BRPI0804559A2 - dimethylmercaptopyrimidylmethane-derived organostannic compound for fungicide formulation - Google Patents

Abstract

It is an organotin compound derived from the reaction between triphenyltin (IV) chloride and bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane of the formula [SnxClxPh3x (R1R2CH2R2R1) (1) {R1 = 4,6-dimethyl- 2-pyrimidyl, R2 = S (sulfur), x = 1, 2, 3, 4} with fungicidal property, usable as a single active ingredient in the formulation of new fungicide or as an ingredient in existing fungicidal formulations for plant disease control and of fungi in environment. Various organotins are known and employed as ingredients in fungicidal composition. However, problems such as fungal resistance, low MIC (Minimum Inhibitory Concentration) value and high active ingredient concentrations make disease control difficult. The present invention aims at the development of fungicidal compound for the control of plant diseases, and other toxicogenic and allergenic fungi. The preparation of organotin involves solid state synthesis technique as well as solution. The results of the fungitoxic test and mycelial growth clearly show activity of the present invention against all tested fungi.

Description

"DIMETHYLMERCAPTOPYRYMYLMETANE ORGANESTANIC COMPOSITE FOR DEFUNGICIDE FORMULATION"

The present invention relates to the preparation and decomposing coordination or organostannic fungicidal effect derived from the reaction between triphenyltin (IV) chloride with bis- (4,6-dimethyl-2-mercaptopyrimidyl) methanate against phytopathogenic, toxicogenic, allergenic and fungal fungi. others. The derivatized organostannic compound, object of the present patent application, has the general formula [SnxClxPh3x (R1R2CH2R2R1)] {R1 = 4,6-dimethyl-2-pyrimidyl, R2 = S (sulfur), x = 1,2,3,4}. The name of the organostannic varies according to the number of chlorotriphenyl tin groups in its formula. For x = 1 no prefix is used, but for x = 2 we use the prefix bis, for x = 3 we use the prefix tris and for x = 4 we use the prefix tetrakis. For x = 2 the name will be bis (4,6-dimethyl-2-mercaptopyrimidyl) methane-7,7'-bis- (chlorotriphenyl tin (IV)) or bis (4,6-dimethyl-2-mercaptopyrimidyl) -methane-3,3'-bis- (chlorotriphenyltin (IV)) or bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane-7,3'-bis- (chlorotriphenyltin (IV)) or bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane-3,7'-bis- (chlorotriphenyl tin (IV)) orbis- (4,6-dimethyl-2-pyrimidylthio) methane-7,7'-bis- (chlorotriphenyltin (IV)) or bis (4,6-dimethyl-2-pyrimidylthio) methane-3,3'-bis- (chlorotriphenyltin (IV)) or bis (4,6-dimethyl-2- pyrimidylthio) methane-7,3'-bis (chlorotriphenyl tin (IV)) or bis (4,6-dimethyl-2-pyrimidylthio) methane-3,7'-bis (chlorotriphenyl tin (IV)). This invention concerns the technical plant health sector of the Agronomy area and synthesis of coordination compounds of the Chemistry area.

State of the art

There are patents that use the metal precursor detriphenyl tin (IV), or other tin precursor in the preparation of materials with fungicidal, bactericidal, algicidal properties, among others.

USPTO 4158001 discloses the use of triorgananes (SnCIR3, R = butyl, phenyl, propyl) in the preparation of hydroxydiazene oxide and N-cyclohexylhydroxydiazene oxide derivatives which have a good fungicidal effect for preserving wood or for use as an emulsion preservative strips, leather, adhesive and paper. The disadvantage of this invention relates to the high concentration of the active ingredient. The present patent application differs from this patent with respect to the industrial application of the active ingredient as well as the chemical nature of the organic precursor, mercaptopyrimidine.

USPTO 3931262 and USPTO 3933877 report the obtaining of detriorgano-stannic salts derived from mercaptocarboxylic acid, 2-mercaptopropionic acid, mercaptoalcanosulfonic acid, among others, with biocidal activity as well as having hydrophilic properties. In these patents, this property lowers the volatile character of the material, which makes its commercial use possible. However, this reduces the application of this invention as a single active ingredient in solid mixtures (powder). Also in these patents, the hydrophilic character is due to a chemical bond of the triorganostannic radical to the mercaptan sulfur. The material, in these patents, has low toxicity and can be applied in the protection of plants against fungal pathogen. The disadvantage of these inventions relates to the high concentration of the active ingredient and the phytotoxic character of the active ingredient.

USPTO 6270810 discloses a fungicidal composition for control of plant phytopathogenic fungi. The principal active ingredient of fungicidal composition is the compound N-O-chloro-S-methyl-oxopentyl-S.6-dichloro-4-methylbenzamide or N-tSX-chloro-S-methyl-oxopentyl-S. 6-dibromo-cyano-benzamide or a mixture of both. The compound disclosed in USPTO 6270810 consists of, in addition to these, the addition of other organostannic fungicides such as phentine hydroxide (detriphenyl tin oxide) and phentine acetate (triphenyl tin acetate), fungicides containing copper (1) and copper (11) salts as well as as component organic fungicides. In this patent, it is evident that to improve compounding effectiveness, addition of existing compounds is required. This invention has the disadvantage of containing a phytotoxic ingredient in its formulation, as well as the fact that the application of the active ingredient in the field establishes high concentration.

USPTO 4115094 discloses the tetravalent herbicidal and pesticidal effect of tetravalent containing three tin-carbonyl bonds of butyl, phenyl as well as sucrose derivatives. The invention can also be used to combat the growth of aquatic plants, paint fixative. Some stable saccharose-derived organotin compounds may be applied in spray, powder, or liquid formulations because when exposed to sunlight or added to the soil, the compounds decompose to a stable inorganic compound, do not produce long-exposure environmental pollution and, in addition, exhibit biological activity at a concentration of 1 ppm analogously to other biocidesorgano-tannins such as tributyltin (IV) oxide. However, this invention has the disadvantage of containing a phytotoxic ingredient in its formulation as well as the fact that the application of the active ingredient in the field establishes a high concentration.

USPTO 4578489 discloses novel organotin deamonium compounds with high biocidal activity, wherein the active compounds contain tributyl, triphenyl radicals attached to the metal center. The preferred active compound is dimethyl benzyl-n-tetradecylammonium tri-n-butyldichloroestanate (IV) or dimethylbenzyl-n-tetradecylammonium tri-n-butyldifluorostanate (IV) has the pententate coordinated metal center. These, among other compounds described in this patent, are water soluble, having a broad spectrum of action as fungicides, acaricides, herbicides and algaecides, and have an industrial application in the protection of wood, paper, leather, paints, rubber, etc. . The advantage of this invention relates to the high concentration of the active ingredient and the high value of the MIC (Minimum Inhibitory Concentration).

USPTO 5,436,267 reports the use of N-phenyl carbamate or its salt as an active ingredient in biocidal composition for pest control in agriculture. Active carbamate may have various substituents such as alkylthio or alkylsulfonyl groups, and others such as benzimidazole, benzothiazolyl, benzimidazolyl, imidazopyridyl, dihydrobenzofuryl, thiazolyl, pyrimidyl, pyrazinyl, benzothiazinyl, among others. The material resulting from this invention may be used in combination with other commercially available fungicides such as triphenyltin hydroxide and triphenyltin acetate. Carbamate, the organic material object of this invention, and its derivatives can be used as active ingredients in agriculture and horticulture against plant diseases. The disadvantage of this invention relates to the high concentration of active ingredient, besides presenting phytotoxic property.

USPTO 4678804 reports the fungicidal and insecticidal effect of benzylthiostannans. The compounds contain radicals such as tributyl, tricyclohexyl and triphenyl attached to the tin (IV) atom. For example, the compounds R'benzylthio triphenylstannane where R '= 2,5-dimethyl-, 2,6-dichlorobenzylthio-, 4-ethyl-, 2-trifluoromethyl-, 3-trifluoromethyl-, 4-trifluoromethyl-, 3-nitro -3,5-dinitro-, 2-chloro-, 2,4,6-trichloro-, 2-bromo-, 4-bromo-, 2-fluoro-, 4-fluoro-, 4-tert-butyl-, 2 -methyl-, 2,4,6-trimethyl-. The invention of this patent is directed to its fungicidal potential in protecting plants against a variety of fungi. The disadvantage of this invention relates to the fact that the active principle does not have a broad spectrum of action as well as the high concentration of active ingredient in the composition of the fungicide.

USPTO 4654368 reports the activity of silatran-derived triorganostannins in pesticidal, fungicidal, insecticidal compositions as well as a protective agent against marine organisms. The active compounds contain sulfur, silicon organometallic and organotin. These latter are derived from various precursors such as trimethyl tin (IV), triethyl tin (IV), tri-n-propyl tin (IV), tri-n-butyl tin (IV), tricycline (IV), tricyclohexyl tin or bromide. (IV) ethenyl tin (IV). The disadvantage of this invention relates to the use of phytotoxic active ingredient, which reduces the application of this material as a good fungicide.

USPTO 4581373 discloses biologically active organostannic derivatives in emulsifying concentrates as well as methods for controlling plant infestations. Organic compounds associated with organotin are lipophilic acids whose derived salts contain sulfur or phosphorus in their chemical composition. Among the organotin radicals are triphenyl tin (IV) and tricyclohexyl tin (IV). The acids also contain carbon chains of 6 to 18 carbon atoms. The compound is derived from the mixture of other fungicides such as deticrylhexyl tin (IV) hydroxide or triphenyltin (IV) hydroxide with lipophilic acids. The concentration of the active ingredient in the emulsifiable concentrate depends on the solvent used, but generally the material is used in sufficient dilute aqueous solution. The disadvantage of this invention relates to the high concentration of the active ingredient, besides presenting phytotoxic property.

USPTO 4514225 discloses the preparation and use of an acetylsalicylate-derived compostotriorganate for the control of microorganisms such as bacteria, algae, marine organisms, as well as wood preservation. Metal precursors of general formula SnCIR3 (R = butyl, phenyl, alkyl and cyclohexyl) were used in the preparation of the compounds. The compounds may be applied in solution, emulsion, water dispersion or through organic solvents. The compounds described herein may be applied in combination with other compounds with biocidal activity. The disadvantage of this invention relates to the high concentration of the active ingredient, besides having an active ingredient derived from a phytotoxic precursor, which reduces the application of this material as a good fungicide.

USPTO 4221811 discloses the fungicidal, bactericidal and fungal and bacterial control process of triorganoic bacteria containing substituent groups such as phenyl-, butyl-, methylbutyl-, methylphenyl-linked to the metal center with up to two metal centers where the fourth group is linked to the metal center. It consists of -OH, -CN, dimethylaminopropylamine (-NH (CH2) 3-NMe2) or the corresponding hydrochloride (-NH (CH2) 3-NMe2.2HCl) groups. The compounds showed activity against fungi, gram-positive and gram-negative bacteria. In this patent it is shown that the solubility of the active compound in water strongly promotes its fungicidal and bactericidal activity. The use of organic solvents in the application of active products has some disadvantages, such as being volatile, flammable and toxic. The present invention has the disadvantage of having a high MIC (Minimum Inhibitory Concentration). The present patent application is distinguished from this patent by the low value of the MIC as well as by the use of the different organic precursor, 4,6-dimethyl-2-mercaptopyrimidine.

Other tin-free compounds, but containing in their chemical composition sulfur and nitrogen atoms, are also fungicidal as described in USPTO 7067668. This invention reports the fungicidal potential of 4-quinolinol derivatives in agriculture and horticulture. Active compounds showed activity against plant pathogenic fungi such as rice (blast), beans (brown spot) and potatoes (anthracnose).

However, this invention has the disadvantage of using high concentration of active ingredient.

USPTO 6270810, USPTO 6267991, USPTO 6264993, USPTO 6075047, USPTO 6060490, USPTO 6057356, USPTO 6004947 report the application of fungicidal composition containing one or more principles, for example, antifungal N-acetonylbenzamide (s) added to other antifungal (s). that act as a breath inhibitor like ziram and fluazinam. N-acetonylbenzamide may also be added to a tin-based fungitoxic metabolite, for example, fentin (triphenyl tin hydroxide or detriphenyl tin acetate). The disadvantage of these inventions relates to the phytotoxic character of the active ingredient.

USPTO 4554367 discloses the application of phosphonium halogenene stannates (IV) as biocidal agents as well as for the preservation of materials and protection of various crops in agriculture.

The phosphonate stannate (IV) complexes stand out for their high water solubility, low volatility and biocidal activity. The main application of this invention relates to the use of this material as a protective paint. This invention has the disadvantage of having a high MIC (Minimum Inhibitory Concentration) value.

USPTO 4474760 reports compound mixing activity containing a combination of 2-mercaptopyridine-1-oxo or derivative (triphenyltin-2-mercaptopyridine-1-oxo), an organophosphate, for example diphenylisodecylphosph among others, and a benzotriazole, e.g. for example 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole. The various antimicrobial combinations are stabilizers of polymeric systems and can be used for protection of adhesives, film sheets and any polymeric system based on materials such as polyvinyl chloride, vinyl acetate devinyl chloride copolymer, acrylonitrile butadiene stirene (ABS), polyurethane among others. However, this invention has the disadvantage of using a high concentration of active ingredient, as well as having a limited fungicidal result under the spectrum of action, in addition to the active ingredient decomposing by heat action.

Several of the patents mentioned below report the use of organic compounds with biocidal activity. These compounds are mixed with known tin or other metal fungicides to form a formulation. The final composition of the mixture may contain one or more distinct metal active ingredients. Some examples are mancozeb, brestan, benomyl and fentin (triphenyltin hydroxide and triphenyltin acetate). Moreover, the chemical nature of the organic material is completely different from that disclosed in the present invention, the subject of patent application.

Other patents involving tin compounds relate to another type of application of these materials and again have the different chemical nature of the present invention with respect to the organic precursor:

USPTO 7316738, USPTO 7194964, USPTO 7070795, USPTO 6811703, USPTO 6624179, USPTO 6399542, USPTO 6303078, USPTO6291399, USPTO 5952496, USPTO 5939357, USPTO 5910496, USPTO 5493627, 5 USPTO , USPTO 5157028, USPTO5134152, USPTO 5131947, USPTO 5118346, USPTO H811, USPTO4923866, USPTO 4766113, USPTO 4710220, USPTO 4666767, USPTO4639393, USPTO 4602011, USPTO 42354, USPTO 430204 USPTO 4141989, USPTO 4107323, USPTO 4094845, USPTO 4051255, USPTO 3984568, USPTO 3979518, USPTO 4125624, USPTO3957847, USPTO 3954992, USPTO 3932448, USPTO 5468715, USPTO4482759, presently filed, co-ordinated object. of the reaction between triphenyltin (IV) chloride and bis (4,6-dimethyl-2-mercaptopyrimidyl) methane. The analysis of the above patents clearly reveals that the compound, which is the subject of this patent application, is completely different in both chemical nature and chemical formula. For example, the organic precursor 2,5-dimethylbenzothiol differs from bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane in that it does not contain nitrogen in its chemical composition besides the fact that the latter has two groups 4,6-dimethyl-2- pyrimidyl and a CH2 group between sulfur atoms. The organostannic compound derived from the reaction with 2,5-dimethylbenzothiol will therefore have a distinct compound structure and chemical formula, which is the subject of the present application.

The present compound, which is the subject of the patent application, is also totally different in structure and chemical composition of known and marketed fungicides, such as triphenyltin (IV) hydroxide and detriphenyltin acetate (IV), as well as all those cited in database patents. national and international data. For example, as noted above, the compound derived from the reaction between triphenyltin chloride and 2,5-dimethylbenzothiol (UPSTO 4678804) will have no chemical bond between the tin atom and the nitrogen atom, which necessarily implies a completely chemical compound. distinct from the object compound of the present patent application.

Combating phytopathogenic fungi in plants is a worldwide problem that greatly determines human survival and social development. Several patents describe the preparation of organostannic derivatives for combating plant diseases as ingredients in fungicidal, insecticidal and bactericidal composition. However, several problems such as fungal resistance, high MIC (Minimum Inhibitory Concentration) value, high active ingredient concentrations stimulate the development of new fungicides for plant disease control. The present invention has for objective the development of a new effective fungicidal compound in the control of plant diseases, and other toxicogenic and allergenic fungi, with low toxicity, low MIC value and low concentration of active ingredient, with broad spectrum of action.

The precursor organic material, bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis- (4,6-dimethyl-2-pyrimidylthio) methane, has no fungicidal or fungistatic activity. With the introduction of the metal precursor, detriphenyl tin (IV) chloride, as part of the chemical composition of bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane, the biological activity of the new patent-pending compound was verified to Various fungi. The solubility of composites in solvents of varying chemical classification enables its application as a powder, spray, solution or emulsion in the agricultural sector during the postharvest cultivation and storage of fruits and seeds.

The compound, subject of the present patent application, differs from patentsUSPTO 4581373, USPTO 4514225, USPTO 42221811, USPTO 6270810, USPTO 4115094, USPTO 5436267, USPTO 4654368 as it may be applied as the sole active ingredient and still has the advantage of use. doses, with higher efficiency and lower environmental risk. The compound under patent application does not exhibit phytotoxicity such as triphenyltin (IV) fungicide hydroxide and triphenyltin (IV) acetate with respect to its concentration in formulations. In addition, the compound and derivative, subject to patent application, decompose to non-toxic light-action residues and are effective even in acid medium and can be applied in soils of varying acidity for various crops of agricultural products. Therefore, the compound, object of patent application, is a novelty both from the point of view of Chemistry and the biological efficacy for combating pathogenic fungi. The compost can be used in the cultivation of fruits such as fan, papaya and grains such as wheat, as well as in their storage. The compound can also be used to formulate fungicide, insecticide, herbicide, acaricide, pesticide or bactericide as well as a single active ingredient or in admixture with existing active ingredients to improve its effectiveness.

The formulations may be solid, liquid or gaseous using inert vehicles such as talc or water to combat pathogenic organisms and others of animal or plant origin. The present invention, object of the present patent application, is effective in the control of plant diseases and other allergic and fungostoxicogenic presenting advantages over those suppressed. For example, low toxicity, low MIC value, low concentration of active ingredient, broad spectrum of action, and less aggressive to the environment due to decomposition of the active compound in soil will lead to the formation of non-toxic byproducts.

Description of the invention

The present invention, which is the subject of a patent application, deals with a fungicidal organostannic compound against phytopathogenic, toxicogenic and allergenic fungi of plants, fruits and seeds for nocturnal application of agricultural products and post-harvest. The preparation of the precursor organic material of the present invention, bis (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis (4,6-dimethyl-2-pyrimidylthio) methane, followed the procedure described in Art 1. Preparation The organostannic material of this invention involves two techniques: Technique 2 and Technique 3.

Detailed Description of the Invention

Technique 1:

In a suitable container, preferably a round bottom flask, 15 to 100 mL of ethanol was placed, and then 1.7 to 100 mmol of 4,6-dimethyl-2-mercaptopyrimidine and 1.5 to 251.6 mmol of ethanol were added. KOH After solids dissolution, 1.3 to 102.3 mmol of dibromomethane was added. The mixture was kept under stirring and reflux for 0.5 to 5.5 hours. The resulting orange-colored solution was then poured into a ground-frozen Becker which was kept in a refrigerator for 4 to 24 hours. After this period a white precipitate separated in the aqueous medium, bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane. The precipitate was filtered and washed with 100 to 1000mL of ice water and then 50 to 150mL of n-hexane. The resulting composter is soluble in usual organic solvents such as dichloromethane, methanol, ethanol, acetonitrile and acetone.Technique 2:

In a suitable container, preferably a previously treated Schlenckdesaer tube kept under an inert atmosphere of nitrogen or argon, 1.05 to 52.3 mmol triphenyltin (IV) chloride, dissolved in a sufficient amount of dichloromethane, was added. use any other chlorinated solvent. To this solution was added 0.2 to 11.6 mmol of bis- (4,6-dimethyl-2-mercaptopyrimidyl) methane, object synthesized in Technique 1. The mixture may be allowed to stir under an inert atmosphere of 1.5 ° C. 3.5 hours. Then the volume was reduced under vacuum to give a light yellow material. The resulting material is air washed with n-hexane and stored in a dry environment under vacuum.

The compound can also be obtained by leaving the mixture to slowly evaporate the solvent in air, so that by reducing the solvent metadata on the first precipitation, the light yellow material is filtered, air washed with n-hexane and stored under vacuum. The patented chemical compound is partially soluble in hydrocarbons but soluble in chlorinated solvents such as chloroform, ethers, sulfoxides, amides, nitriles, alcohols, ketones and in a water / alcohol mixture.

Technique 3:

The compound subject to patent application can also be prepared in solid state under the same conditions as described in Art 2. In a Schlenck tube, 1.01 to 50.3 mmol triphenyltin (IV) chloride and 0.2 to Bis (4,6-dimethyl-2-mercaptopyrimidyl) methane 11.6 mmol. The mixture is heated to 40 to 100 degrees Celsius, maintaining the system in a nitrogen or argon atmosphere for a period of 1.5 to 3.5 hours. After this period, the tube was cooled and the solid material was removed and stored in a dry environment under vacuum. The same solubility properties were observed for the compound prepared via Technique 2, that is, partially soluble in hydrocarbons, but soluble in chlorinated solvents such as chloroform, ethers, sulfoxides, amides, nitriles, alcohols, ketones and in the water / alcohol mixture. The invention involved various analytical and spectroscopic methods which confirmed the chemical binding of tin to solid carbon, nitrogen and chlorine atoms, establishing the pentavalence of the tin atom. In solution, a single 119Sn NMR signal was observed within a range commonly attributed to pentavalent tin as tetravalent. In this context, the present invention solution may have all pentavalent tin atoms, all tetravalent tin atoms or in the pentavalent / tetravalent ratio of 1: 1, 1: 2, 1: 3 and 2: 2 or in the quadrivalent / pentavalent ratio of 1: 2 and 1: 3.

Demonstration Experiment:

The compound synthesized by Technique 2 and / or 3 was tested to determine its fungicidal activity through spore germination and mycelial growth in vitro experiments using 12 different physiologically fungi, representing phytopathogenic fungi, allergenic and toxicogenic. Compound stock solution was prepared in methanol.

Experiment 1

For plant disease caused by a fungus to occur, it is necessary that the conidia / spores of this phytopathogenic fungus germinate. If these spores do not germinate for any cause, no disease will occur, and thus no harm to the farmer.

This experiment was performed to demonstrate the fungicidal effect on fungus spores / conidia using the standard "food poisoning" technique. The stock solution of the compound under patent application was added to the sterile czepeck-Dox agar culture medium to obtain the final concentrations of 0.1 to 6 ppm. The culture medium without the compound serves as a witness. The test use spores / spores were spread on the surface of the culture medium on each plate. After 48h of incubation the number of conidia / spores germinated at each concentration of the new compound was compared and the germination in the culture medium without compost. The fungicidal effect was determined by calculating the percentage of deconides / spores killed relative to the control.

Results: The results of deadly effect on spores / conidia of this fungicidal compound subject to patent application are presented in TABLE 1. It is evident that the compound was spore / conidial fungotoxic of all species tested at dosages ranging from 0.1 to 6 ppm, depending on the fungus. The compound had different deadly effect in different fungi, and the compound was more toxic to P. grisea causing rice and wheat debrusone, causing mortality of 100% conidia nadose of 0.2 ppm, and still in the dose of 0.1. ppm, there was a 97% mortality rate. The compound had an effect on mortality of 100% deconidia / spores of fungi Al. Solani, causer of ebatata tomato black spot, Al. Brassicicola, causing cabbage blight, cauliflower, broccoli and related plants, C. gloeosporíoides, causer of anthracnose of various species of economically important plants and postharvest fruit and vegetable rot, C. musae, cause of banana anthracnose and postharvest banana rot, B. sorokiniana, cause of detritus, barley, rice at a dose of 2 to 3ppm. For the toxicogenic and fungal fungi such as A. ochraceus, A. glaucus and A. flavus, the compound caused 100% conidia / spore mortality at up to 1 ppm. For root and fruit rot fungi, F semitectum eF. graminearum, the compound caused 100% mortality at a concentration of 6 ppm. These results show that the new compound, subject to pending application, is a compound with broad spectrum fungicidal property.

TABLE 1: Mortality of phytopathogenic, toxicogenic and allergenic fungi conidia / spores caused by the compound subject to the depatent application at different doses / concentrations.

<table> table see original document page 14 </column> </row> <table> <table> table see original document page 15 </column> </row> <table>

* Not tested. Average of three repetitions.

Experiment 2

For plant disease caused by a fungus to occur, it is necessary that the conidia / spores of this phytopathogenic fungus germinate and there is mycelium growth that will invade plant tissues. This experiment was made to demonstrate fungitoxic effect that prevents the growth of fungi. The standard "poisonous food" technique was used. The stock solution of the compound under patent application was added to the sterile czepeck-Dox agar culture medium to obtain final concentrations of 0.1 to 6 ppm. The culture medium without the compound served as a control. The medium was seeded in the center on each plate with a 5 mm disc of dormant fungus culture. The cultures were incubated until the growth of the test fungus reached the edges of the plates. The diameter of the fungal colony on the plate containing the compound was then measured. The fungicidal effect was determined by calculating the percentage inhibition of fungal growth relative to the control.

Results: The results of the effect of this new fungicidal compound, subject to patent application, are presented in TABLE 2. It is evident that the compound was fungitoxic for all species tested at a variable dosage of 0.1 to 6 ppm, depending on the fungus. The new compound at the dose of 0.2, completely inhibited the growth of P. grisea, causing rice and wheat blast, and at the 0.1 ppm dose there was 97% inhibition. Al. Solani, causer of tomato and potato black spot, Al. Brassicicola, cause of cabbage, cauliflower, broccoli and related plants, C. gloeosporíoides, anthracnose of various economically important plant species and fruit rot. Postharvest vegetables, C. musae, causing anthracnose and postharvest rot of banana, B. sorokiniana, causing wheat cob, late barley and rice blight were completely inhibited at 2 to 3ppm. The growth of fungostoxicogens such as A. ochraceus and A. glaucus was completely inhibited by up to 1 ppm. For root rot fungi, fruit fruits, F semitectum and F. graminearum, the compost caused 100% inhibition at 6 ppm. These results show that the new compound, the subject of patent application, is a broad spectrum fungicidal property compound.

TABLE 2: Inhibition of mycelial growth of phytopathogenic, toxicogenic and allergenic fungi caused by the compound subjected to the pending application at different doses / concentrations.

Mycelial Growth Inhibition Percentage / Concentration (µg.mL "1)

<table> table see original document page 16 </column> </row> <table> <table> table see original document page 17 </column> </row> <table>

Experimental results clearly demonstrate the fungicidal effect of the present invention, which may be used to formulate novel fungicide by mixing it with solid inert carrier, for example, but not limited to talc, kaolin, bentonite, or other clays; mixing it with a liquid inert carrier, for example, but not limited to organic solvents, oils of vegetable, animal or mineral origin. Depending on the purpose of the new compound, which is the subject of a patent application, an adhesive spreader may be added according to the availability of inert material and the state of the art available for plant disease control and its products. Similarly the same can be done for eliminating fungostoxycogenic and allergenic drugs at very low dosages. The compound and its derivatives, which are the subject of a patent application, can be mixed with existing principles to improve their effectiveness.

The new compound, subject to patent application, has the advantage of being less aggressive to the environment because its decomposition in the soil leads to the formation of non-toxic by-products.

Claims (9)

1. "DEDIMETHYLMERCAPTOPYRIMYLMETHANE DERIVATED ORGANESTATIC COMPOUND FOR DEFUNGICIDE FORMULATION" characterized by the general formula [SnxClxPh3x (R1R2CH2R2R1)] {R1 = -4,6-dimethyl-2-pyrimidyl, R2 = S (1, sulfur), x = S (sulfur) 4} derived from the reaction triphenyltin (IV) trichloride and bis (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis (4,6-dimethyl-2-pyrimidylthio) methane; 2. "DIMETHYLMERCAPTOPYRAMYDYLMETANE-DERIVED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to Claim 1, characterized in that it comprises two pentacoordinated or pentavalent tin atoms where each tin atom is bonded to three phenyl chloro radicals and one of the fine phenyl radicals. to a nitrogen atom of the bis (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis (4,6-dimethyl-2-pyrimidylthio) methane 4,6-dimethyl-2-pyrimidyl fragment; 3. "DIMETHYLMERCAPTOPYRIMIDYLMETANE-DERIVATED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to Claim 1, characterized in that it comprises two pentacoordinated or pentavalent tin atoms which in solution may exhibit partial absence of the tin (IV) -chloro bond. tetracoordinate metallic center; 4. "DIMETHYLMERCAPTOPYRAMYDYLMETANE-DERIVATED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to claim 1, comprising four pentacoordinated or pentavalent tin atoms where each tin atom is bonded to three phenyl chloro radicals and one well as phenyl clo radicals. to a nitrogen atom of the bis (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis (4,6-dimethyl-2-pyrimidylthio) methane 4,6-dimethyl-2-pyrimidyl fragment; 5. "DIMETHYLMERCAPTOPYRAMYDYLMETANE-DERIVATED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to claim 1, comprising four pentacoordinated or pentavalent tin atoms which in solution may exhibit partial absence of the tin-center (IV) -chloro bond tetracoordinate metal; 6. "DIMETHYLMERCAPTOPYRAMYDYLMETANE-DERIVATED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to claim 1, comprising three pentacoordinated or pentavalent tin atoms where each tin atom is bonded to three phenyl chloro radicals and one well as phenyl clea radicals. to a nitrogen atom of the bis (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis (4,6-dimethyl-2-pyrimidylthio) methane 4,6-dimethyl-2-pyrimidyl fragment; 7. "DIMETHYLMERCAPTOPYRIMIDYLMETANE-DERIVED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to claim 1, comprising three pentacoordinated or pentavalent tin atoms which in solution may have partial absence of the tin-center (IV) -chloro bond tetracoordinate metal; 8. "DIMETHYLMERCAPTOPYRIMIDYLMETANE-DERIVED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to Claim 1, comprising a pentacoordinated or pentavalent tin atom which is bonded to three phenyl radicals and one chlorine atom as well as one chlorine atom. nitrogen from the bis (4,6-dimethyl-2-mercaptopyrimidyl) methane or bis (4,6-dimethyl-2-pyrimidylthio) methane 4,6-dimethyl-2-pyrimidyl fragment; 9. "DIMETHYLMERCAPTOPYRIMIDYLMETANE-DERIVED ORGANESTATIC COMPOUND FOR DEFUNGICID FORMULATION" according to claim 1, comprising a pentacoordinated or pentavalent tin atom in solution which may present partial absence of the tin (IV) -chloride bond tetracoordinate metallic.