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WO1993014079A1 - Alkylthiothiophenes and alkylthiopolythiophenes, methods of preparing them, and their use - Google Patents

Alkylthiothiophenes and alkylthiopolythiophenes, methods of preparing them, and their use Download PDF

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Publication number
WO1993014079A1
WO1993014079A1 PCT/EP1993/000060 EP9300060W WO9314079A1 WO 1993014079 A1 WO1993014079 A1 WO 1993014079A1 EP 9300060 W EP9300060 W EP 9300060W WO 9314079 A1 WO9314079 A1 WO 9314079A1
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WO
WIPO (PCT)
Prior art keywords
formula
methylthio
hydrogen
polythiophenes
radicals
Prior art date
Application number
PCT/EP1993/000060
Other languages
German (de)
French (fr)
Inventor
Hans Theobald
Volker Harries
Uwe Kardorff
Peter Baeuerle
Guenther Goetz
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE4201305A external-priority patent/DE4201305A1/en
Priority claimed from DE19924206767 external-priority patent/DE4206767A1/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP93902185A priority Critical patent/EP0624158A1/en
Priority to JP5512139A priority patent/JPH07502998A/en
Publication of WO1993014079A1 publication Critical patent/WO1993014079A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom

Definitions

  • the present invention relates to thiophenes and polythiophenes of the formula I
  • R 1 , R 2 and R 3 independently of one another are hydrogen and Ci-Ci ⁇ -alkylthio
  • R 1 , R 2 and R 3 are not simultaneously hydrogen and where R 1 is not hydrogen if R 2 is methylthio and n is 0.
  • the invention relates to processes for the preparation of these compounds, compositions comprising at least one thiophene or polythiophene of the formula I '
  • R 1 , R 2 and R 3 independently of one another Hydrogen and Ci-Ci ⁇ -alkylthio
  • the invention was based on new active substances suitable for pest control as a task.
  • the introduction of the halogen substituent is generally carried out according to the method described by Taylor et al. described method (p. 1003) in the presence of N-bromosuccinimide or N-chlorosuccinimide.
  • the reaction temperatures are usually 0 ° C to 50 ° C, preferably 10 ° C to 40 ° C.
  • the halogenating agents can generally be used in equimolar amounts or in excess.
  • Halogenated hydrocarbons such as methylene chloride and tetrachloroethane and protically polar solvents such as acetic acid are particularly suitable as solvents.
  • the preparation and implementation of the Grignard compound is advantageously carried out in accordance with the method described by MacEachern et al. described method carried out.
  • the reaction temperatures are usually 10 ° C to 60 ° C, preferably 20 ° C to 50 ° C.
  • the amount of magnesium shavings or Magnesiu gries' is generally at least equimolar, but is usually used in an excess.
  • Suitable solvents are in particular ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether and dioxane, particularly preferably diethyl ether and tert-butyl methyl ether.
  • a halogenated thiophene is reacted with a disulfide in general at low temperatures in an aprotic solvent in the presence of an alkali metal organyl.
  • the reaction temperatures are usually from -100 ° C to 0 ° C, preferably from -80 ° C to -40 ° C.
  • the alkali metal organyls used are generally organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium. into consideration.
  • the alkali metal organyls are generally used in an excess of 10 to 100 mol%, preferably 10 to 50 mol%, based on the halothiophene.
  • Aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane and tetrahydrofu are used as solvents, particularly preferably ethers.
  • the starting materials are generally reacted with one another at least in an equimolar amount. With a view to increasing the yield, however, it may be advantageous to use an excess of 10 mol% to 100 mol%, preferably 10 mol% to 50 mol%, in particular 10 mol%, of the disulfide. % to 20 mol% based on the amount of halogen thiophene.
  • Ci-Cis-alkylthio especially Ci-Ce-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio , 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4- Methylpentylthio, 1, 1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,
  • radicals R 3 it being possible for the radicals R 3 to be different if the value of n is> 1.
  • radicals R 3 it being possible for the radicals R 3 to be different if the value of n is> 1.
  • thiophenes and polythiophenes of the formula I ' are particularly preferred in which the substituents and the index have the following meaning:
  • R 1 , R- and R 3 independently of one another
  • radicals R 3 it being possible for the radicals R 3 to be different if the value of n is> 1.
  • R 1 , R 2 and R 3 independently of one another are hydrogen and methyl thio
  • the compounds of the formula I ' are suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection and in the hygiene, supply protection and veterinary sectors.
  • the harmful insects include from the order of the
  • Butterflies for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneuraoneumoneidomoneirone, fumiferella, choristoneura fumiferellaidia unidirectional fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumifeella, choristoneura fumiferida Diaphania nitidalis, Diatrae
  • Pectinophora gossypiella Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includesoptera, Spyacoda lodipod, frotana, Scrobipalpulaotha, Diana , Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis.
  • Diaptera From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chryso ya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Dylobaculexucaceacita, acylucia pacita, acylucia pacificaceae, Cylobaceapura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Mushroom Domica, Lyi
  • Thrips for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
  • From the order of the hymenoptera for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
  • Heteroptera From the order of the bugs (Heteroptera), for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratidularis, Parsma viralisea, Pira .
  • bugs Heteroptera
  • Acrosternum hilare Blissus leucopterus
  • Cyrtopeltis notatus Dysdercus cingulatus
  • Dysdercus intermedius Eurygaster integriceps
  • Euchistus impictiventris Leptoglossus phyllopus
  • Lygus lineolaris Lygus pratidularis
  • Parsma viralisea Pira
  • suckers for example, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci,
  • Brachycaudus cardui Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola, Dysaulacorthum pseudosolani, E poasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Megodipononium, Macodipononiumia, Macrosiphoniumia, Macodipa bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphu maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vitarifoli, Vite.
  • Orthoptera for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia,
  • arachnids such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, shedelodi, iodine eroniophus, Iotetroniiuncus, Iotetranyius, Iotetronii Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccop
  • Tetranychus kanzawai Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae.
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Hetrodera triflolii, stalks and leaves, e.g. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci,
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Hetroder
  • the active compounds can be sprayed as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oldispersions, pastes, dusts, scattering agents, granules hen, nebulizing, dusting, scattering or pouring can be used.
  • the application forms depend entirely on the Uses; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil
  • coal tar oils as well as oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e.g. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions) by adding water.
  • emulsions, pastes or old dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • III.10 parts by weight of compound no. 4 are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid -N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as grain meal, tree bark, wood and nutshell meal, cellulose powder and other solid carrier substances.
  • Mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay,
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% by weight.
  • the active substance concentrations in the ready-to-use preparations can be varied over a wide range.
  • they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used successfully in the fragrance
  • Ultra-low-volume processes (ULV) are used, it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • the amount of active ingredient applied under field conditions is 0.2 to 10, preferably 0.5 to 2.0 kg / ha.
  • Oils of various types, herbicides, fungicides, other pesticides, bactericides can be used as active ingredients, if appropriate also only immediately before use
  • the active ingredients were:

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention concerns thiophenes and polythiophenes of formula (I), in which the substituents and the degree of polymerization n are as follows: R<1>, R<2> and R<3>, independently of each other, are hydrogen or a C1-C18 alkylthio group; n is 1, 2, 3, 4 or 5 and the R<3> groups may be different when n > 1; with the exception that R<1>, R<2> and R<3> may not simultaneously be hydrogen and R<1> may not be hydrogen when R<2> is methylthio and n is 0.

Description

A KY THIOTHIOPHE E UND ALKYLTHIOPO Y HIOPHENE , VERFAHREN ZU IHRER HERSTELLUNG UND IHRER VERWENDUNG. A KY THIOTHIOPHE E AND ALKYLTHIOPO Y HIOPHENE, METHOD FOR THEIR PRODUCTION AND USE.
Beschreibungdescription
Die vorl iegende Erf indung betrif ft Thiophene und Polythio- phene der Formel IThe present invention relates to thiophenes and polythiophenes of the formula I
Figure imgf000003_0001
Figure imgf000003_0001
in der die Substituenten und der Index die folgende Bedeu¬ tung haben:in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Ci-Ciβ-Alkylthio,R 1 , R 2 and R 3 independently of one another are hydrogen and Ci-Ciβ-alkylthio,
nn
0, 1, 2, 3, 4 oder 5, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2, 3, 4 or 5, where the radicals R 3 can be different if the value of n is> 1,
wobei R1, R2 und R3 nicht gleichzeitig Wasserstoff bedeuten und wobei R1 nicht Wasserstoff bedeutet, wenn R2 für Me¬ thylthio und n für 0 steht.where R 1 , R 2 and R 3 are not simultaneously hydrogen and where R 1 is not hydrogen if R 2 is methylthio and n is 0.
Des weiteren betrifft die Erfindung Verfahren zur Her¬ stellung dieser Verbindungen, Mittel enthaltend mindestens ein Thiophen oder Polythiophen der Formel I'Furthermore, the invention relates to processes for the preparation of these compounds, compositions comprising at least one thiophene or polythiophene of the formula I '
Ri R" R3 i πxj-n ,ι.)Ri R "R 3 i πxj-n, ι.)
in der die Substituenten und der Index die folgende Bedeu¬ tung haben:in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Ci-Ciβ-Alkylthio ,R 1 , R 2 and R 3 independently of one another Hydrogen and Ci-Ciβ-alkylthio,
nn
0, 1, 2, 3, 4 oder 5, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2, 3, 4 or 5, where the radicals R 3 can be different if the value of n is> 1,
und inerte Zusatzstoffe sowie Verfahren zur Bekämpfung von Schädlingen.and inert additives and pest control methods.
Es ist bekannt, daß bestimmte Bis- und Terthienylver- bindungen nematizid wirksam sind (US-A 3,050,442; WO-A 86/005,949; Tetrahedron M# 2403-2413 (1988)). Außerdem wurden derartige Verbindungen mit herbiziden Eigenschaften beschrieben (EP-A 353,667).It is known that certain bis- and terthienyl compounds are nematicidal (US Pat. No. 3,050,442; WO-A 86 / 005,949; Tetrahedron M # 2403-2413 (1988)). In addition, such compounds with herbicidal properties have been described (EP-A 353,667).
Der Erfindung lagen neue, zur Schädlingsbekämpfung geeignete Wirkstoffe als Aufgabe zugrunde.The invention was based on new active substances suitable for pest control as a task.
Demgemäß wurden die eingangs definierten Thiophene und Poly- thiophene gefunden. Außerdem wurden Verfahren zu ihrer Her¬ stellung, sie enthaltende Mittel und deren Verwendung zur Bekämpfung von Schädlingen gefunden.Accordingly, the thiophenes and polythiophenes defined at the outset were found. In addition, processes for their preparation, compositions containing them and their use in combating pests were found.
Die Verbindungen sind nach verschiedenen, an sich aus der Literatur bekannten Verfahren zugänglich. Im wesentlichen bedient man sich der folgenden allgemeinen Verfahren:The compounds are accessible by various methods known per se from the literature. Basically, the following general procedures are used:
A: Halogenierung von Thiophen bzw. Polythiophenen (Gronowitz et al., Acta Chem. Scand. , 13, 1045 (1959); MacEachern et al., Tetrahedron 44 (9), 2403 (1988); Taylor et al., J. Org. Chem., 50, 1002 (1985) ) .A: Halogenation of thiophene or polythiophenes (Gronowitz et al., Acta Chem. Scand., 13, 1045 (1959); MacEachern et al., Tetrahedron 44 (9), 2403 (1988); Taylor et al., J. Org. Chem., 50, 1002 (1985)).
Ausgehend von einem unsubstituierten oder substituierten Thiophen wird die Einführung des Halogensubstituenten im allgemeinen nach der bei Taylor et al. beschriebenen Methode (S. 1003) in Gegenwart von N-Bromsuccinimid bzw. N-Chlor- succinimid durchgeführt.Starting from an unsubstituted or substituted thiophene, the introduction of the halogen substituent is generally carried out according to the method described by Taylor et al. described method (p. 1003) in the presence of N-bromosuccinimide or N-chlorosuccinimide.
Die Umsetzungstemperaturen liegen üblicherweise bei 0°C bis 50°C, vorzugsweise 10°C bis 40°C. Die Halogenierungsmittel können im allgemeinen äquimolar oder in einem Überschuß verwendet werden.The reaction temperatures are usually 0 ° C to 50 ° C, preferably 10 ° C to 40 ° C. The halogenating agents can generally be used in equimolar amounts or in excess.
Als Lösungsmittel eignen sich insbesondere halogenierte Koh¬ lenwasserstoffe wie Methylenchlorid und Tetrachlorethan so¬ wie protisch polare Lösungsmittel wie Essigsäure.Halogenated hydrocarbons such as methylene chloride and tetrachloroethane and protically polar solvents such as acetic acid are particularly suitable as solvents.
Es können auch Gemische der genannten Lösungsmittel verwen¬ det werden.Mixtures of the solvents mentioned can also be used.
B: Herstellung und Umsetzung der Grignard-Verbindungen (MacEachern et al., Tetrahedron 44 (9), 2403 (1988); Jayasuriya et al., Heterocycles 24 (10), 2901 (1986))B: Preparation and implementation of the Grignard compounds (MacEachern et al., Tetrahedron 44 (9), 2403 (1988); Jayasuriya et al., Heterocycles 24 (10), 2901 (1986))
Ausgehend von einem halogenierten Thiophen wird die Herstel¬ lung und Umsetzung der Grignardverbindung vorteilhaft gemäß der von MacEachern et al. beschriebenen Methode durchge¬ führt.Starting from a halogenated thiophene, the preparation and implementation of the Grignard compound is advantageously carried out in accordance with the method described by MacEachern et al. described method carried out.
Die Umsetzungstemperaturen liegen üblicherweise bei 10°C bis 60°C, vorzugsweise 20°C bis 50°C.The reaction temperatures are usually 10 ° C to 60 ° C, preferably 20 ° C to 50 ° C.
Die Menge der Magnesiumspäne bzw. des Magnesiu gries' ist im allgemeinen mindestens äquimolar, üblicherweise verwendet man jedoch in einem Überschuß.The amount of magnesium shavings or Magnesiu gries' is generally at least equimolar, but is usually used in an excess.
Geeignete Lösungsmittel sind insbesondere Ether wie Diethyl- ether, Diisopropylether, tert.-Butylmethylether und Dioxan, besonders bevorzugt Diethylether und tert.-Butylmethylether.Suitable solvents are in particular ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether and dioxane, particularly preferably diethyl ether and tert-butyl methyl ether.
Es können auch Gemische der genannten Lösungsmittel verwen¬ det werden.Mixtures of the solvents mentioned can also be used.
Im Hinblick auf die Umsetzungsgeschwindigkeit und die Aus- beute kann es vorteilhaft sein, der Reaktionsmischung einen Katalysator zuzusetzen.With regard to the rate of conversion and the yield, it may be advantageous to add a catalyst to the reaction mixture.
In diesem Sinne finden Katalysatoren wieIn this sense, catalysts like
Pd (dppf) Cl2 (dppf = l,l'-bis(diphenylphosphino) ferrocen) undPd (dppf) Cl 2 (dppf = l, l'-bis (diphenylphosphino) ferrocene) and
Ni (dppp) CI2 (dppp = 1,3-bis(diphenylphosphino)propan) Verwendung. Die weitere Umsetzung der so erhaltenen Grignard-Verbindung mit einem Halogenthiophen kann direkt (in situ) oder nach vorheriger Isolierung der Zwischenstufe erfolgen.Ni (dppp) CI 2 (dppp = 1,3-bis (diphenylphosphino) propane) use. The further reaction of the Grignard compound thus obtained with a halothiophene can be carried out directly (in situ) or after the intermediate has been isolated beforehand.
C: Umsetzung der Halogenthiophene mit DisulfidenC: Reaction of the halothiophenes with disulfides
(Gronowitz et al, Acta Chem. Scand. , 13(5), 1045 (1959))(Gronowitz et al, Acta Chem. Scand., 13 (5), 1045 (1959))
Die Umstezung eines halogenierten Thiophens mit einem Disul- fid erfolgt im allgemeinen bei niedrigen Temperaturen in ei- nem aprotischen Lösungsmittel in Gegenwart eines Alkalime- tall-Organyls.A halogenated thiophene is reacted with a disulfide in general at low temperatures in an aprotic solvent in the presence of an alkali metal organyl.
Die Umsetzungstemperaturen liegen üblicherweise bei -100°C bis 0°C, vorzugsweise -80°C bis -40°C.The reaction temperatures are usually from -100 ° C to 0 ° C, preferably from -80 ° C to -40 ° C.
Als Alkalimetall-Organyle kommen allgemein metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyl¬ lithium, Butyllithium sowie Phenyllithium. in Betracht.The alkali metal organyls used are generally organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium. into consideration.
Die Alkalimetall-Organyle werden im allgemeinen im Überschuß von 10 bis 100 mol-%, vorzugsweise 10 bis 50 mol-%, bezogen auf das Halogenthiophen verwendet werden.The alkali metal organyls are generally used in an excess of 10 to 100 mol%, preferably 10 to 50 mol%, based on the halothiophene.
Als Lösungsmittel finden aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, Ether wie Di- ethylether, Diisopropylether, tert.-Butylmeth lether, Dioxan und Tetrahydrofu an, besonders bevorzugt Ether Verwendung.Aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane and tetrahydrofu are used as solvents, particularly preferably ethers.
Es können auch Gemische der genannten Lösungsmittel verwen- det werden.Mixtures of the solvents mentioned can also be used.
Die Edukte werden im allgemeinen mindestens in einer äquimo- laren Menge miteinander umgesetzt. Im Hinblick auf eine Er¬ höhung der Ausbeute kann es jedoch vorteilhaft sein, das Di- sulfid in einem Überschuß von 10 mol-% bis 100 mol-%, vor¬ zugsweise 10 mol-% bis 50 mol-%, insbesondere 10 mol-% bis 20 mol-% bezogen auf die Menge an Halogenthiophen einzu¬ setzen.The starting materials are generally reacted with one another at least in an equimolar amount. With a view to increasing the yield, however, it may be advantageous to use an excess of 10 mol% to 100 mol%, preferably 10 mol% to 50 mol%, in particular 10 mol%, of the disulfide. % to 20 mol% based on the amount of halogen thiophene.
Im Hinblick auf ihre biologisch Aktivität sind solche Ver¬ bindungen I' bevorzugt, in denen die Substituenten und der Index die folgende Bedeutung haben: R1, R2 und R3 unabhängig voneinanderWith regard to their biological activity, preference is given to compounds I 'in which the substituents and the index have the following meaning: R 1 , R 2 and R 3 independently of one another
Wasserstoff;Hydrogen;
Ci-Cis-Alkylthio, besonders Ci-Ce-Alkylthio wie Methylthio, Ethylthio, Propylthio, 1-Methylethylthio, Butylthio, 1-Methylpropylthio, 2-Methylpropylthio, 1, 1-Dimethylethyl¬ thio, Pentylthio, 1-Methylbutylthio, 2-Methylbutylthio, 3-Methylbutylthio, 2,2-Di-methylpropyl hio, 1-Ethylpropyl- thio, Hexylthio, 1, 1-Dimethylpropylthio, 1,2-Dimethyl- propylthio, 1-Methylpentylthio, 2-Methylpentylthio, 3-Methylpentylthio, 4-Methylpentylthio, 1, 1-Dimethylbutyl- thio, 1,2-Dimethylbutylthio, 1,3-Dimethylbutylthio, 2,2-Dimethylbutylthio, 2,3-Dimethylbutylthio, 3, 3-Dimethyl- butylthio, 1-Ethylbutylthio, 2-Ethylbutylthio, 1,1,2-Tri- methylpropylthio, 1,2,2-Trimethylpropylthio, 1-Ethyl-l-methylpropylthio und l-Ethyl-2-methylpropylthio, sowie unverzweigtes und verzweigtes Heptylthio, Octylthio, Nonylthio, Decylthio, Undecylthio, Dodecylthio, Tridecyl- thio, Tetradecylthio, Pentadecylthio, Hexadecylthio, Hepta- decylthio und Octadecylthio, vorzugsweise die genannten Cι-C6-Alkylthioreste insbesondere die genannten Cι-C4-Alkyl- thioreste.Ci-Cis-alkylthio, especially Ci-Ce-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio , 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4- Methylpentylthio, 1, 1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-l-methylpropylthio and l-ethyl-2-methylpropylthio, as well as unbranched and branched heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, Tridecyl-thio, tetradecylthio, pentadecylthio, hexadecylthio, hepta-decylthio and octadecylthio, preferably the C 1 -C 6 -alkylthio radicals mentioned in particular e the C 1 -C 4 -alkyl thio radicals mentioned.
nn
0, 1, 2, 3, 4 oder 5, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist.0, 1, 2, 3, 4 or 5, it being possible for the radicals R 3 to be different if the value of n is> 1.
Insbesondere bevorzugt werden Thiophene und Polythiophene der Formel I', in denen die Substituenten und der Index die folgende Bedeutung haben:Particularly preferred are thiophenes and polythiophenes of the formula I 'in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinanderR 1 , R 2 and R 3 independently of one another
Wasserstoff, Ci-Cs-Alkylthio wie vorstehend im allgemeinen und im besonderen genannt undHydrogen, Ci-Cs-alkylthio as mentioned above in general and in particular and
nn
0, 1, 2, 3 oder 4, wobei die Reste R3 verschieden sein kön- nen, wenn der Wert von n > 1 ist. Außerdem, werden besonders Thiophene und Polythiophene der Formel I' bevorzugt, in denen die Substituenten und der In¬ dex die folgende Bedeutung haben:0, 1, 2, 3 or 4, it being possible for the radicals R 3 to be different if the value of n is> 1. In addition, thiophenes and polythiophenes of the formula I 'are particularly preferred in which the substituents and the index have the following meaning:
R1, R- und R3 unabhängig voneinanderR 1 , R- and R 3 independently of one another
Wasserstoff, Cι-C3-Alkylthio wie vorstehend im allgemeinen und im besonderen genannt undHydrogen, -C-C 3 alkylthio as mentioned above in general and in particular and
nn
0, 1, 2, 3 oder 4, wobei die Reste R3 verschieden sein kön¬ nen, wenn der Wert von n > 1 ist.0, 1, 2, 3 or 4, it being possible for the radicals R 3 to be different if the value of n is> 1.
In biologischer Hinsicht von Interesse sind auch Thiophene und Polythiophene der Formel I' , in denen die Substituenten und der Index die folgende Bedeutung haben:Of biological interest are also thiophenes and polythiophenes of the formula I 'in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Methyl¬ thioR 1 , R 2 and R 3 independently of one another are hydrogen and methyl thio
undand
nn
0, 1, 2 oder 3, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2 or 3, where the radicals R 3 can be different if the value of n is> 1,
wobei den Verbindungenbeing the connections
1. 3,4-Di(meth lthio)thiophen, 2. 4,4'-Di(methylthio)-2,2'-bithiophen,1. 3,4-di (meththio) thiophene, 2. 4,4'-di (methylthio) -2,2'-bithiophene,
3. 4,4»-Di(methylthio)-2,2' :5 ' , 2 -terthiophen,3. 4,4 » -di (methylthio) -2,2 ': 5', 2 -terthiophene,
4. 3'-Methylthio-2,2' :5' ,2"-terthiophen und4. 3'-methylthio-2,2 ': 5', 2 "-terthiophene and
5. 4,4' ' '-Di(methylthio)-2,2' :5' ,2":5",2'"-quarterthiophen5. 4,4 '' di (methylthio) -2,2 ': 5', 2 ": 5", 2 '"quarterthiophene
besondere Bedeutung zukommt. Im Hinblick auf die biologische Aktivität außerdem besonders bevorzugte Verbindungen der Formel I' sind in der folgenden Tabelle zusammengestellt:is of particular importance. With regard to the biological activity, particularly preferred compounds of the formula I 'are listed in the following table:
Figure imgf000009_0001
Figure imgf000009_0001
R3 n 0 0 0 0 0 0 0 0 0 0R 3 n 0 0 0 0 0 0 0 0 0 0
4'-Methylthio 1 4'-Ethylthio 1 4'-i-Propylthio 1 4'-i-Propylthio 1 4'-Ethylthio 1 4"-Methylthio 2 4"-Ethylthio 2 4"-i-Propylthio 2 4"-n-Propylthio 2 4"-n-Butylthio 2 4'"-Methylthio 3 4'"-Ethylthio 3 4' "-i-Propylthio 3 4""-Methylthio 4 4""-Ethylthio 4 4""-i-Propylthio 4 4'""-Methylthio 5 4' ""-Ethylthio 5 4' ""-i-Propylthio 5 4'-Methylthio 2 4'-Ethylthio 2
Figure imgf000009_0002
4'-n-Propylthio 2 H H 4'-i-Propylthio 2
4'-methylthio 1 4'-ethylthio 1 4'-i-propylthio 1 4'-i-propylthio 1 4'-ethylthio 1 4 "-methylthio 2 4" -ethylthio 2 4 "-i-propylthio 2 4" -n -Propylthio 2 4 "-n-butylthio 2 4 '" - methylthio 3 4'"- ethylthio 3 4 '" -i-propylthio 3 4 "" - methylthio 4 4 "" - ethylthio 4 4 "" - i-propylthio 4 4 '"" - methylthio 5 4'"" -ethylthio 5 4 '"" -i-propylthio 5 4'-methylthio 2 4'-ethylthio 2
Figure imgf000009_0002
4'-n-propylthio 2 HH 4'-i-propylthio 2
Methylthio H 4' ,4"-Dimethy1thio 2 Ethylthio H 4'-Methylthio; 4"-Ethylthio 2 n-Propylthio H 4'-Methylthio; 4"-n-Propylthio 2 i-Propylthio H 4'-Methylthio; 4"-i-Propylthio 2 Methylthio H 4'-Ethylthio; 4"-Methylthio 2 Ethylthio H 4' ,4"-Dieth lthio 2 n-Propylthio H '-Ethylthio; 4"-n-Propylthio 2 i-Propylthio H 4'-Ethylthio; 4"-i-Propylthio 2 Methylthio H 4'-n-Propylthio; "-Methylthio 2 Ethylthio H 4'-n-Propylthio; "-Ethylthio 2 n-Propylthio H 4' ,4"-Di-n-propylthio 2 i-Propylthio H 4'-n-Propylthio; "-i-Propylthio 2 Methylthio H 4'-i-Propylthio; 4"-Methylthio 2 Ethylthio H 4'-i-Propylthio; 4"-Ethylthio 2 n-Propylthio H 4'-i-Propylthio; "-n-Propylthio 2 i-Propylthio H 4' ,4"-Di-i-propylthio 2Methylthio H 4 ', 4 "-dimethylthio 2 ethylthio H 4'-methylthio; 4" -ethylthio 2 n-propylthio H 4'-methylthio; 4 "-n-propylthio 2 i-propylthio H 4'-methylthio; 4" -i-propylthio 2 methylthio H 4'-ethylthio; 4 "methylthio 2 ethylthio H 4 ', 4" diethylthio 2 n-propylthio H' ethylthio; 4 "-n-propylthio 2 i-propylthio H 4'-ethylthio; 4" -i-propylthio 2 methylthio H 4'-n-propylthio; "-Methylthio 2 ethylthio H 4'-n-propylthio;" -ethylthio 2 n-propylthio H 4 ', 4 "-di-n-propylthio 2 i-propylthio H 4'-n-propylthio;" -i-propylthio 2 Methylthio H 4'-i-propylthio; 4 "-methylthio 2 ethylthio H 4'-i-propylthio; 4" -ethylthio 2 n-propylthio H 4'-i-propylthio; "-n-propylthio 2 i-propylthio H 4 ', 4" -di-i-propylthio 2
Die Verbindungen der Formel I' sind geeignet, Schädlinge aus der Klasse der Insekten, Spinnentiere und Nematoden wirksam zu bekämpfen. Sie können im Pflanzenschutz sowie auf dem Hy¬ giene-, Vorratsschutz- und Veterinärsektor als Schädlingsbe¬ kämpfungsmittel eingesetzt werden.The compounds of the formula I 'are suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection and in the hygiene, supply protection and veterinary sectors.
Zu den schädlichen Insekten gehören aus der Ordnung derThe harmful insects include from the order of the
Schmetterlinge (Lepidoptera) beispielsweise Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea., Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Ma estra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea. Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis.Butterflies (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneuraoneumoneidomoneirone, fumiferella, choristoneura fumiferellaidia unidirectional fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferella, choristoneura fumiferida Diaphania nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea., Hellula undalis, Hibernia defoliaria, Hyphantria cunea Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Ma estra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea. Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includesoptera, Spyacoda lodipod, frotana, Scrobipalpulaotha, Diana , Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis.
Aus der Ordnung der Käfer (Coleoptera) beispielsweise Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicomis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Byus Bruchus pisorusum , Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicomisis, Diabrotica, abbritica, Ebritica sebis, Epabritus histophilus , Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryhynzach Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.
Aus der Ordnung der Zweiflügler (Diptera) beispielsweise Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chryso ya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chryso ya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Dylobaculexucaceacita, acylucia pacita, acylucia pacificaceae, Cylobaceapura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Mushroom Domica, Lyiolia sercaalisica, Lucilia sericalis, Lucilia sericalisaculata, Lucilia sericalisaculata, Lucilia sericalisica, Lucilia sericalisica, Lucilia sericalisata, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.
Aus der Ordnung der Thripse (Thysanoptera) beispielsweise Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.From the order of the thrips (Thysanoptera), for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
Aus der Ordnung der Hautflügler (Hymenoptera) beispielsweise Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.From the order of the hymenoptera, for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
Aus der Ordnung der Wanzen (Heteroptera) beispielsweise Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.From the order of the bugs (Heteroptera), for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratidularis, Parsma viralisea, Pira .
Aus der Ordnung der Pflanzensauger (Homoptera) beispiels¬ weise Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci,From the order of the plant suckers (Homoptera), for example, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci,
Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola, Dysaulacorthum pseudosolani, E poasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphu maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporarioru , Viteus vitifolii.Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola, Dysaulacorthum pseudosolani, E poasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Megodipononium, Macodipononiumia, Macrosiphoniumia, Macodipa bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphu maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vitarifoli, Vite.
Aus der Ordnung der Termiten (Isoptera) beispielsweise Calotermes flavicollis, Leucotermes flavipes, Reticuliter es lucifugus, Ter es natalensis. Aus der Ordnung der Geradflügler (Orthoptera) beispielsweise Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticuliter es lucifugus, Ter es natalensis. From the order of the straight-wingers (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Peranoplascus sprana, Melanopladus sprana Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.
Aus der Klasse der Arachnoidea beispielsweise Spinnentiere (Acarina) wie Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus,From the class of the arachnoid, for example arachnids (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, shedelodi, iodine eroniophus, Iotetroniiuncus, Iotetranyius, Iotetronii Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptesarinis, Saccoptesarinis
Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae.Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae.
Aus der Klasse der Nematoden beispielsweise Wurzelgallen- nematoden, z.B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Zysten bildende Nematoden, z.B. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Hetrodera triflolii, Stock- und Blattälchen, z.B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci,From the class of nematodes, for example, root gall nematodes, e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Hetrodera triflolii, stalks and leaves, e.g. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci,
Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi.Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatusey, Pratylench.
Die Wirkstoffe können als solche, in Form ihrer Formulie¬ rungen oder den daraus bereiteten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspen- sionen oder Dispersionen, Emulsionen, Oldispersionen, Pa¬ sten, Stäubemitteln, Streumitteln, Granulaten durch Versprü¬ hen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewen¬ det werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewähr¬ leisten.The active compounds can be sprayed as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oldispersions, pastes, dusts, scattering agents, granules hen, nebulizing, dusting, scattering or pouring can be used. The application forms depend entirely on the Uses; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Zur Herstellung von direkt versprühbaren Lösungen, Emul¬ sionen, Pasten oder Oldispersionen kommen Mineralöl¬ fraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Benzol, Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol. Butanol, Chloroform, Tetrachlorkohlenstoff, Cyclohexanol, Cyclohexa- non, Chlorbenzol, Isophoron, stark polare Lösungsmittel, z.B. Dimethylformamid, Dimethylsulfoxid, N-Methylpyrrolidon, Wasser, in Betracht.For the production of directly sprayable solutions, emulsions, pastes or old dispersions, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol. Butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Oldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Oldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mit¬ tels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Sub- stanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate her¬ gestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions) by adding water. To prepare emulsions, pastes or old dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-,Alkali, alkaline earth,
Ammoniumsalze von Ligninsulfonsäure, Naphthalinsulfonsäurer Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylaryl- sulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate und Fettsäuren sowie deren Alkali- und Erdalkalisalze, Salze von sulfatiertem Fettalkoholglykolether, Kondensations- produkte von sulfoniertem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Poly- oxyethylenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphenolpolyglykolether, Tri- butylphenylpolyglykolether, Alkylarylpolyetheralkohole, Iso- tridecylalkohol, Fettalkoholethylenoxid-Kondensate, ethoxy¬ liertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpolyglykoletheracetal, Sorbit¬ ester, Lignin-Sulfitablaugen und Methylcellulose in Be¬ tracht.Ammonium salts of lignosulfonic acid, naphthalenesulfonic acid r phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of Naphtalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotidecyl alcohol, fatty alcohol ethylene oxide, ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylates Polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquor and methyl cellulose in consideration.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Beispiele für Formulierungen sind:Examples of formulations are:
I. 5 Gew.-Teile der Verbindung Nr. 1 werden mit 95I. 5 parts by weight of compound no
Gew.-Teilen feinteiligem Kaolin innig vermischt. Man er¬ hält auf diese Weise ein Stäubemittel, das 3 Gew.-% des Wirkstoffs enthält.Parts by weight of finely divided kaolin mixed intimately. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
II. 30 Gew.-Teile der Verbindung Nr. 2 werden mit einer Mi¬ schung aus 92 Gew.-Teilen pulverförmigem Kieselsäuregel und 8 Gew.-Teilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält auf diese Weise eine Aufbereitung des Wirk¬ stoffs mit guter Haftfähigkeit.II. 30 parts by weight of compound no. 2 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesiveness is obtained.
III.10 Gew.-Teile der Verbindung Nr. 4 werden in einer Mi¬ schung gelöst, die aus 90 Gew.-Teilen Xylol, 6 Gew.-Tei- len des Anlagerungsproduktes von 8 bis 10 Mol Ethylen- oxid an 1 Mol Ölsäure-N-monoethanolamid, 2 Gew.-Teilen Calciumsalz der Dodecylbenzolsulfonsäure und 2 Gew.-Tei¬ len des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht.III.10 parts by weight of compound no. 4 are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid -N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
IV. 20 Gew.-Teile der Verbindung Nr. 5 werden in einer Mi¬ schung gelöst, die aus 60 Gew.-Teilen Cyclohexanon, 30 Gew.-Teilen Isobutanol, 5 Gew.-Teilen des Anlagerung¬ sproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctyl- phenol und 5 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht.IV. 20 parts by weight of compound no. 5 are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol and 5 parts by weight of the adduct of 7 mol of ethylene oxide 1 mole of isooctylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
V. 80 Gew.-Teile der Verbindung Nr. 2 werden mit 3V. 80 parts by weight of compound no
Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin- alpha-sulfonsäure, 10 Gew.-Teilen des Natriumsalzes ei¬ ner Ligninsulfonsäure aus einer Sulfit-Ablauge und 7 Gew.-Teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen.Parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 Parts by weight of powdered silica gel mixed well and ground in a hammer mill.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogen- granulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Silicagel, Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Ge¬ treidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulo- sepulver und andere feste TrägerStoffe.Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as grain meal, tree bark, wood and nutshell meal, cellulose powder and other solid carrier substances.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gew.% Wirkstoff, vorzugsweise zwischen 0,5 und 90 Gew.%.The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90% by weight.
Die WirkstOffkonzentrationen in den anwendungsfertigen Zu- bereitungen können in größeren Bereichen variiert werden.The active substance concentrations in the ready-to-use preparations can be varied over a wide range.
Im allgemeinen liegen sie zwischen 0,0001 und 10 %, vorzugs¬ weise zwischen 0,01 und 1 %.In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
Die Wirkstoffe können auch mit gutem Erfolg imThe active ingredients can also be used successfully in the
Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.Ultra-low-volume processes (ULV) are used, it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
Die Aufwandmenge an Wirkstoff beträgt unter Freiland¬ bedingungen 0,2 bis 10, vorzugsweise 0,5 bis 2,0 kg/ha.The amount of active ingredient applied under field conditions is 0.2 to 10, preferably 0.5 to 2.0 kg / ha.
Zu den Wirkstoffen können Öle verschiedenen Typs, Herbizide, Fungizide, andere Schädlingsbekämpfungsmittel, Bakterizide, gegebenenfalls auch erst unmittelbar vor der AnwendungOils of various types, herbicides, fungicides, other pesticides, bactericides can be used as active ingredients, if appropriate also only immediately before use
(Tankmix) , zugesetzt werden. Diese Mittel können zu den er¬ findungsgemäßen Mitteln im GewichtsVerhältnis 1:10 bis 10:1 zugemischt werden. Synthesebeispiele(Tank mix) can be added. These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1. Synthesis examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften wurden unter entsprechender Abwandlung der Aus- gangsverbindungen zur Gewinnung weiterer Verbindungen I ' be¬ nutzt. Die so erhaltenen Verbindungen sind in der an¬ schließenden Tabelle mit physikalischen Daten aufgeführt.The instructions given in the synthesis examples below were used with the corresponding modification of the starting compounds to obtain further compounds I '. The compounds thus obtained are listed in the table below with physical data.
Folgende nicht käufliche Ausgangsverbindungen wurden gemäß den angegebenen Literaturvorschriften hergestellt:The following starting compounds which cannot be purchased were prepared in accordance with the literature instructions given:
1) 3-Methylthiothiophen, Kp. 103-105°C/30 Torr, Ausbeute 80 % (GC > 99 %) ;1) 3-methylthiothiophene, bp 103-105 ° C / 30 torr, yield 80% (GC> 99%);
2) 2-Brom-3-Methylthiothiophen, Kp. 54-56°C/10-3 Torr, Ausbeute 93,4 % (GC > 98 %) ;2) 2-bromo-3-methylthiothiophene, bp 54-56 ° C / 10- 3 torr, yield 93.4% (GC>98%);
3) 2, 5-Dibrom-3-methylthiothiophen, Ausbeute 83 % (GC > 98 %) ;3) 2, 5-dibromo-3-methylthiothiophene, yield 83% (GC> 98%);
4) 2-Brom-4-methylthiothiophen, Kp. 114-116°C/12 Torr, Ausbeute 84 % (GC > 98 %) ;4) 2-bromo-4-methylthiothiophene, b.p. 114-116 ° C / 12 torr, yield 84% (GC> 98%);
Literatur: E.C. Taylor, D.E. Vogel, J. Org. Chem. 5J2. 1002 (1985)Literature: E.C. Taylor, D.E. Vogel, J. Org. Chem. 5J2. 1002 (1985)
5) 3,4-Dibromthiothiophen, Kp. 94-95°C/12 Torr, Ausbeute 60 % (GC > 97 %) ;5) 3,4-dibromothiothiophene, bp 94-95 ° C / 12 torr, yield 60% (GC> 97%);
Literatur: S. Gronowitz, Acta Chem. Scand. 2 (5) 1045 (1959)Literature: S. Gronowitz, Acta Chem. Scand. 2 (5) 1045 (1959)
6) 5,5'-Dibrom-2,2'-bithiophen, Fp. 146-147°C (GC > 99 %)6) 5,5'-dibromo-2,2'-bithiophene, mp 146-147 ° C (GC> 99%)
Literatur: F. Würthner, Diplomarbeit Universität Stuttgart 1990Literature: F. Würthner, diploma thesis University of Stuttgart 1990
Beispiel 1: Herstellung von 3 ,4-Di (methythio) thiophenExample 1: Preparation of 3, 4-di (methythio) thiophene
1.1 Unter Schutzgas-Atmosphäre wurde eine Mischung aus1.1 Under a protective gas atmosphere, a mixture of
107,5 ml (0,172 mol) Butyllithium (1,6-molare Lösung in Hexan) und 40 ml Diethylether bei -80 °C tropfenweise mit einer Lösung aus 19,36 g (0,08 mol) 3,4-Dibromthio- phen in 30 ml Diethylether versetzt. Nach 1 h bei dieser Temperatur wurde die Reaktionsmischung mit einer Lösung von 16,2 g (0,172 mol) Dimethyldisulfid in 20 ml Diethylether versetzt und nach beendeter Zugabe weitere 3 h bei -70 °C gerührt. Nach beendeter Umsetzung ließ man die Reaktionsmischung auf ca. 25 °C erwärmen. Zur Aufarbeitung wurde die Mischung mit 1 n Salzsäure hydro- lysiert und mit Wasser gewaschen. Durch zweifache De¬ stillation der organischen Phase erhielt man 8,31 g (50 % d.Th.) 3- Brom-4-(methylthio)thiophen als farblose Flüssigkeit (Kp. : 112-115 °C/10 Torr; GC-Reinheit > 98 %) .107.5 ml (0.172 mol) of butyllithium (1.6 molar solution in hexane) and 40 ml of diethyl ether at -80 ° C dropwise with a solution of 19.36 g (0.08 mol) of 3,4-dibromothiophene added in 30 ml of diethyl ether. After 1 h at this temperature, the reaction mixture was treated with a solution of 16.2 g (0.172 mol) of dimethyl disulfide in 20 ml Diethyl ether was added and, after the addition had ended, the mixture was stirred at -70 ° C. for a further 3 h. After the reaction was complete, the reaction mixture was allowed to warm to about 25 ° C. For working up, the mixture was hydrolyzed with 1N hydrochloric acid and washed with water. Double distillation of the organic phase gave 8.31 g (50% of theory) of 3-bromo-4- (methylthio) thiophene as a colorless liquid (bp: 112-115 ° C./10 Torr; GC- Purity> 98%).
1.2 Unter Schutzgasatmosphäre wurde eine Mischung aus1.2 Under a protective gas atmosphere, a mixture of
27,5 ml (0,044 mol) Butyllithium (1,6-molare Lösung in Hexan) und 10 ml Diethylether bei -80°C tropfenweise mit einer Lösung aus 8,31 g (0,04 mol) 3-Brom-(4-methyl- thio)thiophen versetzt. Nach 2 h bei dieser Temperatur wurde die Reaktionsmischung mit einer Lösung von 4,12 g (0,044 mol) Dimethyldisulfid in 5 ml Diethylether ver¬ setzt und nach beendeter Zugabe weitere 4 h bei -70°C gerührt. Nach beendeter Umsetzung ließ man die Reakti- onsmischung auf ca. 20°C erwärmen. Danach wird mit 1 N HCl hydrolysiert und neutral gewaschen. Nach Destilla¬ tion der organischen Phase und Chromatographie (Kiesel¬ gel/Hexan) erhielt man 4,2 g (60 % d. Th.) 3,4-Di(methylthio)thiophen als farblose Flüssigkeit (Kp.: 133-135°C/10 Torr; GC-Reinheit > 99 %) .27.5 ml (0.044 mol) of butyllithium (1.6 molar solution in hexane) and 10 ml of diethyl ether at -80 ° C dropwise with a solution of 8.31 g (0.04 mol) of 3-bromo- (4- methyl thio) thiophene added. After 2 hours at this temperature, the reaction mixture was mixed with a solution of 4.12 g (0.044 mol) of dimethyl disulfide in 5 ml of diethyl ether and, after the addition had ended, the mixture was stirred at -70 ° C. for a further 4 hours. After the reaction was complete, the reaction mixture was allowed to warm to about 20 ° C. It is then hydrolyzed with 1N HCl and washed neutral. After distillation of the organic phase and chromatography (silica gel / hexane), 4.2 g (60% of theory) of 3,4-di (methylthio) thiophene were obtained as a colorless liquid (bp: 133-135 °) C / 10 Torr; GC purity> 99%).
Allgemeine Vorschrift zur Synthese der Methylthio-substi- tuierten Oligothiophene am Beispiel des 4,4'-Di(methylt¬ hio)-2,2 '-bithiophen (2) .General instructions for the synthesis of the methylthio-substituted oligothiophenes using the example of 4,4'-di (methylthio) -2,2'-bithiophene (2).
In einem Zweihaiskolben mit Rückflußkühler und Tropfrichter werden zu 0,486 g (20 mM) Magnesium-Spänen (I2-geätzt) in 30 ml absolutem Ether 4,18 g (20 mM) 2-Brom-4-methylthithio- phen unter Stickstoff zugetropft. Nach 3 stündigem Erhitzen unter Rückfluß wird die Grignard-Lösung mittels Kanülentech¬ nik in den Tropftrichter einer zweiten Apparatur transfe¬ riert. Dort sind in einem Dreihalskolben 3,55 g (17 mM) 2-Brom-4-methylthithiophen in 7 ml Ether und 0,078 g (0,14 mM) Ni(dppp)Cl2 (Nickeldiphenylphosphinopropan-Dichlo- rid) als Katalysator vorgelegt. Bei 0°C wird langsam die Grignardlösung zu der vorgelegten Mischung des Dibromthio- phens und des Katalysators zugetropft, wobei sich der Kata¬ lysator sofort unter Braunfärbung auflöst. Nach beendeter Zugabe wird anschließend für 17 h zum Sieden erhitzt. Danach wird mit 1 N HCl hydrolysiert und die vereinigten organi¬ schen Phasen neutral gewaschen. Nach Abziehen des Lösungs¬ mittels wird das Produkt an Kieselgel mit Benzol als Lauf- mittel chromatographiert. Zweimaliges Umkristallisieren des grünlich gefärbten Eluats zunächst aus Benzol/Hexan unter Zusatz von Aktivkohle und anschließend aus Dioxan ergibt 2,92 g (66 % d. Th. ) farblose Kristalle (GC > 99 %) .4.18 g (20 mM) of 2-bromo-4-methylthithiophene are added dropwise under nitrogen to 0.486 g (20 mM) of magnesium shavings (I 2 -etched) in 30 ml of absolute ether in a two-necked flask with reflux condenser and dropping funnel. After heating under reflux for 3 hours, the Grignard solution is transferred into the dropping funnel of a second apparatus by means of cannula technology. There, 3.55 g (17 mM) of 2-bromo-4-methylthithiophene in 7 ml of ether and 0.078 g (0.14 mM) of Ni (dppp) Cl 2 (nickel diphenylphosphinopropane dichloride) are placed in a three-necked flask as a catalyst. At 0 ° C., the Grignard solution is slowly added dropwise to the mixture of dibromothiophene and the catalyst, the catalyst dissolving immediately with a brown color. After finished Addition is then heated to boiling for 17 h. The mixture is then hydrolyzed with 1 N HCl and the combined organic phases are washed until neutral. After the solvent has been stripped off, the product is chromatographed on silica gel using benzene as the mobile phase. Two recrystallizations of the greenish colored eluate first from benzene / hexane with the addition of activated carbon and then from dioxane gives 2.92 g (66% of theory) of colorless crystals (GC> 99%).
Eingesetzte Mengen für die anderen Oligomere:Amounts used for the other oligomers:
4,4"-Di (methylthio)-2,2' ,5' ,2"-terthiophen (3) :4,4 "-di (methylthio) -2,2 ', 5', 2" -terthiophene (3):
5,02 g (24 mM) 2-Brom-4-methylthiothiophen in 40 ml Ether 0,583 g (24 mM) Magnesium (I2-geätzt) 0,011 g (0,02 mM) Ni(dppp)Cl25.02 g (24 mM) 2-bromo-4-methylthiothiophene in 40 ml ether 0.583 g (24 mM) magnesium (I 2 etched) 0.011 g (0.02 mM) Ni (dppp) Cl2
3,638 g (12,6 mM) 2,5-Dibromthiophen in 15 ml Ether Chromatographie Hexan/CH2C12 85:15. Aus der zweiten Fraktion werden 1,44 g (35 % d. Th. ; GC > 99 %) gelbe Kristalle iso- liert.3.638 g (12.6 mM) 2,5-dibromothiophene in 15 ml ether chromatography hexane / CH 2 C1 2 85:15. 1.44 g (35% of theory; GC> 99%) of yellow crystals are isolated from the second fraction.
4,4" '-Di (methylthio)-2,2' , 5'2", 5",2"'-quarterthiophen (4) :4.4 "'di (methylthio) -2,2', 5'2", 5 ", 2" 'quarterthiophene (4):
5,02 g (24 mM) 2-Brom-4-methylthiothiophen in 40 ml Ether 0,583 g (24 mM) Magnesium (I2-geätzt)5.02 g (24 mM) 2-bromo-4-methylthiothiophene in 40 ml ether 0.583 g (24 mM) magnesium (I 2 -etched)
0,026 g (0,04 mM) Ni(dppp)Cl2 0.026 g (0.04 mM) Ni (dppp) Cl 2
3,24 g (10 mM) 5,5'-Dibrom-2,2'-bithiophen in 100 ml3.24 g (10 mM) 5,5'-dibromo-2,2'-bithiophene in 100 ml
Ether/50 ml Benzol gelöstEther / 50 ml of benzene dissolved
Reflux 22 h, Extraktion mit CH2C12, Chromatographie Hexan/CH2Cl2 1:1,Reflux 22 h, extraction with CH 2 C1 2 , chromatography hexane / CH 2 Cl 2 1: 1,
Umkristallisation aus Toluol, Ausbeute 2,65 g (63 % d. Th. ) orangefarbene Kristalle (HPLC > 99 %) .Recrystallization from toluene, yield 2.65 g (63% of theory) of orange crystals (HPLC> 99%).
3'-Methylthio-2,2' ,5' ,2"-terthiophen (5) :3'-methylthio-2,2 ', 5', 2 "-terthiophene (5):
8,17 g (50 mM) 2-Bromthiophen in 50 ml Ether 1,22 g (24 mM) Magnesium (I2-geätzt) 0,27 g (0,5 mM) Ni(dppp)Cl2 8.17 g (50 mM) 2-bromothiophene in 50 ml ether 1.22 g (24 mM) magnesium (I 2 etched) 0.27 g (0.5 mM) Ni (dppp) Cl 2
5,77 g (20 mM) 2,5-Dibrom-3-methylthiothiophen in 30 ml Ether Reflux 40 h, Extraktion mit Ether/CH2C12, Chromatographie Hexan/CH2C12 80:20 und 90:10, Ausbeute 3,82 g (65 % d. Th. ; GC > 99 %) .5.77 g (20 mM) 2,5-dibromo-3-methylthiothiophene in 30 ml ether Reflux 40 h, extraction with ether / CH 2 C1 2 , chromatography hexane / CH 2 C1 2 80:20 and 90:10, yield 3.82 g (65% of theory; GC> 99%).
Figure imgf000020_0001
Figure imgf000020_0001
Nr. R1 R2 R3 n physik. Daten ΓΓP, , KP, (°C)1R 1 R 2 R 3 n physics. Data ΓΓP,, KP, (° C) 1
1 Methylthio Methylthio - 0 2 Methylthio H 4"-Methylthio 2 3 Methylthio H 4' "-Methylthio 3 4 Methylthio H 4""-Methylthio 4
Figure imgf000020_0002
5 H H 4'-Methylthio 2 gelbes öl'
1 methylthio methylthio - 0 2 methylthio H 4 "-methylthio 2 3 methylthio H 4 '" -methylthio 3 4 methylthio H 4 "" - methylthio 4
Figure imgf000020_0002
5 HH 4'-methylthio 2 yellow oil '
250-MHz-1H-NMR in CDC1 /TMS:250 MHz 1 H NMR in CDC1 / TMS:
7,31 (d, d, d, 2H); 7,20 (d, d, 1H) ; 7,15 (d, d, 1H)7.31 (d, d, d, 2H); 7.20 (d, d, 1H); 7.15 (d, d, 1H)
7,07 (s, 1H) ; 7,03 (d, d, d, 2H) ; 2,46 (s, 3H)7.07 (s, 1H); 7.03 (d, d, d, 2H); 2.46 (s, 3H)
AnwendungsbeispieleExamples of use
Die biologische Wirkung der Verbindungen der allgemeinen Formel I ließ sich durch folgende Versuche zeigen:The biological activity of the compounds of the general formula I was demonstrated by the following experiments:
Die Wirkstoffe wurdenThe active ingredients were
a) als 0,1 %-ige Lösung in Aceton oder b) als 10 %-ige Emulsion in einem Gemisch aus 70 Gew.-% Cy- clohexanon, 20 Gew.-% Nekanil® LN (Lutensol® AP6, Netz¬ mittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) und 10 Gew.-% Emulphor® EL (Emulan® EL, Emulgator auf der Basis etho-*<yliertera) as a 0.1% solution in acetone or b) as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent) with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight Emulphor® EL (Emulan® EL, emulsifier based on etho - * <ylierter
Fettalkohole)Fatty alcohols)
aufbereitet und entsprechend der gewünschten Konzentration mit Aceton im Fall von a) bzw. mit Wasser im Fall von b) verdünnt. Nach Abschluß der Versuche wurde die jeweils niedrigste Konzentration ermittelt, bei der die Verbindungen im Ver¬ gleich zu unbehandelten Kontrollversuchen noch eine 80 - 100 %-ige Hemmung bzw. Mortalität hervorriefen (Wirkschwelle bzw. Minimalkonzentration) . processed and diluted according to the desired concentration with acetone in the case of a) or with water in the case of b). After the end of the tests, the lowest concentration was determined at which the compounds still caused an 80-100% inhibition or mortality compared to untreated control tests (action threshold or minimum concentration).

Claims

Patentansprüche Claims
1. Thiophene und Polythiophene der Formel I1. Thiophenes and polythiophenes of the formula I
Figure imgf000022_0001
Figure imgf000022_0001
in der die Substituenten und der Index die folgende Be¬ deutung haben:in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Ci-Cis-Alkylthio,R 1 , R 2 and R 3 independently of one another are hydrogen and Ci-Cis-alkylthio,
nn
0, 1, 2, 3, 4 oder 5, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2, 3, 4 or 5, where the radicals R 3 can be different if the value of n is> 1,
wobei R1, R2 und R3 nicht gleichzeitig Wasserstoff be¬ deuten und wobei R1 nicht Wasserstoff bedeutet, wenn R2 für Methylthio und n für 0 steht.where R 1 , R 2 and R 3 do not mean hydrogen at the same time and where R 1 is not hydrogen if R 2 is methylthio and n is 0.
2. Thiophene und Polythiophene der Formel I gemäß Anspruch2. thiophenes and polythiophenes of the formula I according to claim
1, in der die Substituenten und der Index die folgende Bedeutung haben:1, in which the substituents and the index have the following meaning:
R1, R2 -und R3 unabhängig voneinander Wasserstoff und Ci-Cβ-Alkylthio,R 1 , R 2 and R 3 independently of one another are hydrogen and Ci-Cβ-alkylthio,
nn
0, 1, 2, 3 oder 4, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2, 3 or 4, where the R 3 radicals can be different if the value of n is> 1,
wobei R1, R2 und R3 nicht gleichzeitig Wasserstoff be¬ deuten und wobei R1 nicht Wasserstoff bedeutet, wenn R2 für Methylthio und n für 0 steht. 3. Thiophene und Polythiophene der Formel I gemäß Anspruch 1, in der die Substituenten und der Index die folgende Bedeutung haben:where R 1 , R 2 and R 3 do not mean hydrogen at the same time and where R 1 is not hydrogen if R 2 is methylthio and n is 0. 3. thiophenes and polythiophenes of the formula I according to claim 1, in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Cι-C3-Alkylthio,R 1 , R 2 and R 3 independently of one another are hydrogen and C 1 -C 3 -alkylthio,
nn
0, 1, 2, 0, 1, 2,
3 oder 4, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,3 or 4, where the R 3 radicals can be different if the value of n> 1,
wobei R1, R2 und R3 nicht gleichzeitig Wasserstoff be¬ deuten und wobei R1 nicht Wasserstoff bedeutet, wenn R2 für Methylthio und n für 0 steht.where R 1 , R 2 and R 3 do not mean hydrogen at the same time and where R 1 is not hydrogen if R 2 is methylthio and n is 0.
4. Thiophene und Polythiophene der Formel I gemäß An¬ spruch 1, in der die Substituenten und der Index die folgende Bedeutung haben:4. thiophenes and polythiophenes of the formula I according to claim 1, in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Methylthio undR 1 , R 2 and R 3 are independently hydrogen and methylthio and
nn
0, 1, 2 oder 3, wobei die Reste R3 verschieden sein kön- nen, wenn der Wert von n > 1 ist,0, 1, 2 or 3, where the R 3 radicals can be different if the value of n is> 1,
wobei R1, R2 und R3 nicht gleichzeitig Wasserstoff be¬ deuten und wobei R1 nicht Wasserstoff bedeutet, wenn R2 für Methylthio und n für 0 steht.where R 1 , R 2 and R 3 do not mean hydrogen at the same time and where R 1 is not hydrogen if R 2 is methylthio and n is 0.
5. 3,4-Di (methylthio)thiophen.5. 3,4-di (methylthio) thiophene.
6. 4,4'-Di (methylthio)-2,2'-bithiophen.6. 4,4'-di (methylthio) -2,2'-bithiophene.
7. 4,4'-Di (methylthio)-2,2' :5' ,2"-terthiophen.7. 4,4'-Di (methylthio) -2,2 ': 5', 2 "-terthiophene.
8. 3'-Methylthio-2,2' :5' ,2"-terthiophen.8. 3'-Methylthio-2,2 ': 5', 2 "-terthiophene.
9. 4, 4"-Di (methylthio)-2,2' :5' ,2" :5",2' "-quarterthiophen. 9. 4, 4 "-di (methylthio) -2,2 ': 5', 2": 5 ", 2 '" quarterthiophene.
10. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen n den Wert 0 hat, dadurch ge¬ kennzeichnet, daß man10. A process for the preparation of the compounds of formula I according to claim 1, in which n has the value 0, characterized ge indicates that
a) ein Halogenthiophen der Formel Haa) a halogen thiophene of the formula Ha
Figure imgf000024_0001
Figure imgf000024_0001
in der Hai für ein Halogenatom steht, in an sich bekannter Weise in einem Lösungsmittel in Gegenwart eines Alkalimetall-Organyls mit einem Disulfid derin the shark represents a halogen atom, in a manner known per se in a solvent in the presence of an alkali metal organyl with a disulfide
Formel lilaFormula purple
R1-R1 lilaR 1 -R 1 purple
umsetzt oderimplements or
b) ein Halogenthiophen der Formel Ilbb) a halogen thiophene of the formula IIb
Figure imgf000024_0002
Figure imgf000024_0002
in der Hai für ein Halogenatom steht, in an sich bekannter Weise in einem Lösungsmittel in Gegenwart eines Alkalimetall-Organyls mit einem Disulfid der Formel lila zunächst in eine Verbindung IVin which shark represents a halogen atom, in a manner known per se in a solvent in the presence of an alkali metal organyl with a disulfide of the formula purple, first in a compound IV
R1 HaiR 1 shark
U (IV) s überführt, welche anschließend unter den gleichen Bedingungen mit einem Disulfid der Formel IllbU (IV) s transferred, which subsequently with a disulfide of the formula Illb
R2-R2 IllbR 2 -R 2 Illb
zu I umgesetzt wird.to I is implemented.
11. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, dadurch gekennzeichnet, daß man ein Halogenthiophen der Formel Ilc11. A process for the preparation of the compounds of formula I according to claim 1, characterized in that a halothiophene of the formula Ilc
Figure imgf000025_0001
Figure imgf000025_0001
in der Hai für ein Halogenatom steht, in an sich be¬ kannter Weise in einem Lösungsmittel in Gegenwart von Magnesium in die entsprechende Grignard-Verbindung der Formel Vin which shark represents a halogen atom, in a manner known per se in a solvent in the presence of magnesium in the corresponding Grignard compound of the formula V
Figure imgf000025_0002
Figure imgf000025_0002
überführt, welche anschließend in an sich bekannter Wei- se in einem Lösungsmittel mit einem Halogenthiophen bzw. -polythiophen der Formel Hdtransferred, which is then carried out in a manner known per se in a solvent with a halothiophene or polythiophene of the formula Hd
Figure imgf000025_0003
Figure imgf000025_0003
zu I umgesetzt wird. to I is implemented.
12. Mittel zur Bekämpfung von Schädlingen, enthaltend eine wirksame Menge mindestens einer Verbindung der Formel I'12. Agents for combating pests, comprising an effective amount of at least one compound of the formula I '
R2 R3 XTL)- H (!')R 2 R 3 XTL) - H (! ')
in der die Substituenten und der Index die folgende Be¬ deutung haben:in which the substituents and the index have the following meaning:
R:, R2 und R3 unabhängig voneinander Wasserstoff und Ci-Ciβ-Alkyl hio,R, 'R 2 and R 3 are independently hydrogen and Ci-Ciβ alkyl hio,
nn
0, 1, 2, 3, 4 oder 5, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2, 3, 4 or 5, where the radicals R 3 can be different if the value of n is> 1,
und inerte Zusatzstoffe.and inert additives.
13. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man die Schädlinge und/oder ihren Lebensraum mit einer wirksamen Menge mindestens einer Verbindung der Formel I' gemäß Anspruch 12 behandelt.13. A method for controlling pests, characterized in that the pests and / or their habitat are treated with an effective amount of at least one compound of the formula I 'according to claim 12.
14. Verwendung der Verbindungen der Formel I' gemäß Anspruch 12 zur Bekämpfung von Schädlingen. 14. Use of the compounds of formula I 'according to claim 12 for controlling pests.
Thiophene und Polythiophene, Verfahren zu ihrer Herstellung und ihre VerwendungThiophenes and polythiophenes, process for their preparation and their use
ZusammenfassungSummary
Thiophene und Polythiophene der Formel IThiophenes and polythiophenes of the formula I
Figure imgf000027_0001
Figure imgf000027_0001
in der die Substituenten und der Index die folgende Be¬ deutung haben:in which the substituents and the index have the following meaning:
R1, R2 und R3 unabhängig voneinander Wasserstoff und Ci-Ciβ-Alkylthio,R 1 , R 2 and R 3 independently of one another are hydrogen and Ci-Ciβ-alkylthio,
nn
0, 1, 2, 3, 4 oder 5, wobei die Reste R3 verschieden sein können, wenn der Wert von n > 1 ist,0, 1, 2, 3, 4 or 5, where the radicals R 3 can be different if the value of n is> 1,
wobei R1, R2 und R3 nicht gleichzeitig Wasserstoff bedeuten und wobei R1 nicht Wasserstoff bedeutet, wenn R2 für Methylthio und n für 0 steht. where R 1 , R 2 and R 3 are not simultaneously hydrogen and where R 1 is not hydrogen if R 2 is methylthio and n is 0.
PCT/EP1993/000060 1992-01-20 1993-01-14 Alkylthiothiophenes and alkylthiopolythiophenes, methods of preparing them, and their use WO1993014079A1 (en)

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DEP4201305.4 1992-01-20
DEP4206767.7 1992-03-04
DE19924206767 DE4206767A1 (en) 1992-03-04 1992-03-04 Pesticide compsn. contg. (poly)thiophene deriv.

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US2577566A (en) * 1947-12-13 1951-12-04 Socony Vacuum Oil Co Inc 3-thienyl thioethers
US3250787A (en) * 1962-06-27 1966-05-10 Dow Chemical Co Alkylthio thiophenes
WO1986005949A1 (en) * 1985-04-17 1986-10-23 Fmc Corporation Photoactive bithienyl pesticides

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US3250787A (en) * 1962-06-27 1966-05-10 Dow Chemical Co Alkylthio thiophenes
WO1986005949A1 (en) * 1985-04-17 1986-10-23 Fmc Corporation Photoactive bithienyl pesticides

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Title
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