MXPA98001273A - Carbamoilcarboxami - Google Patents

Abstract

The present invention relates to the carbamoylcarboxamides of the general formula I: (R1 = substituted or unsubstituted alkyl, alkenyl, alkynyl, R2 = hydrogen, halogen, cyano, nitro or alkyl, substituted or unsubstituted alkyloxy, alkylthio or a phenyl group substituted or unsubstituted which is bound through oxygen or sulfur) and the compositions containing them, the processes for their preparation and the use of the compounds I and the composition

Description

CARBAMOILCARBOXAMIDES The present invention relates to the carba-oilcarboxamides of the general formula I. in an isomeric purity of more than 90 ?. by weight, wherein the variables have the following meanings: R1 is C2- C2 alkyl / C2-C8 alkenyl or C-> alkynyl; -Ca, it being possible that these radicals are partially or completely halogenated and / or have attached to them from 1 to 3 of the following groups: cyano, C-C4 alkoxy, C-C haloalkoxy, C-C4 alkylthio, C? -C-alkoxycarbonyl, C3-C7-cycloalkyl, C3-C7-cycloalkenyl, aryl, aryloxy and hetaryl, it being possible for the cyclic and aromatic rings of these groups, in turn, to have attached them from 1 to 3 the following substituents: halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxyalkyl, C 1 -Chaloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C alkylthio, C 1 -C 4 alkoxycarbonyl, aryl, aryloxy and hetaryl; R? is hydrogen, halogen, cyano, nitro, C_-C8 alkyl, Ci-Ci haloalkyl alkoxy, C_-C4 alkoxy / C_-C4 haloalkoxy, C-C4 alkylthio, C? -C4 haloalkylthio, or a a phenyl group bonded through an oxygen or sulfur that is unsubstituted or has attached thereto from 1 to 3 of the following substituents: halogen, C 1 -C 4 alkyl, and C 4 -C 4 alkoxy. (S) represents the configuration S, (R) the configuration R of the asymmetric carbon atom thus marked, according to the nomenclature of the IUPAC. In particular, the configuration of the center S in the compounds of the general formula I corresponds to the configuration of L-valine. For purposes of simplicity, the configuration of the compounds I N- hereinafter will be mentioned as configuration (SR). "Isomeric purity" refers to the percentage of a compound I (configuration (SR)) of all four diasterers of these compounds I that are possible ((SR), (RS), (RR), (SS)) . Furthermore, the invention relates to the process for the preparation of the compounds I. The invention also relates to the compositions containing the compounds I, to a process for the preparation of these compositions and to a method of control of harmful fungi and to the use of the compounds I or the compositions for this purpose. Racemic mixtures or icotic compounds of type I are described mainly in DE-A 43 21 897 and in the earlier German Application P 44 31 467.1. However, these mixtures are still not satisfactory in terms of their fungicidal activity. An object of the present invention is to provide the novel carbamoylcarboxates with high isomeric purity, which have an improved activity against harmful fungi. We have found that this objective is achieved by the compounds I defined at the beginning and the compositions containing them. In addition, we have found the processes for the preparation of the compounds I and the compositions containing them, and also a control method for the harmful fungi and the use of the compounds I or the compositions for this purpose. The compounds I can be prepared in a manner known per se starting from the corresponding carbamoylcarboxylic acids II which are based on L-valine. The compounds I are preferably obtained by processes A and B which are described below (references wHouben-Weil), refer to: Houbven-eil, Methoden der Organischen Chemie [Methods in Organic Chemistry, 4th Edition, Thimie Verlag, Stuttgat).

Process A Carbamoylcarboxates I are obtained by the reaction of carbamoylcarboxylic acids II with amines III.

H3C ^ ^ CH3 CB O Rl- 0- • NH-TCH -C II- OH (II) (S) Those carbamoylcarboxylic acids II which are not yet known can be prepared by the known methods, especially starting from the amino acid L-valine (see, "Houben-Weil", volume 15/1, page 46 to page 305, especially page 117 to page 125). In the same way, those amines III that are not yet known can be easily obtained (See, for example, Organium [Laboratoty Practical Organic - Chemistry], VEB Deutscher Verlag der issenschaften, 15th Edition, Berlin, 1997, page 610 et seq Houben-eil ", olume 15/1, page 648 to page 665, Indian J.Chem, 10, page 366 (1972); J. Am. Chem. Soc. 58, pages 1808-1811 (1936)). The R-isomer can be separated from the racemates of the amines III in a manner known per se, for example, by fractional crystallization with optically active tartaric acid, or preferably, by means of enzyme-catalyzed esterification followed by hydrolysis (cf. for example, WO-A 95/08636). This process A is preferably carried out in such a way that the carbamoylcarboxylic acids II are first converted to the activated carboxyl derivatives, especially the cyanides or acyl anhydrides (cf.

Tetrahedron Letters, volume 18, page 1595 to page 1598 (1973) or "ouben-Weil", volume 15/1, page 28 to page 32.) These derivatives are then reacted with the amines III in the presence of bases. for the preparation of the activated acyl carboxyl cyanides is, for example, the reaction of the carbamoylcarboxylic acids II with diethyl cyanophosphonate, especially in an inert solvent such as tetrahydrofuran or toluene, preferred for the preparation of activated carboxyl anhydrides is the reaction of carbamoylcarboxylic acid II with carbonic chlorides, such as isobutyl chloroformate, in the presence of bases and in the presence or absence of an inert solvent, such as toluene or tetrahydrofuran The reaction of amines III with activated carbamoylcarboxylic acids II carboxyl acids is preferably It is carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.Other substances that can act as bases are the s amines III, and these usually recover normally [sic] from the impure product. In a preferred embodiment of this process step, the * carbamoyl-carboxylic acid II, the amine III, the reagent which is suitable for producing the activated carboxyl derivative of carbamoyl-carboxylic acid II and the base are reacted in a process, in a vessel in the presence or absence of an inert solvent and the impure product is subsequently treated in a manner known per se to produce carbamoylcarboxa ida I.

Process B The carbamoylcarboxamides I are obtained by converting the carbamoylcarboxamides I where the group R ^ O-fCO) is a protective group that can be eliminated in a manner known per se to amino acid IV amides and reacting the latter with chloroformices V esters in the presence of bases.

Step Ba: Preparation of amino acid amides IV The removal of the R1-0- (CO) group from the carbamoylcarboxamides I can be carried out in a manner known per se (see, "Houben-Weil", volume 15/1, page 46 to page 305, especially page 126 to page 129 ). Suitable groups which can be removed contain, as radical R 1, tert-butyl and also [sic] the benzyl group. In the case where R 1 is tert-butyl, the elimination is usually carried out, for example, by means of the reaction with an acid, in particular with a protonic acid, such as hydrochloric acid or trifluoroacetic acid (ibid. , page 126 to page 129). The carbamoylcarboxamides I which are suitable as starting materials can be obtained by the known processes (see "Houben-Weil", volume 15/1, page 28 to page 32) or, in particular by the process A according to the invention.

Step Bb: preparation of the carbamoylcarboxamides I The amino acid amides IV resulting from the synthesis step (Ba) are reacted with the chlorophoric esters V in the presence of bases.

Those chloroformic esters V which are not generally known can be prepared by known processes. The preferred reaction is carried out in an organic solvent, especially toluene, methylene chloride or tetrahydrofuran or mixtures thereof.

The inorganic and organic bases are equally suitable, with organic bases being preferred and, in turn, the tertiary amines such as triethylamine, pyridine and N-methylpyridine. As a general rule, the reaction is carried out from (-40) to 50, preferably from (-10) to 20 ° C. In addition, this reaction is known to those skilled in the art and no further information is required in this context. See, "Houben-Weil", volume 15/1, page 117 to page 139). The reaction mixtures obtained from processes A and B are treated in the customary manner, for example, by mixing with water, separating the phases and, if desired, chromatographic purification of the impure products. Some of the intermediates and final products are obtained in the form of colorless or pale brown viscous oils which can be released from the volatile components under reduced pressure and at moderately elevated temperatures. If the intermediates and final products are obtained in the form of solids, these can also be purified, for example, by recrystallization or digestion. The definition of the compounds I that was given at the beginning uses collective terms that represent the following substituents: Halogen: fluorine, chlorine, bromine, and iodine; Alkyl: straight or branched chain alkyl groups having from 1 to 8 carbon atoms, for example, C _-C6 alkyl, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, n- hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3, 3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; Haloalkyl or partially or fully halogenated alkyl: straight or branched chain alkyl groups having from 1 to 4 or 8 carbon atoms (as noted above), it being possible for the hydrogen atoms in these groups to be partially or completely substituted by halogen atoms (as noted above), for example, haloalkyl of C? -C2 such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoroethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-2- trichloroethyl and pentafluoroethyl Alkoxy: straight or branched chain alkoxy groups having from 1 to 4 carbon atoms, e.g. ex. , C 3 -C alkoxy such as ethyloxy, ethyloxy, propyloxy and 1-methylethyloxy; Alkoxyalkyl: straight or branched chain alkyl groups having from 1 to 8 carbon atoms (as mentioned above) having, in any position, a straight or branched cadmium alkoxy group (as already mentioned) having, in the case of C 1 -C 4 alkoxyalkyl, of 1 to 4 carbon atoms, such as methoxymethyl, ethoxymethyl, n-propoxy ethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2 -n-propoxyethyl and 2-butoxyethyl; Haloalkoxy: straight or branched chain alkoxy groups having from 1 to 4 carbon atoms (as mentioned above), it being possible for the hydrogen atoms of these groups to be partially or completely replaced by halogen atoms (as mentioned in the previous), p. eg, haloalkoxy of C? ~ C2, such as chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoroethyloxy, chlorofluoromethyloxy, dichlorofluoroethyloxy, chlorodifluoromethyloxy, 1-fluoroethyloxy, 2-fluoroethyloxy, 2,2-difluoroethyloxy, 2.2.2 - trifluoroethyloxy, 2-chloro-2-fluoroethyloxy, 2-chloro-2,2-difluoroethyloxy, 2,2-dichloro-2-fluoroethyloxy, 2,2,2-trichloroethyloxy and pentafluoroethyloxy; Alkylthio: straight or branched chain alkyl groups having from 1 to 4 carbon atoms (as mentioned above) which are attached to the main chain via a sulfur atom (-S-), e.g. ex. , C 1 -C 4 alkylthio, such as methylthio, ethylthio, propylthio, 1-methylethylthio, n-butylthio and tert-butylthio; Alkoxycarbonyl: straight or branched chain alkoxy groups having from 1 to 4 carbon atoms (as mentioned above) which are "attached to the main chain by means of a carbonyl group (-C0-); Alkenyl: straight or branched chain alkenyl groups having from 2 to 8 carbon atoms and a double bond in any position, e.g. eg, C2-C6 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyletenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 -propenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl , 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propenyl, 1,2-dimethyl-l-propenyl, 1,2-dimethyl-2-propenyl, 1-ethenyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl -l-pentenyl, 2-methyl-l-pentenyl, 3-methyl-1-pentenyl, 4-methyl-l-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2 -pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl , 4-methyl-3-pentenyl, 1, 1-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1 , 3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2 , 3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, l-ethyl -2-butenyl, l-ethyl-3-butenyl, 2-ethyl-l-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2, trimethyl-2-propenyl, 1 -ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-1-propenyl and l-ethyl-2-methyl-2-propenyl; Alkynyl = straight or branched chain alkynyl groups having from 2 to 8 carbon atoms and a triple bond in any position, e.g. eg, C2-C2 alkynyl, co or ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, -pentinyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, -ethyl-2-propinyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl , 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, , l-dimethyl-2-butynyl, 1, 1-dimethyl-3, butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3, 3-dimethyl-1-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl; Cycloalkyl: monocyclic alkyl groups having from 3 to 7 carbon members in the ring, for example, C3-C7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl and cycloheptyl; Cycloalkenyl: monocyclic alkyl groups having from 5 to 7 carbon members in the ring, containing 1 or more double bonds, for example cycloalkenyl of Ct, -C /, such as cyclopentenyl, cyclohexenyl, cycloheptenyl; Aryloxy: aryl groups (as noted above) that bind to the main chain through an oxygen atom (-0-) such as phenoxy > 1-napthoxy and 2-napthoxy; Hetaryl: mono- or polycyclic aromatic radicals which may additionally contain, in addition to the carbon members of the ring, from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and an oxygen or 1 sulfur atom and an oxygen atom or a sulfur atom, for example,: 5-membered hetaryl containing 1 to 3 nitrogen atoms: 5-membered hetaryl ring groups containing, in addition to the carbon atoms, 1 to 3 nitrogen atoms as members of the ring, for example, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4- i-idazolyl, 1,2,4-triazol-3-yl and, 1, 3 , -triazol-2-yl; - 5-membered hetaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one sulfur atom or oxygen atom, or one oxygen atom or one sulfur atom: 5-membered heteroaryl groups which may contain, in addition to the carbon atoms of 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and a sulfur or oxygen atom or an oxygen or sulfur atom as ring members, for example 2 -furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl , 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, -oxadiazol-3-yl, 1, 2,4-oxadiazol-5-yl, 1,2-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1, 2,4-triazol-3-yl, 1, 3, 4 -oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, benzofused 5-membered hetaryl containing from 1 to 3 nitrogen atoms or a nitrogen atom and / or an oxygen or sulfur atom: the 5-membered hetaryl ring groups which may contain, in addition to the carbon atoms, 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and a sulfur or oxygen atom or an oxygen atom or a sulfur atom as ring members and wherein two adjacent carbon members of the ring or a nitrogen and an adjacent carbon member of the ring can be joined by a bridge of the group buta-1,3-dien-l, 4-diyl; -membered hetaryl bonded through nitrogen and containing 1 to 4 nitrogen atoms or benzofused 5-membered hetaryl, attached through nitrogen and containing from 1 to 3 nitrogen atoms: 5-membered hetaryl ring groups they may contain, in addition to the carbon atoms, from 1 'to 4 nitrogen atoms or from 1 to 3 nitrogen atoms, as ring members and in which two adjacent carbon members of the ring or a nitrogen and an adjacent carbon member of the ring The ring may have a bridge of the group buta-1, 3-dien-l, 4-diyl, these rings being attached to the main chain through one of the nitrogen members of the ring; 6-membered hetaryl containing 1 to 3 or 1 to 4 nitrogen atoms: 6-membered hetaryl ring groups which may contain, in addition to the carbon atoms of the 3 or 4 nitrogen atoms as ring members , for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, -pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1, 2, 4, 5-tetrazin-3-yl; Benzofused 6-membered hetaryl containing 1 to 4 nitrogen atoms: 6-membered hetaryl ring groups in which 2 adjacent carbon members of the ring may have a buta-1,3-diene-1,4-diyl group bridge , for example, quinoline, isoquinoline, quinazoline and quinoxaline.

The term "partially or completely halogenated" is intended to express that in the groups so characterized some or all of the hydrogen atoms may be replaced by identical or different halogen atoms, as noted above. The preferred compounds I with respect to their activity against the noxious fungi are those having an isomeric unit [sic] of not less than 93, in particular not less than 95%. In addition, the preferred compounds I with respect to their activity against harmful fungi are those wherein the radicals R1 and R2 have the following meanings, alone or in combination. The groups mentioned below in the meanings of the radicals can also be substituted as indicated in the claims. R1 is Ci-Cß alkyl, preferably C?-C 4 alkyl, in particular isopropyl, tert-butyl or sec-butyl; R? is hydrogen, halogen, cyano, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, preferably hydrogen, chlorine, cyano, methyl or methoxy, in particular hydrogen.

Very particularly preferred, in terms of their use, are the compounds I which are summarized in Tables 1 and 2 below.

Table 1 Preferred compounds among those mentioned in Table 1, in turn, are those in which the substituent R2 is in the 5 or 6 position of the naphthalene ring system. The novel compounds of the formula I are suitable for controlling harmful fungi. For example, the novel compounds I can be applied in the form of directly sprayable solutions, powders, suspensions, also aqueous, oily or other highly concentrated suspensions or dispersions, emulsions, oil dispersions, pastes, powders, dispersion materials or granules, by means of of aspersion, atomization, dusting, dispersion or spill. The forms of use depend on the proposed purposes; in any case, these should guarantee the finest possible distribution of the active ingredients according to the invention. For the treatment of plants, the plants will usually be sprayed or sprinkled with the active ingredients or the seeds of the plants will be treated with the active ingredients. The formulations are prepared using the customary formulation auxiliaries-as will be illustrated below-and in a manner known per se. For example, by spreading the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, it being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Suitable auxiliaries are essentially: solvents such as aromatics (for example, xylene), chlorinated aromatics (for example, chlorobenzenes), paraffins (for example, fractions of mineral oil), alcohols (for example, methanol, butanol), ketones (for example, example, cyclohexanone), amine (e.g., ethanola, diethylformamide) and water; carriers such as crushed natural minerals (eg, kaolins, clays, talcum, calcium carbonate) and crushed synthetic minerals (eg, silica, highly dispersed silicates), emulsifiers as nonionic and anionic emulsifiers (eg, polyoxyethylene ethers of alcohols) fatty acids, alkylsulfonates and arylsulfonates) and dispersants such as lignin sulfite with lyes and methyl cellulose. Suitable surfactants are alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulphonic acids, for example, ligno-, phenol-, naphthalene- and dibutylnaphthalene acids and their fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulphates and sulfates of fatty alcohols; and salts of sulfated hexa-, hepta- and octadecanols and glycol ether fatty alcohols; condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-ethylphenol [sic] ether, iso-octyl-, octyl or nonylphenol ethoxylate, alkylphenol [sic] polyglycol ether, tributylphenol polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoexethylene alkyl ethers or polyoxypropylene alkyl ethers, alcohol polyglycol ether acetate of lauryl, sorbitol esters, residual legions of lignin sulfite or methylcellulose. The powders, materials for the dispersion and powders can be prepared by mixing or grinding the substances at the same time with a solid carrier. Granules, for example, coated granules, impregnated granules and homogeneous granules can be prepared by agglutinating the active ingredients with the solid carriers. The solid carriers are mineral earth such as silica gel, silicas, silica gels [silica], silicates, talc, kaolin, limestone, quicklime, calcium carbonate ferruginous calcareous clay, loess, dolomite clay, diatomaceous earth, sulfates of calcium, magnesium sulfate, magnesium oxygen, crushed synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of plant origin such as cereal flour, tree bark flour, wood flour and flour of walnut shells, cellulose powders or other solid carriers.

Examples of these preparations are: I. a solution of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for use in the form of microdroplets; II. a mixture of 10 parts by weight of a compound I according to the invention, 70 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide to one mole of oleic acid N-monoethanolamide , 5 parts by weight of calcium dodecylbenzene sulfonate, 5 parts by weight of the addition product of 40 moles of ethylene oxide with one mole of castor oil; A dispersion is obtained by finely distributing the solution in water. III. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mol of castor oil; IV. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 55 parts by weight of a mineral oil fraction from boiling point 210 to 280 ° C and 10 parts by weight of the addition product of 40 moles of ethylene oxide with one mole of castor oil; V. a mixture of, crushed in a hammer mill, 80 parts by weight of the compound I according to the invention, preferably solid, 3 parts by weight of diisobutylnaphthalene-2-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from residual sulphite liquors and 7 parts by weight of pulverulent silica gel; a mixture is obtained for the spray by finely distributing the mixture in water; SAW. an intimate mixture of 3 parts by weight of a compound I according to the invention and 72 parts by weight of finely divided kaolin; this powder contains 3 parts by weight of the active ingredient; VII. an intimate mixture of 30 parts by weight of a compound I according to the invention, and 62 parts by weight of silica gel powder and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel; this formulation provides good adhesion properties to the active ingredient; VIII. a stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the sodium salt of a condensate has been phenolsulfonic / urea / formaldehyde, 2 parts by weight of silica gel and 48 parts by weight water weight; this dispersion can be diluted; IX. a stable oil dispersion of 20 parts by weight of a compound I according to the invention, 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of polyglycol ether of fatty alcohols, 20 parts by weight of the sodium salt of a condensate Phenolsulfonic acid / urea / formaldehyde and 50 parts by weight of a paraffinic mineral oil. The novel compounds are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the Phycomycetes and also from the classes of Deuteromycetes, Ascomycetes and Basidiomycetes. Some of these act systemically and can be used as fungicides that act on leaves and foliage. These are especially important to control a large amount of fungi that infect a number of crop plants such as wheat, rye, barley, oats, rice, corn, turf, cotton, soybeans, coffee, sugar cane, vines fruit species, ornamental and vegetable species such as cucumbers, beans and cucurbits and the seeds of these plants. The compounds that are applied giving the treatment to the medium harmful fungi, or the plants, spaces, areas, or materials to keep them free of these, with an effective amount of the active ingredients. The application is made before or after the infection of the materials, seed plants by fungi. Specifically, the novel compounds are suitable for controlling the following plant diseases: Erysiphe graminis (powdery mold) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton and turfs, Ustilago species in cereals and sugarcane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) on strawberries, grapevines, ornamentals and vegetables, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperenospora cubensis in cucumbers, Fusariu and Verticillium species on a variety of plants, Plasmopara viticulture on vines, Pseudoperenospora hu uli on hops and Alternating species on fruits and vegetables.

The novel compounds can also be used in the protection of materials (protection of wood), for example, against Paecilomyces Varioti. In general, the fungicidal compositions contain from 0.1 to 95, preferably from 0.5 to 90% by weight of the active ingredient. Depending on the nature of the desired effect, the application dose is from 0.025 and 2, preferably 0.1 to 1 kg of the active ingredient per ha. For the treatment of the seeds, the amounts of the active ingredient from 0.001 to 50, preferably 0.01 to 10 g, are generally necessary per kg of seed. In the form of use as fungicides the compositions according to the invention may also be present together with other active ingredients, for example, herbicides, insecticides, growth regulators, fungicides or even fertilizers. Mixtures with fungicides often give rise to a broader spectrum of fungal action. The following list of fungicides together with which the compounds according to the present invention can be used are proposed to illustrate the possible combinations, but does not impose any limitation: sulfur, dithiocarbamates and their derivatives, such as iron (III) dimethyldithiocarbamate. , zinc dimethyldithiocarbamate, manganese ethylene bisdithiocarbamate, manganese zinc ethylene diamine bisdithiocarbamate, tetramethyl thiuram disulfides [sic], zinc ammonium complex, (N, N-ethylenebisdithiocarbamate), ammonium zinc complex (N, N'-propylenebisdithiocarbamate), (N , N'-propylenebisdithiocarbamate) of zinc, N, N'-polypropylenebis (thiocarbamoyl) disulfide; nitro derivatives, such as dinitro (1-ethylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-secbutyl-4,6-dinitrophenyl isopropylcarbonate, diisopropyl 5-nitroisophthalate; heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroaniline) -s-triazine, 0, O-diethyl phthalimidophosphonothioate, 5-amino-l- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) Methyl -2-benzimid-azolcarbamate, 2-methoxycarbonylaminobenzimidazole, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, N- (1,1, 2,2-tetrachloroethylthio) tetrahydroftali ida, N-trichloromethylthio tetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1, -dichloro-2,5-dimethoxybenzene, 4- ( 2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine 2-thiol 1-oxide, 8-hydroxyquinoline or its copper salts, 2,3-dihydro-5-carboxanilido-6-methyl-1, -oxatiin, 2 , 3-dihydro-5-carboxanilido-6-methyl-l, -oxatiin 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2 , 5-dimethyl-furan-3-carboxanilide, 2,4,5-trimethyl-furan-3-carboxanilide, N-cyclohexyl-2,5-dimethyl-furan-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3 -carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholin-2,2,2-trichloroethyl acetal, piperazin-1,4-diylbis (1- (2, 2, 2-trichloroethyl) -formamide [ sic], 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2, 6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2, 6- dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methy1propyl] piperidine, l- [2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-ylethyl] -1H1- [ 2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-ethyl] -1H-1,2, -triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4 -chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene , 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) -lH-1, 2,4-triazole-1-ethanol, l- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-yl-methyl] -lH-1, 2,4-triazole, and a variety of fungicides such as dodecylguanidine acétate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N- (2,6-dimethylphenyl) -N- (2-furoyl) ) Methyl DL-alaninate, DL-N- (2,6-dimethyl-phenyl) -N- (2 * -methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L -2- to inobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo -l, 3-oxazolidine, 3- [(3,5-dichlorophenyl) -5-methyl-5-methoxymethyl] -1,3-oxazolidin-2,4-dione, 3- (3,5-dichlorophenyl) -1 -isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoxy- [2- (2,4-dichlorophenyl) ) pentyl] -lH-l, 2,4-triazole, 2,4-difluoro-a "- (1 H-1,2, 4-triazolyl-l-methyl) benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H-1,2, -triazole, Strobilurins such as methyl E-methoximino- [α- (o-tolyloxy) -o-tolylacetate, methyl E-2-. { 2- [6- (2-Cyanophenoxy) pyridimin-4-yloxy] phenyl} -3-methoxyacrylate, methyl E-methoximino- [a- (2,5-di-ethyloxy) -o-tolyl] acetamide, Anilinopyrimines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (l-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-6-cyclopropylpyrimidine) -2-il) aniline, phenylpyrroles such as 4- (2, 2-difluoro-l, 3-benzodioxol-4-yl) irorol-3-carbonitrile, They are added as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acryloyl orpholine, Synthesis Example The protocol shown in the following synthesis example can be used to obtain other representative compounds I by modifying the initial compound. The physical data of the products prepared following this protocol are shown in Table 2 below. 1. (R) -1-amino-1- (β-naphthyl) ethane 1.1 Preparation of (R) -N- [1- (β-naphthyl) ethyl] methoxyacetamide CH3 3 39 g (0.23 mol) of racemic 1-amino-l- (β-naphthyl) ethane is dissolved in 200 ml of methyl tert-butyl ether. The solution is treated with 29.5 g (0.25 mol) of methyl methoxyacetate, the reaction begins by adding 0.5 g of lipase (approximately 1000 U / mg, Pseudomonas spec. DSM 8246), and the batch is mixed during the reaction on a vibrating table. . After the reaction rate has reached 50% (verified by means of gas chromatography), which is the case after about 48 hours, the enzyme is filtered, the filtrate is concentrated and the concentrate is collected in acid dilute hydrochloric acid (300 ml) and diethyl ether (300 ml). After the ether phase is separated, the acid phase is re-extracted using diethyl ether. After the ether phases are combined, dried and concentrated, 18.7 g (0.08 mol) of (R) -N- [1- (β-naphthyl) ethyl] methoxyacetamide are obtained. After the addition of a sodium hydroxide solution to alkaline pH, it is possible to extract the (S) -1- (β-naphthyl) ethane from the aqueous phase with diethyl ether. Drying and evaporation of the organic phase yields 15 g of (0.09 mol) of (S) -l-amino-1- (β-naphthyl) ethane. After the reaction to give trifluoroacetamide, the enantiomeric excess (= ee) is determined on a chiral GC column (20 m Chiralolex B-F) as 89.5%. 1. 2 hydrolysis of (R) -N- [1- (ß-naphthyl) ethyl] methoxyacetamide 14. 7 g (60.4 mmol) of (R) -N- [1- (β-naphthyl) ethyl] -methoxyacetamide is dissolved in 75 ml of ethylene glycol, and 15 g of a 50% potassium hydroxide solution are added. After heating the mixture for 3 hours at 150 ° C, it is cooled, diluted with 300 ml of water and extracted 4 times using in each case 500 ml of diethyl ether. The combined ether phases are dried and concentrated. This produces 8.1 g (47 mmol) of (R) -1-amino-1- (β-naphthyl) ethane with a value, ee of 94.8%. 2. N- (tert-butyloxycarbonyl) -L-valine (R) -l-naphthylethylenamide 1.0 g (5.9 mmol) of diethyl cyanophosphate and 1.3 g (12 mmol) of triethylamine are added to a solution of 1.2 g (5.8 mmol) of tert-butoxycarbonyl-L-valine and 1.0 g (5.8 mmol) of (R) -1-amino-1- (β-naphthyl) ethane in 50 ml of tetrahydrofuran. Stirring is continued for 1 hour at 0 ° C and for 15 hours at 20 ° C. The solvent is subsequently removed and the residue is taken up in 300 ml of ethyl acetate, the organic phase is washed successively in each case with 200 ml of a 5% sodium hydroxide solution, 10% hydrochloric acid, a 10% sodium hydrogen carbonate solution and water, dried and concentrate There remain 2.0 g (5.4 mmol) of N- (tert-butyloxycarbonyl) -L-valine (R) -1-β-naphthylethylamide (mp 93 ° C, compound 2.1 in Table 2). 3. N- (isopropyloxycarbonyl) -L-valin (R) -1- (β-naphthyl) ethylamide 5 ml of trifluoroacetic acid are added to 1.70 g (4.6 mmol) of N- (tert-butyloxycarbonyl) -L-valine (R) -1- (β-naphthyl) ethylamide, with cooling, and the mixture is stirred for 1 hour at 0 ° C. Subsequently, it is heated to 20 ° C, most of the trifluoroacetic acid is distilled off and the residue is taken up in 100 ml of dichloromethane and washed successively, in each case with 50 ml of a 2N sodium hydroxide solution, 5% sodium hydrogen carbonate solution and water. After the organic phase is dried and concentrated, 1.07 g (4.0 mmol) of -L-valine (R) -1- (β-naphthyl) ethylamide remain as a viscous yellow oil. 0.54 g (2.0 mmol) of this compound and 0.22 g (2.2 mmol) of triethylamine in 40 ml of toluene are treated with 0.24 g (2.1 mmol) of isopropyl chloroformate at 0 ° C, and the mixture is stirred for 15 hours at 20 ° C. After removing the solvent, the residue is taken up in 50 ml of ethyl acetate and washed successively using in each case 40 ml of a 5% sodium hydroxide solution, 10% hydrochloric acid, a carbonate solution 10% sodium acid and water. After the organic phase has dried, the solvent is removed. 0.6 g (1.7 mmol) of the title compound remain as a colorless crystalline residue (mp) 145-7 ° C, Compound 2.2 in Table 2).

Table 2 EXAMPLES OF USE In the following experiments, which are proposed to demonstrate the fungal activity of the compounds I, an emulsion is used which was composed of 10% by weight of the active ingredient of the general formula I and 90% by weight of the mixture of 70% by weight of cyclohexanol, - 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent containing emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor® EL (EmulanTEL, emulsifier based on ethoxylated fatty alcohols). The desired concentration of the active ingredient was adjusted by diluting this emulsion with water.

Plasmopara Vitícola The leaves of the grapes cv. "Müler-Thurgau" in pots were sprayed with an aqueous spray mixture that had been separated as described above. To be able to assess the duration of action of the active ingredient, the plants were placed in the greenhouse for 8 days after the spray coating was dried. Only then the leaves were infected with a suspension of zoospores of Plasmopara viticola (the lanuginous grape mold). The vines were first placed in a chamber with air sutured with steam at 2 ° C, for 48 hours and then in a greenhouse at 20 to 30 ° C for 5 days. After this time, the plants were returned to the humidity chamber for 16 hours to favor the eruption of the sporangiophores. Then, the amount of fungal eruption on the underside of the leaves was visually assessed. The results of the test can be seen in Table 3 below.

Table 3 Results of the test with compounds according to the invention in comparison with the racemates containing them (described in DE-A 43 21 8978) in Plasmopara Vitícola.

The leaves of the plants that had not been treated with one of the aforementioned compounds showed fungal disease on 75% of the lower area of the leaf,

Claims (1)

1. CLAIMS A carbacarboxamidoamide of the general formula I in an isomeric purity of more than 90 t by weight, wherein the variables have the following meanings: R 1 is Ci-Cβ alkyl, C 2 -C alkenyl or alkynyl it is possible that these radicals are partially or completely halogenated and / or have attached to these from 1 to 3 of the following groups: cyano, C? ~ alkoxy, C _-C4 haloalkoxy, C?-C 4 alkylthio, alkoxycarbonyl of C? ~ C4, C3-C7 cycloalkyl, C¿-C7 cycloalkenyl, aryl, aryloxy and hetaryl, it being possible for the cyclic and aromatic rings of these groups, in turn, to be attached thereto from 1 to 3 of the following substituents: halogen, cyano, C1-C4 alkyl, C? -C alkoxyalkyl, C? C haloalkyl, C? -C4 alkoxy, C? -C haloalkoxy, C? -C alkylthio, alkoxycarbonyl of C? -C4, aryl, aryloxy and hetaryl; c = hydrogen, halogen, cyano, nitro, Ci-Cß alkyl, Ci-C-haloalkoxy, C?-C4 haloalkyl, C 1 -C 4 alkoxy, C?-C4 haloalkoxy, C?-C4 alkylthio , haloalkylthio of C _, - C4, or a phenyl group bonded through an oxygen or sulfur that is unsubstituted or has attached thereto from 1 to 3 of the following substituents: halogen, C_C alkyl and C alkoxy; ? _C4. A process for the preparation of a carbamoylcarboxamide of the general formula I according to claim 1, which comprises reacting a carba-oil-caboxylic acid of the general formula II. (S) with an amine of the general formula III The process for the preparation of the carbamoylcarboxamide of the general formula I, according to claim 1, which consists of: a) converting a carbamoylcarboxamide of the general formula I wherein the group R1-0- (CO) is a protecting group that can be removed in a manner known per se in an amino acid amide IV. and b) reacting the resulting amino amide IV with a chloroform ester of the general formula V. R1-O-C-Cl, V) in the presence of a base. A composition suitable for controlling harmful fungi, containing an effective amount of at least one compound of the general formula I according to claim 1, and at least one adjuvant of the customary formulation. A process for the preparation of a composition according to claim 3, which comprises processing a nicotically active amount of at least one compound of the general formula I according to claim 1 together with at least one auxiliary of the customary formulation, in a manner known per se. A method for controlling harmful fungi, which consists of treating the harmful fungus, its environment or the plants, spaces, areas or materials to keep them free thereof, with an effective amount of at least 1 compound of the general formula I of conformity with the claim 1 or with a composition according to claim 3. The use of a compound of the general formula I, according to claim 1 or of a composition according to claim 3, for controlling the harmful fungi.