DK161702B - N- (2-PHENOXYETHYL) NICOTINAMIDE DERIVATIVES, THEIR PREPARATION, FUNGICIDE AGENTS CONTAINING THE DERIVATIVES, AND THE USE OF THE DERIVATIVES AND THE AGENTS - Google Patents

Description

in

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The present invention relates to novel N- (2-phenoxyethyl) nicotinamide derivatives of the general formula I

ISLAND

II

wherein R 1 represents halogen at the 5- and / or 6-position of the pyridyl group, R 1 represents g-alkyl, g-alkoxy-C 1-4 alkyl or optionally in the benzene nucleus with halogen mono-, di- or trisubstituted benzyl, or alkyl, 10 m is 1 or 2, and n represents 1, 2 or 3, and acid addition salts of these compounds.

The compounds of the general formula I and their acid addition salts have fungicidal properties and are suitable as fungicidal active substances, especially for use in agriculture and horticulture.

The invention further relates to a process for the preparation of the compounds of general formula I and acid addition salts thereof, fungicidal agents containing as active substances compounds of the general formula I or acid addition salts thereof, and to the use of such compounds, acid addition salts and antifungal agents in the art. for agriculture and horticulture.

GB 2,129,798 is described, inter alia, fungicidal N-alkyl and N-alkoxyalkyl-N- [2- (halogeno and / or alkylphenoxy) ethyl] nicotinamides, the 3-pyridyl group being optionally substituted by one or two alkyl groups. The compounds of the invention of formula I differ substantially from the known compounds in that the 3-pyridyl group is substituted with halogen instead of being either

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2 substituted with alkyl or unsubstituted. In addition, the compounds of the invention generally have stronger fungicidal activity than the known compounds.

In the above formula I, the term "halogen" includes fluorine, chlorine, bromine and iodine. The alkyl groups may be straight or branched, which also applies to each alkyl moiety in the alkoxyalkyl group. In the disubstituted 3-pyridyl group or the di- or trisubstituted phenyl group, the substituents rA or may be the same or different. Also in cases where R 1 represents di- or trisubstituted benzyl, the halogen substituents may be the same or different.

The presence of at least one asymmetric carbon atom in the compounds of general formula I allows the compounds to occur in optically isomeric forms. Independently of this, atropic isomerism also occurs in some cases. The general formula I should include all 15 of these possible isomeric forms.

As acid addition salts of the compounds of general formula I, physiologically acceptable salts can be used. Preferably, salts of these compounds include inorganic and organic acids such as hydrochloric, nitric, phosphoric, mono- and bifuctional carboxylic acids and hydroxycarboxylic acids, for example acetic, maleic, succinic, fumaric, tartaric, citric, sulfonic acids, for example 1,5-naphthalene disulfonic acid.

As to the preferred meanings of R 2,. R 1, m and n,. the following may be stated: If R 1 represents alkoxyalkyl, it is preferably 2-25 methoxyethyl. (R 2) m preferably represents a single halogen atom at the 5-position of the pyridyl group. The substituents R 1 are preferably in the ortho and / or para positions of the phenyl group.

Preferably, R 1 represents fluorine, chlorine or bromine, R 2 preferably represents g-alkyl, g-alkoxy-C 1-6 alkyl or optionally substituted benzyl, as defined above, in particular ethyl, n-propyl or n -butyl, R 2 preferably represents chlorine or methyl, m is preferably 1, n is preferably 2 or 3. Particularly preferred with (R 2) n-substituted phenyl groups are

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3 2,4,6-trichlorophenyl, 2,4-dichloro-6-methylphenyl and 2,6-dichlorophenyl.

Particularly preferred compounds of the general formula I are: 5-Fluoro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- (n- propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (n-propyl) -N- [2- (2,4,6-trichloro-benoxy) ethyl] nicotinamide 5-Bromo-N- [2- (2,4,6-trichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide and 5-bromo-N- [2- (4,6-tolyloxy) ethyl] N- (n-propyl) -nicotinamide.

Further examples of compounds of general formula I are: 5-Fluoro-N- (4-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotine amide, 5-chloro-N- ( 4-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (4-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotine -15 amide, 5-fluoro-N- (2,4-dichlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- (2,4-dichlorobenzyl) ) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-fluoro-N- (3,4-dichlorobenzyl) -N- [2- (2,4,6- trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- (3,4-dichlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (3.4 -dichlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-iodo-N- (n-butyl) -N- [2- (2,4,6-trichlorophenoxy) ) ethyl] nicotinamide, 5-iodo-N- (n-pentyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-iodo-N-ethyl-N- [2- (4) , 6-dichloro-o-tholyloxyethyl] nicotinamide and 5-iodo-N-ethyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide.

The process of the invention for preparing the compounds of general formula I and their acid addition salts is characterized in that:

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4

a) a reactive derivative of a nicotinic acid of general formula II

COOH

"ΜδΓ

wherein R 2 and m are as defined above, reacted with a 2-phenoxyethylamine of the general formula III

HN-chocho-0th

2 111 r 10 2 - (R 3) n 5 where, R 2 and n have the meaning given above, or

b) an N- (2-hydroxyethyl) nicotinamide of the general formula IV

0

II

✓C “N” CH2CH2OH IV

vv

N

wherein R 2 and m are as defined above are reacted with a phenol of the general formula V

HAY

IOH> n where R 1 and n have the meaning given above,

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5 and a compound thus obtained of the general formula I, if desired by reaction with an acid, is converted to the corresponding acid addition salt.

In process variant a), the reactive derivative of the nicotinic acid of general formula III is preferably an acid halide, especially acid chloride or acid bromide, or the imidazolid. In either case, the reaction is conveniently carried out in the presence of a substantially anhydrous, inert diluent, especially an organic solvent, such as an aliphatic or cyclic ether, for example 1,2-dimethoxyethane, tert-butylmethyl ether, tetrahydrofuran or dioxane; an aromatic solvent, for example benzene or toluene; an aliphatic halogenated hydrocarbon, for example methylene chloride or chloroform; or dimethylformamide or a mixture of such diluents at temperatures between about -20 ° C and about 150 ° C. If an acid halide is used, preferably at temperatures between 0 ° C and the reflux temperature of the reaction mixture, especially at room temperature, and in the case of using an imidazolid, preferably at temperatures between room temperature and ca. 120 ° C, especially at the reflux temperature of the reaction mixture.

Furthermore, the reaction of the acid halide with the 2-phenoxyethylamine is conveniently carried out in the presence of an organic or inorganic acid-binding agent. Examples of suitable acid binding agents are especially tertiary amines such as triethylamine and pyridine, as well as alkali metal carbonates and hydrogen carbonates such as sodium and potassium carbonate and sodium and potassium hydrogen carbonate and sodium and potassium hydrogen carbonate.

When using imidazolides, this is conveniently prepared in situ, with the nicotinic acid of general formula II reacting with carbonyl diimidazole in the presence of a substantially anhydrous inert diluent, in particular one of the above-mentioned organic solvents, and at elevated temperature. especially at the reflux temperature of the reaction mixture. The reaction participants are preferably reacted with one another in substantially equimolar amounts. Then, optionally, after cooling the reaction mixture to room temperature

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6 2-Phenoxyethylamine of the general formula III to the mixture, especially also in equimolar amount, and the reaction of the in situ prepared imidazolid with the amine is then carried out as described above in the same reaction medium. However, the imidazolid can also be isolated in the usual manner and reacted with the amine in a new diluent.

Process variant b) is conveniently carried out using the known Redox reaction system azodicarboxylic acid ester / triphenylphosphine in the presence of a substantially anhydrous inert diluent. As a diluent, especially aprotic organic solvents such as aliphatic or cyclic ethers, eg diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aromatic carbohydrides, e.g. benzene and toluene, halogenated hydrocarbons, e.g. methylene chloride, The reaction temperatures are preferably between ca. 0 and 60 ° C, preferably operating at room temperature. In a manner known per se, either the azodicarboxylic acid ester is added to a solution of triphenylphosphine and the starting materials of the general formulas IV and V at room temperature or a lower temperature, or the triphenylphosphine is added to the other three reactants, the former being the preferred one. . The azocarboxylic acid ester is preferably the diethyl or diisopropyl ester.

To prepare acid addition salts of the compounds of general formula I, these are reacted with the desired acid in the usual manner.

The isolation and purification of the compounds thus prepared of the general formula I or the acid addition salts thereof can then be carried out in a manner known per se. Furthermore, any isomer mixtures of these compounds can be cleaved into the individual isomers in a manner known per se.

The starting materials of general formula IV used in process variant b) are novel and can be prepared by reacting a reactive derivative of nicotinic acid of the above formula II with an ethanolamine of general formula VI

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7

r2hn-ch2ch2-oh VI

wherein R 2 has the meaning given above,

under the same reaction conditions described above in connection with process variant a). A further method of preparation is, for example, reaction of a nicotinic acid lower alkyl ester of the general formula VII

✓COOR4

iRl, m- (Oj VII

N

wherein R 1 and m have the meaning given above and R 2 represents a lower alkyl residue, especially methyl, with an ethanolamine of the above Formula VI. This reaction 10 is conveniently carried out in the presence of an excess of ethanolamine of the general formula VI as a solvent and at elevated temperature, preferably at a temperature between ca. 80 ° G and 160 ° C.

The other starting materials, ie. The nicotinic acids of general formula II and the reactive derivatives thereof, the 2-phenoxyethylamines of general formula III, and the phenols of general formula V are either known or can be prepared in a manner known per se.

The compounds of the invention, i. The compounds of general formula I and their acid addition salts have fungicidal activity and can therefore be used to control fungi in agriculture and horticulture.

These are particularly suitable for growth inhibition or eradication of phytopathogenic fungi on plant parts, eg leaves, stems, roots, tubers, fruits or flowers, and on seeds and in the soil and are particularly effective in controlling Septoria nodorum, Cercosporella herpotrichoides,

Altemaria brassicae and Altemaria brassicicola as well as Erysiphe ci-25 choracearum, and fungi of the genus Podosphaera, Uncinula, Pillow i-nia, Uromyces, Hemileia, Fusarium, Rhizoctonia, Cercospora, Helmin-

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8 thosporium, VerCicillium, Botrytis, Penicillium, Venturia, Sclerotinia and Rhynchosporium.

Furthermore, some representatives of the compounds of the invention have pronounced action against wood-destroying fungi such as Coniophora 5 puteana, Gloeophyllum trabeum, Aureobasidium pullulans and Sclerophoma pithyophila.

The compounds of the invention are distinguished by their preventive and curative effect as well as by high plant tolerability.

The compounds of the invention work under greenhouse conditions 10 already at concentrations of 1-500 mg of active substance per day. liters of spray liquid. In outdoor areas, concentrations of 50 g to 1.5 kg of active substance of the general formula I are preferably used. ha. for each treatment.

For the control of fungi in seeds or soil by pickling methods, dosages of 0.05-1.5 g of active substance of the general formula I are preferably used. kg of seeds or soil.

The effect of the following compounds A-I on various fungi was investigated in the following tests:

Compounds of Compounds Known From the Invention GB 2,129,798

Compound A Compound B

O ci O cl

igj "c3> 7 © r ^ J © L

Cl Cl H Cl Cl (Example 1, 9th Compound) (Compound No. 1, Table I)

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9

Compound C Compound D

0 Cl 0 Cl

Bv ^ Tc # 2CI | f v-k [OJ (PJ CHSCH, 0C »3 H Cl Cl cl cl cl (Example 1, 17 compound) (page 13, line 60) 5

Compound E Compound F

VVt erVé

Cl Cl (Example 1, 12th compound) (Compound No. 4, Table I)

Compound G Compound I

O cl 0 Cl W; - Μ. 0 ^ M.

Cl Cl Cl Cl (Example 1, 3rd Compound) (Compound No. 35, Table IV)

Compound H

virile

Cl Cl (Example 1, 7th Compound) 225449BC.001 / A37 / NO / NO / KW / 26.11.1990

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Test 1: Effect on Septoria nodorum 30-40 sown wheat plants, divided into 2 pots, in the 1-leaf stage, thoroughly sprayed on all sides with an aqueous dispersion of the test substance (as usual custom and use prepared as a spray powder) and then further cultivated in a climate cabin at 15-17 ° C and a photo period of 14 hours / day. Two days after the treatment, the infection of the plants occurred by spraying with an aqueous conidia suspension (about 1 x 10 6 conidia / ml). Then, the wheat plants were incubated for 2 days in a climate cabin at dew point conditions and 24 ° C and then for 10 5 days in the greenhouse. The test result was found in determining the percentage leaf area destroyed by Septoria nodorum relative to the infected, untreated controls.

Test 2: Action against Erysiphe circhoracearum (cucumber mildew)

Two cucumber plants of the "Chinese snake" variety were sprayed thoroughly on all sides on 2 sides with an aqueous dispersion of the test substance (as usual custom and use prepared as spray powder) and then further cultivated in the greenhouse. Twenty-four hours after treatment, the primary leaves of the plants were pollinated with conidia of Erysiphe circhoracearum. The test result was found 7-9 days after infection 20 in determining the percentage leaf surface overgrown with Erysiphe circhoracearum relative to the infected controls not treated with the test substance.

Test 3: Effect against Altema ria brassicae 4 sown cabbage plants, distributed in 2 pots, at the 6-leaf stage, was thoroughly sprayed with an aqueous dispersion of the test substance (as usual practice and use prepared as spray powder) and then further cultivated in a climate cabin at 19 ° C and 16 hours of lighting / day. Two days after treatment, infection of the plants occurred by spraying with an aqueous conidial suspension (approximately 30,000 conidia / ml). Then, the cabbage plants were incubated at 24-26 ° C, dew point conditions and a photoperiod of 16 hours / day. The test result was found 2-5 days after infection in determining the percentage leaf area that

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11 were attacked by Altemaria brassicae, relative to the infected, untreated controls.

Test 4: Effect against Helminthosporium oryzae 15-20 rice sprouts (distributed in 2 pots) were thoroughly sprayed at the 1-leaf stage 5 with an aqueous dispersion of the test substance (as usual custom and use prepared as a spray powder) and then cultivated in a climate booth at 19 ° C and 16 hours of lighting / day. Two days after treatment, the test plant infection occurred by spraying with an aqueous conidial suspension (approximately 80,000 10 conidia / ml). Thereafter, the rice plants were incubated at 24-26 ° C, dew point conditions and a photoperiod of 16 hours / day. The test result was found 2-5 days after infection in determining the percentage leaf area damaged by Helminthosporium oryzae relative to the infected, untreated controls.

The above-mentioned spray powder consisted in each case of 25% by weight test substance (compound of formula I or active substance of the prior art, respectively) and 75% by weight of carrier mixture, the latter having one of the following compositions:

Carrier Blend A Carrier Blend B

20 (for solid test substances) (for liquid test substances)

Component Weight percent- Component Weight percent cent 25 Nonylphenol ethoxylate 3 Nonylphenol ethoxylate 6 High dispersion of silicic acid 6 Methylhydroxyethyl

Methyl hydroxyethyl cellulose 2 cellulose 1 sodium oleate 4

Sodium oleate 2 Polynaphthalic acid 30 Polynaphthalic acid sodium salt 20 Sodium salt 10 Precipitation

Hydrated aluminum silicic acid 68 Aluminum silicate 78 _.

100 100 100

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12

In each case, the amount of water was added to the spray powder to produce a spray liquid of 16, 50, 160 and 500 mg test substance / liter, respectively.

The results are given in the table below: 5 Test Dosage Percentage effect (mg test substance - SeptorLa Erysiphe Alt emar La Helminthostans per 1 nodorum cichoraceabrassicae sporium spray tea liquid) arum oryzae (test 1) (test 2) (test 3) (test 4)

Connect 160 100 Part A 50 95 100 16 95 100 5 - 95 15 .....-......-..................... -.........---- ..... .....................

Connect 160 90 0 part B 50 90 16 70 5 20 ................................................... -------------------------------------

Connect 500 - 70 70 division C 160 80 - 50 50 - 16 20 - 25 ------------------------------ --------------------------------------------

Join 500 500 50 50 Division D 160 - - - 50 - - - 16 - - - 30 ----------------------------- ----------------------------------------------

Connect 500 95 - 95 90 part E 160 85 - 90 60 50 75 85 60 20 16 55 65 20 0 35 5 20

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Test Dosage Percentage effect (mg test substance Septoria Eryslphe Altemaria Helminthostans per 1 nodorum cichoraceous brassicae sporium spray) arum / oryzae 5 (test 1) (test 2) (teea * t 3) (test 4)

Connect 500 80 - 100 20 division F 160 70 30 50 65 90 10 - 10 16 20 85 0 - 5 80

Connect 500 - - 70 70 division G 160 97 0 15 50 90 16 70 5 -

Connection 500 - - 95 90 20 division H 160 95 - 97 30 50 95 100 60 25 16 88 95 60 10 5 85 25 Connection 500 60 - 30 40 division I 160 - 50 95 16 90 5 90 30 ___ means that that has not been evaluated at the dosage in question, but that it must, however, be assumed that the activity is at least as great as the activity at the nearest lower dosage and not greater than the activity at the next higher dosage respectively.

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Conclusion T tests 1 and 2, to which compounds A and B have been subjected, compound A exhibited high fungicidal activity in the dosage range of 160-16 mg / 1 spray and 50-5 mg / 1 spray, respectively. Also, Compound B showed, in Test 1, high efficacy in the particular dosing range, albeit in all cases lower than the corresponding for Compound A at the corresponding single doses. Thus, for example, Compound B exhibited 90% efficacy at the dosage of 160 mg / L spray, while Compound A at this dosage exhibited 100% efficacy. In Test 2, Compound A showed particularly high fungicidal activity (100-95%) in the dosage range of 50-5 mg / 1 spray, while even at the even higher dosage, 160 mg / 1 of spray liquid showed no effect at all.

In Tests 1, 3 and 4 which were subjected to compounds C and D, Compound C showed good fungicidal activity in the dosage range of 160-16 mg / 1 spray liquid and 500 mg / 1 spray liquid and 500 mg / 1 spray liquid, respectively, at which the impact was measured. For example, compound C in test 1 at the dosage 160 showed 20 mg / 1 spray liquid 80% effect, while compound D at the even higher dosage 500 mg / 1 spray showed only 50% effect. In both tests 3 and 4, compound C at the single dose at which the effect was measured showed significantly higher efficacy (in both cases 70%) than that of compound D (50% and 25, 60%, respectively). -

Compounds E and F were subjected to all four tests. In tests 1 and 4, compound E at each of the dosages used showed in all cases higher efficacy than the corresponding dosages of compound F. Especially in test 4, compound E at the dosage showed 500 mg / l of spray liquid 90% effect - in contrast to 20% of the effect of compound F at the same dosage. In test 2, on the other hand, compound F at the doses 50 and 16 mg / 1 of spray liquid showed a slightly higher effect (90% and 85%, respectively) and at the dose of 5 mg / 1 spray liquid (90%) than the effect. of binding compound E at these dosages (85%, 65% and 20% effect, respectively). In test 3, compound F showed a higher effect than

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The compound E (100% vs. 90%) at the highest dosage, 500 mg / L spray. Compound E, admittedly, at the lower doses 160, 50 and 16 mg / l of spray solution had a significantly higher effect (90%, 60% and 20%, respectively) over the effect of compound F (30%, respectively). 's, 10%' s and none). Taking into account the results of all four tests, it turns out that compound E is more effective than compound F.

Finally, compounds G, H and I were also subjected to all four tests. Compounds G and H, at the dosages used, in all cases exhibited higher efficacy in Tests 1, 3 and 4 than Compound I. Compound G showed, in Test 2, essentially no effect at the dosage of 160 mg / L spray and at lower dosages, while Compound I is very effective throughout the range of action, which is also true of compound H. Compounds H and I work equally well in the dosage range of 50-5 mg / l spray liquid, in which range the effect was measured (100-85% relative to 95 -90% effect). Once again, it is clearly seen that compounds G and H are, on the whole, more effective than compound I when the results of all four tests are taken together.

For structural reasons, the effect of compounds A should; C; E; and G and H are compared to the action of compounds B; D; F; and I. Under these circumstances, it is clear and unambiguous that in the vast majority of cases, the fungicidal effect of the compounds is A; C; E; and G and H are higher than the action of compounds B; D; F; and I at the same dosage / against the same fungal species.

It can be concluded that, on the basis of the test results stated and under the same conditions, the compounds of the present invention have excellent fungicidal properties which are generally unique to those of the known compounds 30.

The compounds of the invention can be formulated into various agents, for example, solutions, suspensions, emulsions, emulsifiable concentrates and powdered preparations. The fungicidal agents of the invention are characterized in that they contain an effective amount of at least one compound of the general formula I as defined.

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16 above or an acid addition salt of such a compound as well as formulation adjuvants. Conveniently, the agents contain at least one of the following formulation aids:

Solid carriers: Solvents or dispersants, surfactants (wetting and emulsifying agents), dispersing agents (without surfactant effect) and stabilizers.

As solid carriers, natural minerals such as kaolin, clay soil, diatomaceous earth, talc, bentonite, chalk such as slime, magnesium carbonate, limestone, quartz, dolomite, attapulgite, montmorillonite and diatomaceous earth, synthetic minerals such as high acid, silicates; organic substances such as cellulose, starch, urea and synthetic resins and fertilizers such as phosphates and nitrates, such carriers for example being in the form of granules or powders.

As solvents or dispersants, aromatic hydrocarbons such as toluene, xylene, benzene and alkyl naphthalene, chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene and methylene chloride, aliphatic hydrocarbons such as cyclohexane and paraffins, e.g. such as butanol and glycol, as well as ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and highly polar solvents or dispersants such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, such solvents and dispersants preferably having a flash point of at least 30 ° C and a boiling point of at least 50 ° C, and water.

Among the solvents and dispersants are also the so-called liquid gaseous fillers or carriers which are gaseous at room temperature and under normal pressure. Examples of such products are, in particular, aerosol propellants such as halogenated carbohydrates, such as dichlorodifluoromethane. For example, if water is used as a solvent, organic solvents can also be used as auxiliary solvents.

The surfactants (wetting and emulsifying agents) may be nonionic compounds such as condensation products of fatty acids, fatty alcohols

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17 or fat-substituted phenols with ethylene oxide; fatty acid esters and ethers of sugars or polyhydric alcohols; the products obtained by the condensation of sugars or polyhydric alcohols with ethylene oxide; block polymers of ethylene oxide and propylene oxide or alkyl dimethyl amine oxide.

The surfactants may also be anionic compounds such as soaps, fatty sulfate esters, for example dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate; alkyl sulfonates, aryl sulfonates and fatty aromatic sulfonates such as alkyl benzene sulfonate, e.g., calcium dodecyl benzenesulfonate, more complex fatty sulfonates such as the amide condensation products of oleic acid and N-methyltaurine, and the sodium sulfonate of dioctyl succinate.

The surfactants may finally be cationic compounds such as alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride, alkyl trimethylammonium chloride and ethoxylated quaternary ammonium chlorides.

As dispersing agents (without surfactant effect), there may be mentioned lignin, sodium and ammonium salts of lignin sulfonic acid, sodium salts of maleic anhydride diisobutylene copolymers, sodium and ammonium salts of sulfonated polycondensation products of naphthalene and formaldehyde, and 20 sulfite wastewater.

As dispersants which are particularly suitable as thickening or anti-precipitating agents may be mentioned, for example, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, alginates, ca-senates and blood albumin.

Examples of suitable stabilizers are acid binding agents, e.g., epichlorohydrin, phenylglycide ethers and soy epoxide; antioxidants, for example gallic acid esters and butyl hydroxytoluene; UV absorbers such as substituted benzophenones, diphenylacrylonitrile acid esters and cinnamic acid esters; and deactivators, e.g., salts of ethylenediaminetetraacetic acid and polyglycols.

The fungicidal agents of the invention may contain, in addition to the active substances of general formula I, other active substances, e.g.

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18 fungicides, insecticides and acaricides, bactericides, plant growth regulators and fertilizers. Such combination agents are suitable for broadening the spectrum of effects or for specifically influencing plant growth.

Generally, depending on their nature, the fungicidal agents of the invention contain between 0.0001 and 85% by weight of one or more compounds of the invention as active substances. They may be in a form suitable for storage and transport. In such forms, for example emulsifiable concentrates, the active substance concentration is usually in the higher range of the above concentration range. These forms can then be diluted with the same or different formulation auxiliaries to an active substance concentration suitable for practical use, and such concentrations are usually in the lower range of the above concentration range.

Emulsifiable concentrates usually contain 5-85 wt.%, Preferably 25-75 wt.% Of one or more compounds of the general formula I. ready-to-use solutions, emulsions and suspensions suitable for example as spray liquids. For example, in such spray liquids, concentrations of between 0.0001 and 20% by weight may be present. In the "ultra-low volume" method, spray liquids may be formulated in which the active ingredient concentration is preferably 0.5-20% by weight, whereas the low volume and high volume spray formulations preferably have an active substance concentration of 0.02-1.0 25 or 0.002-0.1% by weight.

The fungicidal agents of the invention may be prepared by mixing at least one compound of the general formula I or an acid addition salt of such a compound with formulation auxiliaries.

The preparation of the agents can be carried out in a manner known per se, for example by mixing the active substances with solid carriers, solution or suspension in suitable solvents or dispersants, optionally winning the use of surfactants as wetting or emulsifying agents or of dispersants, by dilution of an already manufactured

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19 emulsifiable concentrate with solvents or dispersants, etc.

In the case of powdery agents, the active substance can be mixed with a solid carrier, for example by co-grinding, or the solid carrier can be impregnated with a solution or suspension of the active substance, after which the solvent or dispersant is removed by evaporation, heating or suction under reduced pressure. By adding surfactants or dispersants, such powdery agents can easily be wetted so that they can be converted into aqueous suspensions suitable, for example, as spraying agents.

The compounds of the invention can also be mixed with a surfactant and solid support to form a wettable powder which can be dispersed in water or they can be mixed with a solid pre-granulated carrier to form a granular product.

If desired, a compound of the invention can be dissolved in a water-immiscible solvent, for example, an alicyclic ketone, which conveniently contains dissolved emulsifier, so that the solution, by the addition of water, acts self-emulsifying. Alternatively, the active substance may be mixed with an emulsifier and the mixture may then be diluted with water to the desired concentration. In addition, the active substance can be dissolved in a solvent and then mixed with an emulsifier. Such a mixture can also be diluted with water to the desired concentration. This gives emulsifiable concentrates or ready-to-use emulsions.

The use of the compositions according to the invention can be carried out by the usual methods of application in plant protection or agriculture. The method according to the invention for controlling fungi is characterized in that the article to be protected, for example plants, plant parts or seeds, is treated with an effective amount of a compound according to the invention or an agent according to the invention.

The invention is further illustrated by the following examples.

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I. Preparation of Active Formulas of the General Formula I Example 1

To 1.9 g (8.5 millimoles) of 5-bromnicotinic acid chloride in 20 ml of anhydrous methylene chloride are added dropwise with stirring a solution of 2.4 g (8.5 5 millimoles) of N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-propylamine and 0.85 g (8.5 millimoles) of triethylamine in 10 ml of methylene chloride and the reaction mixture is stirred for 1 hour at room temperature. Then the mixture is washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, the remaining dark brown oil is purified chromatographically on silica gel using chloroform as eluent. There is thus obtained 3.7 g (93% of theory) of 5-bromo-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide in the form of a yellowish oil. Mass spectrum m / e: 271 (100%, ET1 "phenol), 186 (76%), 158 (42%).

Analogously, starting from: 5-Bromnicotinic acid chloride and N- [2- (4,6-dichloro-o-tolyloxy) ethyl] -n-propylamine, 5-bromo-N- [2- (4, 6-dichloro-o-tolyloxy) ethyl] -N- (n-propyl) -nicotinamide as a brown oil, mass spectrum m / e: 271 (98%, M + phenol), 186 (48%), 158 (22%) , 5-bromnicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] ethylamine, 5-bromo-N-ethyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, m.p. 84-86 ° G, 5-bromnicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-butylamine, 5-bromo-N- (n-butyl) -N- [2- (2,4,6-Trichlorophenoxy) ethyl] nicotinamide as a colorless oil, mass spectrum m / e: 285 (100%, M + phenol), 196 (40%, phenol), 186 (68%) , 5-bromnicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-pentylamine, 5-bromo-N- (n-pentyl) -N- [2- (2,4,6 - trichlorophenoxy) ethyl] nicotinamide as a colorless oil, mass spectrum m / e: 299 (98%, M + 30 phenol), 196 (90%, phenol), 186 (60%),

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21 5-bromnicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-hexylamine, 5-bromo-N- (n-hexyl) -N- [2- (2,4,6- trichlorophenoxy) ethyl] -nicotinamide as a colorless oil, mass spectrum m / e: 437 (1%, M4-c5h11> * 313 (96%> Pnol), 186 (50%), 5-chloro nicotinic acid chloride and N- [ 2- (2,4,6-trichlorophenoxy) ethyl] ethylamine, 5-chloro-N-ethyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotine amide, m.p. 85-88 ° C , 5-chloro nicotinic acid chloride and N- [2- (4,6-dichloro-o-tolyloxy) ethyl] - n-propylamine, 5-chloro-N- (n-propyl) -N- [2- (4,6-dichloro) dichloro-o-tolyloxy) ethyl] nicotinamide as a brown oil, mass spectrum m / e: 225 (100%, M + phenol), 140 (65%), 112 (50%), 5-chloronicotinic acid chloride and N- [2 - (2,4,6-trichlorophenoxy) ethyl] -n-propylamine, 5-chloro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide as a brown oil, mass spectrum m / e: 225 (100%, MT + pheanol), 140 (86%), 112 (65%), 5-chloronicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ) ethyl] -n-butylamine, 5-chloro-N- (n-butyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl amino-tinamide as a brown oil, mass spectrum m / e: 239 (100%, M4-phenol), 140 (93%), 112 (56%), 5-chloronicotinic acid chloride and N- [2- (2.4, 6-trichlorophenoxy) ethyl] -n-pentylamine, 5-chloro-N- (n-pentyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide as a brown oil, mass spectrum m / e : 253 (100%, M4-phenol), 183 (17%), 140 (91%), 112 (54%), 5-chloronicotinic acid chloride and N- [2- (2,6-dichlorophenoxy) ethyl] -n- prop-ylamine, 5-chloro-N- [2- (2,6-dichlorophenoxy) ethyl] N- (n-propyl) nicotine amide as a brown oil, mass spectrum m / e: 225 (100%, M phenol), 140 (95%), 112 (56%), 5-iodo-nicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -ethylamine, 5-iodo-N-ethyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, m.p. 92-94 ° C,

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22 5-Iodio nicotinic acid chloride and N- [2- (4,6-dichloro-o-tolyloxy) ethyl] -n-propylamine, 5-iodo-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] -N- (n-propyl) nicotinamide as a brown oil, mass spectrum m / e: 317 (100%, M * phenol), 232 (33%), 204 (14%), 176 (1%), 5 5-iodo nicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-prop-ylamine, 5-iodo-N- (n-propyl) -N- [2- (2,4,6 -trichlorophenoxy) ethyl] nicotinamide as a yellowish oil, mass spectrum m / e: 317 (100%, K1 phenol), 232 (47%), 204 (17%), 196 (1%), 5-iodo nicotinic acid chloride and N- [2- (2,6-dichlorophenoxy) ethyl] -n-propyl-arnine, 5-iodo-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide as a brown oil, mass spectrum m / e: 317 (100%, MT + phenol), 232 (60%), 204 (18%), 5-bromnicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ) ethyl] -N- (2-methoxyethyl) amine, 5-bromo-N- (2-methoxyethyl) -N- [2- (2,4,6-trichloro-phenoxy) ethyl] nicotinamide, m.p. 85-86 ° C and 5,6-dichloro nicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-propylamine, 5,6-dichloro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, mp 71-72 ° C.

EXAMPLE 2 To a suspension of 22.0 g (0.1 mole) of 5-bromnicotinic acid chloride in 200 ml of methylene chloride was added 9.2 g (0.11 mole) of sodium bicarbonate.

Then, with stirring, 28.3 g of N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-propylamine are added dropwise so that the temperature of the reaction mixture does not exceed 35 ° C. Then, the reaction mixture, which is a colorless suspension, is stirred for an additional 3 hours at room temperature. The suspension is then poured onto 200 ml of water and shaken, dissolving the solids. When a little saturated sodium bicarbonate solution is added, the pH is adjusted to approx.

7.5. The aqueous phase is extracted twice with 50 ml of methylene chloride each time, the combined organic phases are dried over anhydrous

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23 sodium sulfate and evaporated under reduced pressure. The residue is taken up in 50 ml of toluene and the solution is evaporated and the new residue is added with 100 ml of diisopropyl ether and allowed to crystallize with stirring. After 16 hours, the white suspension is stirred for an additional 1 hour at 0 ° C.

The solvent is suctioned off, the crystal powder washed twice with 20 ml of cold diisopropyl ether each time to give 31.0 g of colorless crystals, mp 50-52 ° C. To obtain additional product, the mother liquor is evaporated, the residue is subjected to a column chromatographic purification of 400 g of silica gel with ethyl acetate / n-hexane (1: 2) as eluent (flash 10 column), the purified fractions are combined and crystallized by 10 ml of diisopropyl ether. This gives an additional 3.4 g of colorless crystals, mp 50-52 ° C. The total yield of the 5-bromo-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide thus obtained is 34.4 g (73.7% of theory) ).

EXAMPLE 3

A mixture of 3.03 g (15 millimoles) of 5-bromnicotinic acid and 2.43 g (15 millimoles) of 1,1'-carbonyldiimidazole is heated in 50 ml of tetrahydrofuran at reflux temperature for 2.5 hours. Then 3.93 g (15 millimoles) of N- [2- (2,6-dichlorophenoxy) ethyl] -n-butylamine in 20 ml of tetrahydrofuran are added at room temperature and the resulting solution is heated for a further 3 hours at reflux temperature. Then the reaction mixture is evaporated, the residue is taken up in ethyl acetate and the solution is washed twice with saturated brine. The organic phase is dried over anhydrous sodium sulfate, evaporated and crystallized by diethyl ether / n-hexane. 2.8 g (42% of theory) yielded 5-bromo-N- (n-butyl) -N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide in the form of colorless crystals, m.p. 62-63 ° C.

Analogously is obtained from 5-fluoronicotinic acid chloride and N- [2- (2,4,6-trichlorophenoxy) ethyl] -n-propylamine, 5-fluoro-N- (n-propyl) -N- [2- ( 2,4,6-trichlorophenoxy) ethyl] nicotinamide, mp 68-69 ° C, and

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24 5 - Fluomicoic acid chloride and N - [2- (2,6-dichlorophenoxy) ethyl] -n-prop -ylamine, 5-fluoro-N- [2- (2,6-dichlorophenoxy) ethyl] N- ( n-propyl) nicotine amide as a colorless oil, IR spectrum: 2963, 1636, 1441, 1419, 1248 cm -1.

EXAMPLE 4

To a solution of 2.68 g (9.8 millimoles) of 5-bromo-N-ethyl-N- (2-hydroxyethyl) nicotinamide, 1.73 g (9.8 millimoles) of 2,4-dichloro-6 -Methylphenol and 2.57 g (9.8 millimoles) of triphenylphosphine in 35 ml of anhydrous tetrahydrofuran are added dropwise with stirring at room temperature 1.98 g of 10 (9.8 millimoles) of azodicarboxylic acid diisopropyl ester in 10 ml of anhydrous tetrahydrofuran and the reaction mixture is stirred. 4 hours. The solvent is then juxtaposed and the residual oil is chromatographically purified twice on silica gel using ethyl acetate as eluent and crystallized by diethyl ether. This gives 2.8 g (66% of the theoretical yield) of 5-bromo-N-ethyl-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] nicotinamide as beige prisms, m.p. 73 ~ 75EC.

Analogously obtained from 5-bromo-N- (2-hydroxyethyl) -N-methylnicotinamide and 2,6-dichlorophenol, 5-bromo-N- [2- (2,6-dichlorophenoxy) ethyl] N-methylnicotinamide, melting point 56-57 ° C and 5-bromo-N- (2-hydroxyethyl) -N-methylnicotinamide and 2,4,6-trichlorophenanol, 5-bromo-N-methyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide as a yellowish viscous oil, mass spectrum m / e: 243 (98%, M + phenol), 196 (5%, phenol), 186 (58%), bromo-N- (2-hydroxyethyl) -N-methylnicotinamide and 2,4-dichloro-6-methylphenol, 5-bromo-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] -N -methylnicotinamide as a yellowish viscous oil, mass spectrum m / e: 243 (94%, M + phenol), 186 (36%), 176 (4%, M + phenol),

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5-Bromo-N-benzyl-N- (2-hydroxyethyl) nicotinamide and 2,4,6-trichlorophenanol, 5-bromo-N-benzyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, m.p. 82-83 ° C, 5-bromo-N-benzyl-N- (2-hydroxyethyl) nicotinamide and 2,4-dichloro-6-methyl-phenol, 5-bromo-N-benzyl-N - [2- (4,6-dichloro-o-tholyloxy) ethyl] nicotinamide, m.p. 71-72 ° C, 5-bromo-N-benzyl-N- (2-hydroxyethyl) nicotinamide and 2,6-dichlorophenol, 5 -bromo-N-benzyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide as a colorless oil, mass spectrum m / e: 480 (3%, M *), 317 (28%, M * phenol) 5-Bromo-N- (2-hydroxyethyl) -N- (n-propyl) nicotinamide and 2,6-dichloro, 5-bromo-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide as a colorless oil, mass spectrum m / e: 269 (100%, M * phenol), 5-bromo-N-ethyl-N- (2-hydroxyethyl) nicotinamide and 2,6-dichlorophenol, 5 -bromo-N-ethyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, m.p. 78-80 ° C, 5-bromo-N- (n-butyl) -N- (2- hydroxyethyl) nicotinamide and 2,4-dichloro-6-methylphenol, 5-bromo-N- (n-butyl) -N- [2- (4,6-dichloro-ot olyloxy) ethyl] nicotinamide as a colorless oil, IR spectrum: 2958, 1637, 1465, 1176 cm -1, 20 5-chloro-N-ethyl-N- (2-hydroxyethyl) nicotinamide and 2,4-dichloroamide. 6-methylphenol, 5-chloro-N-ethyl-N- [2- (4,6-dichloro-o-tholyloxy) ethyl] nicotinamide, m.p. 62-65 ° C, 5-chloro-N-ethyl-N - (2-hydroxyethyl) nicotinamide and 2,6-dichlorophenol, 5-chloro-N-ethyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, mp 65-67 ° C, 5- chloro-N-benzyl-N- (2-hydroxyethyl) nicotinamide and 2,4,6-trichlorophenanol, 5-chloro-N-benzyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide , mp 88-89 ° C,

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26 5-Chloro-N-benzyl-N- (2-hydroxyethyl) nicotinamide and 2,6-dichlorophenol, 5-chloro-N-benzyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, m.p. 66 -68 ° C, 5-chloro-N-benzyl-N- (2-hydroxyethyl) nicotinamide and 2,4-dichloro-6-methylphenol, 5-chloro-N-benzyl-N- [2- (4 , 6-dichloro-o-tholyloxy) ethyl] nicotinamide, m.p. 75-78 ° C, 5-bromo-N- (2,4-dichlorobenzyl) -N- (2-hydroxyethyl) nicotinamide and 2,4,6 -trichlorophenol, 5-bromo-N- (2,4-dichlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, mp 109-110 ° C, 5-bromo-N- ( 2,4-dichlorobenzyl) -N- (2-hydroxyethyl) nicotinamide and 2,6-dichlorophenol, 5-bromo-N- (2,4-dichlorobenzyl) -N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, m.p. 160-161 ° C, 5-bromo-N- (3-chlorobenzyl) -N- (2-hydroxyethyl) nicotinamide and 2,6-trichlorophenyl, 5-bromo-N- (3-chlorobenzyl) - N- [2- (2,4,6-trichlorophenoxy) -ethyl] nicotinamide as a colorless oil, mass spectrum m / e: 353 (58%, M * phenol) 5-bromo-N- (3-chlorobenzyl) - N- (2-hydroxyethyl) nicotinamide and 2,6-dichlorophenol, 5-bromo-N- ( 3-chlorobenzyl) -N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, m.p. 105-106 ° C, 5-bromo-N- (2-chlorobenzyl) -N- (2-hydroxyethyl) nicotinamide and 2,4,6-trichlorophenol, 5-bromo-N- (2-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, mp 134-135 ° C.

EXAMPLE 5

To a solution of 2.0 g (4.3 millimoles) of 5-bromo-N- (n-propyl) -N- [2-25 (2,4,6-trichlorophenoxy) ethyl] nicotinamide in 10 ml of ethanol is added. ml of 4N hydrochloric acid and the reaction mixture is allowed to stand for approx. 16 hours at room temperature. Then the solvent is evaporated, the residual pale yellow oil is dissolved in 10 ml of ethanol, to the solution is added 30 ml of diethyl ether and the mixture is allowed to stand for 20 hours. The resultant

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27 precipitates are sucked off, washed with diethyl ether and dried in an air stream.

There are obtained 2.0 g (93% of theory) of 5-bromo-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide hydrochloride in the form of white crystals which decompose at 120 ° C.

Analogously obtained from 5-fluoro-N- (n-propyl) -N- [2- (2,4,6-trichloro-phenoxy) ethyl] nicotinamide and hydrochloric acid, 5-fluoro-N- (n- propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide hydrochloride in the form of white crystals which decompose in the range 132-138 ° C.

II. Preparation of starting materials of general formula IV

EXAMPLE 6

To a mixture of 2.55 g (28 millimoles) of 2-ethylaminoethanol and 2.84 g (28 millimoles) of triethylamine in 20 ml of methylene chloride is added dropwise with stirring at room temperature a solution of 4.96 g (28 millimoles) of 5-chloronicotinic acid chloride in ml of methylene chloride. The reaction mixture is stirred for 1 hour at room temperature and then filtered. The precipitate is washed with methylene chloride, the solvent of the combined filtrates is distilled off and the residual brown oil is chromatographically purified on silica gel using ethyl acetate as eluent to give 3.88 g (61% of theoretical yield) of 5-chloro-N -20 ethyl-N- (2-hydroxyethyl) nicotinamide in the form of a brown viscous oil.

Analogously is obtained from 5-bromnicotinic acid chloride and 2-methylaminoethanol, 5-bromo-N- (2-hydroxyethyl) -N-methylnicotinamide as a brown oil, 5-bromnicotinic acid chloride and 2-ethylaminoethanol, 5-bromo-N-ethyl -N- (2-hydroxyethyl) nicotinamide as a pale yellow oil, 5-bromnicotinic acid chloride and 2- (n-propylamino) ethanol, 5-bromo-N- (2-hydroxyethyl) -N- (n-propyl) nicotinamide as a brown oil,

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28 5-chloronicotinic acid chloride and 2-methylaminoethanol, 5-chloro-N- (2-hydroxyethyl) -N-methylnicotinamide, 5-chloronicotinic acid chloride and 2- (n-propylamino) ethanol, 5-chloro-N- (2-hydroxyethyl) ) -N- (n-propyl) nicotinamide, 5-iodo-nicotinic acid chloride and 2-methylaminoethanol, 5-iodo-N- (2-hydroxyethyl) -N-methyl-nicotinamide, 5-iodo-nicotinic acid chloride and 2-ethylaminoethanol, 5-iodo- N-ethyl-N- (2-hydroxyethyl) nicotinamide, 5-iodo nicotinic acid chloride and 2- (n-propylamino) ethanol, 5-iodo-N- (2-hydroxyethyl) -N- (n-propyl) nicotinamide.

EXAMPLE 7

A mixture of 20.2 g (0.1 mole) of 5-bromnicotinic acid and 16.2 g (0.1 mole) of 1,1'-carbonyldiimidazole in 200 ml of dry tetrahydrofuran is heated under reflux for 2.5 hours. Then, the reaction mixture is added 15.1 g (0.1 mole) of 2-benzylaminoethanol and stirred for an additional 1.5 hours at reflux temperature. The mixture is then evaporated and the residual oil is purified directly chromatographically on a silica gel solid column using n-hexane / ethyl acetate (2: 1) as eluent. There is thus obtained 22.7 g (68% of theoretical yield) of 5-bromo-20 N-benzyl-N- (2-hydroxyethyl) nicotinamide in the form of a colorless oil.

Analogously obtained from 5-bromnicotinic acid, 1,1'-carbonyldiimidazole and 2- (n-butylamino) ethanol, 5-bromo-N- (n-butyl) -N- (2-hydroxyethyl) nicotinamide as a colorless oil , 5-chlomicotinic acid, 1,1'-carbonyldiimidazole and 2-benzylaminoethanol, 5-chloro-N-benzyl-N- (2-hydroxyethyl) nicotinamide as a colorless oil, 29

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5-bromnicotinic acid, 1,1'-carbonyldiimidazole and 2- (2-chlorobenzyl) amino-ethanol, 5-bromo-N- (2-chlorobenzyl) -N- (2-hydroxyethyl) nicotinamide as a colorless oil, 5-bromonicotinic acid , 1,1'-Carbonyldiimidazole and 2- (3-chlorobenzyl) amino-5-ethanol, 5-bromo-N- (3-chlorobenzyl) -N- (2-hydroxyethyl) nicotinamide as a colorless oil, 5-bromonicotinic acid, 1 , 1'-Carbonyldiimidazole and 2- (2,4-dichlorobenzyl) -aminoethanol, 5-bromo-N- (2,4-dichlorobenzyl) -N- (2-hydroxyethyl) nicotinamide as a colorless oil.

III. Formulation Examples EXAMPLE 8 a) Liquid Active Ingredients 1. Emulsifiable Concentrate g / L 15 Active Ingredient of General Formula I 250

Nonylphenyl (10) Ethoxylate 50-70. Calcium dodecylbenzenesulfonate

Mixture of C ^ Q alkyl alkylbenzenes up to 1 L

The ingredients are mixed together until a clear solution is obtained.

2. Spray powder Weight parts

Active substance of general formula I 25

Hydrated silicic acid 25 25 Sodium lignosulfonate 10

Sodium lauryl sulfate 2

Calcium Carbonate 38 100

Claims (16)

1. N- (2-phenoxyethyl) nicotinamide derivatives of the general formula IO II r 2 wherein halogen is at the 5- and / or 6-position of the pyridyl group, represents g-alkyl, g-alkoxy-C 20 represents the halogen mono-, di- or trisubstituted benzyl, represents halogen or alkyl, DK m 161702 B m is 1 or 2 and n is 1, 2 or 3, and acid addition salts of these compounds. Compounds according to claims 1, 5, characterized in that they represent fluorine, chlorine, or bromine. Compounds according to claim 1 or 2, characterized in that m is 1. Compounds according to claim 3, characterized in that the halogen atom R * is in the 5-position. Compounds according to any one of claims 1-4, characterized in that R 1 represents ethyl, n-propyl or n-butyl. Compounds according to any one of claims 1-5, characterized in that R 2 represents chlorine or methyl. Compounds according to any one of claims 1-6, characterized in that n or 2 or 3. Compounds according to claims 6 and 7, characterized in that the phenyl group substituted with (R 1) is 2,4,6-trichlorophenyl, 2,4-dichloro-6-methylphenyl or 2,6-20 dichlorophenyl. A compound according to claim 1, characterized in that it is selected from 5-fluoro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N - (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (n-propyl) -N- [2- (2,4,6 - trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide and 5-bromo-N- [2- (4,6-dichloro) -o-tolyloxy) ethyl] -N- (n-propyl) -nicotinamide. DK 161702 B A compound according to claim 1, characterized in that it is selected from 5-bromo-N-ethyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (n -butyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (n-pentyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nico tinamide, 5-bromo-N- (n-hexyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nico tinamide, 5-chloro-N-ethyl-N- [2- ( 2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- (n-propyl) -N- [2- (2,4-dichloro-o-tholyloxy) ethyl] nicotinamide, 5-chloro-N- (n-butyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- (n-pentyl) -N- [2- (2,4,6- trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide, 5-iodo-N-ethyl-N- [2- (2, 4,6-trichlorophenoxy) ethyl] nicotinamide, 5-iodo-N- [2- (4,6-dichloro-o-tholyloxy) ethyl] -N- (n-propyl) nicotinamide, 5-iodo-N- (n -propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-iodo-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide , 5-bromo-N- (n-butyl) -N- [ 2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-fluoro-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide, 5-bromo-N-ethyl-N - [2- (4,6-dichloro-o-tholyloxy) ethyl] nicotinamide, 5-bromo-N- [2- (2,6-dichlorophenoxy) ethyl] -N-methylnicotinamide, 5-bromo-N-methyl -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] -N-methylnicotinamide, 5-bromo- N-benzyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N-benzyl-N- [2- (4,6-dichloro-o-tolyloxy) ethyl] nicotinamide, 5-bromo-N-benzyl-N- [2- (2,6-dichlorophenoxy) ethyl] nico-tinamide, 5-bromo-N-ethyl-N- [2- (2,6-dichlorophenoxy) ethyl] nico-tinamide . 5-bromo-N- (n-butyl) -N- [2- (4,6-dichloro-o-toyloxy) ethyl] nicotinamide, 5-chloro-N-ethyl-N- [2- (4, 6-dichloro-o-tholyloxy) ethyl] nicotinamide, 5-chloro-N-ethyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5. chloro-N-benzyl-N- [2- ( 2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-chloro-N-benzyl-N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-chloro-N-benzyl-N- [2- (4,6-dichloro-o-tholyloxy) ethyl] nicotinamide and 5-bromo-N- (2,4-dichlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide. 10 Kaolin and / or clay soil 43 100 The ingredients are mixed with each other and the whole is finely ground in a suitable mill. Compound according to claim 1, characterized in that it is selected from DK 161702 B 5-bromo-N- (2-methoxyethyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotine amide , 5,6-dichloro-N- (n-propyl) -N- [2- (2,4 »6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (2,4-dichlorobenzyl) - N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (3-chlorobenzyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (3-chlorobenzyl) -N- [2- (2,6-dichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (2-chlorobenzyl) -N- [2- (2.4 , 6-trichlorophenoxy) ethylnicotinamide, 5-bromo-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide hydrochloride, and 5-fluoro-N- (n- propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide hydrochloride. 12. A fungicidal agent, characterized in that it contains an effective amount of at least one compound of the general formula IO II C-N-CH R 1 represents halogen at the 5- or 6-position of the pyridyl group, R 2 represents g-alkyl, G 1-6 alkoxy-C 1-6 alkyl or optionally in the benzene nucleus with halogen mono-, di- or trisubstituted benzyl, R- represents halogen or alkyl, 25. is 1 or 2 and n represents 1, 2 or 3, or an acid addition salt of such a compound and formulation auxiliaries. DK 161702 B Fungicide according to claim 12, characterized in that it contains an effective amount of at least one compound selected from 5-fluoro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl ] nicotinamide, 5-chloro-N- (n-propyl) -N- [2- (2,4,6-trichlorophenoxy) ethyl] nicotinamide, 5-bromo-N- (n-propyl) -N- [2 - (2,4,6-trichlorophenoxy) ethyl] nico-tinamide, 5-bromo-N- [2- (2,6-dichlorophenoxy) ethyl] -N- (n-propyl) nicotinamide and 5-bromo-N- [ 2- (4,6-dichloro-o-tolyloxy) ethyl] -N - (n-propyl) nico-tinamide and formulation auxiliaries. A process for the preparation of compounds of the general formula (I). represents halogen at the 5- or 6-position of the pyridyl group, R 2 represents g-alkyl, g-alkoxy-C 1-6 alkyl or optionally in the benzene nucleus with halogen mono-, di- or trisubstituted benzyl, R 2 represents halogen or -alkyl, m is 1 or 2, and n represents 1, 2 or 3, 20 or acid addition salts of these compounds, characterized in that a) a reactive derivative of a nicotinic acid of the general formula II DK 161702 B wherein R * and m have the meaning given above are reacted with a 2-phenoxyethylamine of the general formula III hn-ch2ch2-ov ^^^ * 2 iQ) - (κ3'η 1.1 where R n has the meaning given above, or b) an N- (2-hydroxyethyl) nicotinamide of the general formula IV O »IV CN-CH 2 CH 2 OH 1v (R 1> n> -iO 2 R 2 vv N 5 where R · · ·, R and m has the meaning given above, is reacted with a phenol of the general formula V HO IQ) - \ where R · and n have the meaning given above, and a thus obtained compound with the general formula I happened to the corresponding acid addition salt by reaction with a 10 acid. Method for controlling fungi in agriculture and horticulture, characterized in that the article to be protected is treated with an effective amount of a compound according to any one of claims 1-11 or an agent according to claim 12 or 13. 15 PATENT REQUIREMENTS Use of a compound according to any one of claims 1-11 or an agent according to claim 12 or 13 for controlling 5 fungi in agriculture and horticulture.