MXPA99010487A - Pesticide and parasiticide use of compounds of 2- (substituted tia) tiazolo- [4,5-b] pirid - Google Patents

Abstract

The present invention relates to the pesticic and parasitic use of 2- (substituted thio) thiazolo [4,5-b] pyrirdine compounds having the structural formula

Description

PEST1CIDA AND PARASITICIDE USE OF 2-REAGENT COMPOUNDS REPLACED) TIAZOLO-r4.5-b1PIRIDINE BACKGROUND OF THE INVENTION Pests of nematodes, insects and mites destroy growing and harvested crops. In the United States, agronomists - they must challenge thousands of these pests. In addition, arthropod and helminth parasites cause hundreds of millions of dollars in economic damage to livestock and pet sectors annually, on a global basis. Arthropod parasites are also a nuisance to humans, and can be the vector of organisms that cause diseases in humans and animals. Despite the pesticides, ectoparasiticides, endectocides and commercial anthelmintics available today, damage to crops, gaia-b, companion animals and humans still occurs. Therefore, there is ongoing research to create new and more effective pesticides, ectoparasiticides, endectocides and anthelmintics. Certain azole derivatives that are useful as antiulcer agents are described in EP 405976-B1. However, that patent does not disclose or have any pesticidal or parasiticidal utility for the azole derivatives described therein. Therefore, it is an object of the present invention to provide a method for the control of parasites and pests of helminths, nematodes, insects and mites. Furthermore, it is an object of the present invention to provide a method for the protection of growing and harvested crops, against the damage caused by the attack of nematodes, insects and mites, and against the REF. :: 31865 infestation. Another objective of this invention is the provision of a method for the treatment, control, prevention and protection of warm-blooded animals, fish and humans, against the ipffestation and infection of helminths, mites and en-do and arthropod ectoparasites. These and other objects of the present invention will be more apparent from the description thereof that is set forth below. SUMMARY OF THE INVENTION The present invention provides a method for the control of parasites or pests of helminths, nematodes, insects or mites, comprising contacting said pests or parasites, or their food supply, habitat or breeding soil, with a pesticidal or parasiticidal amount effective of a compound 2- (substituted thio) thiazolo [4,5-b] pyridine having the structural formula I (R).-C N NXN N? S-Q (I) wherein R is halogen, nitro, cyano, C-C- alkyl, C-C4 haloalkyl, C-C4-alkoxy, Cj-C4 haloalkoxy, C-C12-alkylthio, halo-CX-C6-C4, CO ^.,; n is 0, 1, 2, or 3; Q is C ^ -Cg alkenyl, C3-Cg haloalkenyl, C3-C cycloalkyl, C ^ -C ^ haloalkyl, C-C7 cycloalkenyl, C, -C7 haloalkyl, C-alkyl, Cfi optionally substituted with a group C3-C7 cycloalkyl, halocycloalkyl 3-C7, halocycloalkyl C3-C- or C02R2, Haloalkyl C.-C optionally substituted with a C3-C7 cycloalkyl group, halocycloalkyl C-, - C7 or CO and R and R ? are each independently hydrogen, C ..-Cfi alquilo alkyl, CH "(C7-Cg haloalkyl), C_-C al alkenyl, C3-C10 haloalkenyl, a cathyl, benzyl optionally substituted on the ring with -any combination of one to five halogen atoms, one or two cyano groups, one or two nitro groups, one to three C.-C- alkyl groups, one to three C1-CH haloalkyl groups, one to three alkoxy groups, Ci-C i-, not "unnno ao .ure? Ts. - haloalkoxy groups C.-C" or phenyl optionally substituted with any combination of one to five halogen atoms, one or two cyano groups, one or two nitro groups, -one to three C.-C alkyl groups, one to three haloalkyl C.-C- groups, one to three C.-C. alkoxy groups or one to three C.-C, haloalkoxy groups and the agricultural and or pharmaceutically acceptable thereof This invention further comprises pesticidal and parasiticidal compositions containing these compounds., that the compounds of 2- (substituted thio) thiazolo [4,5-b] pyridine, and -compositions containing them, are especially useful for the control of nematode pests. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for the control of parasites or pests of helminths, nematodes, insects or mites, comprising - contacting said pests or parasites, or their food supply, -habitat or nursery soil, with a pesticidal or parasiticidally-effective amount of a 2- (thio substituted) thiazolo [4,5-b] pyridine compound of form 1. The compounds of formula 1, which are especially useful for the control of nematodes, include 2 - [(4,4,3-Trifluoro-3-butenyl) thio] thiazolo [4,5-b] -pyridine; 2 - [(Bromodifluoromethyl) thio] thiazolo [4,5-b3-pyridine; and 2 - [(difluoromethyl) thio] thiazolo [4,5-b] -pyridine, among others. The present invention further provides a method for the protection of growing plants, against attack or infestation of pests of nematodes, insects or mites, which comprises applying to the foliage of the plants, or to the soil or water in which they grow, a pesticidally effective amount of a 2- (thio substituted) thiazo [4,5-b] pyridine compound of formula 1. The compounds of formula 1 of this invention are useful for the control of plant parasitic nematodes, and nematodes who live freely on the ground. Plant parasitic nematodes include, but are not mitigated, ectoparasites such as Xiphinema spp., Longidorus spp. and TrichodD rus spp .; semiparasites such as Tylenchulus spp .; migratory endoparasites such as Pratylenchus spp., Radopholus spp. and Scutellonema spp .; for sedentary sites such as Heterodera spp., Globodera spp. and Meloidogyne -spp .; and stem and leaf endoparasites such as Ditylenchus spp., Aphelen-choides spp. and Hirshmaniella spp. The 2- (substituted thio) thiazolo [4,5-b] pyridine compounds of formula 1 are also useful for the control of insect pests and / or mites. Insects controlled by the compounds of formula 1 of this invention include, but are not limited to, lepidoptera such as taco budworms, cabbage measuring caterpillars, cottonworms, beet fighter caterpillars, southern fighter caterpillars and butterflies. rattle snake; Homoptera, such as aphids, leaf hoppers, plant hoppers and whiteflies; Thysanoptera such as thrips; coleoptera such as cotton weevils, Colorado potato beetles, southern corn rootworms, western corn rootworms and mustard beetles; and orthoptera such as lobsters, crickets, grasshoppers and cockroaches. Mites that are controlled by the compounds of formula 1 of this invention include, but are not limited to, mites such as spider mites, spider mites, carmine spider mites, ribera mite mites, strawberry mites, mites. citrus rust and scaly mites. In practice, generally about 0.1 ppm to about 10,000 ppm, and preferably about 1 ppm to about 5,000 ppm of a compound of formula 1, dispersed in water or other liquid carrier, are effective when applied to plants or to the soil or water in which the plants grow, or will grow, to protect the plants against the attack of nematodes, insects and / or mites, and against infestation. The compounds of 2- (substituted thio) thiazolo [4,5-b] pyridine are also effective for the control of pests of nematodes, insects and / or mites, when applied to the foliage of plants and / or soil or water in which grow said plants or will grow, in sufficient quantity to provide an index of about 0.1 kg / ha to 4.0 kg / ha of active ingredient. Although the compounds of formula 1 of this invention are effective for the control of pests of nematodes, insects and / or agricultural crop mites, both growing and constricted, when used alone, they can also be used in combination with other biological agents used in agriculture, including, but not limited to, other nematicides, insecticides and / or acaricides. For example, the compounds of formula 1 of this invention can be effectively used as a whole or combination with pyrethroids, phosphates, cyclodiene carbamates, Bacillus thuringiensis sotoxin (Bt), formamidines, phenolic tin compounds, chlorinated hydrocarbons, ureas. of benzoi lfeni lo, pirróles and the like. The compounds of this invention can be formulated as emulsifiable concentrates, flowable concentrates or powders for mixing with water, which are diluted with water or other suitable polar solvent, generally in situ, and then they are applied as a diluted spray. Said compounds can furthermore be formulated in dry compacted granules, granular formulations, fine powders, fine powder concentrates, suspension concentrates, microemulsions and the like, all of which lend themselves to applications of seeds, soil, water and / or foliage, to provide the protection required for the plants. Said formulations or compositions of the present invention include a compound of formula 1 of this invention (or combinations thereof) in admixture with one or more solid or liquid carriers -agnetically acceptable lines. These compositions contain a pesticidally effective amount of said compound or compounds, which amount may vary according to the particular compound, target pest and all use. Those skilled in the art can readily determine that it is a pesticidally effective amount, without undue experimentation.

This invention further provides a method for the treatment, cushioning, prevention and protection of warm-blooded animals, including humans and fish, against the infection and infection of helminths, mites and endo and ectoparasites arthropods, which comprises administering orally, topically or parenterally, or apply to said animals, an anthelminthically, -caricidally or endo- or ectoparasiticidally effective amount of a compound of 2- (substituted thio) thiazole I 4, 5-b] pyridine of formula 1. The above method is particularly useful for control and prevention of infestations and infections of helminths, mites and endo- and ectoparasitic arthropods, in warm-blooded animals such as cattle, sheep, pigs, camels, deer, horses, birds, fish, rabbits, goats, dogs and cats, as well as humans. Helminthiasis is a widespread disease found in many farm and companion animals, and is responsible for significant economic losses throughout the world. Among the helminths causing significant damage are members of the Trematoda class, commonly known as flattened parasites or flatworms, especially members of the genera Fasciola, Fascioloides, Paramphistomum, Dicrocoelium, Eurytrema, Ophisthorchis, Fasciolopsis, Echinosto a and Paragoni us. Helminthiasis is also caused by a group of worms referred to as nematodes. The -nematodes cause serious damage to the walls and tissues of the organs in which they reside, including the intestinal tract, heart, lungs and blood vessels, and are a primary cause of anemia. If it is left untreated, it can cause death in infected animals. Nematodes that are most commonly found as the infectious agents of warm-blooded animals include members of the genera Haemonchus, Os-tertaqia, Cooperia, Oesphaqastomum, Nematodirus, Dictyacaulus, Tricnuris, Doryopterygium, Ancyclostoma, Ascaris and the like. Conveniently, the compounds of formula 1 of this invention are useful against agents causing helminthiasis. In addition to controlling helminths, the compounds of formula 1 of this invention control infestations of endoparasitic arthropods such as larvae of cattle and larvae of the stomach. In addition, the infestations of arthropods and mites on warm-blooded animals and on peaches, including but not limited to lice, mites, ticks, larvae, salt, keds, spicy flies, moss flies, flies, larvae of mii-asitic fly, chiggers, gnats, mosquitoes and fleas, can be controlled, prevented or eliminated by means of the 2- (substituted thio) thiazolo [4,5-b] pyridine compounds of this invention. The compounds of formula 1 of this invention can also be used for the control of mites that are parasitic in warm-blooded mammals and birds, including mites of the classes Acá rifor es and Parasitiformes. Arthropod ectoparasites that can be co-ligated by the compounds of formula 1 of this invention include, but are not limited to, spicy lice, sucking lice, larval flies, spider flies, gnats, mosquitoes and fleas. Spicy lice include members of Mallophaga, such as Bovicola bovis, Trichodectes canis and Da-mi lina ovis. Suctioning lice include members of Anoplura, such as Haematopinus eurystemus, Haematopinus suis, Linognathus vituli and Solenopotes capillatus. Spicy flies include members of Haema-tpbia.

For oral administration to warm-blooded animals, the compounds of formula 1 can be formulated as animal feeds, feed premixes, feed concentrates, pills, solutions, pastes, suspensions, baths, gels, tablets, boluses. and capsules. In addition, the compounds of formula 1 can be administered to the animals in their drinking water. For oral administration, the selected dosage form should provide the animal with about 0.01 mg / kg to 100 mg / kg of animal body weight per day of the compound of formula 1. Alternatively, the compounds of formula 1 can be administered to the animals parenterally, for example, by intra-ruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formula 1 can be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formula 1 can be formulated in an implant for subcutaneous administration. In addition, the compound of formula 1 can be administered to the animals transdermally. For parenteral administration, the selected dosage form should provide the animal with about 0.01 mg / kg a? Oo mg / kg body weight of the animal per day of the compound of formula 1. The compounds of formula 1 can also be applied in a Topiary the animals in the form of submerged baths, fine powders, powders, necks, medallions, sprays and pouring formulations. For topical application, dip baths and sprays usually contain about 0.5 ppm to 5,000 ppm, and preferably about 1 ppm to 3,000 ppm of the compound of formula 1. In addition, the compounds of formula 1 can be Formulate as ear tags for animals, particularly quadrupeds such as cattle and sheep. The compounds of formula 1 of this invention can further be used in combination or in conjunction with one or more other parasiticidal compounds, including, but not limited to, anthelmintics, such as benzyl idazoles, piperazine, levamisole, pyrantel, praziquantel and the like.; endectocides such as avermectins, milbemycins and the like; ectoparasiticides such as -arilpyrroles, organophosphates, carbamates, gammabutyric acid inhibitors, including fipronil, pyrethroids, spinosads, imidacloprid and the like; Regulators of insect growth, such as pyriproxyfen, cyromazine and the like; and inhibitors of chitin synthase, such as benzoylureas, including flufenoxuron. The compounds of formula 1 can additionally be used in combination or -in conjunction with one or more conventional synergists, such as piperonyl butoxide, N-octyl bicycloheptene dicarboximide, dipropyl pyridine-2,5-dicaj boxylate and 1, 5a, 6.9 , 9a, 9b-hexahydro-4a (4H) -dibenzofurancarboxaldehyde, to improve efficiency, expand the spectrum and provide a convenient method for the control of parasites. The parasiticidal compositions of the present invention include a compound of formula 1 of this invention (or combinations thereof) in admixture with one or more inert pharmaceutically and / or agronomically acceptable liquid or solid carriers. These compositions contain a parasiticidally effective amount of said compound or compounds. Those skilled in the art can readily determine which is a parasiticidal effective amount, without undue experimentation. The present invention also provides novel compounds of 2- (substituted thio) thiazolo [4,5-b] pyridine, which have the structural formula (the) wherein R is halogen, nitro, cyano, C-C- alkyl, C-C4 haloalkyl, CX alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl or CO 2; n is 0, 1, 2, or 3; Q is haloalkenyl C -Cß, cycloalkyl C3-C-, halocycloalkyl C3-C7 C-C7 cycloalkenyl, C4-C7 halocycloalkenyl > C ^ Cg alkyl substituted with a C3-C7 cycloalkyl or 3-C7 halocycloalkyl group, or C-Cg haloalkyl optionally substituted with a C-C7 cycloalkyl group, or C3-C7 halocycloalkyl, provided that Q is not CF H; and R, is hydrogen, C 1 -Cg alkyl, CH 2 (C 1 Cg haloalkyl, C 3 -C 8 alkenyl, CIC.Q haloalkenyl, a cation, benzyl optionally substituted on the ring with any combination of one to five carbon atoms. halogen, one or two cyano groups, one or two nitro groups, one to three C.sub.1 -C4 alkyl groups _ one to three C1-C4 haloalkyl groups, one to three C, -C4 alkoxy groups, or optionally substituted phenyl with any combination of one to five halogen atoms, one or two cyano groups, one or two nitro groups, one to three C, -C4 alkyl groups, one to three C, -C4 haloalkyl groups, one to three -alkoxy groups C.-C4, or one to three haloalkoxy C.-C4 groups, and the agricultural and / or pharmaceutically acceptable salts thereof In addition, the present invention provides 2 - [(difluoromethyl) thio] thiazolo [4,5- b] ] pyridine Examples of halogen mentioned above are fluorine, chlorine, bromine and iodine The terms "haloalkyl 1-C4", "haloalkyl ^ Cg", "haloalkoxy C. | -C4", ", haloaiquil thio crC4"'" C3-C7II halocycloalkyl > < ? haloalque nyl C3-Cg "," C3-C10 haloalkenyl "and" C4-C7 halocycloalkenyl ", are defined as a C-C4 alkyl group, a C-Cg alkyl group, an alkoxy group -C.-C4, a group C4-C4 alkylthio, a C3-C7 cycloalkyl group, a C3-C4 nyl group, a C-CQ alkenyl group and a C4-C7 cycloalkenyl group, substituted with one or more halogen atoms, respectively. in-formulas 1 and the above, cation designates alkali metals, alkaline earth metals, manganese, copper, iron, zinc, cobalt, lead, silver, nickel, ammonium or organic ammonium.The alkali metals include sodium, potassium and lithium. The alkaline earth metals include calcium and magnesium Organic ammonium cations include, but are not limited to, onoalkyl onium, dialkyl ammonium, trialkylammonium, tetraalkyl ammonium, monoalkenylammonium, dialkyl ammonium, trialkenylammonium, monoalkylammonium, dialkylammonium, monoalkanolammonium, dialkanolammonium. C5-Cg cycloalkylammonium, piperidinium, morpholino, pyrrolidinium, benzylammonium and the like. The compounds of formula 1 of this invention can be prepared by reacting a 2-thiolthiazolo [4,5-b] pyridine compound having the structural formula 11, with an electrophile compound having the structural formula 111, and a base , in the presence of a solvent, as shown below in Reaction Scheme 1.

REACTION SCHEME I (X = Cl, Br or I) (II) Base (I) In addition, certain compounds of formula 1 can be converted to other compounds of formula 1, using conventional procedures known to those skilled in the art. The initial compounds of formula 11 are known in the art, and can be prepared by means of the procedures described by K. Smith et al., In Sulfur Letters, 18 (2), pages 79-95 (1995). To facilitate a better understanding of the invention, the following examples are presented to illustrate more specific details thereof. The invention should not be limited thereto, except as defined in the claims.

EXAMPLES 1 - 6 Prepe Preparation H 3-K4.4.3-Trifluoro-3-buteniIttio1-thiazolor4.5-blpiridirta ÍDJL • 1-0 A solution of thiazolo [4,5-b] pyridine-2-thiol (6.2 g, 0.037 mol) in N, Na? Methylformamide under nitrogen is treated with 1,1-trifluoro-4-bromobutane ( 8.3 g, 0.046 mol) and potassium carbonate (1.5 g), is heated and separated at 60 ° C for 24 hours, cooled, and poured into water. Mix The resulting aqueous is extracted with diethyl ether. The organic extract is dried over anhydrous sodium sulfate, and concentrated in vacuo, to obtain a residue. Column chromatography of the residue using silica gel and a 9: 1 hexanes / ethyl acetate solution gives the product as a colorless oil (8.9 g, 64% yield). C1QH7F3N2S2 Calculated: C, 43.47; H, 2.55; N, 10.14% Found: C, 43.46; H, 2, 58; N, 10.14% Using essentially the same procedure as described in example 1, the following compounds are obtained.

I EXAMPLE 7 Preparation of 2-r (Bromodifluoromethyl) thio 1 -thiazolor-4-b-pyridine A solution of thiazolo [4,5-b] pyridine-2-thiol (2.0 g, 12 mol) in N, N-dimethylformamide is added dropwise to a mixture of sodium hydride (0.96 g, 0.024 mol ) in N, N-dimethylformamide for 30 minutes. The resulting reaction mixture is treated with a solution of dibromodifluoromethane (2.52 g) in N, N-dimethylformamide, stirred at room temperature for -24 hours, and poured into an ice-water mixture. The resulting aqueous mixture is extracted with ethyl acetate. The organic extract is washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo, to obtain a residue. Chromatography of the residue using silica gel and dichloromethane, followed by azeotropic removal of N, N-dimethylformamide (to luene) achieves an oil. The oil is further purified by column chromatography using silica gel and a 20: 1 ethyl acetate / hexanes solution, to provide the title product as a clear yellow liquid (0.61 g, 17% yield).

EXAMPLE 8 Preparation of 2-difluoromethyl thio-1-thiazole-r4.5-b1-pyridine A solution of thiazolo [4,5-b] pyridine-2-thiol (2.0 g, 12 mmol) in dioxane is treated with a solution of sodium hydroxide (4.8 g, 120 mmol) in water, heat up to 70 ° C, treat with a firm stream of rometan chlorodifluous for 75 minutes, and pour over ice. The resulting aqueous mixture is acidified with concentrated hydrochloric acid and extracted with dichloromethane. The organic extract is dried over anhydrous sodium sulfate, and concentrated in vacuo, to obtain a residue. Column chromatography-of the residue using silica gel and various ethyl acetate / hexane solutions, gives the title product as a light yellow solid (0.86 g, 33% yield, mp 41-43 ° C). C7H4F2N2S2 Calculated: C, 38.52; H, 1.85; N, 12.84% Found: C, 38.58; H, 1.73; N, 12.72%.

EXAMPLE 9 Prepare Preparation of 2-r (2.2.2-Trifluoroethynthio-thiazolid4.5-b1-pyridine) A mixture of sodium hydride (suspension 60% in oil, 0.72 g, 0.03 mol) in N, N-dimethylformamide is cooled to 0 ° C, treated by dripping with a thiazolo solution [4,5 -b] pyridine-2-thiol (5.0 g, 30 mmol) in N, N-dimethylformamide, stirred for 30 minutes, treated with a solution of 2,2,2-trifluoroethyl p-toluenesulfonate (3.81 g, 15 mmol) in N, N-imethylformamide, is heated and stirred at 110 ° C for 6 hours, and poured into an ice / water mixture. The resulting aqueous mixture is extracted with diethyl ether. The organic extract is washed with water, dried over anhydrous sodium sulfate, and concentrated in vacuo, to obtain a residue. Column chromatography of the residue using an ethyl acetate / hexanes solution gives the title product as a light yellow liquid (2.91 g, 39% yield).

C8H5F3N2S2 Calculated: C, 38.39, H, 2.01; N, 11.19% Found: C, 38.58; H, 2.08; N, 10.94%.

EXAMPLE 10 Test of soil nematicide with nematode target of root knot, Meloidoavne incognita, in tomato in pot The evaluation compound is solubilized in acetone and diluted with water to the required evaluation concentration. Sooty soil of black soil is soaked in an approximately 7,61 cm (3 inch) pot, with a 3 week tomato transplant, with the evaluation solution. Four thousand larvae of root knot nematodes are dispensed, Meloidogyne incognita J2, in an aqueous suspension, on the ground. The pots are kept in the greenhouse, and 4 weeks after the inoculation of the pots, the roots of the plants are washed to release them from the soil, and they are classified to determine the degree of root excoriation, using the excoriation index root node that is identified below. Etoprofos were included in the test, as an industrial standard. The results are summarized in Table 1.

Root Knot Excoriation index. excoriation index Percentage of the total root system excoriated 0 1 10 2 20 3 30 4 40 5 50 6 60 7 70 8 80 9 90 10 100 TABLE 1 Evaluations of Soil Nematicides Index Compound (ppm) slag index Example 1 50, 1 25 0 10 0 Etoprofos 50 25 0 '10 or 0 Check 7 Phytotoxicity observed EXAMPLE 11 • Evaluation of evaluation compounds against C. elegans Cultures of C. elegans (Bristol strain of Lewis L.) were maintained in E. coli grass on NG agar plates at 20 ° C. New cultures are established weekly. The nematodes for evaluation are washed from the cultures, using Na buffer. The compounds are dissolved in 80% acetone. The evaluation material is poured by micropipette (25 J? I) into a single container of a 96-well sterile tissue culture plate, and the solvent is allowed to evaporate. A freshly prepared volume (50 jal) of C. elegans in Na buffer is added to each treated space, and to several control vessels per plate. The plates are incubated at 2520 ° C. Observations are made to determine the effectiveness under a dissection microscope, at 4 and 24 hours post-immersion. Immediately before reading the plates, they are tapped to stimulate the movement of the worms. The activity is judged subjectively, but in a semi-quantitative way, based on the effects of the drug on the motility of adults and larvae. The criteria are the following: 9 = complete death in 4 hours, 8 = complete death in 24 hours, 7 = markedly reduced motility in approximately 95% of the worms in 24 hours, and 0 = normal motility, same as controls. The results are summarized in Table 11.

TABLE-11 Evaluation of Evaluation Compounds against C. elegans Example C. elegans (300 ppm) 1 7 2 0 3 9 4 9 5 9 6 9 EXAMPLE 12 Evaluation Insecticide and acaricide of evaluation compounds Evaluation solutions were prepared by dissolving the evaluation compound in a mixture of 35% acetone in water, to give a concentration of 10,000 ppm. Subsequent dilutions are made with water, as necessary. Spóaoptera eridania, larvae of the 2nd. pupa caterpillar Southern fighter (SAW) A sheet of Sieva bean, expanded to 7 - 8 cm in length, is immersed in the evaluation solution, with agitation for 3 seconds, and left to be placed in a cap. The sheet is then placed on a 100 x 10 mm petri dish, which has a wet paper filter on the bottom, and ten holes on the 2nd. chrysalis. At 5 days observations are made of mortality, reduced feeding, or any interference with the normal moult.

Diabrotica virgifera virgifera Leconte, worm of the roots of the western corn of the 2nd. chrysalis (WCR) _ A thin talcum powder is placed in a large-mouthed, 30-ml wide-mouthed glass jar. One ml of the appropriate acetone evaluation solution is pipetted onto the talcum so as to provide 1.25 mg of active ingredient per jar. The jars are placed under a moderate airflow, until the acetone evaporates. The dried talc is released, 1 cc of millet seeds is added to serve as food for the insects, and 25 ml of moist soil is added to each jug. The jug is covered and the contents are completely mixed mechanically. After this, ten worms are added from the roots of the 2nd. pupa to each jug, and the jugs are covered in an unadjusted way, to allow the exchange of air for the larvae. The treatments are maintained for 5 days, when mortality counts are made. The larvae that were lost are presumed dead, since they decompose quickly and can not be found. The concentrations of active ingredient used in this test correspond to approximately 50 kg / ha.

Tetranychus urticae (OP resistant strain), expensive two-spotted spider (SST) Sieva bean plants with primary leaves expanded to 7 - 8 cm are selected, and are reduced to one plant per pot. A small piece of an infested leaf taken from the main colony is cut and placed on each leaf of the evaluation plants. This is done approximately 2 hours before the treatment, to allow the mites to move to the evaluation plant to lay eggs. The size of the cut infested leaf is varied to obtain approximately 100 mites per leaf. At the time of processing the test, the piece of leaf used to transfer the mites is removed and discarded. The newly infested plants are immersed in the evaluation solution for 3 seconds with agitation, and placed in the cap to dry. After 2 days, a sheet is removed and the mortality accounts are made.

Aphis gossypii, cotton aphid (CA). Cotton plants are selected in the cotyledon stage, and are reduced to one plant per pot. A heavily infested leaf is taken from the main colony and placed on each cotyledon. The -fans are allowed to transfer to the host plant overnight. In the momejí to the treatment of the test, the sheet used to transfer the mites is removed and discarded. The cotyledons are immersed in the evaluation solution and allowed to dry. After 5 days, death accounts are made.

Spodoptera eridania, southern egg fighter caterpillar and Diabrotica undecimpunctata howardi, southern corn egg worm (SA-Eggs) and (SCR-Eggs). Containers containing artificial diet, with evaluation solutions, are treated and dried . Then the insect eggs are placed - appropriate in the containers. The containers are covered with clear plastic caps, adhesive and with openings. After 7 days, mortality slips are made. The tests are classified according to the scale shown below, and the information obtained is shown in Table III. TABLE III Evaluations Insecticides v Acaricides indices in ppm EXAMPLE 13 Evaluation of ectoparasiticide of evaluation compounds in Lucilia serricata The evaluation compound is dissolved in acetone to a concentration of 100 ppm. 200 μl is added to three 12 mm filter paper discs in 128-well test trays, and allowed to dry. Approximately 20 larvae of the first chrysalis of moscon and 200 larvae of bovine serum are added to the discs. The containers are covered with plastic lids and incubated at approximately 27 ° C. Mortality is determined at 24 and 48 -hours. The results are summarized in Table IV.

TABLE IV Assessment of Evaluation Compounds against Lucilia serricata It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (5)

The invention having been described as above, the content of the following claims is claimed as property: 1. A method for the control of parasites or pests of helminths, nematodes, insects or mites, characterized in that it comprises putting said pests into account. or parasites or their food supply, habitat or breeding ground, with a pesticidal or parasiticidally effective amount of a compound having the structural formula 1 (I) wherein R is halogen, nitro, cyano, C, -C4-alkyl, C-C4-haloalkyl, C.-C4-alkoxy, C.-C- haloalkoxy, C.-C4-alkylthio, C.-C4 haloalkylthio or CO ^ R.; n is 0, 1, 2, or 3; Q is C3-Cg alkenyl, C3-Cg haloalkenyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl, C4-C7 cycloalkenyl, C4-C7 halocycloalkenyl, C- Cg alkyl optionally substituted with a C3-C7 cycloalkyl group, C3 halocycloalkyl -C7 or C0? R2, haloalkyl optionally substituted with a C3-C7 cycloalkyl group, C3-C7 halocycloalkyl or C02R2; and R.j and R2 are each independently hydrogen, alkyl C.-Cg, CH2 (haloalkyl C | -Cg), alkenyl Cg-C10 > haloalkenyl Co-C »a cation, -benzyl optionally substituted in the ring with any combination of -one to zinc halogen atoms, one or two cyano groups, one or two nitro groups, one to three C.-C4 alkyl groups, one to three haloalkyl groups C ..- C., one to three C 1 -C 4 alkoxy groups, or one to three C 1 -C 4 haloalkoxy groups, or phenyl optionally substituted with any combination of one to five halogen atoms, one or two groups cyano, one or two nitro groups, -one to three C 1 -C 4 alkyl groups, one to three C 1 -C 4 haloalkyl groups, one to three C 4 -C 4 alkoxy groups, or one to three C

1 -C 4 haloalkoxy groups, and the agricultural and / or pharmaceutically acceptable salts thereof. 2. The method according to claim 1, characterized in that the compound is selected from the group consisting of 2 - [(4,4,3-trifluoro-3-butenyl) thio] thiazolo [4,5 -b] -pyridine; 2 - [(Bromodifluoromethyl] thio] t azole [4,5-b] -pyridine; and 2 - [(difluoromethyl) thio] t azolo [4,5-b] -pyridine. 3.- A method for the protection of growing plants, against the attack or infestation of plagues of namatodos, insects or mites, terized face because it includes applying to the foliage of the plants, or to the soil or -water in which they grow, a pesticidally effective amount of a com-item that has the structural formula 1. (I) wherein n, R and Q are as described in claim 1. 4. The method according to claim 3, characterized in that the compound is selected from the group consisting of 2 - [(4, 4) 3-trifluoro-3-butenyl) thio] thiazolo [4,5-b] -pyridine; 2 - ['(Bromodifluoromethyl) thio] thiazolo [4,5-b] -pyridine; and 2 - [(difluoromethyl) thio] thiazolo [4,5-b] pyridine. 5 - A method for the treatment, control, prevention or protection of a warm-blooded animal or fish, against the infestation or infection of helminths, mites or endo- or ectoparasites arthropods, characterized in that it comprises administering orally, topical or parenteral, or apply to an animal or fish, an anthelminthically, acaricidally or endo-or ectoparasiticidally effective amount of a compound having the formula is -Structural 1. (I) wherein n, R and Q are as described in claim 1. 6.- A composition for the control of parasites or pests of helminths, nematodes, insects or mites, characterized in that it comprises an agronomically or pharmaceutically acceptable carrier and a pesticidal or parasiticidally effective amount of a compound having the structural formula 1, (I) wherein n, R and Q are as described in claim 1. 7. The composition according to claim 8, characterized in that the compound is selected from the group consisting of 2 - [(4,413-trifluoro-3- butenyl) thio] thiazoium [4,5-b] -pyridine; 5

2 - [(Bromodifiuoromethyl] thio] thiazolo [4,5-b] -pyridine; and 2 - [(difluoromethyl) thio] thiazolo [4,5-b] -pyridine. 8.- A compound that has the structural formula la. (the) characterized in that R is halogen, nitro, cyano, C-C4 alkyl, C-C4 haloalkyl, Cj-C4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio) C 1 -C 4 haloalkylthio or CO 2 R 1; NONE, 1, 2, or 3; Q is C

3-Cg haloalkenyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl, C

4-C6 cycloalkenyl, halocycloalkenyl substituted with a C3-C7 cycloalkyl group or C3-C7 halocycloalkyl, or C-halo haloalkyl optionally substituted with a group " C-C7 cycloalkyl, or C3-C7 halocycloalkyl, provided that Q is not CF ^ H, and R is hydrogen, C-alkyl, Cg, CH2 (C-Cg haloalkyl), C3-C10-alkenyl, C3-haloalkenyl -C, 0, a cation, benzyl optionally substituted on the ring with any combination of one to five halogen atoms, one or two cyano groups, one or two nitro groups, one to three C, -C4 alkyl groups, one to three haloalkyl groups C, -C4, one to three C.sub.1 -C.sub.4 alkoxy groups, or one to three C.sub.1 -C.sub.4 haloalkoxy groups, or phenyl optionally substituted with any combination of one to five halogen atoms, one or two cyano groups, one or two nitro groups, -one to three C alquilo-C4 alkyl groups, one to three haloalkyl groups C.-C4 one to three C alco-C4 alkoxy groups, or one to three groups C1-C4 haloalkoxy, and the aggricultural and / or pharmaceutically acceptable salts thereof. 9. The compound according to claim 8, selected from the group consisting of 2 - [(4,4,3-trifluoro-3-butenyl) thio] thiazolo [4,

5-b] -pyridine; - [(Bromodifluoromethyl) thio] thiazolo [4,5-b] -pyridine. 2 - [(Difluoromethyl) thio] thiazolo [4,5-b] pyridine.