MXPA94002475A - Fungicides for the control of diseases of total rough in the plan - Google Patents

Abstract

The present invention relates to a method for the control of the disease of total rooting in plants, particularly in cereals, by the use of certain substituted aryl compounds, novel compounds to be used in the method, and fungicidal compositions to be put into practice the method

Description

"FUNGICIDES FOR THE CONTROL OF DISEASES OF ARRATOO TOTAL IN THE PLANTS" Inventor (s): DENNIS PAUL PHILLIQN, MATTHEW JAMES GRANETO, JOHN KENNEDY PRATT and SAI CHI WONG, Chemicals, North American domiciled at: 1626 Watson, S. Charles, Missouri 63301; 1510 Voltaire Drive, St. Louis, Missouri 63146: 6210 61st Avenue, Kenosha, Wisconsin 53142 and 14043 Forest Crest Drive, Chesterfield, Missouri 63017, respectively E.U.A.

Causaire: MONSANTO COMPANY, a North American company, organized and existing in accordance with the laws of the State of Delaware, E.U.A, domiciled at: 600 North Lindbergh Boulevard, St. Louis, Missouri 63167, E.U.A.

SUMMARY A method to control the total root disease in the plants, preferably applying to a seed before planting, a fungicide of the formula: a) e) alkyl A is -C (X) -amine; B is -Wm-Q (Rs? 3 and A can <= B when B is A, except when the formula is f), Q can not be Yes; Q is C or Si; W is -NH-, ~ NCH3_ ~ or -0-; X is 0 or S; m is 0 or 1, provided that it is 0 when Q is Si; n is, 1, 2 or 3; p is 0, 1 or 2; and n plus p is equal to or less than 3.

FIELD OF THE INVENTION / This invention relates to a method for the control of the disease of total rooting in plants, particularly in cereals, by the use of certain substituted aryl compounds, novel compounds to be used in the method, and fungicidal compositions to be put into practice the method. V BACKGROUND OF THE INVENTION The disease of total rooting is a serious problem in the production of cereals, particularly wheat and barley. It is caused by the soil fungus Gaeumannomyces graminis (Cg). The fungus infects the roots of the plant and develops throughout the rooted, causing a black rot. The development of the fungus in the roots and in the lower stem prevents the plant from getting enough water and / or nutrients from the soil, and manifests itself as little vigor in the plant and, in cases of severe disease, by the formation of "heads" "white", which are devoid of or contain few wrinkled or shriveled grains. This results in yield losses. The species Gaeu annomyces also infects other cereal crops, for example rice and oats, as well as turf. Currently, the primary means to avoid crop loss due to infestation of the land by Gg, has been to rotate the developed planting to one that is resistant to Gg. However, in areas where primary crops are cereals, rotation is not a convenient practice, and an effective control agent is greatly desired. A chemical means for controlling Gg, and compounds useful for controlling Gg, are described in the co-pending US patent application serial number 07 / 951,997, filed October 2, 1997 (Phillion and co-inventors), which is incorporated here as a reference It is an object of this invention to provide an effective method to control the disease of total plant rooting. It is another object of this invention to provide compounds that control the development of Gg in the soil, so as to reduce crop loss. It is also another or object of this invention to provide fungicidal compositions that can be used to control the disease of total rooting. A process for preparing the compounds of this invention is analogous to the process described in the US application No. 41-21 (3227) A, concurrently filed with the present.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a method for controlling the disease caused by the species Gaeumannomyces, in plants, which comprises applying to its seed a soil, a fungicidally effective amount of a fungicide of the formula: b) Rn ^ kRp and) alkyl A is -C (X) -amin < =. ? 8 is -Wm ~ Q (Rs) 3; and A can be B when B is A, except when the formula is f), Q can not be Yes; Q is C or Si; W is -NH-, -NCHa-- or -0-; X is O or S; m is O or i, provided it is 0 when Q is Si; n is 0, i, 2 or 3; p is, 1 or 2; and n plus p is equal to or less than 3. each R is independently selected from: a) halogen, formyl, cyano, amino, nitro, thiacyanate, isothiocyanate, tri et i Isi li lo and hydroxy; b) alkyl of 1 to 4 carbon atoms, alkenyl, alkynyl, cycloalkyl of 3 to 6 carbon atoms and cycloalkenyl, each of them optionally substituted with halogen, hydraxy, thio, amino, nitro, cyano, formyl, phenyl, alkoxy from 1 to 4 carbon atoms, alkylcarbonyl, alkylthia, alkylamino, dialkylamino, alkocarbonyl, (alkylthio) carbonyla, alkylaminocarbonyl, dialkylaminecarbanyla, alkylsulfinyl, alkylsulfonyl; c) phenyl, furyl, thienyl, pyrrolyl, each optionally substituted by halogen, farmila, cyano, amino, nitro, alkyla of 1 to 4 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, dialkylamino, haloalkyl and haloalkenyl; d) alkoxy of 1 to 4 carbon atoms, alkenoxy, alkyloxy, cycloalkyloxy of 3 carbon atoms, cycloalkylene loxi, alkylthio, alkylsulinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonylamino, aminocarbonyl, alkylaminocarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, (alkylthio) carbonyl, phenylcarbonyl, phenylamino, each optionally substituted by halogen; every R? it is independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cyclaalkenyl and phenyl, each substituted with R ^ or halogen; and wherein, when _ is C, Ra can also be selected from halogen, alkoxy, alkylthio, alkylamino and dialkylamino; where you give groups R_ > they can be combined to form a cycle group with Q; R? + Is alkyl of 1 to 4 carbon atoms, haloalkyl, alkoxy, alkylthia, alkyla ine or dialkyl sheet; to an agricultural salt of it. The term "amine" in -C (X) -amine means an unsubstituted, monosubstituted or disubstituted amine radical that includes nitrogen containing heterocycles. Examples of substituents for the amino radical include, but are not limited to: hydraxy, alkyl, alkenyl, and alkynyl, which may be straight or branched chain or cyclic, alkoxyalkyl, haloalkyl, hydroxyalkyl, alkylthio, alkylalkyl, alkylaryl, Icarboni, alkoxycarbanyl, aminocarbonyl, alkylaminocarbonone, cyanoalkyl, mono- or dialkylamino, phenyl, phenylalkyl or phenylalkenyl, each optionally substituted with one or more alkyl groups of 1 to 6 carbon atoms, alkoxy, haloalkyl, cycloalkyl 3 to 6 carbon atoms, halogen or nitro; alkyl or alkenyl groups of 1 to 4 carbon atoms, substituted with heterocycles, optionally substituted by one or more alkyl groups of 1 to 4 carbon atoms, alkoxy, haloalkyl, halogen or nitro. The exemplary of said nitrogen-containing heterocycles, which are attached in a nitrogen to -C (X) -, include, but are not limited to: morpholine, piperazine, piperidine, paral, pyrrolidine, imidazole and triazoles, each of which it can be substituted apcionalmente with one or more alkyl groups of ia 6 carbon atoms. Specific examples of the amino radicals useful in the present invention include, but are not limited to, ethylamino, methylamino, propylamino, 2-methylethyl-amino, 1-propenylamino, 2-propenylamino, 2-methyl-2-propenylamino, -propylamino, butylamino, 1, id i and il-2-propynyla ina, diethylamino, dimethylamino, N- (methyl) and ylamino, N- (ethyl) -l, 1- (dimethyl) ethylamino, d iprop i lamino, act i lamino, N- (ethyl) -l-methylethylamino, 2-hydroxyethylamino, 1-ethylpropylamino, chloro and ila ina, 2-chlorosti 1-amino, 2-bro-o-ylamino, 3-chloropropylamine, 2,2, 2-trifluoroethylamino, cynomethyl, r.et i Ityomethylamino, (methylsulfonyl) axyethylamino, 2-ethoxyethylamine, 2-methoxyethylamino, N- (et yl) -2-ethoxyethyl amine, i-methoxy-2,2-dimethylpropylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylane, ethoxy-ethylamino, N- (methoxymethyl) and lamino, N- (1-methylethyl) propylamino, 1-met Iheptylamino, N- (ei 15 -1-methyloheptyl-lamino, 6,6-dime-il-2-hepten-4-inylamino, 1, i-dime and 1-2-propynylamino) Other examples include : benzylamino, ethylbenzylamino, 3-methoxybenzylamino, 3- (triflutaryl) benzylamino, N-rns i 1-3- (trifluorome i 1) benzylane, 3,4,5-trimetho-ibenyl-amino, 1 , 3-benzodioxol-5-i Ime i lamino, phenylamino, 3- (i-meleit i 1) phenylamino, etaxifeni lamino, cyclopenphenylamino, methoxyphenylano, nitrof or lamino, 1-phenylethylamine, N- (et il) -3-phenyl-2-pyrpenylamino,, benzotriazoli lpheni lmeti lo, 2-pyridinylmethylamino, N- (ei 1) -2-pi idini Ime il-amino, 2- ienylme i lamino and furylme i lamino. Other examples of amino radicals include: I-ilhydrazine, dimethyldhydrazine, N-et i-lani and 2- met i la The amine may also be subuted with diethyl N-ylphophoramide acid, terbutoxycarbonyl, methoxycarbonyl, ethoxycarbonyl, propaxycarbonyl, etc. Of these examples of the amino radical, ethylamino, propylamino or allylamino are preferred. Examples of B include, but are not limited to, tri-ethylsilyl, ethyldimethylsilyl, diethyldimethyl, triethylsilyl, di-ethylpropyl?;: ] ilo, dipropylmet-ilsilyl, dimethyl-l- (meth il) et i -silyl, tripropylsilyl, butyldimethyl-silyl, pentyldi and ilsilyl, hexyldi and ilsi-lila, cyclopropyl-di-ylsilyl, cyclobutyl-ldimethyl-ylsilyl, cyclopentyl and ilzylsilyl, cyclohexyl dimethyl-lysyl, dimethylethyl-isyl, dimethyl-propyl-silyl, clarometyl-dimethyl-silsilyl, 2-chloroethyl-dimethylsilyl, bro-ometyl-dimethyl-silyl, bicyclohep-dimethyl-silyl, dimethyl-phenyl-silyl, dimethyl-2- (methyl) phenylsilyl, di- and 2-f-chlorophenylsilyl and others of said silyl groups of the formula Si (Rs) a. Of these examples of B, trimethyl isotope is preferred. Other examples of B include: 1, 1-d imet ilet i lo, 1, 1-dimethylpropyl, 1,1-dimethyl-ilbutyl, 1,1-dime-lpentyl, 1-ethyl-i-met-ilbutyl, 2 , 2-d imet ilpropi lo, 2,2-dimet ilbu i lo, 1-methyl-1-et ilpropyl, 1, 1-d iiet i Iprapi lo, 1, 1, 2-trimeti 1-propyl, i, 1 , 2-trime-ilbutyl, 1,1-dimethyl-tetrapropyl, 1,1-dimethyl-2-pyropenyl, 1, 1, 2-trime and 1-2-phenylene, 1,1-dimethyl -2-butenyl, 1, 1-d imet il-2-propini lo, i, 1-dime i 1-2-butipyl, i-cyclopropyl-i-methylethyl, i-cyclobutyl-1-methylethyl, 1 -cyclopene i 1-1-met i le lo, 1- (1-cyclopenteni 1) - 1-me ilet ila, i-cyclohexy 1-1-met i le ilo, l- (1-cyclahexepil) - 1- met i le i lo, i-met i 1-1-phenylethyl, i, 1-d ime i 1-2-chloroethyla, 1, 1-dimet il-3-chloroprapi la, I, 1-dimet i 1-2 -metaxyl ilo, 1,1-dimethyl-2- (meth yla ine) and ilo, 1, 1-dimet i 1-2- (di and ylamino) eti lo, i, 1-dimet i 1-3-chloro- 2-prapeni la, i-met il-1-methoxyethyl, 1-met i 1-1- (met i lt io) et il or, .methyl-l- (me ylamino) and yl, 1-met il-1- (dimethylamino) ei lo, 1-claro-1-meti let i lo, 1-bromo-l-met ilet yl and i-iodo-1-methylenyl. Of these examples of B, 1,1-dimethylpropyl, 1,1-diethylethyl to 1-methyl-1-cyclopentyl are preferred. Other examples of B are: 1, 1-dimethylethylamino, 1,1-dimethylpropylamino, 1, i-dimethyl-ylbutylamino, 1,1-dimethyl-pentylamino, 1-yl-l-meth i-l-butylamino, , 2-d imet i Ipropyl amylamino, 2,2-dimethyl-ilbutylamino, 1-met i 1-i-et-1propylamino, 1,1-diethylpropylamine, i, 1,2-trimethylpropylamino, 1,1 , 2-tri et ilbutylamino, 1, i, 2,2-tetramet-ilpropylamino, l? I-dimethyl-2-propenylamino, i, 1,2-trimethyl-2-y-pentyne, 1,1- dime il-2-butenylamino, 1, 1-dimet i 1-2-propini lamino, 1,1-dimethyl-2-butynylamino, 1-cyclopropyl-1-methylathylamine, 1-cyclobutyl and 1- met i let ilam no, 1-ci lopent i 1-1-met ilet ilamino, l- (ic iclopentenil) -1-met ilet i lamino, 1-cyclohexy-i-methylethylamino, l- (i-cyclohexeni 1 ) -l-me ilet ilamina, 1-methyl-1-phenylethylamino, 1,1-dimet il-2-chloroe ylamino, 1,1-dimethyl-3-cloraprapilamino, 1, 1-dime i 1-2-methoxy ilamino, 1, 1-dimet i 1-2- (meth i lamino) -et ylamino, 1, 1-dimet i 1-2- ídimet i lamino) et ilamino and 1, l ~ dimet il-3-claro-2 -prope I'm not lamino. Of these examples of B, 1,1-dimethyl-ilpropi-lamino, 1,1-i-i-ylamino or -ethyl-i-cyclapentyl-lamino are preferred. Other examples of B include: 1, 1-dime i letoxy, 1, 1-dime i 1 prapoxy, 1, 1-d imet ilbuto i, 1, 1-d imet ilpentoxy, 1-et il-1-methylbutoxy, 2 , 2-dimethylpropoxy, 2,2-dimethylbutoxy, i-me il-i-ylpropoxy, 1,1-die-1 -propoxy, 1,1-trimethyl-1-propoxy, 1,1-trimethylbutoxy, , 1, 2, 2-tetramethylpropoxy, 1, i-dimethyl-2-propenoxy, 1, i, 2-trimethyl-2-propenoxy, 1-di-yl-2-butenoxy, 1, 1- dimet i 1-2-prapin i loxi, 1, 1-dimet i 1-2-butynyloxy, 1-cycloprapyl-1-methyletax, 1-cyclobutyl-1-methylethaxy, 1-cyclopentyl-i-meth i letoxy, l- (i-cyclopenteni 1) -i-met-iletoxy, 1-cyclohexyl-1-methyloxy, 1- (1-cyclohexenyl) -1-methoxy-1, 1-methyl-1-phenylethoxy, 1, i-dimet il-2-chloroethoxy, 1,1-dime-il-3-chloropropoxy, 1, i-dime i 1-2-methoxyethoxy, i'ld ime i 1-2- (me i lamino) ethoxy, 1, i-dimet i 1-2- (d imet i lamino) eto i, 1, 1-dimet i 1-3-chloro-2-? ro? enox i. Of these examples of B, 1,1-dime and Iprspyloxy, i, 1-dieyleoxylo or cyclopenoxy are preferred. Other examples of B include 1-methylocyclopropylo, 1-methylcyclobuyl, 1- and 1-cyclopentyl, 1,1-cyclohexyl, 1-methylcyclopropylamino, 1-yl-cyclobutyl amine, 1-yl-cyclopentyl amine and i- met i lcyclohexy lamino. R,., Can be any substituent that does not unduly reduce the effectiveness of the compounds to function in the disease control method. R ^ is usually a small group; "n" is preferably 0 or 1. R is preferably methyl or halogen. The invention also provides fungicidal compositions, useful in said method. As used herein, the term "alkyl", unless otherwise indicated, means an alkyl radical, straight or branched chain having, unless otherwise indicated, from 1 to 10 atoms of carbon. The terms "alkenyl" and "alkynyl" mean unsaturated radicals having from 2 to 7 carbon atoms. Examples of such alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-prapenyla, 2-meth i 1-2-propenyl, 1-met il-eteni lo and similar. Examples of said alkynyl groups include ethynyl, i-propynyl, 2-propynyl, 1, i-dimethyl-2-propynyl, etc. The substituent groups can also be alkenyl and alkynyl, for example, 6, -dimethyl-2-hepten-4-ynyl. As used herein, the term "alkoxy" means an alkyl group having, unless otherwise indicated, from I to 10 carbon atoms, which are acidified by means of an ether linkage. Examples of such alkoxy groups include: methoxy, ethoxy, propoxy, 1-methyletoxy, etc. As used herein, the term "alkoxyalkyl" means an ether radical having, unless otherwise indicated, from I to 10 carbon atoms. Examples of such alkoxyalkyl groups include: ethoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, etc. As used herein, the terms "monoalkylamino" and "dialkylamino", each means an amino group having, respectively, i or 2 hydrogens, replaced by an alkyl group. As used herein, the term "halogenoalkyl" means an alkyl radical having one or more hydrogen atoms replaced by halogens, including radicals having all hydrogen atoms substituted with halogen. Examples of such haloalkyl groups are fluorometyl, difluoromethyl, trifluoromethyl, chloromethyl, trichlorometyl, etc. As used herein, the term "halogen" means a radical selected from chlorine, bromine, fluorine and iodine.

DETAILED DESCRIPTION OF THE INVENTION The control of Gg diseases, including total rooting, using a chemical control agent, can be achieved in various ways. The agent can be applied directly to the soil infested with Gg, for example, at the time of planting, together with the seed. At the time of planting, it can be applied to the soil after planting or after germination. Preferably, however, it is applied to the seed, in a coating, before planting. This technique is commonly used in many crops to provide fungicides for the control of various fungal diseases. The compositions of the present invention consist of an effective fungicidal amount of one or more compounds described above and of one or more adjuvants. The active ingredient may be present in said compositions at levels of 0.01 to 95% by weight. Other fungicides may also be included to provide a broader spectrum of fungal control. The selection of fungicides will depend on the crop and the known diseases that are going to be treated for that crop, at the site of interest. The fungicidal compositions of this invention, including concentrates that require dilution before application, may contain at least one active ingredient and an adjuvant in liquid or solid form. The compositions are prepared by mixing the active ingredient with an adjuvant, including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. Thus, it is believed that the active ingredient could be used with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any combination thereof. Suitable wetting agents are believed to include alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, sodium sulfosuccinate esters, sulphated or sulfonated fatty acid esters, sulfonates petroleum, sulphonated vegetable oils, acetylenic glycides d iterciarios, derivatives of polioxie ileno of alqu ilfenoles (particularly isooct i Ifenol and nonilfenal), derivatives of polioxie ileno of the esters of monograso superior acid, hexitol anhydrides (for example plo, sorbitan) . Preferred dispersants are methyl, cellulose, polyvinyl alcohol, sodium lignin sulphonates, polymeric alkylnaphthalenesulfonates, sodium naphthalene sulfonate and polymethylene bisnaphthalenesulfonate. Stabilizers can also be used to produce stable emulsions, such as magnesium aluminum silicate and xanthan gum. Other formulations include powder concentrates comprising from 0.1 to 0% by weight of active ingredient, on a suitable extender, optionally including other adjuvants to improve handling properties, eg, graphite. These powders can be diluted by application at concentrations within the scale of approximately 0.1 to 1% by weight. The concentrates may also be aqueous emulsions, prepared by stirring a non-aqueous solution of an active ingredient insoluble in agus and an emulsifying agent, with water, until uniform, and then homogenizing to give a stable emulsion of very finely divided particles. Or, they may be aqueous suspensions, prepared by smelling a mixture of water insoluble active ingredient and wetting agents, to give a suspension; characterized by its extremely small particle size, so that when diluted, the coverage is very uniform. Suitable concentrations of these formulations contain from 0.1 to 60%, preferably from 5 to 50% by weight of active ingredient. The concentrates can be salutions of active ingredient in suitable solvents, together with a surfactant. Suitable solvents for the active ingredients of this invention, for use in the treatment of seeds, include propylene glycol, furfuryl alcohol and other alcohols or glycols, as well as other solvents that do not interfere substantially with the germination of the seed. If the active ingredient is to be applied to the earth, then solvents such as N, N-di and i lformamide, di-ethyl sulphoxide, N-met il-lololidone, hydrocarbons and ethers, esters or ketones, immiscible with water can be used. The concentrated compositions herein generally comprise about 1.0 to 95 parts (preferably 5 to 60 parts) of the ctiv ingredient, about 0.25 to 50 parts (preferably 1 to 25 parts) of surfactant, and when required, about 4 to 94 parts of solvent, all parts being by weight, based on the total weight of the concentrate. For applications to the soil, at the time of planting, a granulated formulation can be used. Granules are physically stable particulate compositions, comprising at least one active ingredient adhered to, or distributed through a basic matrix of a finely divided, inert particle extender. In order to help leach the active ingredient from the particle, a surfactant agent, such as those mentioned above or, for example, propylene glycol, may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite, are examples of operable classes of mineral particle extenders. Preferred extenders are porous, preformed, absorbent particles, such as preformed and screened particulate attapulgite, or particulate vermiculite, expanded with heat, and clays of kaolin, hydrated tapulgite or bentonite clays. These extendedares are sprayed or mixed with the active ingredient so that they form fungicidal granules. The granulated compositions of the invention may contain from about 0.1 to 30 parts by weight of active ingredient per 100 parts by weight of clay and from about 0 to about 5 parts by weight of surfactant per 100 parts by weight of clay. in particles. The method of the present invention can be practiced by mixing the composition comprising the active ingredient in the seed, before planting, at rates of 0.01 to 50 grams per kilogram of seed, preferably 0.1 to 5 grams per kilogram, and better yet, from 0.2 to 2 grams per kilogram. If application to the soil is desired, the compounds can be applied at rates of 10 to 1000 grams per hectare, preferably 50 to 500 grams per hectare. Major application regimes will be needed for light land situations or more rainfall, or both. The compounds useful in the present invention can be prepared by methods known to those of ordinary skill in the art. The following examples illustrate some of these methods and are only illustrative. It should not be considered that they limit the invention in any way. Unless stated otherwise, percentages are given as weight / weight. Melting points and boiling points are reported uncorrected. Thin cap chromatography was carried out with various concentrations of elutations of ethyl acetate and ilo-hexanes. Tetrahydrofuran and ether solvents were distilled from the sodium / benzophenone mixture immediately before use. N, N, N ', N' - (tetramethyl) -ethylenediamine was distilled off from the calcium hydride before use. All other reagents were purchased from Aldrich or Lancaster, and used without purification. A measured physical property is reported, for example, or the elementary analysis is given, at the end of the examples. The following abbreviations have the meanings shown. n-BuLi n-But-il-lithio-BuLi Butyl-lithium secondary DMF Dime il ormamide TMSC1 trimethoxy chloride l l THF Tetrahydrofuran TMEDA N, N, N ', N' - (etramet i 1) ei lendi mine eq equiv lens () aq aqueous sat saturation min minutes h hours Mel Methyl iodide TLC Thin layer chromatography HPLC High CR liquid chromatography CR GLC radial chromatography Gas-liquid chromatography TA ambient temperature pf melting point.

GENERAL METHODS The phrase "worked in the usual manner" refers to the treatment of the reaction mixture with 10% aqueous citric acid, extraction with diethyl ether, washing of the combined organic extracts with saturated brine solution, drying of the organic extract over MgSO 4. and evaporation to dryness under vacuum, to reduce the crude product. The phrase "appropriate" means a compound having the desired substituents for the final product of the reaction.

METHOD A INTRODUCTION IN ORTHO OF ELECTRQFILOS IN N.N- DIALQUILBENZAMIDAS 1.3M s-BuLi in cyclohexane (1.1 to 1.2 molar equivalents) were added dropwise to an I.OM solution of TMEDA, cooled with dry ice / acetone or with ether / liquid nitrogen (1.0 to 1.2 malar equivalents) in THF , and then 1.0 equivalent of the appropriate N, N-dialkylbenzamide in THF was added dropwise. The resulting reaction mixture was stirred for 30 to 60 minutes at a temperature of -76 ° C, to ensure complete formation of the aploidal anion; then it was cooled to a temperature less than or equal to -90 ° C, with the ether / liquid nitrogen bath, and quenched by careful addition of the appropriate electrophile. The reaction was allowed to warm to 0 ° C, and then worked in the usual manner. If necessary, the crude product was purified by chromatography, recrystallization or distillation.

METHOD B INTRODUCTION IN ORTHO OF ELECTROPHILES IN N. N- DIALQUILBENZAMIDAS. BY REVERSE ADDITION 1.3M s-BuLi in 1.2 equivalents of cyclohexane was added dropwise to an i.OM solution of TMEDA (1.2 equivalents), cooled with ether / liquid nitrogen, in THF, followed by the dropwise addition of 1.0 equivalents of the appropriate N, Nd? alkylbenzamide, in THF. The internal temperature of the reaction was maintained between -60 and -95 ° C, during both additions. After the addition, the cooling bath was replaced with dry ice / acetone, and the resulting reaction was stirred at -76 ° C, for 1 hour. This solution was then cannulated in a solution of an excess of the appropriate electrophile in THF, at a rate that maintained the temperature of the internal reaction below -60 ° C, with an ether / liquid nitrogen bath. The resulting reaction mixture was allowed to slowly come to 0 ° C, then purified in the manner described below for each compound.

METHOD C INTRODUCTION IN ORTHOLE OF ELECTROFILOS. IN N-ALQUILBENZAMIDAS 1.3M s-BuLi was added dropwise in 2.1 to 2.2 equivalents of cyclohexane, at l.OM of a solution of 1.0 to 1.2 equivalents of TMEDA in THF, cooled with dry ice / acetone or with ether / liquid nitrogen, followed by the dropwise addition of 1.0 equivalents of the appropriate N-alkylbenzamide, in THF. The resulting reaction mixture is stirred for 30 to 60 minutes at a temperature of -76 ° C, to ensure complete formation of the aryl anion; then it was cooled to a temperature less than or equal to 90 ° C, with an ether / liquid nitrogen bath, and cooled by the careful addition of the appropriate electrophile. The reaction was allowed to slowly warm to -30 ° C, then worked in the usual manner. If necessary, the crude product was purified by chromatography, recrystallization or desiliation.

METHOD D 3 parts of a tertiary alkylamine were added to 1.6M of n-butyl-lyo in 2.5 parts of hexanes, in THF, maintaining the internal reaction temperature at a temperature less than or equal to -70 ° C. The resulting solution was briefly heated to 0 ° C, then cooled again to a temperature less than or equal to -7Q ° C. To this cold solution of N-lithia-teralkylamine, a solution of any of the products of the examples hoi (1 part) dissolved in THF was added, maintaining the internal temperature of the reaction to less than or equal to -50 ° C. It was heated to 0 ° C and stirred for 1 hour, and then partitioned between ether and aqueous sodium bicarbonate. The ethereal phase was washed with water, filtered to remove solids, dried (over gSO), concentrated and purified by chromatography to produce l- (2-oxazolinyl) -2- (teralkylamino) naphne as a oil.

METHOD E The product of method D was stirred with an excess of 30% hydrogen bromide in acetic acid to convert the oxazoline ring to its 2-bra alkylamide. After 30 minutes, the reaction mixture was poured on ice, then divided between methylene chloride and aqueous potassium carbonate in excess. Methylene chloride was added over MgSOn. and concentrated to give a high yield of N- (2-bromoalkyl) 2- (eralkylamino) -1-naphm amide, as a sol.

METHOD F 1.6 parts of tributyltin hydride and a catalytic amount of 2,2'-azobis (2-ethylpropionitrile) were added to a 0.7-0.9M suspension of the product of method E (1 part) in benzene. This was heated in a closed vessel for 13 to 20 hours at 75 ° C, and then partitioned between ether and aqueous sodium bicarbonate. The ether phase was dried (MgSO 4), concentrated and recrystallized from hexanes to give a low yield of N-alkyl 2- (teralkylamino) -l-naph-amide, as a solid.

METHOD G In a Parr apparatus, a solution of a part of the product of method E and 2.2 parts of trie i lamina, in ethanal, was hydrogenated (at 3.5 kg / cpt2 gauge), on a catalytic amount of 5% palladium on charcoal, during two hours. The resulting mixture was filtered through celite, concentrated and the residue was partitioned between methylene chloride and water. The methylene chloride phase was washed with brine, dried (MgSO.sub.4), and purified by chromatography to produce moderate yields of N-ethyl 2- (teralkylamino) -l-naphthamide, as a solid.

METHOD H parts of potassium terbutoxide were added to a 0.3M solution of the product of method D (1 part) in anhydrous DMSO and heated in a sealed container at 110-120 ° C, for 0.5 to 1.0 hours, then the mixture was divided. of reaction between ether and water. The ether phase was washed with water, dried over MgSO.sub.0 < H. and concentrated to yield crude N- (1-propeni 1) 2 -teralkylamino) -1-naph amide. In a Parr apparatus, a solution of this ida alkenyl in methanol (3.51-4.21 kg / cm.sup.12), over PtO? A, was hydrogenated for 3.5-6.0 hours. The resulting mixture was filtered through celite, concentrated and purified by chromatography to produce moderate yields of N-propyl 2- (teralquinyl) -naphthalamide, as a solid.

METHOD I A 35% oil dispersion of 1 part potassium hydride was added to a solution of tertiary alkanol in 1,2-dimethoxyethane eeco. This mixture is refluxed or briefly to obtain the complete formation of the potassium alkoxide; then the temperature was cooled to medium and the product of the pl-axis was added (0.9 parts). The resulting mixture was refluxed briefly to obtain substitution of the chloride with the alkoxide. Then it cooled and it was divided between ether and water. The organic layer was washed with brine, dried over MgSO 4, then activated carbon and then filtered through silica gel and concentrated. The residue was passed through a 10.16 cm plug of silica gel, eluted first with hexanes to remove the mineral oil, then with 1: 4 ethyl acetate / hexanes, to give the desired naphtonitrile. The purified 2-teralkoxy-1-naphthonitrile was dissolved in tertiary amyl alcohol and sufficient pellets of potassium hydroxide were added to maintain saturation during reflux. The mixture was refluxed for 5 hours, then concentrated in vacuo and the residue partitioned between ether and water. The organic layer was washed with brine, dried over MgS0t + and filtered through silica gel. The filtrate was then concentrated and the residue triturated with hexanes to give the 2-teralkoxy-1-naph-amide as a solid.

METHOD 3 It was added to one. solution of the primary naphthamide, of method I, (i part) in dry THF, i.l part of lithium solid (trimeylethyl) amide. After shaking e < The mixture was stirred for 5 minutes, the appropriate alkyl halide (2 to 5 parts) was added, and the reaction was refluxed for 3 hours. It was partitioned between ether and water, and the organic layer was washed with brine, dried over MgSG? +, Filtered through silica gel and concentrated to give the crude N-alkyl-2-teralcaxy-i-naphthamide, which it was purified by recrystallization, not chromatography.

METHOD To a solution of the primary naphtha-ida from Method I (1 part) and 0.02 parts of tetrabuhilamonium acid sulfate in toluene, an equal volume of 50% NaOH and the appropriate alkyl halide (2.2 parts) were added, and the mixture was refluxed for 45 minutes. This was partitioned between ether and water and the organic layer was washed with brine, dried over MgSO 4. , it was filtered through silica gel, and concentrated to give the crude N-alkyl-2-teralcaxy-i-naphthamide, which was purified by recrystallization or chromatography.

METHOD L 2.0 to 3.2 parts of 2- or 3-vinylthiaphene or 2- or 3-vinylurea were added, to 0.9-1.6M of a solution of 1 part of 3-r ime and Isi-1-ylpropionyl chloride in ethylene chloride, and the mixture was heated in a sealed container 3. at 60-6 ° C for 11-64 hours. It was cooled and added to a stirred and cooled mixture with ice water, from 5 to 10 parts of 70% aqueous ethylamine in ethylene chloride, and water. The resulting reaction mixture was stirred at room temperature for 30 minutes, then the organic layer was separated and washed with dilute aqueous HCl, followed by aqueous sodium bicarbonate and then with brine. The organic phase was dried (over gSQt *) and purified by chromatography. This dihydrobenzafuran or dihydrobenza iaphene (1 part) was aromatized with DDQ (1 part) refluxing in toluene for 30 minutes. The resulting solution was filtered, concentrated and purified by chromatography to produce the desired benzofuran or benzothiophene, as a solid.

STARTING MATERIALS EXAMPLE a ACIDS 2- AND 3-BENZQTIOFENCARBQXILICQS To a suspension of 13.4 grams, 0.1 mole, of aluminum chloride in 100 ml of methylene chloride at -60 ° C, under a nitrogen atmosphere, a solution of 11 ml, 0.1 mole of trichloroacetyl chloride in 50 ml was added. ml of methylene chloride, at a temperature between -50 and -60 ° C. After the addition was complete, the mixture was heated to a temperature between -30 and -40 ° C and stirred for another 45 minutes at that temperature scale. After this, 13.4 grams, 0.1 mole of a benzo-iofen solution in 50 ml of methyl chloride was added slowly, at a temperature between -30 and -40 ° C. The resulting reaction mixture was heated to 0 ° C and stirred for 2 hours. The mixture was poured into 50 ml of 2N HCl and extracted with ether. The ethereal solution was washed with water, with saturated sodium bicarbonate with brine; dried and concentrated in vacuo. The crude product was dissolved in 100 ml of THF and treated with a 20% solution of KOH until it became basic. Ether was added and the two layers separated. The aqueous layer was washed with additional ether and then acidified with concentrated HCl. The solid that formed was filtered and dried with air to give 6 grams of a mixture of acids. 3-Benzothiophenecarboxylic acid was the main component. EXAMPLE b N-ETHYL-3-BENZOTIOFENCARBOXYAMIDE A mixture of 3.6 grams, 20 mmol, of the acids of example a, in 16 ml of thianyl chloride, which heated a few drops of DMF, was refluxed for 3 hours, then cooled and the excess of the chloride was removed. Thionyl, at reduced pressure, to give a mixture of acid chlorides. A solution of this mixture of acid chlorides in methylene chloride was added dropwise to 20 ml of 70% aqueous ethylamine at -20 ° C, then heated to room temperature and room temperature. it was stirred for 2 hours. Water was added and the layers were separated. The organic layer was washed with brine, dried and concentrated in vacuo. The residue was purified by flash chromatography with 30% ethyl acetate-hexane to give 3.1 grams of the product.

EXAMPLE c 2-BENZOTIQFENCARBOXILICO ACID To a solution of 20 grams, 0.15 mole, of benzothiophene in 120 ml of THF at -30 ° C, 2.5M of n-BuLi in 70 ml, 0.175 moles, of hexane at a temperature between -20 and -30 ° C. The solution was warmed to 0 ° C, stirred for 3 hours and poured into dry ice. Water and ether were added. The aqueous layer was separated and acidified with concentrated HCl. The solid that formed was filtered and dried in air overnight to give the crude acid.

EXAMPLE d N-ETHYL-2-BENZOTIOFENCARBOXYAMIDE .4 grams of the acid of example c were refluxed in 20 ml of thianyl chloride containing 6 drops of DMF, for 2 hours; it was then cooled and the excess thionyl chloride was removed under reduced pressure. The crude acid chloride was dissolved in ethylene chloride and added slowly to 20 ml of methylene chloride and 30 ml of 70% ethylamine at -20 ° C. After 2 hours at room temperature, the mixture was poured into water and extracted with ethylene chloride. The organic layer was washed with brine, dried and concentrated in vacuo. The residue was chromatographed on silica gel with 35% ethyl acetate / hexane as eluent to give 1.9 grams of analytically pure product.

EXAMPLE e 2- AND 3-TRICLQRQACETILBENZOTIOFENOS Six times greater quantities of the reagents used in the method of Example a, with omission of the hydrolysis step with eodium hydroxide, yielded 130 grams of a mixture of 2- and 3-trichloroacet-ylbenzo-iofenos, of which isomer 3 was the main component.

EXAMPLE f N-ALIL-3-BENZQTIOFENOCARBOXIAMIDA To a solution of 9 grams of the mixture of example e, in 40 ml of ethylene chloride, at 10 ° C, 4 grams of allylamine were added dropwise, and the resulting reaction solution was stirred at room temperature for 16 hours . The solution was washed with 2N HCl and with brine, dried and concentrated. Flash chromatography of the residue with 20% ethyl acetate-hexane gave 2.7 grams of the desired product.

EXAMPLE or ACID 2-MET0XI-1-NAFT0IC0 Ili grams, 603 mmoles, of potassium carbonate were added to a mixture of 50.0 grams, 266 mMas, of 2-hydraxy-1-naphthalic acid and 169 grams, 1.330 mMas, of methyl iodide, in 500 ml of DMF. The resulting mixture was heated at 60 ° C, overnight, then partitioned between ether and water. The organic layer was washed with dilute aqueous HCl, dried over MgS0t + and concentrated to yield methyl 2-methoxynaphthoate, as an oil. 50% aqueous sodium hydroxide was added to a solution of this ethyl 2-methoxynaphthoxide in 400 ml of methanol. The mixture was refluxed and 300 ml of water was added at a rate that kept the sodium 2-methoxynaphthate which formed in solution. After water was added, the reaction was refluxed for 3 hours, then allowed to stand at room temperature overnight. The resulting solid mass was acidified with concentrated HCl, then diluted with water (1 liter) and the product was collected by filtration. Drying to empty day 50.96 grams of 2-methoxy-l-naphthoic acid, a yield of 95%.

EXAMPLE h 2- (2-METOXY-l-NAFTIL) OXAZOLINE 6.3 grams, 49.6 mmol, of oxalyl chloride were added to a suspension of the product of example g (5.0 grams, 24.6 mmol), and 2 drops of DMF or catalyst in 25 ml of methylene chloride were added. After about 30 minutes, the reaction formed a solution which was briefly put to the reflux of haeta which ceased the evolution of gas. This was concentrated in vacuo to remove excess oxalyl chloride. The hydrochloric acid chloride was dissolved in 10 ml of methylene chloride and added dropwise to a mixture cooled with ice water and mechanically stirred, of 10.15 grams, 49.5 mmoles, of 2-bramoyla ine bromohydrate and 6.64 grams, 49.5 mmoles, of potassium carbonate in 50 ml of water and 40 ml of methylene chloride. The resulting mixture was stirred at room temperature for 15 minutes, then partitioned between methylene chloride and water. The organic layer was washed with aqueous HCl, followed by aqueous sodium bicarbonate, then dried over MgS0t + and concentrated to yield 5.5 grams of solid N- (2-bro-ethyl) -2-meta-1-naphthamide, in a yield of 72%. 30 ml of 50% aqueous sodium hydroxide were added to a solution of 13 grams, 42.2 mmoles of N- (2-bromoethyl) 2- etho i-1-naphidolamide and 1.2 grams, 5.3 mmoles of benzyl chloride ltriet i lamonio sn 120 ml of methylene chloride. The resulting mixture was stirred vigorously at room temperature for 2 hours, then diluted with water and the layers were separated. The organic phase was washed with brine, dried over MgSO 2, and concentrated to give 9.5 grams of solid 2- (2-methoxy-1-naph i 1) oxazalin, in a yield of 99%.

EXAMPLE i 2- (2-MET0XI-l-NAFTIL) -5-METILQXAZ0LINA 6.3 grams, 49.6 mmoles of oxailochloride were added to a suspension of the p-axis (5.0 grams, 24.6 mmoles, and 2 drops of DMF as a catalyst in 25 ml of methyl chloride). 30 minutes, the reaction formed a solution which was briefly refluxed until gas evolution ceased.This was concentrated in vacuo to remove excess oxalyl chloride.The solid acid chloride was dissolved in 10 ml. The mixture was added to qotas to a cooled mixture with ice water of 9.3 grams, 124 mmol, of 2-hydroxypropyl sheet in 40 ml of methylene chloride, The resulting reaction mixture was heated to room temperature and washed with water. Aqueous HCl, followed by aqueous sodium bicarbonate.The organic phase was dried over MgSO.sub.4 and concentrated to an oil which was crystallized from ethyl acetate to give 4.00 grams of N- (2-hydroxy-i-propyl) 2 solid-methoxy-1-naphthamide, in a 62% yield. they added 4.00 grams, 15.4 mmoles, of this N- (2-hydroxy-l-propyl) 2-methoxy-1-naphthamide, to 7.4 grams, 62 mmoles, of thionyl chloride cooled with ice water. This was then stirred at room temperature and after 1 hour the suspension that had formed was diluted with ether and collected by filtration; then it was divided between ether and aqueous sodium hydroxide. This ethereal solution was dried over gSO ^ and concentrated to yield 2- (2-metho-l-naphthyl) -5-methylaxazaline as an oil.

EXAMPLE i 2-CLQRQ-1-NAFT0NITRIL0 Ethyl cyanoacetate (111.0 grams, 962 mM) was added to a suspension of 52.0 grams, 769 grams of potassium hydroxide pellets and 16.0 grams, 246 mmoles of potassium cyanide in DMF (500 ml). The mixture was stirred at room temperature for 30 minutes, then 40.0 grams, 197 mmoles, of 65% 2-n-1-ronaf alene were added to the reaction mixture. After stirring at room temperature for 2 hours, the reaction was refluxed for 10 minutes, then 300 ml of 10% NaOH was added and the reflux was continued for another two hours. The resulting mixture was cooled and poured onto crushed ice and extracted with chloroform. The organic phase was washed with water, followed by brine, then dried over MgSOn. , decolorized with activated carbon and filtered through silica gel. The filtrate was concentrated and triturated first with ether and then with a 1: 1 mixture of ethyl acetate / water to give 23.0 grams of 2-naphine-1-naphthyl, co or a yellow oil. 23.5 grams, 205 mmoles of tert-butyl nitride were added dropwise to a cooled mixture with ice water of 20.3 grams, 151 mmoles, of cupric chloride in a solution of 23.0 grams, 137 mMas, of 2-amino-1-naphthonitrile. in 250 ml of dry acetonitrile. The evolution of gas was controlled by the addition regime of tert-butyl nitride. The resulting reaction mixture was stirred at 0 ° C for 30 minutes, then at room temperature for 30 minutes. This was poured into dilute, cold aqueous HCl, and the precipitate that formed was filtered, dried under vacuum and distilled in a Kugelrohr (160 ° C, 3.5 torr) to give 15.5 grams of 2-chloro-1-n-nitrile. crystalline, white, a yield of 60%.

EXAMPLE 1 N-ETIL-4-FLU0R0-2- (TRIMETILSILIL) -1-NAFTALENCARB0XIAMIDE A 1.3M solution of 40.7 ml, 52.9 mmoles of s-BuLi in cyclohexane, was added to a cooling solution with 6.66 ml liquid nitrogen, 57.5 mmoles, of TMEDA in 50 ml of THF, maintaining the reaction temperature at -90 °. C during the whole addition. The resulting solution was stirred for 5 minutes, a solution of 5.00 grams, 23.0 mmoles of N-et il-4-f luoro-1-naphthalenecarboxyamide in 15 ml of THF was added, and the resulting purple solution was stirred for 10 minutes at room temperature. -90 ° C. 676 ml, 69.0 mmoles of TMSC1 were added and, after 10 minutes, the cold bath was removed. The mixture was slowly heated to room temperature. The mixture was cooled with 100 ml of 25% citric acid and extracted with ether (3 x 200 ml). The combined extracts were dried over MgSO 4 and concentrated to a yellow powder, which was purified by chromatography with ethyl acetate / hexanes, to give 1.36 grams of the desired amide, a yield of 20%. p.f. 134-i36 ° C.

EXAMPLE 2 . -DYTHYL-2-C (YODOMETIL) DIMETILSILIL3-1-NAFTALENCARBOXIAMIDA A solution of 1.3M of s-BuLi in 20.3 ml, 26.4 mmoles of cyclohexane, was added dropwise to a solution cooled with ether / liquid nitrogen, 4.0 ml, 26.5 mmoles of TMEDA in 15 ml of THF, before the temperature of internal reaction lower than -60 ° C. To this mixture was added a solution of 5.0 grams, 22.0 mmoles of N, N-diethi-1-naph alencarboxyamide in 10 ml of THF, again maintaining the internal reaction temperature below -60 ° C. The resulting solution was stirred with cooling by dry ice / acetone, for 30 minutes, and then recovered at a temperature below -60 ° C, with an ether / liquid nitrogen bath, while 3.6 ml, 26.6 mmoles was added dropwise. of chloride of chlorame i ldimet i leililo. The mixture was warmed to room temperature to yield a green solution which was diluted with ether and extracted with dilute aqueous citric acid (2 X), followed by saturated aqueous NaHCO. The ether solution was dried over MgSO 4, concentrated and chromatographed with 3: 7 ethyl acetate / hexanes to yield 4.3 grams of N, N-diethyl-2-C-chloromethyl) dimethylsilyl-1-naphthalenecarboxyamide, as a yellow oil, a yield of 59%. A solution of 1.0 grams, 3.0 mmol, of this naphthalenecarboxyamide and 13.5 grams, 90 mmol of Nal, in 90 ml of acetonitrile, was put overnight at reflux overnight. It was then diluted with ether and filtered through celite to remove most of the salts. The filtrate was then concentrated and diluted through a plug of silica gel with ethyl acetate. The concentration of ethyl acetate yielded 1.25 grams of the desired compound, co or a yellow oil, a yield of 96%.

EXAMPLE 3 N.N-DIETIL-2- (TRIMETILSILIL) -1-NAFTALENCARBQXIAMIDE N, N ~ diet i 1-1-naphthalenecarboxyamide was reacted with 2 eq of TMSC1, according to the general method A. The resulting reaction mixture was worked up in the usual way, then purified by chromatography with 20% acetate of ethyl / 60% hexanes, to yield 2.1 grams of the desired compound, as a clear oil, a yield of 71%.

EXAMPLE 4 N-ETHYL-2-ÍTRIMETILSILID-1-NAFTALENCARB0XIAMIDA The N-ethyl-2-naphthalenecarboxyamide was reacted with 2 eq of TMSC1 according to the general method C. The reaction mixture was worked up in the usual manner, then purified by recrystallization from ethyl acetate / hexanes. cold, to produce 1.6 grams of the desired compound as a white solid, a yield of 56%. p.f. 141-143 ° C.

EXAMPLE 5 N-ETIL-3- (TRIMETILSILIL) -2-NAFTALENCARBOXYAMIDE N-ethyl-2-naph alencarboxyamide was reacted with 2 eq of TMSC1, according to the general method C. The resulting reaction mixture was worked in the usual way, then purified by chromatography with 3: 7 ethyl acetate. / hexanes, to yield 3.3 grams of the desired compound, co or a white solid, a yield of 17%. p.f. i32 ~ 136 ° C.

EXAMPLE 6 2- (1.1-DIMETILETOXI) -n-ETIL-l-NAFTALENCARBOXIAMIDA A solution of 1.3M s-BuLi in 34 ml, 44 mmoles of cyclahexane was added dropwise to a solution cooled to -76 ° C, 20 mmoles of N-e-1-naphthalenecarboxyamide and 6.0 ml, 40 mmoles of TMEDA, in 100 ml of THF. After 30 minutes, 15.5 grams, 60 moles of MgBrs-Eta0 were added in portions, and the reaction was briefly warmed to room temperature, and then cooled again to -76 ° C.

After 1 hour at -76 ° C, 4.3 grams, 22 mmoles of tert-butyl peroxybenzoate were added. The resulting reaction mixture was heated to -30 ° C and worked in the usual manner; it was then purified by chromatography with 3: 7 ethyl acetate / hexanes to yield 1.7 grams of the desired compound, as a white solid, at 33% yield. p.f. 127-127 * 0.

EXAMPLE 7 N-ETIL-2- (TRIMETILSILIL) -lH-INDOL-l-CARBOXYAMIDE 0.9 grams, 37.5 mmoles of NaH, were added in portions to a cooled solution at 0 ° C of 2.93 grams, 25 mmoles of indole, in 100 ml of THF. After 30 minutes, 1.76 grams, 25 mmoles of ethyl isocyanate were added dropwise. The reaction mixture was stirred at room temperature overnight, then cooled with 25% citric acid in 50 ml of water and extracted with ethyl acetate (3 X). These organic extracts were combined, dried over MgSO 4 and recrystallized from ether / hexanes to yield 1.3 grams of N- (et i laminocarbanyl) indole as a solid cinnamon colan, a yield of 26%. p.f. 71-73 ° C. 6.97 ml, 11.66 mMas, of a 1.3 M e-BuLi solution in cyclohexane were added dropwise, to a cooling solution at -76 ° C of 1.0 grams, 5.3 mmoles, of N ~ (ethylalkylcarbonyl) indole and 0.75 grammes. , 5.3 mmol, of 2, 2, 6, 6-tetramethylpiperidine in 50 ml of THF. After 30 minutes, 0.9 grams, 6 mmoles of TMSC1 were added in a single portion, then the cold bath was removed to allow the reaction to warm for 1 hour. This reaction mixture was quenched with 25% citric acid in water (50 ml) and extracted with ethyl acetate (3 X). The organic extracts were combined, dried over MgSO 4. , concentrated and recrystallized from ether / hexane to produce 1.1 gram of the desired compound, as a white solid, in a 60% yield. p.f. 96-99 ° C.

EXAMPLE 6 N-ETIL-2- (TRIMETILSILIL) -BENZOCb3TI0FENQ-2-CARB0XIAMIDE A solution of 2 grams, 10 mmol, of the compound of Example b, in THF, was treated with 2.5M of n-BuLi in hexane, and quenched with TMSC1 under the conditions used in Example 9, to give 2.3 grams of the product desired, as a white powder, a yield of 62.7%. p.f. 121-124 ° C.

EXAMPLE 9 N-ETIL-3- (TRIMETILSILIL) BENZOEb 1TI0FEN0-2-CARB0XIAMIDE A 1.5 gram, 7.5 mmoles, of the. Amide of example d in 40 ml of THF at -76 ° C, under a positive atmosphere of Nffi, a solution of 2.5M of n-BuLi in 7.5 ml, 16 mmol of hexane was added dropwise, and stirring was continued for 0.5 additional hours Then 5 ml of TMSC1 was slowly added at a temperature below -70 ° C. After 0.5 hours at a temperature below -70 ° C, the solution was warmed to 0 ° C and quenched with ice water. Methylene chloride was added. The aqueous layer was separated and extracted with additional methylene chloride. The combined organic layers were washed with brine, dried and concentrated in vacuo. The residue was chromatographed on silica gel with 20% ethyl acetate, to give 1.6 grams of the product as a white solid, with a yield of 65.7%. p.f. 131-134 ° C. EXAMPLE 10 N-ETIL-l-METHYL-2- (TRIMETILSILIL) -1H-INDOL-3-CARBOXYAMIDE To a solution of 6.5 g, 60 mmol, of indole, in 25 ml of THF at 10 ° C, 12 ml, 60 mmol, of trifluoroacetic anhydride was added, and the resulting reaction mixture was stirred at 10-20 ° C. , for 30 minutes. The mixture was then poured into water and the precipitate was filtered and air dried to give 11.5 g of 3-trif luoroacetyl-iH-indole. To a solution of 11 g, 50 mmole of this compound in 100 ml of acetone, 10 ml, 150 mmole of Mel and 16 g of potassium carbonate was added and stirring was continued at room temperature for 2 hours. Acetone was removed under vacuum. Water and methylene chloride were added to the residue. The organic layer was separated, washed with brine, dried and concentrated under vacuum to yield 1,1-methyl-3-f luoroacet-il-IH-indal. 12 g of NaOH in 60 ml of water were added thereto, and the mixture was refluxed for 1.5 hours. The solution was cooled and acidified with concentrated HCl. The solid was filtered and dried with air to give 7.5 g of 1-methyl-1H-indol-3-carbaxyl acid. The title compound was obtained as a white solid in total yield of 56.6% from 1-met yl-lH-indole-3-carboxylic acid and ethylamine, followed by reaction with TMSC1 using the methods of Example 9. P.f. 119-122 ° C.

EXAMPLE 11 N-ETIL-3- (TRIMETILSILIL) -2-BENZ0FURANCARB0XIAMIDA The title compound was obtained as a solid yellow with a total yield of 5.2% from 2-benzofurancarboxylic acid and ethylamine, followed by the reaction with TMSC1, using the methods of Example 9. P.f. 92-96 ° C.

EXAMPLE 12 N-ETIL-2- (TRIMETILSILIL) -3-BENZ0FURANCARB0XI MID To a solution of 25 g of benzofuran in 50 ml of carbon disulfide, at -25 ° C, was added a solution of 35 g of bromine in 50 ml of carbon disulfide, at a temperature between -20 and -10 ° C. , and stirring was continued at -10 ° C for 2 hours. The precipitate was filtered and washed with hexane to give 43 g of 2,3-dibrama-2,3-dihydrobenzafurane co to a yellow solid. 11.3 g of KOH (176 mmol) in 100 ml of ethanol at 0 ° C, in small portions, 22 g of 2,3-dibromo-2,3-dihydrabenzofuran, were added, and the resulting reaction mixture was stirred at 0 °. C for 3 more hours. Then most of the solvent was removed under vacuum. Water was added and ether was added to the residue. The aqueous layer was separated and extracted with ether. The combined ethereal extractors were washed with water and with brine, dried over MgSO ^ and concentrated to give 17 g of 3-bromobenzofuran. To a solution of 10.5 g of 3-bromobenzofuran in 120 ml of ether at a temperature lower than -110 ° C, under a positive nitrogen atmosphere, 2.5 moles of n-BuLi in 23 ml of hexane was added., at a temperature below -100 ° C, and stirring was continued at less than -100 ° C for 3 hours. Solid carbon dioxide was added and the mixture was warmed to 0 ° C. Water was added and the two layers were stopped. The aqueous layer was acidified with HCl and extracted with methylene chloride. The methylene chloride solution was washed with brine, dried over gSOip. and concentrated to give 3 g of solid 3 ~ benzofurancarboxylic acid. To a solution of 4 ml of diisopropylamine in 20 ml of THF at -60 ° C, 2.5 M of n-BuLi in 17 ml of hexane was added, and the solution was stirred at a temperature between -20 and -0 ° C during 1 hour. To this was added a solution of 2.6 g of 3-benzofurancarboxylic acid in 30 ml of THF at a temperature less than -70 ° C. After i hour 7 ml of TMSC1 was added at a temperature lower than -70 ° C and stirring was continued for an additional hour. The solution was allowed to warm to 0 ° C, cooled with 2 N HCl and extracted with methylene chloride. The organic solution was washed with brine, dried and concentrated to give 3.6 g of 2- (rime i lei 1 i 1) -3-benzafurancarboxylic acid. A solution of 0.6 g, 2.6 mmole, of this crude acid in 6 ml of thionyl chloride, which contained 6 drops of DMF under reflux for 3 hours, was then cooled, then cooled and concentrated in vacuo to give the acidic crude. One was added. solution of the acid chloride in 6 ml of methylene chloride to 6 ml of 70% aqueous ethylamine at -20 ° C. After 3 hours at room temperature, water was added. The organic layer was separated, washed with brine, dried and concentrated in vacuo. The residue was purified by flash chromatography with 10% ethyl acetate-hexane to give 0.4 g of the product as a white solid with a yield of 56.9%. P.f. 141-144 ° C.

EXAMPLE 13 N-2-PRQPENIL-2- (TRIMETILSILIL) BENZOCB3TIOFENO-3-CARBQXIAMIDA The title compound was prepared as a white solid in a yield of 26.1%, from the product of Example f, using the method of Example 9. P.f. 72 -75 ° C.

EXAMPLE 14 N.N-DIETIL-2- (TRIMETILSILIL) BENZOCB3TIOFENO-3-CARBOXIAMIDA To a mixture of 3.7 g of acids of Example a, in 60 ml of THF at -70 ° C, 2.5 ml of n-BuLi in 19 ml of hexane, at a temperature lower than -65 ° C, was added and stirring at a temperature below -70 ° C for 1.5 hours. Then 9 ml of TMSC1 was added dropwise to the solution, at a temperature below -70 ° C. After 1 hour at a temperature below -70 ° C, the solution was warmed to 0 ° C and poured into ice water. Methylene chloride was added. The aqueous layer was separated and extracted with methylene chloride. The combined organic layers were washed with brine, dried and concentrated in vacuo to give 4.5 g of eolide. Trituration of the eolide with 5% ethyl acetate / hexane yielded 4.1 g of analically pure 2- (trimetheyl) i3) -3-benzothiophene-carboxylic acid. The title coat was obtained as an orange oil in a yield of 62.2% of sete acid, and diethylamine using the method of example b. nE > ?? - < í '1.5663.

EXAMPLE 15 1. 1-DI0XID0 OF N-ETIL-2- (TRIMETILSILIL) BENZ0CB3TI0FEN0-3- CARBOXIAMIDA A mixture of 0.6 g, 2.2 mmol, of the product of Example 6 and 1 g of 60-65% 3-chloroperoxybenzoic acid in 16 ml of ethylene chloride was refluxed for 2 hours, then cooled and diluted with additional methylene chloride. The solution was treated sequentially with saturated sodium metabisulfite, 1.25 N NaOH and brine; then it was dried and concentrated in vacuo. Flash chromatography of the residue with 35% ethyl acetate-hexane gave 0.5 g of the desired product as a soft solid, a yield of 74.5%. P.f. 135-146 ° C.

EXAMPLE 16 N-ETHYL- N- (MEYLTHYL) -2- (TRIMETHYLILYL) BENZOCBUTIQFENO-3- CARBOXYAMIDE To a solution of product 6 (1.1 g, 4 mmol) in 20 ml of THF at a temperature below -60 ° C, under a positive nitrogen atmosphere, 2.5 M of n-BuLi in 2.2 ml of hexane were added dropwise. , at a temperature below -60 ° C, and the solution was stirred for 0.5 hours. A 0.6 g, 4.6 mM solution of methyl methane-io-sulfonate was added in 2 ml of THF at a temperature below -60 ° C. After 1 hour at room temperature, the solution was poured into ice water and extracted with methylene chloride. The organic layer was washed with brine, dried and concentrated in vacuo. The residue was purified on a column of silica gel, using 6% ethyl acetate-hexane, to give 1 g of the desired product as a viscous yellow oil, with a yield of 76.9%. nD21 * 1.5666.

EXAMPLE 17 N-HYDROXY-N- (1-METHYLTHYL) -2- (TRIMETILSILYL) BENZOCBDTIOFENQ-S- CARBOXYAMIDE A mixture of 0.6 g, 3.2 mmol, of 2- (trimethylsilyl) benzathofencarboxylic acid, made as in example 14, and 6 ml of thionyl chloride, was refluxed for 2 h. Excess thionyl chloride was removed under reduced pressure. The crude acid chloride was dissolved in 20 ml of methylene chloride and added to a mixture of 0.4 g, 3.6 mmol of N-isoprapylhydroxy hydrochloride and 4 g of sodium bicarbonate in 20 ml of methylene chloride and 20 ml of water at 0 ° C. The resulting mixture was stirred at room temperature for 2 hours. The organic layer was separated, washed with brine and concentrated in vacuo. The crude product was chromatographed on a column of silica gel, with 10% ethyl acetate / hexane, to give 0.65 g of the title compound, as a yellow solid, at 66.1% yield. P.f. ÍÍ5 ~ Íld ° C. The following compounds were prepared using methods D and E.

Compound Example P.F.

Number 16 N- (2-bromaethyl) 2C (i, 1-dimet i let il) 203 ° C des. amine3-1-naf amide. 19 N- (2-bromoethyl) 2C (1, i-dime i lpropi 1) 151-I53 ° C amino] -l-naf amide.

The following compounds were prepared using method F.

COMPUTING EXAMPLE P.F. Number 20 N-ethyl 2Ci 1, 1-dimethylethyl) U49-1500C amino] -l-naphtamide. 21 N-propyl 2C (i, 1-dimet i le il) 142-143 ° C amino3-1-naph amide.

The following compounds were prepared using method G. Example Compound P.F. Number 22 N-ethyl 2r- (1, 1-dimethylpropyl) 126-229 ° C amino 3-1-n-amide.

N-ethyl 2C (1, 1-di-ethylhethyl) 101-10 ° C amine-1-naphthamy a.

The following compounds were prepared using the H method.

Execute Compound P.F. Nú was 24 N-prapil 2L (1, 1-diet ilet il) 93-96 ° C to ina3-1-naphtamide.

N-propyl 2C (1, I-d imet ilpropyl) 104-107 ° C amine 3-i-na amide. The following compounds are prepared using methods 3 or K.

Compound Example Method P.F.

Number 26 N-ethyl 2-C (1, l-dimethylpropyl) J 91-93 ° C oxy 3-1-naphtha ida. 27 N-allyl 2- (1,1-dimethypropyl) 79-dl ° C oxy 3-1-naphthamide. 26 N-ethyl 2-C (1, 1-diethylethyl) 65-66 ° C or i 3-1-naph amide. 29 N-allyl 2-C (1,1-d -tyle-letyl) K 70-72 ° C oxy 3-1-naph amide.

N, N-diethyl 2-C (1, 1-diet i 1 J Oil et il) axi-1-naphthamide. 31 N-prapil 2- (1, 1-diethyl ether) K 65-66 ° C oxy 3-1-naph amide.

N-ethyl 2- (1,1-diethylpropyl) K 105-106 ° C or i 3-i-naf amide. 33 N-allyl 2-C (i, 1-diethylpropyl) K 7d-79 * C oxy 3-1-naphtamide. 34 N-propyl 2-C (1,1-d-ylpropyl) 3 101-102 ° C axi 3 -1-naphthamide.

N, N-diproyl-2-C (1,1-diethylpropyl) J Oxy-3-y-naphthamide oil. 36 N-ethyl 2-C (l-methyl-i-cyclopentyl) J 93-94 ° C to i 3-1-naphthamide. 37 N-ali 1 2- (1-met il-1-cyclapent il) 94- -? 6CO-oxy-1-naphtamide. 36 N-et i 1 2-C (1-met i l • l ~ c iclahex i l) K 123-124 ° C or i -1-naf amide. 39 N-allyl 2- (1-met il-1- ihehehe) K 91-94 * 0 oxy -i-naph amide. 40 N-prapil 2- (1-meth i 1-cyclohexy 1) K 63-64 ° C to i 3-1-naph tamida.

The following compounds were prepared using the method L. Example Compound P.F. Number 41 N-ethyl 5-trimethylsilylbenzathiafen-153-155 ° C 4-carboxy ida. 42 N-Ethyl 5-trimethylsilyl-benzofuran- 102-104 ° C 4-c rbo ida. 43 N-ethyl 6-trimethylei 1 ibenzot iofena- 130-134 ° C 7-carboxyamide. 44 N-ethyl 6-trimeleleyl Ibenzofuran-10β-109 ° C 7-carboxyamid.

OTHER COMPOUNDS Comets can be prepared in which the X of -CyX) amine is S by mixing the corresponding axamide with Lawesson's reagent in xylene and refluxing overnight. The mixture is then cooled and filtered. The filtrate is divided between ether and water; the organic layer is washed with 10% HCl, dried over MgSO 4. and concentrates. The crude product can be purified by chromatography. The compounds in which W is -CHjg- and Q is Si, are prepared by introducing the methyl group in the ortho position with respect to the amide, using any of the general methods A, B or C. The compound resulting from the The mixture is worked up and purified by chromatography. It is then reacted with TMSC1 using one of the general methods A, B or C. The dried product is worked up in the usual manner and purified by chromatography.

BIOLOGICAL ANALYSIS The compounds prepared in the above examples have demonstrated control of Gqt in one or more of the following test etodae. The results are shown in the table below.

ANALYSIS IN VITRO The test compounds (0.25 ml of the appropriate stock solution in acetone) are incorporated into 25 ml of minimal medium agar (prepared by autoclaving a solution of 17.5 g of Czapek Dox broth (Difca), 7.5 g of purified agar from Bacto-agar (Difco), and 500 ml of distilled / deionized water, and then adding 50 μl of i mg / ml of thiamine hydrochloride and 50 μl of 1 mg / ml of biotin in 5% ethanol) and plates were prepared . Each plate was inoculated by placing in a triangular shape three 4 mm caponee of Gaeumannomycee qraminis var. tritici (Gqt)., developed in a minimum average agar, described above. The plates are incubated in the dark at 19-20 ° C, for 4 to 5 days. The development of the fungus is measured as the diameter of the development of the icelium. The result is represented with the inhibition percentage, calculated as Cl - C (mm of development on treated plate - 4) / (mm of development on control plate -4) 33 x 100.

IN VIVO ANALYSIS Compounds are tested for the control of Gqt on the varieties 'Bergen' and 'Anza' of wheat grown in 19.35 cm2 pots, which contain soil infested with Gqt. Infestation is achieved by mixing the soil with a prepared inoculum developed Gqt on potato dextroea agar, with a concentration of 1/4 (4.675 g of potato dextroea agar, 5.0 g of Bacto agar, 500 ml of deethylated water, deionized) in plates, and using caps of the plates to infest sterile oats (400 cm3 of whole oats, 350 ml of deionized water, autoclaved). After incubating for a period of one month, at room temperature, the oats are dried and mixed with earth at 4% volume / volume. Four wheat seeds are placed on top of the soil of each pot. The test compounds are prepared as a 1: 2 ratio of acetone / water in volume / volume, containing 0.16% Tween® 20 to provide a treatment regimen of 0.5 and / or 0.1 g of active ingredient per pot, treated with a 3 ml test solution, per pot. Five pots are used for each level of treatment, and controls, which are pots inoculated and not inoculated, untreated. After a 1-hour drying period, the seeds are covered with more soil and a layer of vermiculite. The pots are placed in a development chamber and watered every day. After four weeks of development, each pot is evaluated to demonstrate the disease by examining the similar roots of each plant, under a dissecting microscope. A rating scale of 0 to 5 is used, which has the following meanings: = no hiccup develops or no injury present. 1 = developing hyphae and a few small lesions present in less than 10% of the root septa. 2 = developing hyphhoses and small lesions present in 10. 25% of the root system. 3 = hy droids that develop and lesions present in the 25 to 50% of the root system. 4 = Hypertrophs that develop and many large lesions, caalescent, in more than 50% of the root system. 5 = root and culmination of the whole flooded by reads and hyphae in development. For each series of five duplicates, a high or low annotation can be eliminated, to ensure that better representative annotations are used to calculate a duplicate mean, by averaging the remaining annotations. This average annotation is then compared to the control annotation in which a percentage of disease control is calculated. The results of these in vitro and in vivo tests are reported in the following table. If the calculation results in "0" or less, compared to the untreated control, an "N" is shown to indicate no control.

TEST RESULTS I Example In vitro (ppm) In vivo (ppm) No. 10 1 0.1 0.5 .1 0.02 mq / pot i 79 79 0 - 16 2 100 46 15 NN 3 lOO 0 0 66 - 4 lOO 100 lOO 99 65 5 lOO 94 0 27 16 6 93 66 21 - 53 7 i00 100 66 79 40 6 100 93 97 71 43 9 66 0 0 - M 10 65 60 13 - - 11 62 42 27 - ... 12 100 97 97 97 65 13 1 0 100 100 94 64- 14 100 92 42 94 76 15 63 30 10 - ... 16 100 100 100 93 67 17 100 100 96 46 42 16 96 66 10 14 0 0 19 96 93 66 22 0 0 100 96 60 61 24 5 21 97 97 95 76 60 35 22 96 96 95 7 41 11 Example I? - \ vitrc In vivo (ppm) No. 10 1 0.1 0.5 0.1. 2 mq / pot 23 43 21 21 65 65 50 24 100 95 95 76 36 32 i00 100 95 76 57 17 26 96 95 76 64 56 17 27 96 96 93 95 75 27 26 96 96 74 76 40 19 29 96 96 96 75 57 40 96 96 91 26 43 31 31 96 17 7 3 0 0 32 97 97 67 56 35 15 33 100 100 97 59 45 19 34 95 95 95 49 44 16 5 19 0 1 0 0 36 100 96 76 60 0 0 37 96 96 93 63 53 26 36 30 43 0 without dates * 39 96 96 57 26 11 0 40 96 63 74 60 32 41 100 96 96 100 99 75 42 100 96 90 91 67 66 43 100 100 96 66 79 50 44 100 96 96 no data ** * In vitro activity insufficient to ensure second tests ** was not tested.

TEST RESULTS II E.j mplo No. In vitro (IC50- *) 24 0.000614 25 0.001000 23 0.006625 21 0.006500 22 0.009162 20 0.071644 33 0.006473 34 0.006625 37 0.007429 30 0.007429 29 0. 06143 27 0.006435 32 0.042239 * The IC50 is determined from the following maner-a? To determine the IC50 values, an in vitro test was carried out on each compound, at the concentrations of i, 0.1, 0.01, 0.001 and 0.0001 ppm. The inhibition percentage was calculated for each concentration, using the equation described in the in vitro analysis, under the Biological Analysis section. Using the two ordered pairs of (concentration,% inhibition), which comprises 50% inhibition of fungal development, the concentration for 50% inhibition is calculated from the following equation: Clßo = íSO -? ^ Ca. + (1 ^ - 50 Ca3 ÍI? - Ia), where C = 10C, a.

IN VIVO ANALYSIS (6 WEEKS) A seed treatment, in advance of 6 weeks, in an in vivo analysis, on the land, is as follows: IN VIVO ANALYSIS Compounds are tested for Ggt control in the 'Bergen' to 'Anza' wheat varieties grown in 15.24 cm round pots, which contain soil (equal to two thirds of Metro-ix land, sand, and sedimentary field land- rill, completely sterilized with steam). The seeds are treated with a mixture of the composition of the present invention, at 10 ppm of acetone stock solution. 20 mg in 10 ml will treat 10 g of seed, each to a classification of 4. Using a 10,000 ppm stock solution for each compound, the following series of dilutions are formed: GRAMS OF ACTIVE INGREDIENTS / 100 KT OF COMPOSITION 1 100 1 ml of mother material 50 1 ml of mother material + 1 ml of acetone 3 25 1 ml tt 2 + 1 ml acetone 4 12.5 1 ml * 3 + 1 ml acetone (discard i ml or proceed) 5 6.25 1 ml tt 4 + i ml acetone (discard 1 ml) (5 is optional and it is not used in all tests) * each ampoule of solution must contain 1 ml to treat 10 g of seeds. 10 g of wheat seed are prepared (variety 'Bergen'), one for each treatment. A fraeco de tratamiento doe times with 3 ml of acetone. Then 1 ml of the solution is quickly stirred to cover the base of the bottle. 10 g of the seed are added to the bottle and capped, after which the flask is shaken rapidly and shaken until all the seeds obtain a fast and uniform covering. After about 30 to 50 seconds the cap is removed and shaking is continued. After 1 minute, the bottle is allowed to dry. When it is dry, the seeds are again poured into a plant to be planted in the pots or stored for planting. The method for planting as follows: ANALYSIS OF TOTAL ROOT IN GREENHOUSE. WITH LARGE POTS .16 cm pots are packed, up to its edge, with the previous earth mixture. Method: a) The treated seed is placed on the surface of the soil (packed to the brim) at a rate of 6 seeds per pot, with the seeds at a distance of approximately 5.6-7.62 cm. 5 pots (duplicates) are planted per treatment. b) 15 ml of oat inoculum (approximately 4 g) are measured and sprayed uniformly on the soil surface of each pot. c) Cover the seed / seed / inoculum with 160 ml of the soil mixture (same as antee). A 150 ml beaker is filled to the upper bar of approximately 160 ml. d) Initially, each of the prepared pots is watered, lightly, several times, to moisten the soil without washing the seeds. e) In the cold winter months, the prepared pots are left in the greenhouse at 16 - 16 ° C, the only entity with a minimum of complementary light. In the warmer months, prepared pots are placed in a growth chamber, set at 17 ° C for 3-4 weeks, to establish the disease, then placed in a haeta greenhouse that is harvested. The wheat is harvested, washed and the roots are sorted after 7 to 10 weeks. f) A percentage of diseased root area is assigned values, using 1, 5, 10-, 20, 30, 40, 50, 60, 60 or 100%. Each plant pot gets a single qualification.

TEST RESULTS III Percentage of control (the classifications are in q / q of seaillas) Ejeiplo No. The 0.5 q 0.25 q 0.125 q untreated No. test 26 25 4 25 25 46 32 27 25 0 21 21 46 32 37 i »4 i» 4 4 33 3 9 0 17 46 36 30 13 0 22 46 36 29 i * 4 0 46 36 40 22 13 13 46 35 FIELD TESTS Compounds of Example 1 to 44 are combined with various adjuvants, carriers and other additives and mixed with wheat and barley seeds, at a rate of 0.01 to 50 g of active substance per kilogram of seed, which reduces the amount of seed. incidence of Gg in previously infested fields, in comparison with the check field.

Spread with untreated eemilla.

EXAMPLES OF COMPOSITION Suspension concentrate: Percentage by weight Compound No. 21 46,900 Polyoxiprapi lena-polyoxyethylene block copolymer 2,550 Sodium ligninsulfonate 2.04O 10% Di-ilpol isi loxane emulsion 1020 1% solution of xanthan gum 0.990 Water 43,250 Emulsifiable emulsifiable concentrate: Percentage by weight Compound No. 23 13.5 Sorbitol ethoxide (20 0E) 5.0 Aromatics of C9 61.5 Wettable powder: Percentage by weight Compound No. 41 75.0 Sodium ligninsulfonate 3.0 N-me il-N-ol il-taurate sodium 1.0 Clay from kaolinite 11.0 Granule: Percentage by weight Compound No. 42 1.0 Propylene glycol 5.0 Montmarilonite (24/46 meshes) 94.0 Powder: Percentage by weight Compound No. 43 50.0 Graphite 10.0 Clay from kaolinite 40.0 It should be understood that certain aspects and subcombinations are useful and can be used without reference to other aspects and eubcambinacianee. This is contemplated by, and is within the scope of the claims. Since many embodiments of the invention can be made, without departing from its scope, it is understood that all the material indicated herein should be interpreted as illustrative and not in a limiting sense.

Claims (1)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A method to control the disease in a plant, caused by Gaeumanno ycee s. in said plant, characterized in that it comprises applying to the seed or the soil of the plant, a fungicidally effective amount of a fungicide of the formula: h) A ee -C (X) -amine; B is -Wm-Q (R3) 3; and A can be B when B ee A, except when the formula ee f), Q can not be Si; Q is C or Si; W is -NH-, -NCH3_- or -0-; X is O or S; is 0 to 1, provided that m is O when Q is Si; n is 0, 1, 2 or 3; p is O, i to 2; and n plus p is equal to or less than 3. Each R is independently selected from: a) halogen, formyl, cyano, amine, nitro, thiocyanate, isotiocyanate, trime ilsi li and hydroxy; b) alkyl of 1 to 4 carbon atoms, alkenyl, alkynyl, cycloalkyl of 3 to 6 carbon atoms and cycloalkenyl, each optionally substituted by halogen, hydraxy, thio, amine, nitro, cyano, formyl, phenyl, alkoxy, 4 carbon atoms, alkylcarbonyl, alkylthio, alkylamino, dialkylamino, alkoxycarbonyl, (alkyloxy) carbonyl, alkylaminocarbonyl, dialkylaminecarbonyl, alkylaulfinyl or alkylsulfonyl; c) phenyl, furyl, thienyl, pyrrolyl, each optionally substituted with halogen, formyl, cyano, amino, nitro, alkyl of 1 to 4 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, dialkylamino, haloalkyl and haloalkenyl; d) alkoxy of 1 to 4 carbon atoms, alkenoxy, alkyloxy, cycloalkyloxy of 3 to 6 carbon atoms, cycloalkenyloxy, alkylthio, alkylsulfonyl, alkylsulfonyl, alkylamino, dialkylamine, alkylcarbonylamino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl Each of them is optionally substituted with halogen, each R_ is independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and phenyl, each substituted with R? Or halogen, and in dande, when Q is C, Rs can also be selected from halogen, alkoxy, alkylthio, alkylamino and dialkylamine, wherein two R3 groups can be combined to form a cyclo group with Q; to 4 carbon atoms, halagenoalkyl, alkoxy, alkylthio, alkylamino or dialkylamino, or an agricultural salt thereof »2.- The method of compliance with the reivi ndication 1, further characterized in that the formula is a), b), g), h), a i). 3.- The method in accordance with the claim 2, further characterized in that A is -C (0) -amine, wherein the amino radical is substituted with one or two groups selected from hydraxy; alkyl, alkenyl and alkynyl, which can be straight chain to branched or cyclic; alkoxyalkyl, haloalkyl, hydroxyalkyl, alkylthio, alkylthiaalkylaryl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, cyanoalkyl, mono- or dialkylamino, phenyl, phenylalkyl or phenylalkenyl, each optionally substituted with one or alkyl of 1 to 4 carbon atoms. carbon, alkoxy, haloalkyl, cycloalkyl of 3 to 6 carbon atoms, halogen or nitro groups; alkyl groups of 1 to 4 carbon atoms or alkene of 1 to 4 carbon atoms, substituted with pyridinyl, thienyl or furanyl; and wherein the amino radical can be an N-linked heterocycle, selected from morpholine, piperazine, piperidine, paral, pyrrolidine, imidazole and triazoles; each of which optionally substituted with alkyl groups of 1 to 6 carbon atoms. 4. The method according to claim 3, further characterized in that B is trimethylsilyl. 5. The method according to claim 3, further characterized in that B is independently selected from 1,1-dimethylpropyl, 1,1-diethylol or i-met il-1-cyclopentyl. 6. The method of compliance with claim 3, further characterized in that it is 1 and W ee NH or NCH3. 7. - The method according to claim 3, further characterized in that n is 1 and W is -0-. 6. The method according to claim 7, further characterized in that Rs is alkyl of 1 to 4 carbon atoms or haloalkyl. 9. The method of compliance with claim 3, further characterized in that each B ss 1,1-d imet ilpropi lamino, 1, 1-dimet iletila ino, i-methyl-1-cyclopentylamino. 10. The method according to claim 7, further characterized in that each B is 1,1-dimethylpropyloxy, i, 1-die-ilet-yloxy, i-methyl-1-cyclopentyl-loxi. 11. The method according to claim d, further characterized by A is and ilaminocarbonila, prapilaminocarbonilo or alilaminocarboni la. 12. The method according to claim 11, further characterized park A is the inocarboni la. 13. A fungicidal composition for use in the method according to claim 1, further characterized in that it comprises an adjuvant and an amount of the compound described herein, which is effective in controlling total root disease. 14.- A compound in accordance with the formula: d) i) alkyl A is -C (X) -amine; B is -Wm ~ Q (Ra) 3; and A can be B when B is A, except when the formula is f); Q can not be Yes; Q ee C o Si; W ee -NH-, -NCH3_- to -0-; X ee 0 or S; m ee O o l, provided that m is 0 when Q is Si; n ss 0, 1, 2 or 3; p ee 0, i or 2; and n plus p is equal to or less than 3; each R ee independently selected from: a) halogen, formyl, cyano, amine, nitro, thiocyanate, isothiocyanate, trimethylsilyl and hydroxy; b) alkyl of 4 carbon atoms, alkenyl, alkynyl, cycloalkyl of 3 to 6 carbon atoms and cycloalkene, each optionally substituted with halogen, hydroxy, thio, amine, nitro, cyano, formyl, phenyl, alkoxy 4 carbon atoms, alkylcarbonyl, alkylthia, alkylamino, dialkylamine, alkoxycarbonyl, (l-lyl) carbonyl, alkylaminocarbonyl, dialkylaminecarbonyl, alkylsulfonyl or alkylsulfonyl; 60 c) phenyl, furyl, thienyl, pyrrolyl, each optionally substituted with halogen, formyl, cyano, amino, nitro, alkyl of 1 to 4 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, dialkylamino, halogenated alkyl and haloalkenyl; d) alkoxy of 1 to 4 carbon atoms, alkenaxy, alkynoxy, cycloalkyloxy of 3 to 6 carbon atoms, cycloalkenyloxy, alkylthia, alkylenediyl, alkylenyl, alkylamino, dialkylamino, alkylcarbonylamine, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbanyl, alkylcarbonyl, alkylcarbonylaxy, alkoxycarbonyl, (alkyl io) carbonyl, f-norcarbonyl, phenylane, each optionally substituted by halogen; each Rs is independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and phenyl; each of them substituted with R or halogen; and wherein, when Q is C, R_, it can also be selected from halogen, alkoxy, alkylthio, alkylamine and dialkylamino; where two groups R_¡ can combine to form a cycle group with Q; R is alkyl of 1 to 4 carbon atoms, haloalkyl, alkoxy, alkylthio, alkylamino or dialkylamino; or an agricultural salt thereof. 15. The compound according to claim 14, further characterized in that the formula is a), b), g), h) or i). 16.- The compound in accordance with 61 claim 15, further characterized in that A is A is -C (0) -amine, wherein the amino radical is substituted with one to two selected hydroxy groups; alkyl, alkenyl and alkynyl, which may be straight chain or branched to cyclic; alkoxyalkyl, haloalkyl, hydroxyalkyl, alkylthio, alkylthioalkyl, alkylcarbanyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, cyanoalkyl, manno- or dialkylamino, phenyl, phenylalkyl or phenylalkenyl; each of them optionally substituted with one or alkyl of 14 carbon atoms, alkoxy, haloalkyl, cycloalkyl of 3 to 6 carbon atoms, halogen or nitro; and alkyl of 1 to 4 carbon atoms or alkenyl of 1 to 4 carbon atoms, substituted by pyridinyl, thienyl or furanyl; and in dande the amino radical can be an N-linked heterocycle, selected from morpholine, piperazine, piperidine, paral, pyrrolidine, imidazole and triazoles; each of which is optionally substituted with alkyl groups of I to 6 carbon atoms. 17. The compound according to claim 16, further characterized in that B is trimethylsilyl. 16. The compound according to claim 16, further characterized, Park B is independently selected from 1, 1-d imet i Ipropi la, 1,1-diethylethyl or 1-me il-i-cyclapentyl. 62 19. The method according to claim 16, further characterized in that each B is 1,1-di-ethylpropylamino, i, i-dimethylethylamino, 1-methyl-1-cyclopentyllamino. 20. The method according to claim 16, further characterized in that each B is 1,1-di et ilpropyloxy, i, 1-diethyloxyloxy, l-methyl-i-cyclopentyloxy. 21. The method according to claim 16, further characterized in that A is and ilaminocarbonyl, propylaminecarbonyl or allylaminocarbonyl. In testimony of which I sign the above in this City of Mexico, D.F., on the 5th day of the month of April of 1994. BY MONSANTO COMPANY CR / CRG *