DE3100648A1 - (Thiono)(thio)phosphates, -phosphonates, -phosphoramidates or -phosphonamidates of substituted pyrazolo[3,4-b]pyridines, their preparation and their use as pesticides - Google Patents

Abstract

(Thiono)(thio)phosphates, -phosphonates, -phosphoramidates or -phosphonamidates of substituted hydroxypyrazole[3,4-b]pyridines of the formula <IMAGE> in which R1 denotes alkyl, cyanoethyl, (substituted) benzyl or (substituted) phenyl, R2 denotes alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or allylamino, R3 denotes alkyl, R4 denotes hydrogen, alkyl, halogen, NO2, CF3, COO(C1-C2)alkyl or phenyl and X denotes oxygen or sulphur, are effective insecticides, acaricides and fungicides.

Description

(Thiono) (thiol) phosphorus (phosphonic) acid ester or ester

Amides of substituted pyrazolo [3,4-b] pyridines, their preparation and their use as pest control agents The invention relates to compounds of the formula I wherein R1 = (C1-C4) -alkyl, CH2CH2CN, benzyl or phenyl optionally substituted by (C1-C4) -alkyl, halogen, trifluoromethyl; R2 = (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylthio, (C1-C4) -alkylamino, di- (C1-C4) -alkylamino or allylamino; R3 = (C1-C4) -alkyl; R4 = hydrogen, (C1-C4) alkyl (single or double) halogen, NO2, CF3, COO- (C1-C2) alkyl or phenyl; X = oxygen or sulfur.

"Halogen" here and below preferably means chlorine or bromine, especially chlorine.

The invention also relates to a process for the preparation of compounds of the formula I, which is characterized in that 3-hydroxy-pyrazolo, 4-b7-pyridines of the general formula II in which Rl and R4 have the meaning given above, in the presence of acid-binding agents with (thiono) (thiol) phosphorus (phcsphon) acid ester halides, ides or ester amide halides of the general formula III, in which R2, R3 and X have the meaning given above.

The reactions take place advantageously in one under the reaction conditions inert solvents such as

a low molar ketone, acetonitrile, dimethylformamide, dimethyl sulfoxide, Glycol dimethyl ether, diisopropyl ether, benzene, toluene, xylene, chlorobenzene, ethyl acetate or dichloroethane at temperatures between room temperature and the boiling point of the solvent used, preferably at 40 - 90 00. To bind the released Hydrogen halide requires the addition of an acid-binding agent. as such alkali metal alcoholates or carbonates are advantageously used or organic bases such as pyridine or triethylamine.

Instead of adding acid-binding agents, you can use the compound of the formula II can also be used in the form of their alkali metal salts. The as starting material 3-Hydroxypyrazol- [3,4-b] pyridines of the general formula II used are for the most part already described and can be produced by methods known from the literature, z. B. after Ann. Chim. (Rome) 60, 403 (1970); Bull.Soc.

Chim.Belg. 1978, 87, 4: 309-2; J. Hererocycl. Chem. 16: 773 (1979); J.Am.Chem. Soc. 65 (1943), 52 or Aust. J.

Chem. 1965, 18, 1267-71. The (thiono) (thiol) phosphorus (phosphonic) acid ester halides used respectively.

Esteramide halides of the general formula II are known and can are prepared by customary processes [Houben-Weyl, Vol. XII / 1, p.550; Vol. XII / 2, S.

274, 607, 621, 755; SU-PS 184 8637.

The compounds of formula I are characterized by good acaricidal properties and insecticidal effectiveness. The latter is directed against both sucking and also against pointing insects. The compounds have systemic properties on.

The sucking insects with the compounds according to the invention can be controlled include, for example, aphids (Aphidae) such as the green one Peach aphid (Myzus persicae), black bean (Doralis fabae), customer bean (Aphis craccivora), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and Potato mouse (Macrosiphus solanifolii), also the currant gall Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and bed bugs, for example beetroot (Piesma quadrata), cotton (Dysdercus intermedius, Oncopeltus fasciatus), bed (Cimex lectularius), predatory (Rhodnius prolixus) and Chagas bug (Triatoma infestans), as well as cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects the following should be mentioned: caterpillars (Lepido.ptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), golden afters (Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small F, ostspanner (Cheimatobia brumata), Oak moth (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large wax moth (Galleria mellonella).

Furthermore, pointing insects include beetles (Coleoptera) e.g. Corn (Calandra granaria), potato (Leptinotarsa decemlineata), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table bean (Acanthoscelidec obtectus), Bacon (Dermestes frischi), Khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Sitophilus zeamais), bread (Stegobium paniceum), commoner Flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis); Scrape like the German (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea maderae Oriental (Blatta orientalis), Giant (Blaberus giganteus) and giant black cockroach (Blaberus fuscus); also orthopters, e.g. the cricket (Acheta donesticus).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small parlor- (Fannia canicularis), glossy (Phormia aegina) and Blowfly (Calliphora erythrocephala) and the calf stinger (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), Ilaus (Culex pipiens) and malaria mosquito (Anopheles stephensi).

The mites (Acari) include especially the spleen mites (Tetranychidae) like the bean (Tetranychus urticae) and the fruit tree spider mite (Panonychus ulmi). Gall mites, e.g. the currant gall mite (Eriophyes ribis) and tarsonemids, e.g. the tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus).

When used against hygiene and storage pests, especially Flies and mosquitoes, the process products are also characterized by excellent Residual effect on wood and clay.

The invention therefore also relates to acaricides and insecticides Agent, characterized by a content of compounds of the formula I in addition to customary formulation auxiliaries and inert substances and the use of the compounds to combat acarids and insects.

The compounds of the formula I according to the invention are distinguished by an excellent fungicidal effect. Already penetrated into the plant tissue fungal pathogens can be successfully combated curatively. This is especially important and beneficial for those fungal diseases that are after Infection can no longer be effectively combated with the usual fungicides. The spectrum of activity of the claimed compounds includes, for example, in addition to piricularia oryzae, different types of rust, Phytophthora infestans, Plasmopara viticola, but above all powdery mildew fungi in fruit, vegetable, cereal and ornamental plant cultivation. Particularly noteworthy is the excellent effect of the compounds against powdery mildew, which are resistant to benzimidazole derivatives (e.g. benomyl, carbendazim).

The compounds of formula I are also suitable for use in technical area, for example in wood preservatives, in the paint sector and as a preservative.

The fungicidal compounds can be used in crop protection of formula 1 in the usual way as dusts, wettable powders, mordants, dispersions, Solutions or emulsion concentrates can be formulated. The content of active ingredients of formula I is generally between 2 and 95% by weight, preferably 10 - 95% by weight. In addition, the active ingredient formulations mentioned may contain

the usual adhesive, wetting, dispersing, emulsifying, penetration, Solvents, fillers and carriers, also mixtures or mixed formulations with other active ingredients, such as insecticides, acaricides,; 4erbicides or fungicides as well as fertilizers or growth regulators are possible.

The agents according to the invention contain the active ingredients of the formula I generally at 1-95% by weight. They can be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual preparations be applied.

Wettable powders are preparations that can be dispersed evenly in water, which, in addition to the active ingredient, apart from a diluent or inert substance, also wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenyl sulfonates and dispersants such as sodium lignin sulfonic acid, 2,2'-dinaphthylmethane-6,6'-disulfonic acid Sodium, sodium dibutylnaphthalenesulfonic acid or oleylmethyltauric acid Contain sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or several emulsifiers. As emulsifiers, for example, can be used be: alkylarylsulfonic acid calcium salts such as calcium dodec-benzene sulfonate or non-ionic Emulsifiers such as fatty acid polyglycol esters, alkyl acryl polyglycol ethers, fatty alcohol polyglycol ethers, Propylene oxide-ethylene oxide condensation products, fatty alcohol-propylene oxide-ethylene oxide condensation products, alkyl polyether, sorbitan fatty acid ester, polyoxethylene sorbitan fatty acid ester or Polyoxethylene sorbitol ester.

Dust is obtained by grinding the active ingredient with finely divided, solid substances, e.g. talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.

Granules can either be sprayed onto adsorptive, Granulated inert material can be produced or by applying active ingredient concentrates by means of adhesives, e.g. polyvinyl alcohol, polyacrylic acid sodium or mineral oils on the surface of carrier materials such as sand, kaolinite, or granulated Inert material. Even. can be suitable active ingredients in the for the production of Manure granules in the usual way - if desired in a mixture with Fertilizers - to be produced.

In wettable powders, the active ingredient concentration varies e.g.

between about 10 and 80%, the remainder being those given above Formulation additives. In the case of emulsifiable concentrates, the active ingredient concentration can likewise about 10% to 80 7o. Contain dusty formulations mostly 5 - 20% active ingredient, sprayable solutions around 2 - 20%. With granules The active ingredient content depends in part on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.

The commercially available concentrates are optionally used for use diluted in the usual way, e.g. with wettable powders and emulsifiable concentrates by means of water.

The ready-to-use suspensions preferably contain 0.05 to 2, in particular 0.1 to 1% active ingredient. Dust-like and granulated preparations as well Sprayable solutions are no longer mixed with other inert substances before use diluted.

Preparation Examples Example 1 3- (0,0-Diethyl-thionophosphoryl) -1,4,6-trimethylpyrazolo [3,4-b] -pyridine 6.8 g (49 mmol) of potassium carbonate are suspended in 150 ml of absolute acetonitrile and 8 g (45 mmol) of 3-hydroxy-1,4,6-trimethylpyrazolo [3,4-b] pyridine are added. The mixture is stirred at 50 ° C. for about 30 minutes. After adding 8.5 g (45 mmol) of O, O-diethylthiophosphoryl chloride, the reaction mixture is stirred for 4 hours at 50-60 ° C. and then concentrated in vacuo. The residue is dissolved in 150 ml of toluene and the solution is extracted successively with 100 ml of water, 100 ml of 1N sodium hydroxide solution at 10-15 ° C. and another 100 ml of water. The organic phase is dried with sodium sulfate. After the solvent has been distilled off in vacuo, 12.5 g of 3- (0,0-diethylthionophosphoryl) -1,4,6-trimethyl-pyrazolo [3,4-b] pyridine with the refractive index n3D 9ff: 1.5368 are obtained.

The following compounds of the formula are obtained in an analogous manner Table 1 At- R1 R2 R3 R4 X Physics. game data 2 CH3 OC2H5 C2H5 4,6 -diCH3 0 Mp: 44-9 ° C 3 CH3 SC3H7-n C2H5 4,6-diCH3 0 nD20: 1.5429 4 CH3 SC3H7-n C2H5 4,6-diCH3 S nD22: 1.5705 5 CH3 CH3 C2H5 4,6-diCH3 S nD23: 1.5597 6 CH3 C2H5 C2H5 4,6-diCH3 S nD24.5: 1.5493 7 CH3 C2H5 C3H7-i 4,6-diCH3 S nD23: 1.5447 8 CH3 NHC3H7-i C2H5 4,6-diCH3 S M.p .: 94-7 ° C 9 CH3 OC2H5 C2H5 HS nD25: 1.5429 10 CH3 SC3H7-n C2H5 HO nD21: 1.5456 11 CH3 CH3 C2H5 HS nD25: 1.5672 12 CH3 C2H5 C2H5 HS nd25: 1.5592 13 CH3 SC3H7-n C2H5 H s nD25: 1.5778 14 C2H5 CH3 C2H5 HS 15 C2H5 C2H5 C2H5 HS 16 C2H5 C2H5 C2H5 HO At- RRR game 1 2 3 R4 | 17 C2H5 OC2H5 C2H5 HS 18 C2H5 SC3H7-n C2H5 HO 19 C2H5 SCH3H7-n C2H5 HS 20 CH4H9-n CH3 C2H5 HS 21 C4H9 C2H5 C2H5 HS 22 C4H9 OC2H5 C2H5 HO 23 C4H9 OC2H5 C2H5 HS 24 C4H9 SC3H7-n C2H5 HO 25 CH2CH2CN CH3 C2H5 HS 26 CH2CH2CN C2H5 C2H5 HS 27 CH2CH2CN OC2H5 C2H5 HO 28 CH2CH2CN OC2H5 C2H5 HS 29 C6H6 CH3 C2H5 HS 30 C6H5 C2H5 C2H5 HS 31 CH3 CH3 C2H5 5-CH3 S 32 CH3 CH3 C2H5 5-Cl S 33 CH3 CH3 C2H5 5-Br S 34 CH3 CH3 C2H5 5-NO2 S Formulation Examples Example a An emulsifiable concentrate. obtained from 15 parts by weight of active ingredient 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol (10 AeO) as emulsifier.

Example b A wettable powder easily dispersible in water is obtained by adding 25 parts by weight of active ingredient 64 parts by weight of active silica as an inert substance 10 parts by weight of calcium lignosulfonic acid and 1 part by weight of oleylmethyltauric acid Mixes sodium as a wetting and dispersing agent and grinds it in a pin mill.

Example c A dusting agent is obtained by adding 10 parts by weight Mixes active ingredient and 90 parts by weight of talc as inert and in a hammer mill crushed.

Example d A granulate consists, for example, of about 2-15 parts by weight of active ingredient 98 - 85 parts by weight of inert granulate materials such as attapulgite, pumice stone and quartz sana.

Biological examples Example 1 With bean spider mites (Tetranychus urticae, normally sensitive) strongly infested bean plants (Phaseolus vulgaris) with the aqueous dilution of a wettable powder concentrate containing 0.0125% by weight of the Containing active ingredient from Example 3, injected up to the stage of beginning dripping. Microscopic control eight days after treatment showed that all mobile and immobile stages of the population were killed.

Tested in the same way, the compounds according to the example were found 4, 17, 12, 11, 10, 9 as equally effective.

Example II With fruit tree spider mites (Panonychus ulmi, resister strain) heavily populated plants (apple trees) were with the aqueous suspension of a Wettable powder concentrate containing 0.025% by weight of the active ingredient from Example 13, Sprayed to the stage of beginning dripping and at approx. 22 ° C in the greenhouse set up.

The acaricidal effectiveness was determined eight days after treatment and resulted in 100% mortality for the compounds from Examples 11 and 10.

Example III Heavily infested with customer bean aphids (Aphis craccivora) Field beans (Vicia faba) were mixed with the aqueous suspension of a wettable powder concentrate, which contained 0.0125% by weight of the active ingredient from Example 6, up to the stage of dripping off injected. After the plants were placed in the greenhouse, three days after the Treatment found a 100% kill of the test animals. Just as effective The compounds according to Examples 5, 3, 4, 13, 12, 11, 10 and 9 proved to be.

Example IV On the inside of the lid and bottom of a detri dish were using a pipette 1 ml from Example 11 as the active ingredient in acetone with a Concentration of 0.025% by weight applied evenly and until complete Leave the pan open to evaporate the solvent. After that there were 10 houseflies each (Musca domestica placed in the Petri dishes, the dishes closed with the lid and 100% death of the test animals was found after 3 hours.

The compounds according to Example 6, 12, 10, 9.

Example V As described in Example IV, the compound according to Example 11 as an active ingredient in acetone at a concentration of 0.025% by weight uniformly on the inside of the Lid and bottom of a Petri dish applied and let dry. Then 10 larvae (L 4) were placed in each Petri dish the German cockroach (Blatella germanica), the bowls are closed with the lid and after 72 hours a death of 100 of the test animals was determined.

The compound according to Example 6, 5, 4, 13, 12, 9.

Example VI Leaves of cotton (Gossypium sp.) Were with a aqueous emulsion of the compound according to Example 3 in a concentration of 0.025 Weight, based on active ingredient, sprayed (= 600 1 spray mixture / ha) and treated in the same way Caterpillars (10 pieces, stage L 3-4) of the common cotton worm (Prodenia litura) are added. Leaves and caterpillars were placed together in observation cages and after 48 hours 100% death of the test animals was found.

The compounds according to Example 4 were found to be just as effective, 13, 11, 10.

Example VII Leaves of the bean (Phaseolus vulgaris) were with a aqueous emulsion of the compound from Example 12 in a concentration of 0.0125 % By weight (based on active ingredient) treated and treated identically to larvae des Mexican Bean beetle (Epilachna varivestis) placed in observation cages. An evaluation after 48 hours, the test animals were killed off 100%.

The compounds according to the .xls proved to be equally effective Example 3, ll.

Claims (4)

Claims: 1. Compounds of the formula I wherein R1 = (C1-C4) -alkyl, CH2CH2CN, benzyl or phenyl optionally substituted by (C1-C4) -alkyl, halogen, trifluoromethyl; R2 = (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylthio, (C1-C4) -alkylamino, di- (C1-C4) -alkylamino or allylamino; R3 = (C1-C4) -alkyl; R4 = hydrogen, (C1-C4) alkyl (single or double), halogen, NO2, CF3, COO- (C1-C2) alkyl or phenyl; X = oxygen or sulfur. 2. Process for the preparation of the compounds of the formula I, characterized in that compounds of the formula II in which R1 and R4 have the meaning given above, with compounds of the formula III in which R2, R5 and X have the meaning given above and Hal is chlorine or bromine, is reacted in the presence of an acid acceptor. 3. Pesticides, characterized by a content of compounds of the formula I. 4. Use of compounds of the formula I for combating pests.