CS214681B2 - Fungicide means - Google Patents

Abstract

1. Claims (for the contracting States : BE, CH, DE, FR, GB, IT, NL, LU, SE) An N-substituted carboxanilide of the formula I see diagramm : EP0013360,P15,F3 where R**1 denotes C1 -C4 -alkyl, R**2 denotes C1 -C4 -alkyl, R**4 denotes methoxy, ethoxy, isopropoxy, phenoxy, benzyl or 1-phenylethyl or unsubstituted phenyl or phenyl monosubstituted by fluors, chloro, bromo, iodo, methyl, methoxy or nitro, or R**4 denotes -CH2 -Y, Y denoting methoxy, ethoxy, phenoxy or benzyloxy, and A denotes pyrazole, imidazole or 1,2,4-triazole attached via a nitrogen atom, and its acid addition salts. 1. Claims (for contracting state AT) A fungicide containing an N-substituted carboxanilide of the formula I see diagramm : EP0013360,P16,F2 where R**1 denotes C1 -C4 -alkyl, R**2 denotes C1 -C4 -alkyl, R**4 denotes methoxy, ethoxy, isopropoxy, phenoxy, benzyl or 1-phenylethyl or unsubstituted phenyl or phenyl monosubstituted by fluoro, chloro, bromo, iodo, methyl, methoxy or nitro, or R**4 denotes -CH2 -Y, Y denoting methoxy, ethoxy, phenoxy or benzyloxy, and A denotes pyrazole, imidazole or 1,2,4-triazole attached via a nitrogen atom, and its acid addition salts.

Description

The present invention relates to a fungicidal composition comprising, as an active ingredient, novel valuable N-substituted carboxylic acid anilides. The invention further relates to a process for the preparation of these novel compounds as well as to their use as fungicides.

It is already known to use N-trichloromethylthlophthalimide as a fungicide (Chemical Week, 1972, June 21, p. 63J). In addition, N - (R) - (R) - (R) is known. (The use of herbicides as herbicides (cf. DOS 26 48 088 and DOS 27 04 281)) However, no mention is made of the fungicidal activity.

It has now been found that the novel N-substituted carboxylic acid anilides of formula I,

in which it means

R1 is C1-C3 alkyl,

R ² is alkyl having 1 to 3 carbon atoms,

R 4 is C 1 -C 2 alkyl optionally substituted by halogen, methylthio, methoxy, ethoxy, phenoxy, benzyloxy, dihalobenzyloxy or halophenylthio; furthermore represents an alkoxy group with. 1 to. 3 carbon atoms, cyclopropyl or phenyl optionally substituted by methyl, halogen, nitro, methoxy, methylthio; further means. thienyl, furyl or. a cyclopropyl group,

Z is methylene or. an ethylene group which is substituted with methyl,

And a residue of imidazole, triazole or pyrazole, said heterocyclic radicals being optionally substituted by up to 2 methyl groups or halogen atoms, as well as their acid addition products and complex compounds with metal salts. have a good fungicidal effect.

The novel compounds of the formula I can be prepared by reacting N214681

- halomethylcarboxanilide of formula II,

in which

R1, ^R2 and R4 have the above meanings and

Hal represents halogen, in particular chlorine or bromine, with the azoles of formula (III),

A — M (III) wherein

A is as defined above and

M is hydrogen or an alkali metal, optionally in the presence of a diluent and optionally in the presence of an acid binding agent, and optionally the acid or salt is then added to the compound thus obtained. metal.

In the case of the reaction of 2,6-dimethyl-N-chloromethylbenzanilide and imidazole, the progress of the reaction can be illustrated by the following reaction scheme:

In the general formula (I), R1 is preferably methyl or ethyl, while R2 is preferably methyl, ethyl, isopropyl.

Hal is preferably chlorine in formula II, but may also be bromine.

:. ^'4 R · · · in formula' I · represents for example methyl. ethyl, dichloromethyl. trichloromethyl, trifluoromethyl, 1-chloroethyl (-CH-CH 3),

Cl .........................

1,1-dichloroethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl,

2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-methoxyphenyl,

3-methoxyphenyl, 4-methoxyphenyl, 4-methylthiophenyl, 2-iodophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-difluorophenyl, 3, 4,5-trimethoxyphenyl, 3,5-dimethylphenyl, 3,5-dichlorophenyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl.

Z is preferably a methylene group —CH2 — but may also be —CHo — CH—.

AND

CH ₃ or -CH-CH 2 -.

AND

CH3

The preparation of the N-halomethylcarboxanilides of the formula II is carried out by addition of an acid halide of the formula R4-CO-Hal on the Schiff base of the formula VI according to the following reaction scheme:

R ^-CO-Hat

whereas

Hal is halogen and

R1, R2 and R4 have the meanings given above.

This process variant is the subject of U.S. Pat. Nos. 3,630,716 and 3,637,847 and DOS 15,450,950 when R ^{@ 4} -COHal is a benzoic acid or alkanecarboxylic acid halide.

U.S. Pat. Nos. 3,714,299 and 3,810,981 further disclose compounds of formula II wherein R4 is alkoxy, alkoxyalkyl, alkenyl, or cycloalkyl.

Furthermore, DOS 2119 518 describes the preparation of N-aryl-N-chloromethylcarbamates by chloromethylation of N-arylcarbamates, while it is expressly emphasized that according to the process described therein, compounds of the formula can also be obtained. Ha (see below), which are not available by the addition of O-aryl chlorocarboxylic acid esters to hexahydrotriazines (= Trimeric Schiff bases). However, as shown in the following examples, the addition of the chlorocarboxylic acid esters, even then, is successful on the 2,6-dialkyl-N - [(1 < 1 >) hylenanilines of formula VI when O-aryl chlorocarboxylic acid esters. This reaction is carried out according to the following reaction scheme:

w

The cited patents do not disclose the reaction of heterocyclic carboxylic acid halides with Schiff's bases of formula VI. However, this reaction also proceeds with very good yields, as shown in the following examples:

Example a

315 parts by volume of a toluene solution containing 1 mol of 2,6-dimethylphenylazomethine (for preparation see U.S. Pat. No. 3,637,847J) dropwise to a solution of 130.5 parts by weight of 2-furancarboxylic acid chloride with stirring at 5-10 ° C in 100 parts by volume of toluene under cooling, and then stirred at room temperature for 10 hours, after cooling, filtering and drying in vacuo, 198 parts by weight of N-chloromethylfuran-2-carboxylic acid 2 ', 6'-dimethylanilide are obtained. 124 to 126 degrees Celsius.

Although the reaction of, for example, benzoyl chloride with 2,6-dimethyl-N-methylamine is the subject of the cited US patent specification, no data on the properties and reactions with N-chloromethyl-2,6-dimethyl-N-benzoylanine can be found in the literature. One of the following examples illustrates this reaction. The N-chloromethylcarboxamides required as starting materials are listed in Table I below.

ch ₂ ci

N 'CO-R

Table I

number R ¹ R ² R ⁴ physical constants 1 CH ₃ CH ₃ CH ₃ viscous mass 2 CH ₃ c ₂ H _:; CH ₃ viscous mass 3 C ₂ H ₅ C ₂ H _S CH ₃ oil 4 CH ₃ CH ₃ c ₂ H ₅ oil 5 CH ₃ C ₂ Hr, C2H5 oil 6 c ₂ h ₅ c ₂ H ₅ C2H5 oil 7 ch ₃ CH ₃ CHC1 ₂ mp 102-104 ° C 8 CH ₃ c ₂ H ₅ I WANT, mp 88-90 ° C 9 C ₂ H ₅ C ₂ H ₅ CHC1 ₂ 10 ch ₃ CH ₃ CC1 ₃ oil 11 CH ₃ c ₂ H ₅ cclg 12 c ₂ h ₅ c ₂ H ₅ CC1 ₃ 13 ch ₃ CH ₃ CHCl ₃ -CH mp 95 ° C 14 CH ₃ CH ₃ cyclopropyl mp 82 ° C 15 Dec CH ₃ c ₂ H ₅ cyclopropyl oil 16 c ₂ h ₅ c ₂ H ₅ cyclopropyl oil 17 C ₂ H ₅ c ₂ H ₅ cyclohexyl melting point 97-100 ^e C 18 CH ₃ CH ₃ —CH2OCH3 mp 70 ° C 19 Dec CH ₃ c ₂ H ₅ —CH ₂ OCH ₃ 20 May C ₂ H ₅ c ₂ H ₅ -CH ₂ OCH ₃ oil 21 ch ₃ CH ₃ -CH ₂ -S-CH ₃ crystalline matter 22nd CH ₃ c ₂ H ₅ -CH ₂ -S-CH ₃ mp 127 ^e C 23 C ₂ H ₅ C ₂ Hs -CH ₂ -S-CH ₃ oil 24 ch ₃ CH ₃ CH ₂ -OC ₂ H ₅ 25 CH ₃ CH ₃ 26 CH ₃ CH ₃ mp 87 ° C 27 Mar: C ₂ H ₅ c ₂ H ₅ -ch ₂ -o - @> 28 ch ₃ CH ₃ 29 CH ₃ CH ₃ —C1 ₂ —CH ₃ 30 CH ₃ CH ₃ phenyl mp 133 ° C 31 CH ₃ C ₂ H ₅ phenyl 32 , c ₂ H ₅ C ₂ H ₅ phenyl mp 98-99 ° C 33 C3H7-I C3H7-I phenyl mp 107-108 ° C 34 CH ₃ CH ₃ 2-methylphenyl mp 118-119 ° C 35 CH ₃ CH ₃ 3-methylphenyl mp 133-135 ° C 36 CH ₃ CH ₃ 4-methylphenyl mp 119-120 ° C 37 CH ₃ CH ₃ 2-chlorophenyl mp 93 ° C 38 CH ₃ CH ₃ 3-chlorophenyl mp 145 ° C 39 C ₂ H ₅ c ₂ H ₅ 3-chlorophenyl 40 CH ₃ CH ₃ 4-chlorophenyl mp 126 ° C 41 C ₂ H ₅ C ₂ H ₅ 4-chlorophenyl 42 ch ₃ ch ₃ 2-fluorophenyl mp 86-88 ° C 43 c ₂ H ₅ c ₂ h ₅ 2-fluorophenyl

number R ¹ R ² R ⁴ physical constants 44 CH ₃ CH ₃ 3-fluorophenyl mp 114-115 ° C 45 CH ₃ CH ₃ 4-fluorophenyl mp 141-143 ° C 46 CH ₃ CH ₃ 3-bromophenyl 47 CH ₃ CH ₃ 2-iodophenyl 48 CH ₃ CH ₃ 2-nitrophenyl mp 205-207 ° C 49 C2H5 C2H5 2-nitrophenyl 50 CH ₃ CH ₃ 3-nitrophenyl mp 152-154 ° C 51 C2H5 C2H5 4-nitrophenyl mp 118-120 ° C 52 CH ₃ CH ₃ 2-methoxyphenyl 53 CH ₃ CH ₃ 3-methoxyphenyl mp 107-108 ° C 54 CH ₃ CH ₃ 4-methoxyphenyl mp 92-93 ° C 55 CH ₃ CH ₃ 4-methylthiophenyl 56 CHj CH ₃ 2,3-dichlorophenyl 57 c ₂ h ₅ C ₂ H ₅ 2,3-dichlorophenyl 58 C ₂ H ₅ C2H5 2,4-dichlorophenyl mp 68-69 ° C 59 CH ₃ CH ₃ 2,4-dichlorophenyl mp 108 ° C 60 C ₂ H ₅ C2H5 2,5-dichlorophenyl 61 CHj CH ₃ 3,5-dlchlorophenyl 62 CH) CH ₃ 3,5-dimethylphenyl 63 CH ₃ CH ₃ 2,6-difluorophenyl 64 CH ₃ CH ₃ 2-furyl mp 124-126 ° C 65 C ₂ H ₅ C ₂ H, 5 2-furyl mp 69-70 ° C 66 CH) CH ₃ 3-furyl 67 C2H5 C2H5 3-furyl 68 CH) CH) 2-thienyl mp 94-97 ° C 69 C2H5 C ₂ H ₅ 2-thlenyl 70 CH ₃ CH ₃ 3-thienyl it is further processed as a toluene solution 71 C ₃ H _{7 -} c ₃ H ₇ -i 2-thienyl mp 94-95 ° C 72 C ₃ H ₇ -i C3H7-1 2,6-difluorophenyl mp 135 ° C 73 CH ₃ CH _{3 -CH2 -CH2} -Cl oil

Examples of starting materials of formula (II) include the following N-chloromethyl-N-arylcarbamates of formula (VII), which were prepared according to the following reaction scheme:

whereas

R ¹ , R ² , R ⁵ and X are as defined above.

Table II

X physical constants number R ¹ R ²

R ⁵

74 СНз СН3 СН3 O oil 75 С ₂ Н ₅ С2Н5 СН3 O oil 76 СН3 СН.3 С2Н5 O oil 77 C ₂ H5 С2Н5 С2Н5 O oil 78 СН3 СН3 C2H7-I O 79 C2H5 С2Н5 СН3Н7-1 O 80 С2Н5 С2Н5 n-ClHg O 81 ⁰ 2 ^Н 5 С2Н5 sec.C ₄ H ₉ O 82 C2H5 C2H5 iso-C ₄ H ₉ O 83 C ₂ H5 С2Н5 t-C ₄ H _fl with 84 С2Н5 С2Н5 СН3 with 85 С2Н5 С2Н5 phenyl with 86 СН3 СН3 cyclohexyl O 87 СНз СН3 phenyl O melting point 113—115'C 88 С ₂ Н5 C2H5 phenyl O melting point Mp 94-95 ° C 89 СзН ₇ -1 ^C 3 ^H 7 ^- I phenyl O melting point Mp 115-116 ° C 90 СНз CH ₃ 4-fluorophenyl O 91 С2Н5 O2H5 2-chlorophenyl O 92 C2H5 C2H5 2,4-dichlorophenyl O 93 С2Н5 C2H5 2,3-dichlorophenyl O 94 С2Н5 С2Н5 3-chlorophenyl O 95 О2Н5 С2Н ₅ 4-chlorophenyl O 96 C2H5 С2Н5 2-chloro-5-methoxyphenyl O 97 C2H5 С2Н5 2-methyl-4-chlorophenyl O 98 С2Н5 С2Н5 2,6-dimethoxyphenyl O 99 С2Н5 C2H5 3,5-dimethoxyphenyl O 100 ALIGN! CH ₃ СН3 3,5-dichlorophenyl 0 101 СН3 С2Н5 3-trifluoromethylphenyl O 102 СНз С2Н5 2,3-dibromophenyl O 103 СН, О2Н5 4-nitrophenyl O 104 С2Н5 С2Н5 4-isopropylphenyl O 105 C2H5 С2Н5 4-tert-butylphenyl O 106 C2H5 C2H5 4-methylthiophenyl O 107 C2H5 С2Н ₅ 2-methylphenyl O 108 СН3 СН3 3-methylphenyl 0

The Schiff bases of formula VI, which is required in addition to the symbol M in formula III, preferably as starting materials, can be prepared according to known methods (e.g., U.S. Pat. No. 3,637,847) from the corresponding anilines and paraformaldehyde in toluene. and

In formula I, A is preferably

1-pyrazolyl, 1-imidazolyl, 1,2,4-triazol-1-yl,

2-methylimidazol-1-yl, 4-chloropyrazol-1-yl, 4-bromopyrazol-1-yl, 4,5-dichloroimidazol-1-yl, 3,5-dimethylpyrazol-1-yl.

hydrogen, sodium, or potassium. Compounds [of formula III are generally known compounds [of organic chemistry.

The secanilines of formula IV, which are also required as starting materials, are generally defined by this formula. They are produced by generally known methods of organic chemistry. [Preferred examples of these secanilines are given in the following table. Their production is illustrated in the examples.

nh-a-a

Table III

number R1 R ² OF AND physical constants 109 CH3 CHa -CH-CH ₂ - 1,2 '- boiling point 1 CH3 145 ° C / 26.7 Pa 110 CH3 CHa -CH-CH ₂ - iinidazole 111 CHa CHa CHa —CH2 — CH2— pyrazole boiling point 123-126 ° C / 6.7 Pa * 112 CH3 CHa —CH2-CH— 1,2 ', 4' - 4 '- 4' iriazole

CHa

Suitable solvents for the process are toluene and ethyl acetate. However, other (inert under the reaction conditions) solvents such as diethyl ketone, propionitrile, acetonitrile, tetrahydrofuran, dioxane, xylene, chloroform, carbon tetrachloride, chlorobenzene or dimethylformamide may also be used.

Inorganic acid binding agents such as alkali metal carbonates, for example sodium carbonate, potassium carbonate or sodium bicarbonate or tertiary amines, such as triethylamine, dimethylbenzylamine or pyridine, can be used as acid-binding agents. It is also possible to use the corresponding azoles in excess.

Reaction temperatures may vary between -10 and 150 ° C, preferably in the range of 20 to 120 ° C.

In the preparation of the novel compounds, preferably 1 to 2 mol of the azole (III) and 1 mol of the acid-binding agent are used per 1 mol of the compounds of the formula (II) and 1 to 1.2 mol of the carboxylic acid halide (V).

1.1 to 1.3 moles of an acid binding agent.

For example, to isolate the compounds of formula I, the reaction mixture is filtered, the filtrate is washed with water, dried and concentrated. The residue is optionally purified by fractional crystallization or distillation.

Physiologically acceptable acids such as, for example, hydrochloric, orthophosphoric, nitric, maleic, citric, acetic, p-toluenesulfonic and methanesulfonic acids are suitable for the preparation of acid addition salts of the compounds of the formula I.

Conventional methods are used to prepare such salts, for example by dissolving a compound of formula I in an inert solvent such as toluene, followed by acid addition, filtration, isolation and, optionally, recrystallization purification.

Chlorides or nitrates of magnesium, copper, iron, manganese or nickel are preferably used for the preparation of complex compounds of the formula I with metal salts. The metal salts are dissolved in ethanol and then an equivalent amount (or less) of the compound of formula I is added, the complex salt isolated by filtration and optionally purified by recrystallization.

Example 1

(C ₁₉ H ₂₀ N ₄ O ₂ )

1. To a solution of 34.1 g (0.2 mol) of phenoxyacetyl chloride in 50 ml of ligroin is slowly added dropwise at 0-5 ° C a solution of 26.6 g (0.2 mol) of N-methylene-2,6-climethylaniline in 100 ml toluene. After stirring at room temperature for 16 hours, the precipitated product is filtered off. After drying in vacuo, 47 g of N-chloromethyl-2,6-dimethylphenoxyacetanilide (78% yield) is isolated, m.p. 87 ° C.

2. 10.7 g (155 mmol) of 1,1'-thiazole are suspended in 100 ml of toluene and then 23.5 g (77.5 mmol) of N-chloromethyl-2 are added. 6-dimethyl (phenoxyacetyl) anilide. Then

214881, the reaction mixture was heated at 130 [deg.] C. for 1 hour and the residue from steps 1a. Rest the filtrate aside. The filtrate was concentrated and dried to give 17 g of a colorless solid (65%, theory), m.p. 84 ° C.

Celsius, so that the reaction mixture Vreoci ^hl shifting the reatórn zfihtiije mixture, the filter was washed with toluene and concentrated. The residue on the filter is given the value of the ethanol formula obtained in Example 2

(C21H23N3O2)

1. To a solution of 31.3 g (0.2 mol) of phenyl chloroformate in 100 ml of ligroin is added a solution of 32.2 g (0.2 mol) of N-methylene-2 at 15 to 20 ° C with slight cooling, 6-diethylaniline in 50 ml ligroin. After stirring for 16 hours, 49.2 g (76% yield) of N-chloromethyl-N-2,6-diethylcarbamic acid O-phenyl ester, m.p. 94-95 ° C, are isolated after filtration and drying.

2. 20 g (63 mmol) of the above N-chloromethylcarbamate are mixed with 8.6 g (126 mmol) of imidazole in 100 ml of toluene. The reaction mixture was then heated to reflux for 1 hour. The reaction mixture is then filtered while still hot. The oil remaining after evaporation of the solvent crystallized upon trituration with lignin. After filtration and drying, 13.9 g (63% of theory) of N-imidazolylmethyl-N-2,6-diethylphenylcarbamic acid O-phenyl ester of melting point 115 DEG-116 DEG C. are obtained.

Example 3

25.8 g (0.213 mol) of 2,6-dimethylaniline are mixed with 34.8 g (0.23 mol) of 1,2,4-triazolylacetone (prepared by boiling 1,2,4-triazole with excess · chloroacetone) in 250 ml of toluene, a spatula tip of p-toluenesulfonic acid is added to the tip and the mixture is heated to boiling for 2 hours.

During this time, the reaction water is collected in a water separator. Concentrate and overcoat. mp 88-90 ° C

To 22.8 g (0.1 mol) of this Schiff base dissolved in 150 ml of methanol was added portionwise at 0-10 ° C 14.4 g (0.3 mol) of sodium borohydride. After stirring for 1 hour, the reaction mixture is heated to boiling for 1 hour, then concentrated, 100 ml of water are added to the residue and extraction is carried out three times with 150 ml of methylene chloride. After drying and concentration of the methylene chloride ettract, the product of the formula is obtained

oil; The _D 22 - 1.5588 g (0.092 mol) of the thus obtained aniline is dissolved in 100 ml of toluene and 10.6 g of anhydrous sodium carbonate is added. Subsequently, 11 g (0.102 mol) of methoxyacetyl saccharide are added dropwise while the reaction mixture is cooled to 10 ° C. After 16 hours of stirring, 100 ml water, the organic phase is separated, washed with 0.5 N hydrochloric acid, neutralized with sodium bicarbonate solution, washed with water, dried over sodium sulfate and concentrated ^row. The oil thus obtained crystallizes after trituration with petroleum ether. Melting point 106 ° C.

Correspondingly, the preparations were <

The compounds of formula (I) are summarized in Table IV, the compounds of Examples 1 and 2 being re-listed.

The preparation of the new N-azotylalkylcarboxylic acid anilides of the general formula I in which Z represents a radical —CH — CH2— or

AND

CH 3 - CH 2 - CH, and the remaining symbols have from above

CH3 as defined above is accomplished by reacting the secondary aniline of formula IV,

R4-c0-Hal (V) (IV) wherein

R ¹ , R ² , A and Z are as defined above, with a carboxylic acid halide of formula (V) wherein:

Hal represents halogen, in particular fluorine, chlorine or bromine, and

R ⁴ is as defined above, optionally in a solvent.

This reaction is preferably carried out in toluene, but can also be carried out in diethyl ether, tetrahydrofuran or chloroform.

Preferred reaction temperatures range from 10 to 20 ° C.

Per 1 mol of the compound of formula IV, preferably 1.0 to 1.2 mol of the compound of formula V and, optionally, 1.1 to 1.3 mol of the acid-binding agent are used in the reaction.

Table IV number R ¹ R ² Z

R ⁴ A melting point (° C) or other physical constants

113 CH ₃ CH, CH ₂ CH, pyrazole 92 114 CH _; CH, CH ₂ CH, 1,2,4-triazole 100 ALIGN! 115 CH ·, CH, CH, CH, imidazole 116 CH, C, H ₃ CH ₂ CH, imidazole oil 117 CH, C2H5 CH ₂ CH, 1,2,4-triazole oil 118 C ₂ H ₃ C2H5 CH ₂ CH, pyrazole 61 119 C2H5 c ₂ H ₃ CH, CH, imidazole oil 120 C2H5 C2H5 CH ₂ CH, 1,2,4-triazole oil 121 CH, CH, CH ₂ C2H5 imidazole oil 122 CH, CH ·, CH ₂ C, H ₃ 1,2,4-triazole 103 123 CH, C2H5 CH ₂ C2H5 imidazole oil 124 CH, C, H ₃ CH ₂ C, H ₃ 1,2,4-triazole 68 125 C2H5 C, H ₃ CH ₂ C2H5 imidazole oil 126 C, H ₃ C, H ₅ CH ₂ C, H ₃ 1,2,4-triazole 80 127 CH ;. Target;. CH ₂ —CH — CH, 1 Cl pyrazole 95 128 CH, Target, CH ₂ —CH — target ·. 1 Cl imidazole 119 129 Target·; CH, CII ₂ —CH — CH, 1 Cl 1,2,4-triazole 131 130 CH, CH, CH ₂ -I WANT, pyrazole 98 131 CH, CH, CH ₂ - I WANT, imidazole 118—121 132 CH ·. CH ·. CH ₂ -I WANT, 1,2,4-triazole 133 133 CH ;; CH, CH ₂ -I WANT, 3,5-dimethylpyrazole 124 134 CH, C-, H ₃ CH ₂ -I WANT, pyrazole 57—59 135 CH, c ₂ H-> CH ₂ —CHC1J imidazole 121 136 CH; c ₂ h ₅ CH ₂ -I WANT, 1,2,4-triazole 96 137 C9H5 C2H5 CH ₂ -CHC1 ₂ imidazole 108 138 C ₂ H ₅ C2H5 CH ₂ -CHC1 ₂ 1,2,4-triazole 139 CH ·, c ₂ H _n CH ₂ CC1, 1,2,4-triazole 87 140 C ₂ H ₅ C2H5 CH ₂ c ₂ H ₅ pyrazole boiling point 135 ° C / 13.3 Pa 141 CH, CH ₃ CH ₂ C2H5 pyrazole 94—96

number R ¹ R ²

OF

R4

A melting point (° C), or other physical constants

142 CH ₃ ch ₃ CH3 AND CHC1 ₂ 1,2,4-triazole 128 143 C, CH ₃ AND CH2- CH3 CH ₂ —O — CH ₃ 1,2,4-triazole 106 144 CH, CH, Λ CH2- CH2 —OCH, pyrazole 91—94 145 CH, CH, CH ₂ —OCH, imidazole 146 CH, CH, CH, —OCH, 1,2,4-riazole 110 147 CH, CH3 CH2 —OC2H3 1,2,4-riazole 57—59 148 C2H5 C2H5 CH2 -OC2H5 1,2,4-triazole 149 CH. ·, CH ·, CH2 —OC3H7-I 1,2,4-riazole 150 CH ,, CH, CH2 —OC3H7-1. imidazole 151 CH, CH3 CH2 —CH ₂ —OCH ₃ pyrazole 113 152 CH, CH ·, CH2 —CH2 — OCH, imidazole n _D 25 = 115 ^ 82 153 / CH, CH, CH2 —CH2 — OCH, 1,2,4-riazole 87 7154 · C2H5 C2H5 CH2 —CH ₂ —OCH ·, pyrazole 74 7155 U9H5 C2H5 CH2 —CH, —OCH, imidazole oil / 156 ' C2H5 C2H5 CH2 —CH, —OCH, 1,2,4-triazole oil 1.57 ' CH ·. CH, CH, —CH2 —S — CH3 pyrazole 96 158 CH, CH, CH2 —CH2 —S — CH3 imidazole 103 159 CH ·, CH, CH2 CH, -S-CH ₃ 1,2,4-triazole 60 160 C9H5 C, H ₅ CH2 —CH2 —S — CIH3 pyrazole 86 161 C2H5 C2H5 CH2 —CH2 —S — CH3 1,2,4-triazole 79 162 CH, C2H5 CH2 cyclopropyl pyrazole oil 163 CH, CH ·, CH2 cyclopropyl 1,2,4-triazole 87 164 CH ₃ C9H5 CH2 cyclopropyl 1,2,4-triazole 80 165 C2H5 C2H5 CH, cyclopropyl pyrazole 52 166 C2H5, C2H5 CH2 cyclopropyl imidazole oil 167 C2H5 C9H5 CH2 cyclopropyl 1,2,4-triazole 47 168 CH ₃ CH, CH2 CH2-O-C2H5 1,2,4-riazole 169 CH ₃ CH3 CH2 1,2,4-triazole 170 CH3 CH ₃ CH ₂ pyrazole 171 CH3 CH ₃ CH ₂ ^ m- ^0-- © imidazole 84 172 CH ₃ CH) CH ₂ -ch ^ o 1,2,4-riazole 110—112 173 C, H ₅ C, H ₅ CH ₂ 1,2,4-triazole 174 CH ·) CH3 CH ₂ 1,2,4-triazole 175 CH ·, CH, CH ₂ —Cc12 — ch ₃ 1,2,4-triazole 176 CH ₃ CH ·, CH2 phenyl pyrazole 121—125 177 CH ₃ CH, CH2 phenyl imidazole 128 178 CH ₃ CH ₃ CH2 phenyl 1,2,4-riazole 135 179 c ₂ H ₅ C2H5 CH2 phenyl pyrazole 108

R ⁴

A melting point (° C) or other physical constants R ¹ R ²

180 C ₂ H ₃ C2H5 CH ₂ phenyl imidazole 123 181 c ₂ H ₅ C ₂ H ₅ CH ₂ phenyl 4,5-dichloroimidazole 134 182 c ₂ h ₅ C9H5 _CH3 CH ₂ phenyl 1,2,4-triazole 112—115 183 CH) CH ₂ phenyl 4,5-dichloroimidazole 194 184 CH) CH ·) CH ₂ 2-methylphenyl imidazole 129—130 185 CH) CH ₃ CH ₂ 2-methylphenyl 1,2,4-triazole 190—192 186 CH.) CH ₃ CH, 2-methylphenyl pyrazole 182—184 187 CH) CH) CH ₂ 3-methylphenyl imidazole 188 CH ·. CH) CH ₂ 3-methylphenyl 1,2,4-triazole 189 c ₂ H ₅ C2H5 CH ₂ 3-methylphenyl imidazole 190 CH ₃ CH) CH ₂ 4-methylphenyl imidazole 180 191 CH ₃ CH ₃ CH ₂ 4-methylphenyl 1,2,4-triazole 162—165 192 CH ·) CH ₃ CH ₂ 2-chlorophenyl 1,2,4-triazole 193 CH) CH ₃ CH ₂ 3-chlorophenyl imidazole 151 194 CH ·) CH ₃ CH ₂ 3-chlorophenyl 1,2,4-triazole 114—116 195 CH) CH ₃ CH ₂ 4-chlorophenyl imidazole 155—156 196 CH ₃ CH) CH ₂ 4-chlorophenyl 1,2,4-triazole 131—132 197 CH ₃ CH) CH ₂ 2-fluorophenyl imidazole 147—149 198 CH ·) CH ₃ CH ₂ 2-fluorophenyl 1,2,4-triazole 117—120 199 CH. CH) CH ₂ 3-fluorophenyl imidazole 105—108 200 CH ·. CH ₃ CH ₂ 3-fluorophenyl 1,2,4-triazole 122—124 201 CH) CH ₃ CH ₂ 4-fluorophenyl imidazole 138—139 202 CH ₃ CH ·) CH ₂ 4-fluorophenyl 1,2,4-triazole 104—105 203 CH ₃ CH ₃ CH ₂ 3-bromophenyl 1,2,4-triazole 211—212 204 CH ₃ CH ₃ CH ₂ 2-iodophenyl pyrazole 205 CH ₃ CH3 CH ₂ 2-iodophenyl imidazole 154—155 206 CH ₃ CH ₃ CH, 2-iodophenyl 1,2,4-triazole 222—223 207 CH ₃ CH ₃ CH ₂ 2-nitrophenyl imidazole 127—129 208 CH ₃ CH ₃ CH, 2-nitrophenyl 1,2,4-triazole 175—180 209 C, H ₅ C ₂ H ₅ CH ₂ 2-nitrophenyl imidazole 210 C, H ₅ C ₂ H ₅ CH, 2-nitrophenyl 1,2,4-triazole 211 CH) CH ₃ CH ₂ 3-nitrophenyl imidazole 146—148 212 CH ₃ CH ₃ CH ₂ 3-nitrophenyl 1,2,4-triazole 113—115 213 C, Hr, C9H5 CH ₂ 4-nitrophenyl imidazole 97—100 214 c, Hr, C ₂ H ₅ CH ₂ 4-nitrophenyls 1,2,4-triazole 117—120 215 from _{2 to 5} C, H ₅ CH ₂ 2,4-Cl ₂ -phenyl pyrazole 145 216 C ₂ H ₅ c ₂ h-> CH ₂ 2,4-Cl ₂ -phenyl imidazole 119 217 C, H ₅ C9H5 CH ₂ 2,4-Cl ₂ -phenyl 1,2,4-triazole 163 218 c ₂ h ₅ C2H5 CH ₂ 2,4-Cl ₂ -phenyl 4,5-dichloroimidazole 120 219 CH ₃ CH-. CH ₂ 2,4-Cl, -phenyl imidazole 220 CH _{; 1} CH ·. CH, 2,4-Cl ₂ -phenyl 1,2,4-triazole 221 CH ·. CH ₃ CH ₂ 2,6-difluorophenyl 1,2,4-triazole 222 C.) H ₇ i C ₃ H ₇ i CH ₂ 2,6-difluorophenyl 1,2,4-triazole 165—167 223 C ₃ H ₇ i C ₃ H ₇ i CH, 2,6-difluorophenyl imidazole 134—135 224 C ₃ H ₇ and C ₃ H ₇ Si C ₃ H ₇ and C ₃ H ₇ and CH, phenyl imidazole 125 225 CH, phenyl 1,2,4-triazole 130—132 226 C ₂ H ₅ C ₂ H ₅ CH, OCH ₃ 1,2,4-triazole 58 227 CH ₃ CH ·. CH, 2-furyl imidazole oil 228 CH) CH) CH ₂ 2-furyl 1,2,4-triazole 140 229 C ₂ Hr, C ₂ H ₅ CH ₂ 2-furyl imidazole 89 230 c ₂ H _r> C2H5 CH ₂ 2-furyl 1,2,4-triazole 104

number R1 R2

OF

R ⁴ A melting point (° C ') or other physical constants

231 232 СНз СН3 СНз СНз СНз ^А СН ₂ СНз А СИ, 2-furyl phenyl 1,2,4-triazole 1,2,4-triazole 86 104 233 СНз СНз CH, Л ' СН, 2-: methylphenyl 1,2,4-triazole 130 234 СНз СНз СНз ^А CH, 2,4-Cl ₂ -phenyl 1,2,4-triazole 108—110 235 СНз СНз CH, 3-thienyl pyrazole 236 C _;! H ₇ i Сз1 ^ CH ₉ 2-thienyl imidazole 148—149 237 СзИ ₇ 1 CзH7i СН, 2-thienyl 1,2,4-triazole 130—131 238 СНз СНз CH, 3-furyl imidazole 239 CH, CPI ·, СН, 3-furyl 1,2, ‘4 - (-) - jriazole 240 C2H5 C ₂ H ₅ СН, 3-furyl 1,2,4-triazole 241 СНз СНз СН, 2-methoxyphenyl 1,2,4-: riazole 242 СНз СНз СН, 4-methoxyphenyl 1,2,4-: riazole 243 СНз СНз CH, 4-methylthiophenyl 1,2,4-: riazole 244 СНз СНз СН, 2,3-diclorophenyl 1,2,4-triazole 245 С ₂ Н ₅ С2Н5 CH ₂ 2,3- (4-chlorophenyl) 1,2,4-triazole 246 С2Н5 С2Н5 CH9 2,5-dichlorophenyl 1,2,4-triazole 247 СНз СНз CH9 3,5-dichlorophenyl 1,2,4-triazole 248 СНз СНз СН, 3,5-dimethylphenyl 1,2,4-: riazole 249 C. ₃ H7i CзH7i СН, phenyl 2-methylimidazole 133—135 250 СНз СНз CH, —Ch ₂ —ch ₂ —f imidazole 251 СНз СНз СН, —CH2 — CH2 — F 1,2, -? -? -? Iriazole 89— 91

The new active substances show a strong fungitoxic activity against phytopathogenic fungi, in particular from the class of Phycomycetes. The novel compounds described are therefore suitable, for example, for controlling Phytopthora infestans on tomato and potatoes, Phytopthora parasitica. on strawberries, Phytopthora cactorum on apples, Pseudoperonospora cubensis on cucumbers, Pseudoperonospora humuli on hops, Peronospora destructor on onion, Peronospora sparsa on roses, Peronospora tabacina (tobacco peronospora) on tobacco. Plasmopara viticola (grape vine) on grapevine, Plasmopara halstedii on sunflower, Sclerospora macrospora on corn, Bremia lactucae on salad, Mucor mudedo on fruit, Rhizopus nlgricans on beet.

The fungicidal compositions contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight of active compound. Depending on the type of effect desired, the consumption varies between 0.1 and 5 kg of active substance per ha.

Some of the disclosed compounds exhibit curative properties, i.e., the composition can be administered even after infection of the plant by the causative agent to achieve a reliable result. In addition, many of the novel compounds are systemically active, so that the protection of above-ground parts of the plant can be achieved by treating the roots with such compounds.

Known active ingredients were used as comparative agents in the following examples

Compound A

The active compounds according to the invention can also be mixed and applied together with other active compounds, such as, for example, herbicides, insecticides, growth regulators and fungicides, or also together with fertilizers. In many cases, the fungicide compositions also have an increased effect on the fungicidal spectrum. Many of these fungicidal compositions also exhibit synergistic effects, i.e. the fungicidal activity of the combined product is greater than the sum of the efficacy of the individual components. A particularly favorable fungicidal spectrum of action is obtained with the following fungicides:

manganese zinc ethylene bis-dithiocarbamate, manganese zinc ethylene bis-dithiocarbamate, zinc ammoniacal complex, zinc N-N-ethylene-bis-dithiocarbamate, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylphthalimide, 5-ethoxy-3-thiol , 2-methoxycarbonylaminobenzimidazole, 2-rhodanmethylthiobenzthihzole, 1,4-dioh-or-2,5-dimethoxybenzene, 1,3-dlthloo-6-methyl-1,4-oxaline-5-carboxanilil, 2-methyl-r , 6-dihydro-4-H-pyray-5-carboxhyilil,

2,4,5- ^ x106 ^ 1-3 ^ 0-0 ^ 10013 ^^

2-Ethylfuran-5-carboxayilide, 2,5-dimethyl-huran-γ-carboxylic acid cyclohexylamide, 2,5-dimethylfuran-γ-carboxylic acid, N-cyclohexyl-N-methoxyam, methyl-5-methyl-3- (y, r) -dichlorophenyl) -2,4-dioxo-1, 5-oxazolidine,

3- (3,5-dichlorophenyl) -1'-methyl-5-methoxymethyl-1,1'-oxazolidin-2,4-dione.

The following list of fungicides with which the compounds of the invention may be combined is intended to illustrate, but not limit, the combination possibilities.

The fungicides which may be combined with the active compounds according to the invention are, for example, the following: lithiocaramates and derivatives thereof, such as ferric dimethyl lithium thiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebis-dithiocarbamate, tetramethylthiurodisulfides,

Zinc Ν, pr-propyley-bis-dithiocarbamate, ammoniacal complex, NlN´-propyley-bis-dithiocarbamate, and

N, N-polypropylene-bis- (thiocarbamoyl) disulfide;

nitroderivatives such as dinitro (1-meeny Пае pty 1) phenyl crotonate,

2-sec-butyl-4,6-diyitrophenyl-U, U-limethyl acrylate,

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, by heterocyclic compounds such as

2-heptalecyl-2-imidazoline acetate,

2,4-Dichloro-β- (o-chloroanilino) -s-triazine

O, C) -diethylphthalimidophosphoyothioate,

5mmmo-1- (bis- (dimethylamino) phosphinyl) -3-phenyl-1,2,4-riazole),

2,3-Licyan-1,4-dithiaanthraquinone,

2-thfo-O, γ-dimethyl-4- [4,5-b] quinoxalic acid, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester,

4- (2-chlorophenylhydrazono) -y-methyl-5-tsoxazo-o, pyridine-2-thio-O-oxide,

8-Hyoroxycamine or its copper (I) salt,

2,3- _{dihydro-r-carboxanilido-6-methyl-0,4-oxathny-4:} 4-ltoxil,

2 У-dihydro-r-kar0oxαnililo-ϋ-meΐhyl-l, 42- (f ur-2-yl ^j beyzimilazo-, piperaztУ-l, 4-diyl 0ts- [1- (2,2,2- -richloroethyl) formamide,

2-thiazol-4-yl) Oenzimidazole,

5-Butyl-2-limethylamino-4-hylroxy-6-methylpyrimilin, bis- (p-chlorophenyl) -O-pyridinmethanol,

1,2-Ois- (3-ethoxycarbonyl-2--1-methoxyl) benzene,

1,2-bis [ω-methoxy-carbonyl-2-thienyl (lo) benzene;

as well as various fungicides such as dolecylguanidiyacetate,

3- (3- (1,5-Dimethyl-2-oxy-cyclohexyl) -2-hydroxy-ethyl) -gthalenamide;

heKach-orbe-uzen, N-dichlorofluoromethylthio-N'lN'-limethy - N-phenyldiamide sulfuric acid,

2,5-dimethylfuran-5-carboxanilide,

2-methylbenzanilide1

2-iodobenzayil,

1- (3,4--11Sulfonyl) -1-formyl-amino-2,2,2-trichloroethane,

2,6-limethyl-N-trilecymorloline or its salts,

2,6-dimethyl-N-cyclododecymorpholine, or salts thereof,

1- (4-chlorophenoxy) -3,3-pentyl-1- (1H-1,2,4-triazol-1-yl) --- butanone,

1- (4-Chlorophenoxy) -3,3-thiophenol-1- (1H-1,2,4-triazol-1-yl) -2-butanol, α- (2-chlorophenyl) -a- (4 -chlorophenyl] -5-pyrimidinemethanol.

The novel active compounds are used, for example, in the form of sprayable solutions, powders, suspensions, as well as high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, dusts, granules, by spraying, fogging, dusting or watering. . The use forms depend entirely on the intended use. In any case, they are intended to ensure the finest possible dispersion of the new active substances.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable fractions of mineral oil of medium to high boiling point, such as kerosene or oil for diesel engines, tar oils, etc., oils of vegetable or animal origin, aliphatic , cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc., strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by adding water. In order to prepare emulsions, pastes or oil dispersions, the substances as such or soluble in oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. Concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and, optionally, solvent or oil, which are suitable for dilution with water, may also be prepared.

Suitable surfactants are: alkali metal, alkaline earth metal, ligninsulfonic acid salts, ammonium salts, naphthalenesulfonic acids, phenolsulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali or alkaline earth metal dibutylnaphthalenesulfonic acid salts, lauryl ether sulfates sulfated fatty alcohols, alkali metal and alkaline earth metal fatty acid salts, sulfated hexadecanols, heptadecanols, octadecanols, sulfated glacol ethers of fatty alcohols, condensation products of sulfonated naphthalene and derivatives of naphthalene with formaldehyde, condensation products of naphthalene and naphthalene formaldehyde, polyoxyethylenoctylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products ethylene oxide with fatty alcohols, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and dusts can be prepared by mixing or comminuting the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral clays such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, attaclay, limestone, chalk, bolus, loess, go, dolomite, diatomite, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and plant products such as cereal flour, tree bark flour, wood flour and ground nut shells, powdered cellulose and other solid carriers.

Example 4

Fungicidal activity against grapevine peronospora (Plasmopara viticolaj on vines).

The leaves of 'Muller-Thurgau', grown in pots, are sprayed with an aqueous dispersion containing, in the dry matter, 80% (by weight) of the active substance to be tested and 20 · ·% of lignin sulphonic acid sodium. After spraying, the leaves are infected with a grapevine (Plasmopara viticola ') zoospore suspension (Plasmopara viticola'), which are then placed in a vapor-saturated (wet) chamber for 16 hours at room temperature. 20 ° C and then for 8 days in a greenhouse at a temperature between 20 ° C and 30 ° C.

After this time, the plants are again placed in a humid chamber for 16 hours to accelerate and intensify disease development. The leaf infestation is then assessed on the undersides of the leaves. Non-greened infected plants serve as controls.

The test results are shown in the following table, where 0 means no attack, graded to 5, which means total attack.

Table active substance attacking the leaves after spraying % of suspensions 0.1 0.05 178 1 2 179 1 2 183 1 2 189 1 2 194 1 2 196 1 2 197 1 2 199 0 1 201 0 0 204 1 2 240 0 1 244 1 2 246 1 2 250 1 2 256 0 0 262 0 0 276 0 1 277 0 1 298 1 2 302 0 0 304 0 0 347 0 1 373 1 2 374 1 2 A (known) 2 3 inspection (untreated) 5

Example 5

Table

Fungicidal activity against Phytophthora infestans.

active ingredient infestation of leaves after spraying

0.1% suspensions

The leaves of 'Professor Rudloff' tomato plants are sprayed with aqueous suspensions containing 80% by weight of the active substance to be tested and 20% of lignin sulphonic acid sodium salt in the dry matter. A 0.1% suspension (calculated on the dry substance) is used. After the spray layer has dried, the leaves are infected with a zoospore suspension of Phytophthora infestans. The plants are then placed in a chamber with saturated water vapor (humid) at temperatures between 16 and 18 ° C. After 5 days, the disease develops on untreated but infected control plants to such an extent that the fungicidal efficacy of the test substances can be assessed.

The test results are shown in the following table, where 0 means no attack, scaled up to 5, which means total attack (control);

1892

2002

2012

2502

2560

2611

2700

2762

3160

3321

3650

3681

3951 control (untreated) 5

After this time, the plants are again placed in a humid chamber for 16 hours to accelerate and intensify disease development. The leaf infestation is then assessed on the undersides of the leaves. Untreated infected plants serve as controls.

The test results are shown in the following table, where 0 means no attack, graded to 5, which means total attack.

Table

active substance attacking the leaves after spraying % of suspensions 0.1 0.05 128 1 2 129 1 2 133 1 2 139 1 2 143 1 2 145 1 2 146 1 2 148 0 1 150 0 0 157 0 1 161 1 2 163 1 2 167 1 2 168 0 0 170 0 0 1 174 0 1 175 0 1 183 1 2 187 0 0 < 189 0 0 224 0 1 242 1 2 243 1 2 A (known) 2 3 inspection (untreated) 5

Example 6

Fungicidal activity against Phytophthora infestans

The leaves of tomato plants of the type "Professor Rudloff" are sprayed with aqueous suspensions containing, by dry weight, 80% by weight of the active substance to be tested and 20% by weight of lignin sulphonic acid sodium salt. A 0.1% suspension (calculated on the dry substance) is used. After the spray layer has dried, the leaves are infected with a zoospore suspension of Phytophthora infestans. The plants are then placed in a chamber with saturated water vapor (wet) at temperatures between 16 and 18 ° C. After 5 days, the disease on untreated but infected control plants develops so greatly that the fungicidal activity of the test substances can be assessed.

The test results are shown in the following table, where 0 means no attack, scaled up to 5, which means total attack (control).

Table of active ingredient infestation of leaves after spraying

0.1% suspensions

139

149

150

167

168

169

174

201

213

237

238

250 inspection (untreated)

Example 6

W parts by weight of compound 1 'are mixed with 10 parts by weight of N-methyl-α214681

-pyrrolidone to give a mixture which is suitable for use in the form of minimal drops.

Example 7 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide per mole of N-monoethanoic acid ω, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight. parts by weight of the addition product of 43 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 8 parts by weight of compound 2 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mole of isoocylphenol and 10 parts by weight of the adduct. Ethylcyclohexane is mixed with 1 mol of castor oil. Pouring and finely distributing this solution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

EXAMPLE 9 parts by weight of compound 2 are dissolved in a mixture consisting of 25 parts by weight of cyclone aura, C1 parts by weight, of an oil fraction having a boiling point of 210 to 280 parts by weight of addition product 4; mole of ethylene oxide per mole of castor oil. By pouring and finely distributing this solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

EXAMPLE 2 parts by weight of active compound 2 are mixed well with 3 parts by weight of diisobutylnaphthalene-1-sulfonic acid sodium salt, 17 parts by weight of lignin sulphonic acid sodium salt from sulphite waste liquors and 00 parts by weight of powdered silica gel and ground by hammer mill. By finely distributing the mixture in 20,000 parts of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example 11 The weight of compound 1 is thoroughly mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

Example 12 parts by weight of compound 2 are intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, an active substance preparation with good adhesion is obtained.

Example 13 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of the condensation product of phenol sulphonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water yields an aqueous dispersion containing 0.04% by weight of active ingredient.

Example 14 parts of active ingredient 2 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid calcium, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenol, urea and formaldehyde and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Example 15

a] 140.5 g (1 mol) of benzoyl chloride are dissolved in 200 ml of ligroin and then a solution of 133 g (1 mol) of N-methylene-2,6-dimethylaniline in toluene is added dropwise at 5-10 ° C. After stirring at 25 ° C for 14 hours, the precipitated solid was collected by filtration. After drying under high vacuum, 215 g (79%) of N-chloromethyl-N-benzoyl-2,6-dimethylaniline of melting point 133 ° C are obtained, of the formula:

In an analogous manner, N-chloromethyl-N-benzoyl-2 is obtained _; 6-diethylaniline, m.p. 98-99 ° C.

b) A solution of 54.7 g (0.2 mol) of N-chloromethyl-N-benzoyl-2,6-dimethylaniline in 250 ml of tetrahydrofuran is added dropwise to a suspension of 13.8 g (0.2 mol) at 5-10 ° C. of triazole in 100 ml of tetrahydrofuran and 20.2 g (0.2 mol) of triethylamine. After stirring at room temperature (25 degrees Celsius) for 16 hours, the precipitated triethylammonium hydrochloride is filtered off. After evaporation of the solvent, the recovered solid was dissolved in 250 ml of methylene chloride and extracted with 100 ml of 5% (w / w) hydrochloric acid. After drying over sodium sulfate, the organic phase is concentrated. The residue is recrystallized from toluene / ligroin (3: 2).

Yield: 44.6 g (73% of theory) of N-triazolylmethyl) -N-benzoyl-2,6-dimethylaniline

mp 135 ° C.

N- (triazolylmethyl) -N-benzoyl-2,6-diethylaniline was prepared in the same manner, m.p.

Example 16

а) to a solution of 51.4 g (0.24 mol) of chloride

Of 2,6-dichloropyridine-4-carboxylic acid in 250 ml of toluene is added dropwise 38.6 g (0.24 mol) of N-methylene-2,6-diethylaniline. Cooling the water bath keeps the reaction mixture at 35-40 ° C. After stirring for 10 hours, toluene was evaporated in vacuo (rotary evaporator) and the residue was dissolved in ligroin and recrystallized. After filtration and drying, 67 g (75% of theory) of N-chloromethylanilide, m.p. 79 DEG-80 DEG C., are obtained:

(C ₁₇ H ₁₇ C1 ₃ N ₂ O)

b) A mixture of 22.3 g (0.06 mol) of this N-chloromethylanilide and 9 g (0.132 mol) of imidazole was refluxed in 100 ml of toluene for 1 hour.

The reaction solution is then filtered while hot. The filtrate was cooled and the precipitated solid was collected. This material was recrystallized from ligroin / toluene (1: 1).

Yield after recrystallization: 11 g (46% of theory)

Melting point: 120-122 ° C.

Claims (1)

OBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and, as an active ingredient, at least one N-substituted carboxanilide of the formula I, in which: R ¹ is alkyl having 1 to 3 carbon atoms, R ² is alkyl having 1 to 3 carbon atoms, R ^Z1 is alkyl having 1-2 C atoms, which is optionally substituted with halogen, methylthio, methoxy, ethoxy, phenoxy, benzyloxy, or dihalogenbenzyloxyskupinou halogenfenylthioskupinou; furthermore is C1-C3 alkoxy, cyclopropyl or phenyl optionally substituted by methyl, halogen, nitro, methoxy, methylthio; furthermore represents a thienyl group, a furyl group or a cyclopropyl group, Z is a methylene group or an ethylene group which is substituted by methyl, And a residue of imidazole, triazole or pyrazole, said heterocyclic radicals being optionally substituted with up to 2 methyl groups or halogen atoms, or an acid addition product thereof or a complex thereof with a metal salt.