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

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 AND ALKYLTHIOPO Y HIOPHENE, METHOD FOR THEIR PRODUCTION AND USE.

description

The present invention relates to thiophenes and polythiophenes of the formula I

in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another are hydrogen and Ci-Ciβ-alkylthio,

n

0, 1, 2, 3, 4 or 5, where the radicals R ³ can be different if the value of n is> 1,

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.

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 "R ³ i πxj-n, ι.)

in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another Hydrogen and Ci-Ciβ-alkylthio,

n

0, 1, 2, 3, 4 or 5, where the radicals R ³ can be different if the value of n is> 1,

and inert additives and pest control methods.

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).

The invention was based on new active substances suitable for pest control as a task.

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.

The compounds are accessible by various methods known per se from the literature. Basically, the following general procedures are used:

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)).

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.

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.

Mixtures of the solvents mentioned can also be used.

B: Preparation and implementation of the Grignard compounds (MacEachern et al., Tetrahedron 44 (9), 2403 (1988); Jayasuriya et al., Heterocycles 24 (10), 2901 (1986))

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.

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.

Mixtures of the solvents mentioned can also be used.

With regard to the rate of conversion and the yield, it may be advantageous to add a catalyst to the reaction mixture.

In this sense, catalysts like

Pd (dppf) Cl ₂ (dppf = l, l'-bis (diphenylphosphino) ferrocene) and

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: Reaction of the halothiophenes with disulfides

(Gronowitz et al, Acta Chem. Scand., 13 (5), 1045 (1959))

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.

Mixtures of the solvents mentioned can also be used.

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.

With 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

Hydrogen;

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.

n

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.

Particularly preferred are thiophenes and polythiophenes of the formula I 'in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another

Hydrogen, Ci-Cs-alkylthio as mentioned above in general and in particular and

n

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:

R ¹ , R- and R ³ independently of one another

Hydrogen, -C-C ₃ alkylthio as mentioned above in general and in particular and

n

0, 1, 2, 3 or 4, it being possible for the radicals R ^{3 to be} different if the value of n is> 1.

Of biological interest are also thiophenes and polythiophenes of the formula I 'in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another are hydrogen and methyl thio

and

n

0, 1, 2 or 3, where the radicals R ³ can be different if the value of n is> 1,

being the connections

1. 3,4-di (meththio) thiophene, 2. 4,4'-di (methylthio) -2,2'-bithiophene,

3. 4,4 ^» -di (methylthio) -2,2 ': 5', 2 ^• -terthiophene,

4. 3'-methylthio-2,2 ': 5', 2 "-terthiophene and

5. 4,4 '' di (methylthio) -2,2 ': 5', 2 ": 5", 2 '"quarterthiophene

is of particular importance. With regard to the biological activity, particularly preferred compounds of the formula I 'are listed in the following table:

R 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

4'-n-propylthio 2 HH 4'-i-propylthio 2

Methylthio 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

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 (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.

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.

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.

From the order of the thrips (Thysanoptera), 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.

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 .

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, 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.

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.

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.

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 curvitatusey, Pratylench.

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.

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.

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.

Alkali, alkaline earth,

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.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Examples of formulations are:

I. 5 parts by weight of compound no

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 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 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 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 parts by weight of compound no

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.

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.

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.

In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used successfully in the

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

(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

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.

The following starting compounds which cannot be purchased were prepared in accordance with the literature instructions given:

1) 3-methylthiothiophene, bp 103-105 ° C / 30 torr, yield 80% (GC> 99%);

2) 2-bromo-3-methylthiothiophene, bp 54-56 ° C / 10- ³ torr, yield 93.4% (GC>98%);

3) 2, 5-dibromo-3-methylthiothiophene, yield 83% (GC> 98%);

4) 2-bromo-4-methylthiothiophene, b.p. 114-116 ° C / 12 torr, yield 84% (GC> 98%);

Literature: E.C. Taylor, D.E. Vogel, J. Org. Chem. 5J2. 1002 (1985)

5) 3,4-dibromothiothiophene, bp 94-95 ° C / 12 torr, yield 60% (GC> 97%);

Literature: S. Gronowitz, Acta Chem. Scand. 2 (5) 1045 (1959)

6) 5,5'-dibromo-2,2'-bithiophene, mp 146-147 ° C (GC> 99%)

Literature: F. Würthner, diploma thesis University of Stuttgart 1990

Example 1: Preparation of 3, 4-di (methythio) thiophene

1.1 Under a protective gas atmosphere, a mixture of

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 Under a protective gas atmosphere, a mixture of

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%).

General instructions for the synthesis of the methylthio-substituted oligothiophenes using the example of 4,4'-di (methylthio) -2,2'-bithiophene (2).

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%).

Amounts used for the other oligomers:

4,4 "-di (methylthio) -2,2 ', 5', 2" -terthiophene (3):

5.02 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-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" 'quarterthiophene (4):

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) Cl ₂

3.24 g (10 mM) 5,5'-dibromo-2,2'-bithiophene in 100 ml

Ether / 50 ml of benzene dissolved

Reflux 22 h, extraction with CH ₂ C1 ₂ , chromatography hexane / CH ₂ Cl ₂ 1: 1,

Recrystallization from toluene, yield 2.65 g (63% of theory) of orange crystals (HPLC> 99%).

3'-methylthio-2,2 ', 5', 2 "-terthiophene (5):

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-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%).

R 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

5 HH 4'-methylthio 2 yellow oil '

250 MHz ¹ H NMR in CDC1 / TMS:

7.31 (d, d, d, 2H); 7.20 (d, d, 1H); 7.15 (d, d, 1H)

7.07 (s, 1H); 7.03 (d, d, d, 2H); 2.46 (s, 3H)

Examples of use

The biological activity of the compounds of the general formula I was demonstrated by the following experiments:

The active ingredients were

a) 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

Fatty alcohols)

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

Claims

1. Thiophenes and polythiophenes of the formula I

in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another are hydrogen and Ci-Cis-alkylthio,

n

0, 1, 2, 3, 4 or 5, where the radicals R ³ can be different if the value of n is> 1,

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. thiophenes and polythiophenes of the formula I according to claim

1, in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another are hydrogen and Ci-Cβ-alkylthio,

n

0, 1, 2, 3 or 4, where the R ³ radicals can be different if the value of n is> 1,

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:

R ¹ , R ² and R ³ independently of one another are hydrogen and C ₁ -C ₃ -alkylthio,

n

0, 1, 2,

3 or 4, where the R ³ radicals can be different if the value of n> 1,

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. thiophenes and polythiophenes of the formula I according to claim 1, in which the substituents and the index have the following meaning:

R ¹ , R ² and R ^{3 are} independently hydrogen and methylthio and

n

0, 1, 2 or 3, where the R ³ radicals can be different if the value of n is> 1,

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) thiophene.

6. 4,4'-di (methylthio) -2,2'-bithiophene.

7. 4,4'-Di (methylthio) -2,2 ': 5', 2 "-terthiophene.

8. 3'-Methylthio-2,2 ': 5', 2 "-terthiophene.

9. 4, 4 "-di (methylthio) -2,2 ': 5', 2": 5 ", 2 '" quarterthiophene.

10. 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) a halogen thiophene of the formula Ha

in 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

Formula purple

R ¹ -R ¹ purple

implements or

b) a halogen thiophene of the formula IIb

in 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

R ¹ shark

U (IV) s transferred, which subsequently with a disulfide of the formula Illb

R ² -R ² Illb

to I is implemented.

11. A process for the preparation of the compounds of formula I according to claim 1, characterized in that a halothiophene of the formula Ilc

in 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

transferred, which is then carried out in a manner known per se in a solvent with a halothiophene or polythiophene of the formula Hd

to I is implemented.

12. Agents for combating pests, comprising an effective amount of at least one compound of the formula I '

R ² R ³ XTL) - H (! ')

in which the substituents and the index have the following meaning:

R, ^{'R 2} and R ³ are independently hydrogen and Ci-Ciβ alkyl hio,

n

0, 1, 2, 3, 4 or 5, where the radicals R ³ can be different if the value of n is> 1,

and inert additives.

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. Use of the compounds of formula I 'according to claim 12 for controlling pests.

Thiophenes and polythiophenes, process for their preparation and their use

Summary

Thiophenes and polythiophenes of the formula I

in which the substituents and the index have the following meaning:

R ¹ , R ² and R ³ independently of one another are hydrogen and Ci-Ciβ-alkylthio,

n

0, 1, 2, 3, 4 or 5, where the radicals R ³ can be different if the value of n is> 1,

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.