydroxytetrahydroquinoline carbonates of general formula I for use as insecticides.
,° /“3 0-C-N^ CA" ^ R-f N ^R1 jossa on vety tai 1-3 hiiliatomia sisältävä alkyyli, ja R2 ja R^ merkitsevät yhdessä kaavan -CH=CH~CH=CH— tai kaavan -CH^-CH^-CE^-CH^- mukaista ryhmää, jossa voi olla substituenttina fluoriatomi, yksi tai kaksi 1-3 hiiliatomia sisältävää alkyyliryhmää, 1-3 hiiliatomia sisältävä alkoksiryhmä tai trifluorimetyyliryhmä, tai R2 ja R^ merkitsevät yhdessä kaavan ςχ 2 58774 mukaista ryhmää.Wherein O or R 1 is hydrogen or alkyl having 1 to 3 carbon atoms, and R 2 and R 2 together represent -CH = CH-CH = CH- or -CH 2 - CH 2 -CE 2 -CH 2 -, which may be substituted by a fluorine atom, one or two alkyl groups having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a trifluoromethyl group, or R 2 and R 2 together represent a group of formula ςχ 2 58774 .
Keksinnön mukaisia yhdisteitä voidaan valmistaa saattamalla kaavan IIThe compounds of the invention may be prepared by reacting a compound of formula II
OHOH
(Ά E3 R1 yhdiste sinänsä tunnetulla tavalla reagoimaan kaavan III mukaisen karbamoyyli-halogenidin kanssa(Ά E3 R1 compound for reaction with a carbamoyl halide of the formula III in a manner known per se
Hal-C-N IIIHal-C-N III
jossa Hai tarkoittaa halogeeniatomia, varsinkin klooria tai bromia. Kaavan III mukaista yhdistettä käytetään vähintään stökiometrinen määrä.wherein Hal represents a halogen atom, especially chlorine or bromine. The compound of formula III is used in at least a stoichiometric amount.
Tarkoituksenmukaisesti kaavan III mukaista halogenidia käytetään kuitenkin 10-100 %:n ylimääränä. Reaktion suorittamiseksi liuotetaan tai suspendoidaan kaavan II mukainen yhdiste vedettömään, inerttiin liuottimeen tai laimennusainee-seen, kuten kloroformiin, alifaattiseen ketoniin, asetonitriiliin tai dimetyyli-formamidiin, ja orgaanista emästä, kuten esim. trietyyliamiinia, pyridiiniä, kino-liinia, tai epäorgaanista emäksistä yhdistettä, kuten esim. natrium-, kalium- tai kalsiumkarbonaattia lisätään vähintään stökiometr isinä määrinä: tämän jälkeen lisätään lämpötiloissa 0-Ö0°C N,N-dimetyylikarbamoyylihalogenidi·Suitably, however, the halide of formula III is used in an excess of 10-100%. To carry out the reaction, a compound of formula II is dissolved or suspended in an anhydrous, inert solvent or diluent such as chloroform, aliphatic ketone, acetonitrile or dimethylformamide, and an organic base such as, e.g., triethylamine, pyridine, quinoline, or an inorganic base. such as sodium, potassium or calcium carbonate is added in at least stoichiometric amounts: then N, dimethylcarbamoyl halide is added at temperatures from 0 to 0 ° CN ·
Emäslisäyksen jälkeen syntyneiden ambidenttisten anionien halutun 0-asyloin-nin saavuttamiseksi on osoittautunut toisinaan edulliseksi käyttää mahdollisimman polaarisia liuottimia ja mahdollisimman alhaisia reaktiolänpötiloja. Yli 30°C:n olevat reaktiolämpötilat tosin edistävät reaktiota, kuitenkin joissakin tapauksissa N-asylointituotteen osuus kasvaa lämpötilan kohotessa O-asylointituotteen kustannuksella.In order to achieve the desired O-acylation of the ambient anions formed after the addition of the base, it has sometimes proved advantageous to use the most polar solvents and the lowest possible reaction temperatures. Although reaction temperatures above 30 ° C promote the reaction, in some cases the proportion of N-acylation product increases as the temperature rises at the expense of the O-acylation product.
Reaktioaika vaihtelee kulloinkin käytetyn emäksen mukaan, ja se on tavallisesti U-12 tuntia.The reaction time varies depending on the base used in each case, and is usually U-12 hours.
Menetelmän toisen muunnoksen mukaan voidaan kaavan II mukainen yhdiste saattaa karbamiinihappohalogenidien sijasta reaktioon myös sinänsä tunnetulla tavalla fosgeenin tai kloorimuurahaishapon esterien kanssa, ja saattaa saadut välituotteet reaktioon dimetyyliamiinin kanssa tarkoituksenmukaisesti liuottimen tai sopivan emäksen läsnäollessa.According to a second variant of the process, instead of the carbamic acid halides, the compound of the formula II can also be reacted with esters of phosgene or chloroformic acid in a manner known per se, and the resulting intermediates can be reacted with dimethylamine in the presence of a solvent or a suitable base.
Tetrahydrokinoliinikarbamaatteja voidaan myös valmistaa hydraamalla vastaavista tyydyttämättömistä yhdisteistä.Tetrahydroquinoline carbamates can also be prepared by hydrogenation of the corresponding unsaturated compounds.
Kaavan I mukaisten yhdisteiden eristäminen reaktioseoksesta tapahtuu tavallisella tavalla suodattamalla erottuneet amiinihydrohalogenidit tai alkali- tai maa- alkalihalogenidit ja haihduttamalla suodos, joka sisältää reaktiotuotteen. Jos menetelmään liittyy pelkistysvaihe, poistetaan tällöin samalla tavalla myös katalysaat— 3 58774 tori. Raakatuott eiden lisäpuhdistamiseksi voidaan tarpeen mukaan tislata tyhjössä tai kiteyttää tavallisista orgaanisista liuottimista.Isolation of the compounds of the formula I from the reaction mixture takes place in the customary manner by filtration of the separated amine hydrohalides or alkali or alkaline earth metal halides and evaporation of the filtrate containing the reaction product. If the process involves a reduction step, the catalyst is removed in the same way. To further purify the crude products, it is possible, if necessary, to distill under vacuum or crystallize from common organic solvents.
Kaavan I mukaiset yhdisteet ovat värittömiä tai heikon kellertäviä kiteisiä kiinteitä aineita tai korkeaviskoosisia nesteitä. Ne liukenevat useimpiin orgaanisiin liuottimiin, veteen ne eivät kuitenkaan juuri liukene. Vesiliuokset reagoivat heikosti emäksisestä.The compounds of formula I are colorless or slightly yellowish crystalline solids or highly viscous liquids. They are soluble in most organic solvents, however, they are barely soluble in water. Aqueous solutions react weakly from alkaline.
Kaavan II mukaiset 1ähtöyhdisteet voidaan valmistaa kirjallisuudesta tunnetuilla menetelmillä tai analogiamenetelmillä. Sopivien 1ähtöyhdisteiden valmistus on esim. kuvattu seuraavissa kirjallisuusviitteissä: US 1 147 760;, DE 2 0 58 002; DE 1 620 066; DE 2 103 728; Chem. Rev. 43, 43-68 (1948); J. Am. Chem. Soc. 68, 2685 (1946); 68, 2686 (1946); 69, 365 (1947); 69, 371 (1947); 69, 374 (1947); Monat sh ef te fiir Chemie 100, 132-135 (1969).The starting compounds of formula II can be prepared by methods known from the literature or by analogous methods. The preparation of suitable starting compounds is described, for example, in the following literature references: US 1 147 760; DE 2 0 58 002; DE 1 620 066; DE 2 103 728; Chem. Rev. 43, 43-68 (1948); J. Am. Chem. Soc. 68, 2685 (1946); 68, 2686 (1946); 69, 365 (1947); 69, 371 (1947); 69, 374 (1947); Monat sh ef te fiir Chemie 100, 132-135 (1969).
Keksinnön mukaisille kaavan I mukaisille yhdisteille on ominaista erittäin hyvä selektiivinen insektisidinen teho varsinkin lehtikirvoja vastaan, ja huomattavan hyvät systeemiset ominaisuudet. Ne vaikuttavat sekä kasvien vihreän osan väli- ) tyksellä että juuriston kautta. Siten voidaan torjua varmasti myös piilossa elävät lehtikirvalajit, jotka elävät kasviäkämissä ja muissa ei suoraan saavutettavissa kasvinosissa. Myös fosforiesteriresistentit lehtikirvalajit voidaan varmasti torjua näillä yhdisteillä. !The compounds of the formula I according to the invention are characterized by very good selective insecticidal activity, in particular against aphids, and remarkably good systemic properties. They act both through the green part of the plants and through the root system. Thus, it is also possible to control hidden aphid species that live in plant huts and other parts of plants that are not directly accessible. Phosphorus ester-resistant aphid species can certainly also be controlled with these compounds. !
Esimerkkejä lehtikirvoista, jotka voidaan tuloksekkaasti torjua keksinnön mukaisilla yhdisteillä, ovat Brevicoryne brassicae (kaalikirva), Myzaphis rosarium, Aphis Schneideri; kilpikirvat, kuten Eriosoma lanigerum (verikirva); sappikirvat kuten Pemphigus laji, sekä Myzodes persicae.Examples of aphids that can be successfully controlled by the compounds of the invention include Brevicoryne brassicae (cabbage aphid), Myzaphis Rosarium, Aphis Schneideri; aphids such as Eriosoma lanigerum (blood aphid); aphids such as Pemphigus species, as well as Myzodes persicae.
Hyödylliset hyönteiset kovakuoriaisten ryhmästä (kuten esim. leppäpirkot), perhoset, suorasiipiset, pistiäiset (kuten esim. loispistiäiset) ja petopunkit eivät sensijaan kuole edes korkeita tehoaineväkevyyksiä käytettäessä. Samoin on vaikutus vesieläimistöön vähäinen. Vasta korkeissa väkevyyksissä osoittavat yhdisteet vedessä vaikutusta kaloihin.Useful insects from the group of beetles (such as alder woodpeckers), butterflies, straight-winged, stingrays (such as parasitic beetles) and predatory mites, on the other hand, do not die even at high active ingredient concentrations. Similarly, the impact on aquatic fauna is negligible. Only at high concentrations do compounds in water show an effect on fish.
Keksinnön mukaisia yhdisteitä tai valmisteita, jotka sisältävät näitä yhdisteitä, voidaan käyttää monella tavalla. Käsittely voi kohdistua lehdistöön ja/tai sen sairastuneisiin osiin tai toisaalta kasvia ympäröivään maaperään.The compounds or preparations of the invention containing these compounds can be used in a variety of ways. The treatment may be directed at the press and / or its affected parts or, on the other hand, at the soil surrounding the plant.
Näitä yhdisteitä sisältävät valmisteet voivat olla pölytysvalmist eitä, jauheita tai granulaatteja, joissa tehoaine on sekoitettuna kiinteisiin laimennus- tai kantoaineisiin, kuten esim. inerttiaineisiin jauhe-tai granulaattimuodossa. Keksinnön mukaisten yhdisteiden pitoisuus näissä valmisteissa on yleensä 3-75 %· Sopivia kiinteitä laimennus- tai kantoaineita ovat esim. kaoliini, bentoniitti, piimää, dolomiitti, kalsiumkarbonaatti, talkki, jauhettu magnesia (liitu), Fuller-maa, kipsi, diatomiitti, savi. Valmisteita voidaan käyttää myös ruiskejauheiden muodossa, jotka tehoaineen lisäksi sisältävät tunnetulla tavalla kostutusainetta ja/tai dispergointi-ainetta ja lisäksi mahdollisesti vielä täyteaineita ja/tai emulgaattoreita.Preparations containing these compounds may be in the form of dusts, powders or granules in which the active ingredient is mixed with solid diluents or carriers, such as, for example, inert substances in powder or granular form. The content of the compounds according to the invention in these preparations is generally from 3 to 75%. Suitable solid diluents or carriers are, for example, kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, ground magnesium (chalk), Fuller's earth, gypsum, diatomaceous earth, clay. The preparations can also be used in the form of injection powders which, in addition to the active ingredient, contain, in a known manner, a wetting agent and / or dispersant and, in addition, optionally further excipients and / or emulsifiers.
4 587744 58774
Valmisteet voivat olla myös nestemäisinä valmisteina ruiskeliuoksiksi sopivien emulsioväkevöitteiden muodossa, jotka sisältävät normaalisti tehoaineen yhden tai useamman kostutusaineen, dispergointiapuaineen tai emul-gaattorin läsnäollessa. Nestemäisten valmisteiden saamiseksi voidaan käyttää myös orgaanisia liuottimia.The preparations may also be in the form of liquid preparations for injection, in the form of suitable emulsion concentrates, which normally contain the active ingredient in the presence of one or more wetting agents, dispersing aids or emulsifiers. Organic solvents can also be used to obtain liquid preparations.
Kostutus-, dispergointi- ja emulgointiapuaineet voivat olla tyypiltään kationisia, anionisia tai ionittomia.Wetting, dispersing and emulsifying agents can be of the cationic, anionic or nonionic type.
Kaavan I mukaiset yhdisteet voivat olla myös savutusaineiden aktiivisina aineosina.The compounds of the formula I can also be active ingredients in smoking agents.
Keksintöä valaistaan lähemmin seuraavilla esimerkeillä:The invention is further illustrated by the following examples:
ValmistusesimerkkejäPreparation Examples:
Esimerkki 1_ 0C0N(CH3)2Example 1_ 0CO0 (CH3) 2
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5 2-metyyli-4-dlmetyyliaminokarbonyylioksikinoliini a) 2-metyyli-4-hydroksikinoliinin (75 g, 0,47 moolia) suspensioon 1 litrassa asetonitriiliä lisättiin huoneen lämpötilassa 130 g vedetöntä kaliumkarbonaattia, ja seosta sekoitettiin voimakkaasti noin 2 tuntia palau-tustislauslämpötilassa 80°C). Seoksen jäähdyttyä huoneen lämpötilaan lisättiin 76,7 g (0,71 moolia) dimetyylikarbamiinihappokloridia ja reaktio-seosta sekoitettiin huoneen lämpötilassa voimakkaasti noin 8 tunti. Tämän jälkeen ei reaktioseoksesta voitu ohutlevykromatografiällä enään osoittaa 2-metyyli-4-hydroksikinoliinia. Reaktioseoksesta poistettiin imusuodatuk-sella epäorgaaniset suolat, sakka pestiin asetonitriilillä. Suodos ja pesunesteet yhdistettiin ja asetonitriili poistettiin vesipumpputyhjössä.2-Methyl-4-dimethylaminocarbonyloxyquinoline a) To a suspension of 2-methyl-4-hydroxyquinoline (75 g, 0.47 mol) in 1 liter of acetonitrile at room temperature was added 130 g of anhydrous potassium carbonate, and the mixture was stirred vigorously for about 2 hours at reflux temperature. C). After the mixture was cooled to room temperature, 76.7 g (0.71 mol) of dimethylcarbamic acid chloride was added, and the reaction mixture was stirred vigorously at room temperature for about 8 hours. Thereafter, 2-methyl-4-hydroxyquinoline could no longer be detected in the reaction mixture by thin layer chromatography. Inorganic salts were removed from the reaction mixture by suction filtration, and the precipitate was washed with acetonitrile. The filtrate and washings were combined and the acetonitrile was removed in a water pump vacuum.
Jäännöksenä saatu öljy fraktioitiin tyhjössä. 15Θ - l6l°C:ssa (0,05 mm) tislautui 100 g väritöntä, korkeaviskoosieta nestettä, jonka alkuaineana-lyysiarvot vastasivat 2-metyyli-4-(dimetyyliaminokarbonyylioksi)-kinoliinin teoreettisia arvoja, ja joka osoittautui ohutlevykromatogrammin ja NMR-spektrin mukaan yhtenäiseksi. NMR-spektrin ohella varmistivat IR-spektrin arvot, että kyseessä oli karbamaatti.The residual oil was fractionated in vacuo. At 15 DEG-11 DEG C. (0.05 mm), 100 g of a colorless, high-viscosity liquid with elemental analytical values corresponding to the theoretical values of 2-methyl-4- (dimethylaminocarbonyloxy) quinoline distilled off and proved to be uniform by thin-layer chromatogram and NMR spectrum. . In addition to the NMR spectrum, the values of the IR spectrum confirmed that it was a carbamate.
b) 24 g (0,15 moolia) 2-metyyli-4-hydroksikinoliinia liuotettiin 200 ml:ssa dimetyyliformamidia (vesi- ja amiinivapaa), liuokseen lisättiin 5 58774 23 g (O,22 moolia) trietyyliamiinia ja sitten siihen tiputettiin vielä 24 g (0,22 moolia) dimetyylikarbamiinihappokloridia. Reaktioseosta kuumennettiin 60°C:ssa niin kauan (noin 8 tuntia), että siitä otetussa näytteessä ei o enään voitu osoittaa ohutlevykromatofrafiällä lähtöainetta. 0-10 Cseen jäähdytetty reaktioseos suodatettiin amiinihydrokloridin poistamiseksi, suodos ja sakan pesuneste (vähäinen määrä dimetyyliformamidia) yhdistettiin ja liuotin poi-tettiin tyhjössä. Öljymäinen jäännös fraktiotislattiin.b) 24 g (0.15 mol) of 2-methyl-4-hydroxyquinoline were dissolved in 200 ml of dimethylformamide (anhydrous and amine-free), 5 58774 g (0.22 mol) of triethylamine were added to the solution and then a further 24 g were added dropwise. (0.22 moles) of dimethylcarbamic acid chloride. The reaction mixture was heated at 60 ° C for so long (about 8 hours) that no starting material could be detected in the sample by thin layer chromatography. The reaction mixture cooled to 0-10 ° C was filtered to remove the amine hydrochloride, the filtrate and the precipitate wash (a small amount of dimethylformamide) were combined and the solvent was removed in vacuo. The oily residue was fractionally distilled.
Saatiin 21 g väritöntä korkeaviskoosista nestettä, joka tislautui 145°C:ssa (0,01 mm)21 g of a colorless, high-viscosity liquid were obtained, which was distilled at 145 ° C (0.01 mm).
Esimerkki 2 0C0N(CH5)2 CH? 2-metyyli-4-<iimetyyliaminokarbonyylioksi-5,6,7»8-tetrahydrokinoliini a) 1650 mitään kloroformia (alkoholi- ja vesivapaa) liuotettiin 287 g (1,76 moolia) 2-metyyli-4“hydroksi-5»6,7>8-tetrahydrokinoliinia. Tähän liuokseen lisättiin peräkkäin 267 g (2,64 moolia) trietyyliamiinia ja 284.5 g (2,63 moolia) dimetyylikarbamiinihappokloridia. Seosta kuumennettiin (sisäinen lämpötila 50°C) nyt niin kauan (noin 6 tuntia), että reaktioseoksesta otettu näyte ei ohutlevykromatografian mukaan enään sisältänyt lähtöyhdis-te+tä. Jäähdyttämisen jälkeen huoneen lämpötilaan reaktioseokseen tiputettiin sekoittaen noin 1 litra jäävettä, jolloin reaktiossa erottunut amiini-hydrokloridi liukeni ja muodostui kaksi nestefaasia. Kloroformifaasin erottamisen jälkeen vesifaasista orgaaninen faasi pestiin vähällä vedellä, kuivattiin ja haihdutettiin kuiviin.Example 2 0CO0 (CH5) 2 CH? 2-Methyl-4-methylaminocarbonyloxy-5,6,7,8-tetrahydroquinoline a) In 1650 any chloroform (alcohol and water free) was dissolved 287 g (1.76 moles) of 2-methyl-4'-hydroxy-5,6,6 7> 8-tetrahydroquinoline. To this solution were successively added 267 g (2.64 moles) of triethylamine and 284.5 g (2.63 moles) of dimethylcarbamic acid chloride. The mixture was heated (internal temperature 50 ° C) for so long (about 6 hours) that the sample taken from the reaction mixture no longer contained the starting compound according to thin layer chromatography. After cooling to room temperature, about 1 liter of ice water was added dropwise to the reaction mixture with stirring, whereby the amine hydrochloride separated in the reaction dissolved and two liquid phases formed. After separation of the chloroform phase from the aqueous phase, the organic phase was washed with a little water, dried and evaporated to dryness.
Jäännöksestä tislattiin pois joitakin millilitroja öljymäistä, esteri-mäieesti tuoksuvaa sivutuotetta 100°C:n haudelämpötilassa ja noin 2 - 3 mm paineessa. Jäljelle jäänyt öljymäinen jäännös liuotettiin kiehuvaan n-heksaaniin. Jäähtyneestä liuoksesta kiteytyi 347 g väritöntä tuotetta, sul.p. 89 - 90°C. Tämä osoittautui ohutlevykromatogrammilla yhtenäiseksi, ja sen alkuaineanalyysiarvot olivat 2-metyyli-4-dimetyyliaminokarbonyylioksi- 5,6,7,8-tetrahydrokinoliinin arvojen mukaiset. IR- ja NMR-spektrit vahvistivat odotetun O-asylointituotteen muodostumisen.A few milliliters of oily, ester-like odorous by-product were distilled off from the residue at a bath temperature of 100 ° C and a pressure of about 2 to 3 mm. The remaining oily residue was dissolved in boiling n-hexane. 347 g of a colorless product crystallized from the cooled solution, m.p. 89-90 ° C. This was found to be uniform by thin layer chromatography, and its elemental analysis values were consistent with those of 2-methyl-4-dimethylaminocarbonyloxy-5,6,7,8-tetrahydroquinoline. IR and NMR spectra confirmed the formation of the expected O-acylation product.
b) 150 mlsaan kloroformia (vesi- ja alkoholivapaa) liuotettiin 16,3 g (0,1 moolia) 2-metyyli-4-hydroksi-5f6,7.8-tetrahydrokinoliinia, ja tämä 6 58774 liuos tiputettiin korkeintaan +10°C:ssa etukäteen valmistettuun liuokseen, jossa oli noin 20 g (0,2 moolia) fosgeenia 100 ml:ssa kloroformissa. 2 tunnin seisotuksen jälkeen +10°C:ssa reaktioseos sai seistä huoneen lämpötilassa vielä tunnin ajan. Reagoimaton fosgeeni ajettiin sitten pois liuoksesta kuivalla typellä ja liuotin poistettiin huoneen lämpötilassa tyhjössä. Puolikiinteä jäännös liuotettiin uudelleen kuivaan, alkoholivapaaseen kloroformiin, liuos jäähdytettiin +10°C:een, ja siihen johdettiin tässä lämpötilassa ylimäärin dimetyyliamiinia. 2 tunnin seisotuksen jälkeen huoneen lämpötilassa kloroformi tislattiin pois tyhjössä huoneen lämpötilassa, jolloin ylimääräinen amiini poistui samalla. Jäännöstä digeroitiin jää-veden kanssa, vesi dekantoitiin pois ja jäännös liuotettiin tolueeniin. Kuivaamalla ja haihduttamalla tolueeniliuos saatiin 7 g haihdutusjäännöstä, joka kiteytyi sitä hierottaessa n-heksaanin kanssa. Uudelleenkiteyttämällä n-heksaanista saatiin ^ g yhtenäistä kiteistä tuotetta, jolla oli sulamispiste 88-Ö9°C. Se osoittautui identtiseksi esimerkin (2a) mukaan saadun tuotteen kanssa.b) 16.3 g (0.1 mol) of 2-methyl-4-hydroxy-5β, 6,7,8-tetrahydroquinoline were dissolved in 150 ml of chloroform (anhydrous and alcohol-free), and this 6 58774 solution was added dropwise at not more than + 10 ° C in advance to a prepared solution of about 20 g (0.2 moles) of phosgene in 100 ml of chloroform. After standing for 2 hours at + 10 ° C, the reaction mixture was allowed to stand at room temperature for another hour. The unreacted phosgene was then run off the solution with dry nitrogen and the solvent was removed at room temperature in vacuo. The semi-solid residue was redissolved in dry, alcohol-free chloroform, cooled to + 10 ° C, and treated with excess dimethylamine at this temperature. After standing for 2 hours at room temperature, the chloroform was distilled off in vacuo at room temperature, while the excess amine was removed at the same time. The residue was digested with ice-water, the water was decanted off and the residue was dissolved in toluene. Drying and evaporation of the toluene solution gave 7 g of an evaporation residue which crystallized on trituration with n-hexane. Recrystallization from n-hexane gave ^ g of a uniform crystalline product with a melting point of 88-9 ° C. It turned out to be identical to the product obtained according to Example (2a).
c) Esimerkin (1) substanssin (20 g) liuokseen 1 litrassa tolueenia lisätään 5 g ’’nikkelikontakti 55/5JttäM (Ruhrchemie, 50 paino-)? nikkeliä piimaalla) ja seosta kuumennetaan sekoittaen 2 litran teräsautoklaavissa 100 aty:n vedyn paineessa 100°C:ssa. 20 tunnin kuluttua jäähdytetään, katalysaattori suodatetaan, pestään tolueenilla ja suodos haihdutetaan. Jäännös tislataan, jolloin saadaan 11 g tuotetta (kP.Q i 130-ΐί+2Ο0). Tämä tuote kiteytyi ja osoittautui identtiseksi esimerkin (2a) mukaan saadun tuotteen kanssa.c) To a solution of the substance (20 g) of Example (1) in 1 liter of toluene is added 5 g of nickel contact 55 / 5JttäM (Ruhrchemie, 50 wt.)? nickel in diatomaceous earth) and the mixture is heated with stirring in a 2 liter steel autoclave under 100 aty hydrogen pressure at 100 ° C. After 20 hours, cool, filter the catalyst, wash with toluene and evaporate the filtrate. The residue is distilled to give 11 g of product (kP.Q i 130-ΐί + 2Ο0). This product crystallized and proved to be identical to the product obtained according to Example (2a).
Seuraavassa taulukossa esitetään muita esimerkkien (1) - (2) mukaan valmistettuja yhdisteitä, jolloin sarakkeessa (1) on esimerkin n:o, sarakkeessa (2) kyseisen yhdisteen rakennekaava, sarakkeessa (3) käytetty emäs ja liuotin, sarakkeessa (U) reaktiolämpötila ja reaktioaika ja sarakkeessa (5) sulamispiste s«kä liuotin, josta kiteytys suoritettiin, ja kiehumapiste ja vastaava paine.The following table shows other compounds prepared according to Examples (1) to (2), wherein column (1) has the structural formula of Example No. in column (1), the base and solvent used in column (3), the reaction temperature in column (U), and the reaction time and, in column (5), the melting point and the solvent from which crystallization was carried out, and the boiling point and the corresponding pressure.
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Biologisia esimerkkejäBiological examples
Esimerkki I:Example I:
Ruukuissa olevia härkäpapuja (Vicia faba) tartutetaan mustilla papu-kirvoilla (Dolaris fabae), 200 eläintä kasvia kohti, ja populaation tasoituttua kasvit suihkutetaan esimerkin (1) yhdisteen emulsioväkevöitteen alenevilla vesilaimennuksilla tippumismärkyyteen asti. 3 vuorokauden kuluttua määritetään kuolleisuusprosentit laskemalla elävät ja kuolleet eläimet.Kidney beans (Vicia faba) in pots are infected with black bean aphids (Dolaris fabae), 200 animals per plant, and once the population is leveled, the plants are sprayed with decreasing aqueous dilutions of the emulsion concentrate of the compound of Example (1) to dripping wetness. After 3 days, mortality rates are determined by counting live and dead animals.
Seuraavassa taulukossa on esitetty näin saatu kuolleisuus riippuvana aktiivisubstanssin (AS) pitoisuudesta vesilaimennuksessa ja verrattuna samankaltaisen rakenteen tai vaikutusasteen omaavien yhdisteiden vaikutukseen.The following table shows the mortality thus obtained as a function of the concentration of active substance (AS) in the aqueous dilution and in comparison with the effect of compounds having a similar structure or degree of activity.
i5 58774i5 58774
Taulukko ITable I
Vertailuyhdiste tai yhdiste Paino-% AS suihku- Kuolleisuus-^ esimerkistä n:o tusliemessä °’°°6 100 l] 0,003 98 0,0015 60 OCONiCHgJg 0,0006Reference compound or compound Weight% AS spray Mortality from Example No. in broth ° 100 ° 6 100 l] 0.003 98 0.0015 60 OCONiCHgJg 0.0006
Vertailuyhdiste IReference compound I
(NL 6 6θ6 695) ch(ch3)2 0,005 100 S 0,0025 96 (CH3)2N-€-0-^^ 0,0012 60 / 0,0006 20 H GH3(NL 6 6θ6 695) ch (ch3) 2 0.005 100 S 0.0025 96 (CH3) 2N- € -0 - ^^ 0.0012 60 / 0.0006 20 H GH3
Vertailuyhdiste II (“Isolani GB 68l 376) 0 „ 0,0063 100 ti (ch3)2nk:o-6 ji 0,0031 85 ^^\CH 0,0016 60 3 0,00078 33Reference compound II (Isolani GB 681 376) 0 0.0063 100 ti (ch3) 2nk: o-6 ji 0.0031 85 ^^ \ CH 0.0016 60 3 0.00078 33
Vertailuyhdiste III Q 00039 0 (tyrolan; GB· 68l 37 6) o-con(ch3)2 0,00075 100 0,000375 80 ΛνΛ ch3 ch3Reference compound III Q 00039 0 (tyrolan; GB · 68l 37 6) o-con (ch3) 2 0.00075 100 0.000375 80 ΛνΛ ch3 ch3
Vertailuyhdiste IV (GB 68l 376) 1 0,00019 100 0,000095 98 o,ooooU8 80 2 0,0 0037 5 99Reference compound IV (GB 681 376) 1 0.00019 100 0.000095 98 o, oooU8 80 2 0.0 0037 5 99
0,00019 8U0.00019 8U
16 5 877416 5 8774
Taulukko I (jatkoa) yertailuyhdiste tai yhdiste .Paino-% AS suihku- Kuolleisuus-^ esimerkistä n: o tusliemessä 3 0,0006 100 0,000375 90 6 0,0015 100 0,00075 90 7 0,00019 9Ö 0,000095 70 8 0,000375 100 0,00019 90 9 0,000375 100 0,00019 85 10 0,0015 100 0,00075 95 12 0,00075 100 0,00019 95 0,000095 90 15 0,00019 100 16 0,00019 98 0,000095 60 17 0,00019 98 0,000095 85 19 0,00075 100 0,000375 95 21 0,0015 100 0,00075 95 22 0,00037 5 100 0,00019 98 0,000095 92 58774Table I (continued) Reference compound or compound .Weight% AS spray- Mortality- ^ from Example No. in broth 3 0.0006 100 0.000375 90 6 0.0015 100 0.00075 90 7 0.00019 9Ö 0.000095 70 8 0.000375 100 0.00019 90 9 0.000375 100 0.00019 85 10 0.0015 100 0.00075 95 12 0.00075 100 0.00019 95 0.000095 90 15 0.00019 100 16 0.00019 98 0.000095 60 17 0.00019 98 0.000095 85 19 0.00075 100 0.000375 95 21 0.0015 100 0.00075 95 22 0.00037 5 100 0.00019 98 0.000095 92 58774
Esimerkki IIExample II
Noin 25 cm korkean ruukussa olevan härkäpavun varren ympärille kiedotaan puuvillaa (vanua), joka peitetään sellofaanilla. Vanutukkoon jaetaan nyt tasaisesti injektioruiskun avulla 2 ml esimerkin (l) yhdisteen ruiskutejauhesuspension vesilaimennusta ilmoitetussa tehoainepitoisuudessa.A cotton (cotton wool) is wrapped around a stem of a kidney bean about 25 cm high in a pot, which is covered with cellophane. 2 ml of an aqueous dilution of the syringe powder suspension of the compound of Example (I) at the indicated active ingredient concentration are now evenly distributed in the pad.
Kasvin lehdillä olevat lehtikirvat kuolevat 3 vrk:n havaintoahan kuluessa käytetyillä tehoainemäärillä seuraavasti:The aphids on the leaves of the plant die within 3 days with the amounts of active substance used as follows:
Paino-# AS ruisku- 0,25 0,125 0,06 0,03 0,015 teliemessä __________________ kuolleisuus-# 100 100 86 ^ 70 <20 Tämä todistaa tehoaineen pystyvän tunkeutumaan kasvisolukkoon ja kulkeutumaan siellä johtoratoja pitkin. Tämä (Muinaisuus on myös muilla esimerkissä I mainituilla yhdisteillä.Weight- # AS syringe- 0.25 0.125 0.06 0.03 0.015 in batch __________________ mortality- # 100 100 86 ^ 70 <20 This proves that the active substance is able to penetrate the plant cell and migrate there along the conduits. This (The other compounds mentioned in Example I also have an antiquity.
Esimerkki IIIExample III
Vaikutusta hyötyhyönteisiin, kuten esim. loispistiäiseen (Coccygomimus turionellae (L·)) lehtikirvojen torjunnassa käytetyillä väkevyyksillä ei ole havaittu.No effect on beneficial insects such as parasites (Coccygomimus turionellae (L ·)) has been observed with the concentrations used to control aphids.
Suorakaiteen muotoisia suodatinpapereita (150 cm ) kostutetaan tasaisesti pipetin avulla tehoaineen asetoniliuoksella alenevilla pitoisuuksilla. Kuivumisen jälkeen suodatinpaperi työnnetään siten lasiputkeen, että putken koko sisäpinta peittyy suodatinpaperilla. Tämän jälkeen jokaiseen näin käsiteltyyn lasiputkeen viedään 10 £ loispistiäistä ja putket suljetaan porarei'illa varustetuilla korkeilla, joiden lävitse johdetaan jatkuva ilmavirta (10 1 ilmaa/h) (mahdollisen kaasufaasin muodostumisen ehkäisy, ulkoilman ilman liikkeiden matkiminen). Käytettäessä esimerkin (l) yhdistettä saadaan esim. Seuraa-vat kuolleisuusluvut 2k tunnin kuluttua. Jotta voitaisiin paremmin verrata käytännön olosuhteisiin, on tämän taulukon sarakkeessa 3 esitettynä vesipitoisen suihkuteliemen väkevyydet, joilla niitä käytettäessä 600 1/ha saadaan sama aktiivisubstanssin pitoisuus pinta-ala-yksikköä kohti.Rectangular filter papers (150 cm) are evenly moistened with a pipette with decreasing concentrations of the active substance in acetone solution. After drying, the filter paper is inserted into the glass tube so that the entire inner surface of the tube is covered with filter paper. Then 10 pounds of parasitic pellets are introduced into each glass tube thus treated and the tubes are closed at high holes with boreholes through which a continuous flow of air (10 l of air / h) is passed (prevention of possible gas phase formation, mimicking the movements of outside air). When using the compound of Example (1), e.g. the following mortality rates are obtained after 2k hours. In order to better compare with the practical conditions, column 3 of this table shows the concentrations of the aqueous spray liquor at which the same concentration of active substance per unit area is obtained at 600 l / ha.
18 58774 mg AS suodat- Paino-# AS suihku- Kuolleisuus-# timella telimessä18 58774 mg AS filter- Weight- # AS shower- Mortality- # with scaffold
Esimerkin (l) 0,012 0,2 100 yhdiste (keksinnön 0,006 0,1 Uo mukainen 0,003 0,05 0 0,0012 0,02 0 0,0006 0,01 0Compound of Example (I) 0.012 0.2 100 (0.006 0.1 Uo of the invention 0.003 0.05 0 0.0012 0.02 0 0.0006 0.01 0
Karbaryyli 0,0006 0,01 100 (Vertailuaine V) 0,0003 0,005 100 o-co-nh-ch3 0,00015 0,0025 1+0 0,000075 0,0012 0 "Isolan" 0,003 0,05 100 (Vertailuaine II) 0,0012 0,02 8o 0,0006 0,01 0Carbaryl 0.0006 0.01 100 (Reference substance V) 0.0003 0.005 100 o-co-nh-ch3 0.00015 0.0025 1 + 0 0.000075 0.0012 0 "Isolan" 0.003 0.05 100 (Reference substance II) 0.0012 0.02 8o 0.0006 0.01 0
Esimerkissä I mainitut yhdisteet suhtautuvat samantapaisesti tai yhtä edullisesti kuin esimerkin (l) yhdiste.The compounds mentioned in Example I are treated in the same way or as preferably as the compound of Example (1).
Esimerkki IVExample IV
Myös petona eläviin, pääasiassa lehtikirvoja käyttäviin leppäpirkkoihin (Coccinellidae) ei tehoaineilla ole lehtikirvojen torjunnassa käytetyillä pitoisuuksilla mitään vaikutusta. Mainitussa esimerkissä on tämä osoitettu lajin Coccinella septempunktata täysikasvuisilla hyönteisillä:The concentrations of the active substances used in the control of aphids also have no effect on alder woodpeckers (Coccinellidae), which live as predators and use mainly aphids. In this example, this has been demonstrated in adult insects of the species Coccinella septempunktata:
Suodatinpaperilla peitetyille petrinmaljoille pannaan kullekin yllä mainittujen eläimiä 10 kpl, ja sitten suodatinpaperit suihkutetaan alenevia väkevyyksiä sisältävillä emulsioväkevöitteiden vesilaimennuksilla, jotka sisältävät keksinnön mukaista esimerkin (l) yhdistettä (vastaten 600 1/ha). 2h tunnin kuluttua saadaan seuraavat kuolleisuusluvut: 58774 19 mg AS suodattimena paino-# AS ruiskute- kuolleisuus-# ________liemessä 0,003 0,05 10 0,0015 0,025 0 0,0006 0,01 o 0,0003 0,005 o 0,00015 0,0025 o10 of each of the above animals are placed on filter paper-covered petri dishes, and then the filter papers are sprayed with aqueous dilutions of emulsion concentrates containing decreasing concentrations containing the compound of Example (I) of the invention (corresponding to 600 l / ha). After 2 hours, the following mortality rates are obtained: 58774 19 mg AS as filter in weight # AS spray mortality # ________ broth 0.003 0.05 10 0.0015 0.025 0 0.0006 0.01 o 0.0003 0.005 o 0.00015 0.0025 o
Sarakkeen (2) selitys: katso esimerkkiIV Esimerkki VExplanation of column (2): see example IV Example V
Tuotteiden määrittelemistä ympäristösuojeluystävällisiksi osoittavat mainitut yhdisteet mm. edullisen kalamyrkyllisyytensä kautta: 3 viikon vanhoja miljoonakaloja saatetaan alttiiksi nouseville emul-sioväkevöitteen vesilaimennuksille 48 tunnin ajan 2 litran vesiastioissa. Saadaan seuraavat myrkyllisyydet:The above-mentioned compounds show that the products are defined as environmentally friendly. through its beneficial fish toxicity: 3-week-old million fish are exposed to increasing dilutions of emulsion concentrate in water for 48 hours in 2-liter water containers. The following toxicities are obtained:
Tehoaineväkevyys Kuolleisuus-# __PPm__Active Ingredient Concentration Mortality- # __PPm__
Esimerkin (l) yhdiste 100 100 50 70 30 10 10 0Compound of Example (1) 100 100 50 70 30 10 10 0
Carbaryyli 100 100 (Vertailuaine V) 50 100 30 100 10 100 5 100 3 ΘΟ 1 20Carbaryl 100 100 (Reference substance V) 50 100 30 100 10 100 5 100 3 ΘΟ 1 20
Kaikella muilla esimerkissä I mainituilla tämän ryhmän yhdisteillä on samankaltainen kalamyrkyllisyys.All other compounds of this group mentioned in Example I have similar fish toxicity.
HB
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2361438 | 1973-12-10 | ||
| DE2361438A DE2361438C3 (en) | 1973-12-10 | 1973-12-10 | 4-Hydroxyquinoline and 4-Hydroxytetrahydroquinoline-N ^ N-dimethylcarbamates, processes for their preparation and insecticidal compositions containing them |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| FI352474A FI352474A (en) | 1975-06-11 |
| FI58774B FI58774B (en) | 1980-12-31 |
| FI58774C true FI58774C (en) | 1981-04-10 |
Family
ID=5900372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI3524/74A FI58774C (en) | 1973-12-10 | 1974-12-05 | SAOSOM INSEKTICIDER ANVAENDBARA 4-HYDROXIKINOLIN- OCH 4-HYDROXITETRAHYDROKINOLINKARBAMATER |
Country Status (31)
| Country | Link |
|---|---|
| JP (1) | JPS5088073A (en) |
| AT (1) | AT342072B (en) |
| BE (1) | BE823171A (en) |
| BG (1) | BG25977A3 (en) |
| CA (1) | CA1042892A (en) |
| CH (1) | CH611488A5 (en) |
| CS (1) | CS177887B2 (en) |
| DD (1) | DD115421A5 (en) |
| DE (1) | DE2361438C3 (en) |
| DK (1) | DK142113C (en) |
| EG (1) | EG11557A (en) |
| ES (1) | ES432594A1 (en) |
| FI (1) | FI58774C (en) |
| FR (1) | FR2253743A1 (en) |
| GB (1) | GB1489906A (en) |
| HK (1) | HK58178A (en) |
| HU (1) | HU172372B (en) |
| IE (1) | IE40296B1 (en) |
| IL (1) | IL46200A (en) |
| IT (1) | IT1049333B (en) |
| KE (1) | KE2878A (en) |
| LU (1) | LU71438A1 (en) |
| MY (1) | MY7800375A (en) |
| NL (1) | NL7415870A (en) |
| OA (1) | OA04867A (en) |
| PL (1) | PL98709B1 (en) |
| RO (2) | RO65069A (en) |
| SE (1) | SE7415355L (en) |
| SU (1) | SU797544A3 (en) |
| ZA (1) | ZA747735B (en) |
| ZM (1) | ZM17174A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4655816A (en) * | 1984-11-06 | 1987-04-07 | Monsanto Company | Herbicidal 2-trifluoromethyl 3-pyridine carboxylic acid derivatives |
| FR2582514B1 (en) * | 1985-05-30 | 1988-02-19 | Rhone Poulenc Sante | AMIDE DRUGS, NEW AMIDES AND THEIR PREPARATION |
| US4670045A (en) * | 1987-04-07 | 1987-06-02 | The Dow Chemical Company | Fungicidal control employing ester derivatives of 4,6-disubstituted 2-pyridinols |
| AU2616595A (en) * | 1995-05-23 | 1996-12-11 | Hoechst Schering Agrevo Gmbh | Substituted 2,3-cycloalkenopyridines, process for preparing the same, agents containing the same and their use as pestic ides and fungicides |
| TW521072B (en) * | 1997-06-02 | 2003-02-21 | Meiji Seika Kaisha | 4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture |
| WO2006013896A1 (en) * | 2004-08-04 | 2006-02-09 | Meiji Seika Kaisha, Ltd. | Quinoline derivative and insecticide containing same as active constituent |
| JP6112724B2 (en) * | 2013-10-31 | 2017-04-12 | 日本化薬株式会社 | 1,5-naphthyridine derivative and insecticide comprising the same as an active ingredient |
| CN110452167B (en) * | 2018-04-16 | 2020-08-21 | 东莞市东阳光农药研发有限公司 | Quinoline derivatives, preparation method and application thereof |
| CN115124463B (en) * | 2022-07-01 | 2023-11-28 | 浙江工业大学 | Substituted quinoline compound and preparation method and application thereof |
-
1973
- 1973-12-10 DE DE2361438A patent/DE2361438C3/en not_active Expired
-
1974
- 1974-12-04 ES ES432594A patent/ES432594A1/en not_active Expired
- 1974-12-04 ZA ZA00747735A patent/ZA747735B/en unknown
- 1974-12-05 BG BG7428370A patent/BG25977A3/xx unknown
- 1974-12-05 FI FI3524/74A patent/FI58774C/en active
- 1974-12-05 CH CH1619574A patent/CH611488A5/en not_active IP Right Cessation
- 1974-12-05 NL NL7415870A patent/NL7415870A/en not_active Application Discontinuation
- 1974-12-06 GB GB52964/74A patent/GB1489906A/en not_active Expired
- 1974-12-06 RO RO7400088211A patent/RO65069A/en unknown
- 1974-12-06 RO RO7400080721A patent/RO63735A/en unknown
- 1974-12-06 DK DK636174A patent/DK142113C/en active
- 1974-12-06 IL IL46200A patent/IL46200A/en unknown
- 1974-12-06 IT IT30286/74A patent/IT1049333B/en active
- 1974-12-07 DD DD182875A patent/DD115421A5/xx unknown
- 1974-12-07 EG EG536/74A patent/EG11557A/en active
- 1974-12-09 JP JP49140594A patent/JPS5088073A/en active Pending
- 1974-12-09 LU LU71438A patent/LU71438A1/xx unknown
- 1974-12-09 PL PL1974176285A patent/PL98709B1/en unknown
- 1974-12-09 HU HU74HO00001751A patent/HU172372B/en unknown
- 1974-12-09 IE IE9699/74A patent/IE40296B1/en unknown
- 1974-12-09 SU SU742081001A patent/SU797544A3/en active
- 1974-12-09 SE SE7415355A patent/SE7415355L/xx unknown
- 1974-12-09 ZM ZM171/74A patent/ZM17174A1/en unknown
- 1974-12-09 AT AT980074A patent/AT342072B/en active
- 1974-12-10 BE BE151347A patent/BE823171A/en unknown
- 1974-12-10 OA OA55363A patent/OA04867A/en unknown
- 1974-12-10 FR FR7440435A patent/FR2253743A1/en active Granted
- 1974-12-10 CA CA215,586A patent/CA1042892A/en not_active Expired
- 1974-12-10 CS CS8417A patent/CS177887B2/cs unknown
-
1978
- 1978-08-24 KE KE2878A patent/KE2878A/en unknown
- 1978-09-28 HK HK581/78A patent/HK58178A/en unknown
- 1978-12-30 MY MY375/78A patent/MY7800375A/en unknown
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