DK170336B1 - 2-Hydrazinopyrimidine derivatives and acid addition salts and metal complexes thereof, processes for their preparation, agrochemicals containing them and methods for controlling or preventing attacks on cultured plants of harmful organisms - Google Patents

Abstract

Compounds of the formula <IMAGE> in which: R1 denotes phenyl or phenyl which is monosubstituted to trisubstituted by R4; R2 denotes hydrogen, C1-C5-alkyl, C1-C5-alkyl substituted by the radicals OR5 or SR5, C3-C6-cycloalkyl, C3-C6-cycloalkyl monosubstituted to trisubstituted by C1-C4-alkyl or halogen, C2-C5-alkenyl, C2-C5-alkynyl or the formyl radical; R3 denotes hydrogen, C1-C4-alkyl, C1-C4-alkyl which is substituted by halogen, cyano or the radicals OR5 or SR5, C3-C6-cycloalkyl or C3-C6-cycloalkyl which is monosubstituted to trisubstituted by C1-C4-alkyl or halogen; R4 denotes halogen, C1-C3-alkyl, C1-C2-haloalkyl, C1-C3-alkoxy or C1-C3-haloalkoxy; R5 denotes hydrogen, C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or the radical (CH2)n-X-C1-C3-alkyl; R7 denotes the group -NH2, <IMAGE> or <IMAGE>; R8 denotes hydrogen, C1-C3-alkyl or C1-C3-haloalkyl; R9 denotes hydrogen, C1-C8-alkyl, C1-C3-alkyl substituted by hydroxyl, OR12, SR12 or N(R12)2, C3-C6-cycloalkyl, cyclopropyl substituted by SR12, C3-C10-alkenyl, C1-C3-haloalkyl, phenyl, phenyl which is monosubstituted to trisubstituted by halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C2-haloalkyl, hydroxyl, nitro, cyano, amino or dimethylamino, 1- or 2-naphthyl, 1-, 2- or 3-pyridyl, <IMAGE> or <IMAGE>; R8 and R9, together with the carbon atom in the radical R7, form a saturated or unsaturated ring consisting of 4 to 7 carbon atoms; R10 denotes CH(R8)R9, phenyl, C3-C5-alkenyl, C3-C5-alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R11 denotes hydrogen, C1-C5-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R12 denotes CH3 or C2H5; X denotes oxygen or sulphur; Z denotes O, S, NH or NCH3; and n denotes 1 to 3; including their acid addition salts and metal salt complexes, have useful microbicidal properties. The novel active compounds can be employed in plant protection for preventing the attack of crop plants by phytopathogenic microorganisms or by harmful insects and for controlling these pests.

Description

in DK 170336 B1

The invention relates to novel 2-hydrazinopyrimidine derivatives of the formula I below and to acid addition salts and metal complexes thereof, a process for preparing these compounds and agrochemicals containing at least one of these compounds. The invention also relates to a method for controlling harmful organisms, above all from plant harmful microorganisms, preferably fungi.

The 2-hydrazonopyrimidine derivatives of the invention are characterized in that they have the general formula I

Riv> T = \> —C> (i) r7 Λ3 wherein

R 1 is phenyl or up to three times with R 4 substituted phenyl, R 2 is hydrogen, C 1-5 alkyl, with the groups OR 5 or SR 5 substituted C 1-5 alkyl, C (3-6) - cycloalkyl, with C (1-4) alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, R3 means hydrogen , C (1-4) alkyl, with halogen, cyano or the groups OR5 or SR5 substituted C (1-4) alkyl, C (3-6) -cycloalkyl or with C (1-4) alkyl or halogen until three times substituted C (3-6) -cycloalkyl, R4 means halogen, C (1-3) -alkyl, C (1-2) -haloalkyl, C (1-3) -alkoxy or C (1-3) -haloalkoxy, R5 means hydrogen, C (1-5) -alkyl, C (3-5) -alkenyl, 0 (3-5) -alkynyl or a group (CH2) nXC (1-3) -alkyl, 2 DK 170336 B1 r8 r10 // R7 means a group -NHt0, -N = C or -N 5 \ \ r9 r11

R 5 represents hydrogen, C 1 -C 3 alkyl or C 1 -C 3 halo-alkyl, R 9 represents hydrogen, C 1 -C 8 alkyl, with hydroxy, OR 12, SR 12 or N (R 1 substituted C (1-3) alkyl, C (3-6) -cycloalkyl, with SR12 substituted cyclopropyl, C (3-10) -alkenyl, C (1-3) -haloalkyl, 1-, 2- or 3-pyridyl, <1> or <>; T 'z or Rg and Rg together with the carbon atom of the group R7 means a saturated or unsaturated ring consisting of 4 to 7 carbon atoms,

R10 represents CH (Rg) Rg, phenyl, C (3-5) -alkenyl, C (3-5) -alkyl or cyanoalkyl of 2 or 3 carbon atoms in the alkyl group, Ru represents hydrogen, C (1- 5) -alkyl, C (3-5) -alkenyl, C (3-5) -alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl group,

R 12 represents CH 3 or C 2 H 5, X represents oxygen or sulfur, Z represents NH or NCH 3, and n means 1 to 3, or are acid addition salts or metal salt complexes thereof.

By alkyl itself or as a constituent of another substituent, such as haloalkyl, alkoxy or haloalkoxy, depending on the number of said carbon atoms, for example, methyl, ethyl, propyl, butyl or pentyl and their isomers as .g. isopropyl, isobutyl, tert-butyl or sec-butyl. Halogen means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, haloalkyl and haloalkoxy means once until perhalogenated groups, e.g. CHC12, CH2F, CCI3, CR2C1, CHF2, CF3, CH2CH2-Br, C2Cl5, CH2Br, CHBrCl, etc., preferably CF3. Cycloalkyl means, depending on the number of said carbon atoms, e.g. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The compounds of formula I are at room temperature stable oils, resins or solids which exhibit valuable microbicidal properties. They can be used preparatively and curatively to control plant harmful microorganisms in the agricultural sector or in related fields. The active substances of I according to the invention are distinguished by low application concentrations not only by an excellent insecticide and fungicide effect, but also by very good plant compatibility.

The invention relates, as mentioned, to both the free compounds of formula I and their addition salts with inorganic and organic acids as well as their complexes with metal salts.

In particular, salts of the invention are addition salts with harmless inorganic or organic acids, e.g., hydrogen halide acids, e.g. hydrochloric acid, hydrobromic acid or hydrogen iodide acid, sulfuric acid, phosphoric acid, phosphoric acid, nitric acid, or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, succinic acid, citric acid, citric acid, citric acid benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalenedisulfonic acid.

4 DK 170336 B1

Metal salt complexes of formula I consist of the underlying organic molecule and an inorganic or organic metal salt, e.g. halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc. of the elements of the second major group, such as calcium and magnesium, and of the third and fourth major groups, such as aluminum, tin or lead as well as the first to eighth side groups, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. The side group elements from the fourth period are preferred. The metals can thereby be present in their different valences. The metal salt complexes can occur in single or multi-core, ie. they may contain one or more organic moieties as ligands.

Important groups of plant fungicides are compounds of formula I having the following symbolic meanings:

Group 1 (Substituents) R 1 is phenyl or up to three times with R 4 substituted phenyl, R 2 represents hydrogen, C 1-5 alkyl, with the groups OR 5 or SR 5 substituted C 1-5 alkyl, C 3 6) -cycloalkyl, with C (1-4) -alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, R 3 represents C (1-4) alkyl, with halogen, cyano or the groups OR5 or SR5 substituted C (1-4) alkyl, C (3-6) -cycloalkyl or with C (1-4) alkyl or halogen until three times substituted C (3-6) -cycloalkyl, R4 means halogen or C (1-3) -alkyl, R5 means hydrogen, C (1-5) -alkyl, 0 (3-5) -alkenyl, 0 (3-5) -alkynyl or a group (CH2) n "x" c (1_3) -alkyl, "

Rg represents hydrogen, C (1-5) alkyl, C (3-6) -cycloalkyl, 0 (3-5) -alkenyl or C (1-3) -haloalkyl, or 5

Rg and Rg together with the carbon atom of the group R7 means a saturated or unsaturated ring consisting of 5 or 6 carbon atoms, R7, R10, R10, Ru, R12 and Z have the meanings given in the formula I and halogen preferably represents fluorine, chlorine or bromine, X means oxygen or sulfur, n means 1 to 3.

Group 2 (Substituents)

R 1 is phenyl or a halo substituted phenyl, R 2 is hydrogen, C 1-5 alkyl, with OR 5 substituted C 1-5 alkyl, C 3-6 cycloalkyl, C 1 -C 6 4) -alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, R3 means C (1-4) -alkyl , with halogen, cyano or OR5 substituted C (1-4) alkyl, C (3-6) -cycloalkyl or methyl substituted C (3-6) -cycloalkyl, R5 means hydrogen or C (1-2) - alkyl,

Rg represents hydrogen, C (1-5) alkyl, C (3-6) -cycloalkyl, C (3-5) -alkenyl or C (1-3) -haloalkyl, or Rg and Rg together with the carbon atom of the group R7 means a saturated or unsaturated ring consisting of 5 or 6 carbon atoms, and Rη, R10, R10, R12 or R12 have the meanings set forth in Formula I, and halogen preferably represents fluorine, chlorine or bromine.

Group 3 (Substituents) R 1 is phenyl or up to three times with R 4 substituted phenyl, R 2 represents hydrogen, C 1-5 alkyl, with groups OR 5 or SR 5 substituted C 1-5 alkyl, C 3 6) -cycloalkyl, with C (1-4) -alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, B1 R3 is C (1-4) alkyl, with halogen, cyano or groups OR5 or SR5 substituted C (1-4) alkyl, C (3-6) -cycloalkyl or with C (1-4) alkyl or halogen until three times substituted C (3-6) -cycloalkyl, R4 means halogen, C (1-3) -alkyl, C (1-2) -haloalkyl, C (1) -3) alkoxy or C (1-3) haloalkoxy, R5 means hydrogen, C (1-5) alkyl, C (3-5) -alkenyl, C (3-5) -alkynyl or a group (CH2) ) nXC (1-3) alkyl, R7 means -NH2, X means oxygen or sulfur, and n means 1-3, including their acid addition salts and metal salt complexes.

Group 4 (Substituents) R 1 is phenyl or up to three times with R 4 substituted phenyl, R 2 represents hydrogen, C 1-5 alkyl, with groups OR 5 or SR 5 substituted C 1-5 alkyl, C 3- 6) -cycloalkyl, with C (1-4) -alkyl or halogen, up to three times substituted 20C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, R 3 represents C (1-4) alkyl, with halogen, cyano or the groups OR5 or SR5 substituted C (1-4) alkyl, C (3-6) cycloalkyl or with C (1-4) alkyl or halogen up to three 25 times substituted C (3-6) -cycloalkyl, R4 is halogen, R5 is hydrogen, C (1-5) -alkyl, C (3-5) -alkenyl, C (3-5) -alkynyl or a group (CH 2) nXC (1-3) alkyl, X means oxygen or sulfur, and 30 n means 1-3.

Group 5 (Substituents)

R 1 is phenyl or up to three times with halogen substituted phenyl, R 2 is hydrogen, C 1-5 alkyl, with the groups OR 5 or * SR 5 substituted C (1-5) alkyl, C (3-6) cycloalkyl , with C (1-4) -alkyl or halogen up to three times substituted 7, 170336 B1 C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, R3 means C (1-4) alkyl, with halogen, cyano or groups OR5 or SR5 substituted C (1-4) alkyl, C (3-6) -cycloalkyl or with C (1-4) -alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, R5 means hydrogen, C (1-5) -alkyl, C (3-5) -alkenyl, C (3-5) -alkynyl or a group (CH2) n "x" C (1-3) alkyl, X means oxygen or sulfur, n means 1-3.

Group 6 (Substituents)

R 1 is phenyl or once with chlorine or fluoro substituted phenyl, R 2 is C (1-5) alkyl, with OR 5 substituted C (1-2) alkyl, C (3-6) cycloalkyl, with C (1) -4) alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or a formyl group, R3 means C (1-4) - alkyl, C (1-4) -haloalkyl, C (3-6) -cycloalkyl or methyl substituted C (3-6) -cycloalkyl, and R5 is hydrogen or C (1-2) -alkyl.

Particularly preferred are such compounds of groups 5 and 6 in which R 2 and / or R 3 independently of each other means methyl, fluoromethyl, chloromethyl, bromomethyl, C (3-6) -cycloalkyl or methoxymethyl.

The following groups of single compounds are preferred:

Group 1 (Compounds) N- (4-fluoromethyl-6-cyclopropylpyrimidyl-2) -N-phenylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Nm-fluorophenyl-hydrazine, and N- (4-methyl-6-cyclopropylpyrimidyl-2) -Np-fluorophenyl-hy- drozin. *

Group 2 (Compounds) N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenylhydrazine, 5N- (4,6-dimethylpyrimidyl-2) -N-phenyl-hydrazine and N- (4-methyl -6-methoxymethylpyrimidyl-2) -N-phenyl-hydrazine.

Group 3 (Compounds) N- (4,6-dimethylpyrimidyl-2) -N-phenyl-propionaldehyde hydrazone, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-isobutyraldehyde hydrazone, N- (4 -methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-isobutyraldehyde hydrazone, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-propion-aldehyde hydrazone, N- (4-methyl-6- cyclopropylpyrimidyl-2) -N-phenyl-propional-dehydhydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-n-butyral-dehydhydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) ) -N-phenyl-isobutyral-dehydhydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-trichloro-acetaldehyderazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Np-fluorophenyl acet-aldehyde hydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Np-fluorophenyl-iso-butyraldehyde hydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Nm-fluorophenyl-iso-butyraldehyde hydrazone, 30 N- (4,6-dimethylpyrimidyl-2) -N-phenyl-Ν'-methylhydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-N1-dimethylhydrazine, N- (4,6-dimethylpyrimidyl) 2) -N-phenyl-N'- n-propylhydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-Ν'-isobutylhydrazine, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-N'-methylhydrazine , N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-N'-n-propylhydrazine, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl -N * dimethylhydrazine, 5 N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N'-methylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N- phenyl-N * -isobutylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N * -dimethyl-hydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N -phenyl-N'-diethyl-hydrazine,, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N * -methyl-N'-ethylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl) -2) -Np-fluorophenyl-N * -ethylhydrazine, N- (4-methyl-6-methoxymethylpyrimidyl-2) -Nm-fluorophenyl-N '-isopropylhydrazine.

The process of the invention for the preparation of the compounds of formula I is characterized by the characterizing part of claim 6 *. The individual methods are described in the following:

Process a)

A pyrimidine derivative of formula II

/ 2 (II) v / 25 \ 3 is reacted with a phenylhydrazine derivative of formula III R 1 -NHNH-R (III) in the presence of a base in aprotic solvents at temperatures from -50 to 150 ° C, Y being halogen, 30 is chloro, a group of SO2R6 or N® ((313) 3, Rg represents C (1-4) alkyl, phenyl or methyl or chloro substituted phenyl, and R has the meanings for Rio ° 9 R11 / 'and these and R1-R3 correspond to the meanings given in formula I.

Method b)

A pyrimidine hydrazine derivative of formula IV is reacted with an aldehyde or ketone of formula V to compounds of formula VII under the decomposition of water Άζ Rz> N— (Ro. Ri.

4 w R 3 R 2 '3 (IV) (V) (VII) 10 in any solvent in the presence of an acid at temperatures of -20 to 120 ° C, preferably 10 to 50 ° C, with R1-R3 and Rg and R9 have the meanings given under formula I.

To remove the water from the reaction mixture, azeotropic distillation or molecular sieves can be used. Furthermore, desiccants, e.g. calcium chloride or sodium sulfate. The reaction of the derivative IV with an aldehyde can often be waived for removal of the water from the reaction mixture.

Method c)

A hydrazone derivative of formula VII

S * / 2

Riv / -v R., · Reduction Ri-R—. Is reduced with a reducing agent, e.g. borohydride ether, NaBH4, NaCNBHg or LiAlH4 / in an inert solvent, e.g. suitable alcohols, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures 5 from 0 to 50 ° C or by catalytic hydrogenation with catalysts, e.g. nickel, platinum, palladium or rhodium.

Method d)

A pyrimidine hydrazine derivative of formula IV

- / 2 10 '*! - * <> <IV> KHz. K = *

is reductively alkylated with an aldehyde or ketone of formula V

0

II

Rg-C-Rg (V) in the presence of a reducing agent, e.g. borohydride etherates, NaBH4, NaCNBHg or LiAlH4, in an inert solvent, e.g. suitable alcohols, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures 20 from 0 to 50 ° C.

Process e)

A pyrimidine hydrazine of formula IV or VIII is alkylated with an alkyl halide RgHal 12 DK 170336 B1 a _ / 2 _ / 2

Ri1h; C> + R ° Hsl - * · τΟ k3 K \ \ 3 oo (IV) (IX) Μ Ά2 ji— (^ 0 "\, 0 Xv \, chr8 (r9) r 'CHRb (R9) (VIII) ) (X) in an inert solvent in the presence of a base at temperatures of 0-60 ° C, preferably 10-40 ° C, where R g 5 represents C (1-4) alkyl, as additional alkylating agents, dialkyl sulfates are suitable.

In the above-described processes (a-e), R 1 -R g have the meanings given under formula I.

In the methods described, both inorganic and organic bases, e.g. the following: the hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium or hydrides, e.g. sodium hydride, and alcohol esters, e.g. potassium tert.butylate, as well as tertiary amines, such as triethylamine, triethylenediamine or pyridine.

As reaction media, e.g. Depending on the reaction conditions, the following solvents and diluents are used: Aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes and petroleum ether, 20 halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachlorethylene, ethers and ether-like compounds such as dialkyl ethers, e.g. diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc., anisole, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Ν, dial-dialkylated amides such as dimethylformamide, and mixtures of such solvents with each other.

The pyrimidine derivatives of formula II wherein Y represents halogen can be prepared by known methods, cf. D.J. Brown, The Pyrimidines, Interscience Publishers, 1962.

0

A frequently used synthesis route consists in condensation of urea with γ-diketones to 2-hydroxypyrimidines, which are then converted to 2-halogenopyrimidines as follows:

Ra ^ H

\ = o h2n. y = \ ym \ 15 <+> -0 -% / - ° H - \ Z * "1531 • = o HzK> -k / - *

As a halogenating agent, phosphorus oxychloride or phosphorus oxybromide may be used.

Another possibility of obtaining the 2-halo pyrimidines of formula II is to prepare them over the 2-aminopyrimidines. The 2-aminopyrimidines are obtained by known methods (cf. D. J. Brown, The pyrimidines, Interscience Publishers, 1962), then diazotized and converted by the Sandmeyer reaction to the 2-halo pyrimidines. The 2-aminopyrimidines are obtained e.g. by condensation of / 5-diketones 25 with guanidine as follows: HK »1) NaNO2 / H> -N.

/ + W - /> - **, - S> -Hal ™ „/ = / 2) H.1® / Cu® y- * R 3 ^ 3 R 3 14 DK 170336 B1

The pyrimidine derivatives of formula II wherein Y is in SO 2 'C (1-4) -alkyl or SO2-aryl are obtained according to known methods by oxidation of the corresponding alkyl or 5-alkyl mercaptopyrimidines, the preparation of which is also known, cf. D.J. Brown, The Pyrimidines, Interscience Publishers, 19 62.

In addition to condensation of the corresponding 10 diketones as described above, pyrimidine derivatives of formula II wherein R 3 is haloalkyl can also be prepared by reacting the hydroxyalkyl derivatives with phosphorus halide or thionyl halide in inert solvents in the presence of tertiary bases.

Pyridine derivatives of formula II

/ 112 / N - (15 Y V. / (II), where Y is halogen or SO 2 -R 6 and R 6 is C 1-4 alkyl or aryl and R 2 and R 3 have the formula In the meanings given are partly known.

The following groups of pyridine derivatives of formula II are novel: 1. Compounds in which R2 represents C (1-5) alkyl or with the groups OR5 or SR5 substituted C (1-5) alkyl, R3 means with halogen, cyano or the groups OR5 or SR5 are substituted C (1-4) alkyl, R5 is hydrogen, C (1-5) alkyl, C (3-5) -alkenyl, C (3-5) -alkynyl or a group 1703 B1 (CH2) nXC (1-3) alkyl X means oxygen or sulfur, n means 1-3, Y represents halogen, preferably chlorine, or SO2 R5, ° 9 R6 means C (1-4) alkyl or aryl , with the exception of the compounds 2-chloro-4-methyl-6-methoxymethylpyrimidine and 2-chloro-4-methyl-6-trichloromethylpyrimidine.

2. Compounds in which R 2 represents hydrogen, C 1-5 alkyl or with the groups OR 5 or SR 5 substituted C 1-5 alkyl, R 3 represents C (2-5) alkenyl or C 2 -C 5 alkynyl, R5 is hydrogen, C (1-5) alkyl, C (3-5) -alkenyl, C (3-5) -alkynyl or a group (CH2) nxC (1-3) alkyl, and Y means halogen.

The hydrazine derivatives of formula III are known or can be prepared by methods known to those skilled in the art.

EP 270111 discloses 2-anilinopyrimidine derivatives with fungicidal properties and EP 19450 A1 known phenyl hydride derivatives used in agriculture against microorganisms.

It has been found in accordance with the invention that the compounds of formula I have a very favorable biocidal spectrum for phytopathogenic microorganisms, especially against fungi, for practical needs. They have very beneficial curative, preventive and especially systemic properties and are used for the protection of numerous cultural plants. With the active substances of formula I, the occurring harmful organisms on plants 30 or plant parts (fruits, flowers, leaves, stems, tubers or roots) in different crops can be kept within certain boundaries or destroyed, since also later growing plant parts can be spared. . for phytopathogenic 16 DK 170336 B1 microorganisms.

Compounds of formula I e.g. active against phytopathogenic fungi belonging to the following classes: Fungi imperfecti 5 (especially Botrytis, also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria), Basidiomycetes (e.g. Rhizootonia, Hemileia and Puccinia). Moreover, they act against the class of Ascomycetes (e.g. Venturia and Erysiphe, furthermore Podosphaera, Monilinia and Uncinula) and 10 Oomycetes (e.g. Phytophthora, Pythium and Plasmopara). Furthermore, the compounds of formula I can be used as a dressing agent for the treatment of seed (fruits, tubers and grains) and plant cuttings to protect against fungal infections and against soil phytopathogenic fungi.

In addition, compounds of formula I are effective against harmful insects, e.g. against harmful organisms in cereals, especially rice.

The compositions of the invention are characterized in that, as active components, they contain at least one compound 20 of formula I or an acid addition salt or metal complex thereof together with a suitable carrier material.

The method of the invention for controlling or preventing an attack on cultured plants of harmful insects or phytopathogenic microorganisms is characterized by applying as an active substance a compound of formula I or an acid addition salt or metal complex thereof on the plant, plant parts or their habitat. .

As target cultures for the plant-protecting application disclosed herein, within the scope of the invention, for example, the following plant species apply: cereals, e.g. wheat barley? rye, oats, rice, maize, sorghum and related species, beets, e.g. sugar beet and fodder beet, kernel, stone and berry fruit, 18 DK 170336 B1 holds at least one of these active substances, is the application to the foliage (leaf application). The rate of application and the amount applied therefore are based on the attack pressure of the disease developer. However, the active substances of formula I can also reach the soil through the roots of the plants (systemic effect), by wetting the place of residence of the plant with a liquid preparation or introducing the substances into the soil in solid form, e.g. in the form of granulate 10 (soil application). The compounds of formula I may also be applied to seed (coating), the grains either being wetted with a liquid composition of the active substance or coated with a solid composition.

The compounds of formula I are used in unchanged form 15 or preferably as agents together with the aids common in the formulation technique. In addition, they are conveniently processed in a known manner e.g. for emulsion concentrates, spreadable pastes, direct sprayable or dilute solutions, diluted emulsions, 20 spray powders, soluble powders, powders, granules and capsules in e.g. polymeric substances. The methods of application, such as spraying, misting, powdering, sprinkling, lubricating or watering, are selected as the agents in accordance with the objectives and conditions given. Advantageous application rates are usually at 50 g to 5 kg of active substance per day. per hectare, preferably 100 g to 2 kg of active substance per hectare. per hectare, especially 200 g to 600 g of active substance per hectare. acres.

The formulations, ie. the agents containing the active substance of formula I and a solid or liquid additive are prepared in known manner, e.g. by thoroughly mixing and / or grinding the active substances with extenders, e.g. with solvents, solid carriers and optionally surfactants (surfactants).

17 DK 170336 B1 1 e.g. apples, pears, plums, peaches, almonds, cherry berries, strawberries, raspberries and blackberries, legumes, e.g. beans, lentils, peas and soy, oil cultures, e.g. rapeseed, 5 mustard, poppies, olives, sunflowers, coconut, castor, cocoa and peanuts, cucumber plants, e.g. pumpkins, cucumbers and melons, fiber plants, e.g. cotton, flax, hemp and jute, citrus fruits, e.g. oranges, lemons, grapefruit and tangerines, vegetable varieties, e.g. spinach, main salad, 10 asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes and peppers, laurel plants, e.g. avocado, cinnamon and camphor, or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, banana and natural rubber plants, and ornamental plants.

Active substances of formula I are usually used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active substances. These other active substances may be fertilizers, trace element intermediates 20 or other preparations affecting plant growth. Thereby, selective herbicides as well as insecticides, fungicides, bactericides, nematodicides, molluscicides or mixtures of several of these compositions can also be used together with any other carriers, surfactants or other application-promoting additives commonly used in the formulation technique.

Suitable carriers and additives may be solid or liquid and correspond to the substances useful in the formulation technique, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting, adhesives, thickeners, binders or fertilizers.

. A preferred method of applying an active substance of formula I or an agrochemical agent containing

As solvents may be used: Aromatic hydrocarbons, preferably fractions C (8-12), e.g. xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene ethyl acetate, ethylene glycol monomethyl, ketones such as cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized plant oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, e.g. For powders and dispersible powders, natural stone flour, such as kaloite, talc, kaolin, montmorillonite or attapulgite, is usually used.

To improve the physical properties, high-dispersion silicic acid or high-dispersion sugary polymerisates can also be added. As granular adsorptive granular carriers 20 may be used porous types such as e.g. pumice, brick, sepiolite or bentonite, as non-sorptive carriers e.g. calcite or sand. In addition, a variety of inorganic pre-granulated materials, such as dolomite in particular, or finely divided plant residues can be used.

Non-ionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties can be used as surfactants, depending on the nature of the active substance of formula I to be formulated. Surfactants also include surfactant mixtures.

Suitable anionic surfactants can be both the so-called water-soluble soaps and water-soluble synthetic surfactants.

DK 170336 B1

As soaps, mention is made of alkali metal, alkaline earth metal or - optionally substituted ammonium salts of higher fatty acids C (10-22), e.g. the sodium or potassium salts of oleic acid or stearic acid, or of naturally occurring fatty acid by breaths, e.g. can be extracted from coconut or tallow oil. Furthermore, the fatty acid methyl laurine salts must also be mentioned.

More often, however, the so-called synthetic surfactants are used, especially 10 alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are usually present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and have an alkyl group of 8 to 15 carbon atoms, the alkyl also comprising the alkyl moiety in acyl groups, e.g. the sodium or calcium salt of lignin sulfonic acid, of dodecyl sulfuric acid ester, or of a fatty alcohol sulfate mixture prepared from natural fatty acids. These include the salts of sulfuric acid esters and 20 sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue having 8-22 C atoms. Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid formaldehyde condensation product.

Furthermore, similar phosphates, e.g. salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct are used.

As nonionic surfactants, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in it ( aliphatic) hydrocarbon group and from 6 to 18 carbon atoms in the alkyl group of the alkyl phenols.

Other suitable nonionic surfactants are water-soluble 5 polyethylene oxide adducts for polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The said compounds usually contain 1 to 5 ethylene glycol units per liter. the propylene glycol-ness.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide addition products, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Also mentioned are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants mainly comprise 20 quaternary ammonium salts containing as N substituents at least one alkyl group having 8 to 22 carbon atoms and as other substituents having lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, e.g. stearyl trimethylammonium chloride or benzyldi- (2-chloroethyl) ammonium bromide.

Other conventional surfactants in the formulation technique are known to those skilled in the art or may be obtained from the relevant literature.

The agrochemicals usually contain 0.1 to 99%, in particular 0.1 to 95% of active substance of formula I, 99.9 to 1%, especially 99.9 to 5% of a solid or liquid additive. And 0 to 25%, in particular 0.1 to 25% surfactant. * Contrary to commodities, which are often preferred as concentrated funds, the end consumer usually uses 5 diluted funds.

The agents may also contain other additives such as stabilizers, anti-foaming agents, viscosity regulators, binders, adhesives, and fertilizers or other active substances to achieve special effects.

The invention is further illustrated by the following non-limiting examples.

1. Preparation Examples

Example 1.1 2-Hydroxy-4-methyl-6-cyclopropyl-pyrimidine hydrochloride (Starting product) <pH3 / µl HCl BO7 V \ 6/0 g (0.10 mol) of urea and 12.6 g (0.10 mol) of cyclopropylbutane-1,3-dione are dissolved at room temperature (about 20 ° C) in 20 ml of ethanol and 15 ml of 32% aqueous hydrochloric acid. After standing for 10 days at room temperature, the solution is evaporated on a rotary evaporator at a bath temperature of maximum 45 ° C. The residue is dissolved in 20 ml of ethanol; after a short time the product begins to secrete in the form of the hydrochloride.

With stirring, 20 ml of diethyl ether is slowly added and the product is separated from the solvent by suction filtration, washed with a mixture of diethyl ether and ethanol and dried at 60 ° C in vacuo. 7.14 g (38.2% of theory) of 5 2-hydroxy-4-methyl-6-cyclopropyl-pyrimidine hydrochloride are obtained.

Evaporation of the filtrate, after recrystallization from 10 ml of ethanol and 20 ml of diethyl ether, an additional 5.48 g of substance (29.2% of theory) is obtained.

Analysis: C8H10N2O * HCl (MV: 186.64) 10% calcd. % found C 51.48 51.47 H 5.94 5.97, N 15.01 15.15

Cl 18.99 18.89 Example 1.2 2-Chloro-4-methyl-6-cyclopropyl-pyrimidine hydrochloride (Starting product) fHs 'f S |' |

c / VV

52.8 g (0.24 mol) of 2-hydroxy-4-methyl-6-cyclopropylpyrimidine hydrochloride are introduced into a mixture of 100 ml of phosphorus oxychloride and 117 g (0.79 mol) of diethylaniline and stirred; the exothermic reaction starts slowly, raising the temperature from room temperature to 63 ° C. Thereafter, the oil bath is heated at 100-110 ° C for 2 hours at internal temperature. After cooling to room temperature, the mixture is poured into a mixture of ice water and methylene chloride with stirring. After one hour, the organic phase is separated into the separatory funnel and washed neutral with sodium hydrogen carbonate solution. After removal of the solvent, 116.4 g of crude product consisting of 2-chloro-4-methyl-6-cyclopropyl-pyrimidine and diethylaniline are obtained. Chromatographic separation using silica gel and a mixture of 25% ethyl acetate and 75% hexane as a solvent gives 35.7 g (89.4% of theory) of pure 2-chloro-4-methyl-6-cyclopropyl-ethylene pyrimidine as colorless oil.

Example 1.3 2-Amino-4-di ethoxymethyl-6-cyclopropylpyrimidine (Starting product)

'T II

• ·

Hal / V 4 Sch (oc 2 H 2) 2 74.8 g (0.42 mol) of guanidine carbonate and 74.1 g (0.35 mol) of 4-cyclopropyl-2,4-dioxo-butyraldehyde diethyl acetal are boiled for 10 hours in 250 ml of ethanol. . Then it is evaporated on a rotary evaporator and the residue is extracted with water and ethyl acetate. After evaporation of the ethyl acetate, 79.2 g of crude product remains, the recrystallization from hexane affording 70.4 g of 15 (85.8% of theory) of pure substance. Mp. 77-78 ° C.

Example 1.4 2-Chloro-4-formyl-6-cyclopropylpyrimidine (Starting product)

• I> I I

\ / / \ 1 !! ci7 V ncho 20 70.3 g (0.30 mol) of 2-amino-4-diethoxymethyl-6-cyclopropylpyrimidine are dissolved in 340 ml of 32% aqueous hydrochloric acid and cooled with dry ice to -25 ° C. Then, a solution of 40.9 25 B1 g (0.59 mol) of sodium nitrite in 80 ml of water is slowly added dropwise at -20 to -25 ° C, thereby developing nitrogen and a solid product. After 2 hours the cooling is removed. The mixture 5 is brought to room temperature and extracted with ethyl acetate. Drying of the extract with sodium sulfate and solvent removal results in 21.9 g of crude product as oil. The further purification by column chromatography (silica gel, solvent 30 parts ethyl acetate and 70 parts hexane) gives 16.1 g of pure material as colorless liquid. Refractive index n§5 = 1.5603.

Analysis: C8H7C1N2O (MV: 182.61)% calcd. % found $ mu - ....

C 52.6 52.6 H 3 3.9 4.1 N 15.3 14.8

Cl 19.4 18.7

Example 1.5 2 - Chloro-4-hydroxymethyl-6-cyc lopropylpyr imidine 20 (Starting product) Λ ·. ·

Cl7 Y NCH20H

15.4 g (0.084 mol) of 2-chloro-4-formyl-6-cyclopropylpyrimidine are dissolved in 125 ml of methanol and reduced by the addition of 1.6 g of sodium borohydride. Evaporation, extraction with 25 ethyl acetate and removal of the solvent on a rotary evaporator yield 14.5 g of crude product which is recrystallized from a mixture of 20 ml of toluene and 20 ml of cyclohexane. The pure yield is 13.7 g (88.4% of theory); smp.l02-104 ° C.

26 DK 170336 B1

Analysis: C8HgClN2O (MV: 184.63)% calcd. % found C 52.04 52.05 5 H 4.91 4.90 N 15.17 15.27

Cl 19.20 19.28

Example 1.6

Mesylate of 2-chloro-4-hydroxymethyl-6-cyclopropylpyrimidine 10 (starting product) 0 · · Λ ·. · ¢ / V sch2oso2ch3

To 9.5 g (0.05 mole) of 4-hydroxymethylpyrimidine and 5.7 g of triethylamine in 150 ml of tetrahydrofuran is added dropwise with cooling a solution of 6.5 g of methanesulfonyl chloride in 30 ml of tetrahydrofuran. Immediately suctioned triethylamine hydrochloride is extracted. Evaporation gives 14.7 g of crude product which is chromatographed on silica gel (25 parts of ethyl acetate and 75 parts of hexane). 13.6 g of pure substance is obtained. Mp. 64-66 ° C.

Analysis: CgH1: LClN2O3S (MV: 262.71)% calcd. % found C 41.15 41.32 H 4.22 4.33 N 10.66 10.56 25 S 12.20 12.16 27 DK 170336 B1

Example 1.7 2-Chloro-4-fluoromethyl “6-cyclopropylpyrimidine (Starting product) • .1.

c / Y W

13.4 g (0.05 mol) of mesylate is refluxed for 5 hours in 70 ml of propionitrile with 9.4 g (0.16 mol) of potassium fluoride and 0.8 ml of 18-krone-6 as a catalyst. Removal of the solvent and subsequent extraction with water and 10 ethyl acetate gives a crude product which is purified by column chromatography (silica gel; 15 parts ethyl acetate and 85 parts hexane). The pure yield is 7.5 g (78.6% of theory); mp. 37-39 ° C.

Analysis; C8H8C1FN2 (MV: 186.62) 15% calcd. % found C 51.49 51.73 H 4.32 4.45 N 15.01 14.90 F 10.18 10.26 20 Cl 19.00 18.50

Example 1.8 2-Chloro-4-methyl-6- (2-methylcyclopropyl) -pyrimidine (Starting product) qis Λ c / YYh, 28.4 g (0.47 mole) of 2-amino-4-methyl 6- (2-methylcyclopropyl) pyrimidine prepared by boiling guanidine carbonate with acetylmethyl-2-methylcyclopropyl ketone in ethanol 5 is dissolved in 536 g of 32% hydrochloric acid and cooled to -25 ° C. Then, 2 g of copper powder is added and a solution of 71.4 g (1.03 mole) of sodium nitrite in 200 ml of water is added dropwise at -25 ° C over 3 hours to develop nitrogen and nitrous gases. Then the mixture is brought to room temperature and extracted with ethyl acetate and the extracts washed with water and dried with sodium sulfate. After removal of the solvent, 27.7 g of crude product are obtained. The residue is chromatographically purified on silica gel with a mixture of 20 parts of ethyl acetate and 80 parts of hexane as a solvent. 32.2 g of pure substance are obtained; refractive index n§4 = 1.5334.

Analysis: C9H11CIN2% calcd. % found C 59.18 59.16 20 H 6.07 6.15 N 15.34 15.25

Cl 19.41, 19.20

Example 1.9 2 - (- Phenylhydrazine) -4,6-dimethylpyrimidine (Compound 1.12) / CH2 · NS · NS · i_. γ nN - (ch 3 4.77 g (0.033 mol) of phenylhydrazine hydrochloride is suspended under nitrogen in 60 ml of tetrahydrofuran, to which is added 7.41 g (0.066 mol) of K-tert-butylate, and then a solution of 5.59 is added. g (0.030 mol) of 2-methylsulfonyl-4,6-dimethyl-170-ylpyrimidine in 15 ml of tetrahydrofuran at 25-35 ° C. After 2 hours, the mixture is extracted at pH 6 with ethyl acetate and water with the addition of a little acetic acid. drying of the organic phase with sodium sulfate and removal of the solvent on a rotary evaporator afforded 5.88 g of crude product. Chromatographic purification by silica gel and a mixture of 35 parts of ethyl acetate and 65 parts of hexane yields 2.89 g of pure material which, after recrystallization from n-hexane 10 melts at 41-43 ° C.

Example 1.10 2- (g-Phenylhydrazino) -4,6-dimethylpyrimidine (Compound 1.12)) ''Cib 7.06 g (0.035 mol) of 2-trimethyl-ammonium-4,6-dimethylpyrimidine chloride (W Klötzer, Monatshefte f. Chemie 87, 131 (1956) and 5.78 g (0.04 mole) of phenylhydrazine hydrochloride are suspended in 50 ml of tetrahydrofuran and a solution of 5.04 g (0.045 mole) of potassium is added dropwise. -tert-butylate in 25 ml of tetrahydrofuran. The exothermic reaction is maintained by cooling at 5-10 ° C. After the mixture has warmed to 20 ° C, extracted with ethyl acetate and water, and the extract is dried with sodium sulfate. After evaporation, 5.9 g of crude product is obtained, which is purified by column chromatography (silica gel, solvent: mixture of 25 parts of ethyl acetate and 75 parts of hexane). 3.94 g of pure substance is obtained.

N- (4-methyl-6-cyclopropylpyrimidinyl-2) -N-phenylhydrazine (Compound 1.4)

Example 1.11 DK 170336 B1 A fHj V / \

c ITII

5 HH + w / g 2.20 g (0.013 mole) of 2-chloro-4-methyl-6-cyclopropylpyrimidine and 1.62 g (0.015 mole) of phenylhydrazine are dissolved in 20 ml of tetrahydrofuran under cooling at 20-25 ° C. To this solution is added a solution of 2.02 g (0.018 mole) of potassium tert-butylate in 20 ml of tetrahydrofuran. After 30 minutes no more starting pyrimidine can be detected by thin layer chromatography. The mixture is then extracted with water and ethyl acetate. After removal of the ethyl acetate on rotary evaporator, 3.13 g of crude product is obtained, which is purified by column chromatography on silica gel (solvent: 35% ethyl acetate / 65% hexane). 2.83 g of pure substance (90.2% of theory) is obtained, which is recrystallized from a mixture of 8 ml of n-hexane and 1 ml of cyclohexane to give 1.62 g of substance (mp 46 ° C). Evaporation of the mother liquor and recrystallization yields an additional 0.42 g of product (mp 45-46 ° C). The total yield of recrystallized product is 2.04 g (65.3% of theory).

Analysis: C 14 H 15 N 4 (MV: 240.31)% calcd. % found 25 C 69.98 69.81 H 6.71 6.77 N 23.32 23.49 N- (4-methyl-6-cyclopropylpyrimidinyl-2) -N-phenyl-isobutyraldehyde hydrazone 5 (Compound 3.26)

Example 1.12 31 DK 170336 B1 • - i \ /

/ \ / V

I II T II

νγΥν .6.25 (0.026 mole) of N- (4-methyl-6-cyclopropylpyrimidinyl-2) ~ N -phenylhydrazine and 2.25 g (0.031 mole) of isobutyraldehyde are dissolved in 30 ml of methanol, thereby initiating a slight exothermic reaction . After standing for two hours at room temperature, the solvent is removed on a rotary evaporator. 7.8 g of crude product is obtained in the form of a viscous oil. Of this, 3.2 g is purified by column chromatography on silica gel (solvent: 72% hexane / 18% ethyl acetate / 10% methanol). The pure yield 15 is 2.92 g of substance, m.p. 53-55 ° C. This corresponds to a yield of 93% of theoretical in conversion to purification of the total crude product.

Analysis: (MV: 294.40)% calcd. % found 20 C 73.44 73.25 H 7.53 7.64 N 19.03 18.92 N- (4-Methyl-6-cyclopropylpyrimidinyl-2) -N-phenyl-N * -isobutylhydrazine 5 ( Compound 4.87)

Example 1.13 321 170336 B1 '\ 7' a 'a.

i i? i1 n7 S? 7 xch3. HNCH2CH (CH3) 2 8.55 g (0.029 mol) of N- (4-methyl-6-cyclopropylpyrimidinyl-2) -N-phenyl-isobutyraldehydrazone are dissolved in 30 ml of methanol and 2 ml of glacial acetic acid. Then 2.14 g (0.029 mol) of sodium cyanoborohydride is added in portions with stirring. The reaction proceeds exothermically; the temperature is kept by cooling at 10-15 ° C. After 1 hour, the mixture is worked up by extraction with ethyl acetate and water, the organic phase is evaporated on a rotary evaporator and 8.5 g of crude product are obtained. Purification by column chromatography on silica gel (solvent: 85% hexane / 15% ethyl acetate) gives 7.6 g of oil (89% of theory) having a refractive index of n§5 = 1.5733.

Analysis: 0 ^ 3 ^ 24 ^ 4 (MV: 296.42) 20% calcd. % found C 72.94 72.90 H 8.16 8.21 N 18.90 18.83 N- (4-Methyl-6-methoxymethylpyrimidinyl-2) -N-phenyl-N'-methylhydrazine 5 (Compound 4.17)

Example 1.14 33 DK 170336 B1 / \ / \

I IJ T IJ

Dissolve 3.70 g (0.33 mole) of potassium tert-butylate in 25 ml of molecular sieves dried tetrahydrofuran to which 3.67 g (0.03 mole) of N-methyl-N'-phenylhydrazine is added. (K. Kratzl, 10 Monatshefte f. Chemie 89, 83 (1958)), and then added dropwise under nitrogen at -20 ° C a solution of 4.22 g (0.025 mol) of 2-chloro-4-methyl-6-methoxymethylpyrimidine for 30 min. ml of anhydrous tetrahydrofuran. Thereby, a yellow-brown suspension is formed, which is gradually brought to room temperature. After extracting for 4 hours with water and ethyl acetate, the crude product is isolated by evaporation of the solvent and purified by column chromatography on silica gel (solvent: 65% hexane / 35% ethyl acetate). The pure product is obtained as oil having a refractive index of n $ 4 = 1.5793.

Analysis: C ^H ^ gN / OO (mv: 258.33)% calcd. % found C 65.09 65.08 H 7.02 7.09 N 21.69 21.05

Example 1.15 34 B1 N- (4,6-Dimethylpyrimidinyl-2) -N-phenyl-N1-methylhydrazine (Example 4.1) (JHs ✓ \ / * \

I II Ί II

5 µV VCH 3 NHCHs, 4.03 g (0.02 mol) of 2-trimethylammonium-4,6-dimethylpyrimidine hydrochloride (W. Kldtzer, Monatshefte f. Chemie 87, 131 (1956)) is stirred with 3.05 g (0.025 mol) of N-methyl-N'-phenylhydrazine in 30 ml of anhydrous tetrahydrofuran under nitrogen, and at room temperature a solution of 3.36 g (0.03 mol) of potassium tert-butylate in 15 ml is added dropwise. tetrahydrofuran. The mixture is allowed to react overnight at room temperature and extracted with water and ethyl acetate, the solvent is removed and the product is purified by column chromatography on silica gel (solvent: 70% hexane / 30% ethyl acetate). 3.09 g of substance are obtained as oil.

Analysis: C13H16n4% calcd. % found C 68.40 68.01 20 H 7.07 7.09 N 24.54 24.13

Example 1.16 N- (4,6-Dimethylpyrlmidinyl-2) -N-phenyl-N * -dimethylhydrazine (Compound 4.13) <j: H3

I II T II

3.42 g (0.016 mol) of N- (4,6-dimethylpyrimidinyl-2) -N-phenylhydrazine are dissolved in 20 ml of methanol together with 3, 28 g (0.042 mole) of 38% formaldehyde and 2 ml of glacial acetic acid and to this add 1.33 g (0.018 mole) of sodium cyanoborohydride in portions at approx. 5 ° C. The reaction proceeds exothermically and is completed after one hour. Extract with ethyl acetate and water, remove the solvent on a rotary evaporator and give 3.25 g of crude product. Chromatographic purification by silica gel and a mixture of 76% hexane, 19% ethyl acetate and 5% methanol gives 1.80 g (46.4% of theory) of pure material as oil; n $ 5 = 1.5673.

Example 1.17 N- (4-Methyl-6-cyclopyrimidinyl-2) -N-phenyl-N1-methyl-N '-isobutylhydrazine (Compound 4.102)

CjlH 3! CH3AcH2CH (CH3) 2 4.55 g (0.0153 mol) of N- (4-methyl-6-cyclopropylpyrimidinyl-2) -N-phenyl-N'-isobutylhydrazine are dissolved together with 1.45 g 20 (0.0184 mole) of 38% formaldehyde in 25 ml of methanol and 2 ml of glacial acetic acid are added 1.24 g (0.0168 mole) of sodium cyanoborohydride in portions at 10 ° C. The reaction proceeds exothermically and the mixture is extracted after one hour with water and ethyl acetate. After removal of solvent 25, 4.95 g of crude product is obtained, which is purified by column chromatography on silica gel (solvent: 85% hexane / 15% ethyl acetate). The yield is 4.4 g of an oil; refractive index n§0 = 1.5613.

36 DK 170336 B1

Analysis; CigH26N4 (MV; 310.45)% calcd. % found C 73.51 73.94 5 H 8.44 8.58 N 18.05 17.93 37

Table 1: Compounds of formula DK 170336 B1 / 3 v

Conn. rx R2 r3 Physical No · Data 1.1 C6H5 H ch3 1.2 4-CF3C6IU CH3 CH3

1.3 4-F-CbIH Η H Mp.129-131 ° C

1.4 C6H5 CH3 - ^ Mp. 45-46 ° C

1.5 C6H5 C (CH3) 3 CH2OCH3

1.6 CeH5 CH2 OCH3. ' - m.p. 37-38 ° C

1.7 C6H5 CH3 CH2OCH3 Mp. 60-61 ° C

1.8 C6H5 ch2oc2h5 c (ch3) 3 1.9 c6h5 ch2 and (ch3) c2h5 ch3 1.10 3,4- (C2H50) 2-C6H3 CH3 CH2OC2H5 1.11 c6h5 ch3 ch2oc2h5

1.12 C6H5 CH3 CH3 Mp. 41-43 ° C

1.13 4-CH30-C6IU C (CH3) 3 CH2OC2H5 1.14 CgH5 ch3 chci2 1.15 3,5-Cl2-C6H3 CH3 CH2OCzH5

1.16. 3,5-Cl2-C6H3 CH3 CH3 Mp. 154-156 ° C

1.17 3,5-Cl2-C $ H3 C (CH3) 3 CH2OC2H5 1.18 3,5-Cl2-C6H3 - ^ CH2 OCH3 1.19 3.4- (C2H50) 2-C6H3 CH2OC2Hs C (CH3) 3

1.20 4-0Η30-06Ηι * CH3 CH3 Mp. 90-92 ° C

1.21 4-CH30-C6Hi * ch2oc2h5 ch3 1.22 3,4- (C2H50) 2-C6H3 - ^ CH2OCH3 1.23 C6H5 CH3 CH2OCH2CH = CH2 1.24 4-CH3-C6Hi »CH3 CH3 n30 1,604 38

Conn. Ri R2 R3 Physical No. data

Table 1 (continued) DK 170336 B1 1.25 4-0CH3-C6H., - ^ CH2OCH3! 1.26 3,5-Cl2-C6H3 CH3 CH2OCH (CH3) C2H5 1.27 4-OCH3 CH3 CH2OCH (CH3) C2H5

1.28 2-Br-CeHi, CH3 CH3 Mp. 55-57 ° C

1.29 3,5-Cl2-C6H3 CH20CH2CH = CH2 CH3 1.30 4-CH30-C6Hi, C (CH3) 3 CH20CH3 1.31 3,5-Cl2-C6H3 CH3 CHC12

1.32 3-Cl-CeHi, CH3 CH3 Mp. 47-48 ° C

1.33 3,4- (C2H5Oi, -C6H3 CH3 CH2OCH (CH3) C2H5 1.34 4-CH30-C6Hi, CH3 CH2OCH3 1.35 3.4- (C2H50) 2-C5H3 C (CH3) 3 'CH2OCH3 1.36 3.5-Cl2- C6H3 CH3 CH2OCH3

1.37 2,4,6-Cl3-C6H2 CH3 CH3 Mp 150-152 ° C

1.38 3,4- (C2H50) 2-C6H3 CH3 CH2OCH3 1.39 3,5-Cl2-C6H3 CH2OCH2CsCH CH3 1.40 C6H5 ch2och2c = ch ch3 1.41 4-CH3O-C6IU CH20CH2C = CH ch3

1.42 3,5- (CF3) 2-C6H3 CH3 CH3 Mp. 88-90 ° C

1.43 C6H5 CH20CH3 CH2OCH3 1.44 C6H5 CH2SCH3 CH3 1.45 C6H5 CH3 CH (OCH3) 2 1.46 C6H5 CH3 CH (0C2Hs) 2

Conn. Ri R2 r3 Physical No. Data 39 DK 170336 B1

Table 1 (continued) 1.47 C6H5 “\ / * CH3

1.48 4-Br-CsHu CH3 CH3 Mp. 92-93 ° C

1.49 C6H5 CH3 Cyclo-CeHn 1.50 C6H5 CH3 CF2C1 1.51 C6H5 - (I CF3 * • · 1.52 C6Hs - (I ~ \ | • · 1.53 C5H5 - (CF2Cl

1.54 3-CH 3 -C 3 H 1 * CH 3. CH3 m.p. 72-73 ° C

1.55 C6H5 C2H5 - (n "1.6063 * 1.56 C6H5 CH3 ~ * \ | / CH3 nD ° 1.6072

1.57 C6H5 CH (CH3) z - (I

1.58 C6H5 CH2OCH3 CEs 1.59 C6H5 - (I CH (OCH3) 2 1.60 c6h5 ch2och3 ch2ch (ch3) 2

1.6Γ C6H5 CHO - (I

• 1.62 C6H5 CH2OCH3 - · (CH3 · 1.63 C6H5 CH2CH2CH3 CH2OCH3 1.64 C6HS CH (CH3) 2 CH2OCH3 1.65 4-F-CgHi, CH3 - ^ \ h3 n “1,5883 1.66 CsH5 CH20H - (|

Porb. Rx r2 R3 Physical No · Data 40 DK 170336 B1

Table 1 (continued) 1.67 C6H5 (CH2) 3CH3 CH2OCH3 1.68 C6H5 C2H5 CH2OCH3 n2lf 1.5923 1.69 C6H5 CH2OCH3 -i '1.70 CgH5 CH2OCH3 CF2C1 1.71 C5H5 - ^ CH2C1 1.72 C6H5 CH2OCH3

1.73 4-F-CgHu CH3 CH3 Mp. 78-79 ° C

1.74 4-Cl-CgHi, CH3 CH3 Mp. 101-102 ° C

1.75 4-F-CgHu CH3 C2H5 n25 1.5723 1.75 C6H5 - ^ · CHCl2 t 1.77 C6H5 - ^ CH2Br 1.78 CeH5 CH2OCH3 CF2CF3 1.79 C6H5 - ^ CH2F n ^ 2 1.6150 1.80 c6h5 ch (ch3) c2h5 ch2g3 CH20CH3 1.82 C6H5 (CHz) 3CH3 - ^ 1.83 CgHg (CH2) 2CH3 - ^ 1.84 C6H5 - ^ CH (CH3) C2H5 1.85 C6H5 - CH2CH (CH3) 2 / Cl • ·

1.86 CgHg - / | -(IN

CH3 · * 1.87 4-CF3-C6HU CH3 CH2OCH3 1.88 4-Br-CgHu CH3 CH2OCH3

Fo'rb. Ri R2 R3 Physical No. Data 41 DK 170336 B1

Table 1 (continued) 1.89 C6H5 CH2 OH CH2OCH3 1.90 C6H5 - (CF2CF3 1.91 CeHs CH2OCH3 CH2C1 1.92 4-CH3-C6IU CH2OCH3 CH3 1.93 C6H5 CH (OC2H5) 2 n “1,5763 1.94 2-CF3-CsH4 CH C6H5 CH3 - · (ch3 ·

1.96 C6H5 CH3 'CHO

/ · 1.97 c6h5 - '• · 1.98 4-Cl-C6tU CH3 CH2OCHs 1.99 4-Cl-3-CF3-C6H3 CH3 CH2OCH3' 1,100 3-CH3-C6Hu ch3 CH2OCH3 1.101 3-F-CeH., CH3 CH (OC2H5) 2 1.102 3-CF3-C6Hi * CH2OCH3 CH3 1.103 3-Cl-CeHu CH2OCH3 CH3 1.104 3-F-CeIU CH2OCH3 CH3 1.5863

1,105 4-F-CeIU CH2OCH3 CH3 Snip. 70-72 ° C

• 1,106 4-CI-C & H1, CH3 —x

Porb. Ri R2 R3 · Physical No. Data 42 DK 170336 B1

Table 1 (continued) 1.107 c6h5 ch3 ch2oh

1,108 4-F-CeH ^ CH3 - ^ | Snip. 93-95 ° C

1.109 C6H5 CH2OCH3 CH2Br 1.110 C6H5 CH3 CH2C1 1.111 4-Cl-3-CF3-C6H3 - ^ CH3 1.112 c6h5 ch2och3 ch2f • · 1.113 C6H5 - ([“* \ | / CH3 • · 1.114 C6H5 CH3 CH2Br

1.115 C6H5 CH3 'CH2F

1.116 C6Hs C (CH3) 3 C (CH3) 3 1.117 C6H5 (CH2) wCH3 CH3 1.118 C6H5 C2H5 C2H5 n “1.5923 1.119 C6H5 CH3 C2H5 n ^ 1.5953

1.120 C6H5 CH3 C = CH

1.121 C6H5 ch3 C = CCH3

1.122 3-F-CeHi, CH3 - ^ Mp. 41-42 ° C

1,123 3-F-CeIU - ^ CH 2 F

1,124 3-F-CeIH CH3 - n n 1.5943 · -CH3 d 1.125 C6Hs H - ^ 1.126 C6H5 CH2CH2CH (CH3) 2 CH3 DK 170336 B1

Conn. Ri R2 R3 Physical No. data

Table 1 (continued) 43 1.127 4-F-CeHt, C2H5 C2H5 n

1.128 4-F-C6FU CH2OCH3 - ^ Mp. 56-57 ° C

1.129 3-F-C6Hi, CH3 CH3 Mp. 60-62 ° C

1,130 3-F-CsHu CH3 C2H5 n ^ 1.5873 1.131 3-F-CeHi, CH2OCH3 - ^ n ^ 5 1,5873 1,132 C5H5 CH3 CF3 1,5543 1,133 4-F-CsHn CH2OCH3 C2H5 1,5733 1,134 2 -F-CeHu CH3 CH3 1,5863 1.135 2-F-CsHi * CH3 'CH2OCH3 n "1,5773 1.136 2-F-CeHi, CH3 - ^ n ^ 7 1.5811 1.137 4-F-C6H !, C2H5 - ^ n ^ 2 1.5813 1.138 3-F-CeHu C2H5 - ^ n ”1.5894 1.139 C6H5 CH2CH2CH3 CH2CH2CH3. n "1.5743 1.140 3-F-C6H., CH2CH2CH3 CH2CH2CH3 n" 1.5633 1.141 2-F-C6H <, - ^ NCH3 CH3 1.5854

1.142 C6H5 Η H Mp. 75-77 ° C

44 DK 170336 B1

Table 2: Compounds of formula / 3 N— · Y-v>

Conn. r2 R3 Y Physical No. data 2.1 CHO - ^ Cl n ”1,5603 2.2 t-butyl CH2OC2H5 Cl 2.3 CH3 CH2OCH (CH3) C2H5 Cl 2.4 CH3 CH2OC2H5 Cl 2.5 CH3 CHC12 Cl 2.6 CH3 CHzOCH2CH = CH2 Cl 2.7 CH3 CH2OCH2CSCH Cl 2.8 CH2OCH3 CH2OCH3 Cl 2.9 CH2OCH3 - Q Cl n “1.5344 2.10 CH3 CH (OCH3) 2 Cl 2.11 CH3 CH (OC2H5) 2 cl 2.12 CH3 CF2C1 Cl 2.13 CH2OCH3 CF3 Cl 2.14 CH (OC2H5) 2 - ^ Cl Oil 2.15 n- propyl CH2 OCH3 Cl 2.16 i-propyl CH2OCH3 Cl 2.17 n-butyl CH2OCH3 Cl 2.18 CH2OCH3 C2H5 Cl 1.5064 2.19 CH2OCH3 CH (OCH3) 2 Cl 2.20 CH2OCH3 CF2CF3 Cl 2.21 CH20H CH2OCH3 Cl 2.22 CH2OCH3 CH2CH3 Cl2 CH3 CH2 45 DK 170336 B1 υ o ϋ

ooo U U

00 00 U "| o o

ΦΙ — I m o ΟΊ f> CM 00 O CM

h rt rt r * · f> oo i i i i i i o o o σν to M> (cnortin mm m • HnJ ή (Λ o · ί m »» «»

th φ) fH Η Η i-H Γ-H r— «r — C

Or 0 «0 * 0 * 0 * ιή. * · _ **> _ CM

Φ £ £ £ £ £ <m Q cm fl nC3 cm q _. tt to (Λ tt w C cc c σν C4 I · «r>. · * n

55 / \ O

l /> ιΛ ΙΟ ιΛ ro / \ O

S rt S 53 K U m ro ro ro ro · · rs) cokkcmcmmi ffiscK κ κ \ / ¾ _ ppopopcppp o o »- * p

CO

tf / \ • ·

I I

irt · · Γ0 EC \ / ro ro ro 23 32 cm · EC 22 23

2 2 2 2 2-22 UP O i P O P

i * 1 irt irt irt irt irt tn '

Pi K S3 35 K 33 s ro ro Γ0 ro ro ro

PP «P W PP P

I I 32 I 32 rs I I I

OOPO P Ko o o

Γ-H I— {O Ή ΙΛ o ry r— (rH fH

ro fO O O »'ΐ CM ϋ JCJ CM« Ό ζ_5 ϋ (J (J

fi .a:? >> ^ K22> oNK3; i> · »· >> ^ ΡΡϋΟΡΡϋΡΡΡ c o o o

C

CD

rh

em «o« Ul • d <u C ro m ro ro ro ro ro ro ro ro rj ro ro ro R SSSSSSS CCS SS X sss OUUUOOOUUUOUCJ o Η η γμ - —— .— ----- '.... ......... — .....- --- CD Bi · Pi ω \ / V / h ri i ® akg \ // C · ri -i • Hl «s ri S! o M / \ ininininintninmltn m in in in O rksccekekpmkkxx æ

{i} Poll tø vO vD i £> vrt O O I vD vD 10 VD

II uoooouaomcjuou u n / <J ^ 1 '00 <n

Pi Di fH · QJ Λ · o MM o i-ι m <m vo

* Say oh CM CO in VO r> CO ^ H r— <1-H f-H r-H r-H

• 0 p «#» ········ · Ef 111 η μ η n tn pi ni men en en en <n en 46 DK 170336 B1 - —— o OO ϋ ooo O oooo CM t — i - O MN -im CM -d Φ i — i σ \ oo com f-ι r — i js ill II I i

m -ί rt CO CO> —1 ON

"1 O O 'co com cm ro

O IU r-l i — I I — I

10 -P. . . . .

flj 0 «0c CL Qi CL CL CL

1¾¾ SEE EE E E

ΙΛ w! Λ mm Vi in 01 pi 33 33 κ u o> o o

CM y-N Cm CM CM

Ό CM S CO C— \ toKcomcoinincoco] | ro

K ηϋΚΐΰΙΒ S 9 S ro co to to in J · nH

O K W CM CM 1 CM CMUOKKfUWc- ^ c-M KU

w U U U U C C QwwUUOO MCMKKKK k kuo --K K - u u

n-x v_x I

I I K

ro O

39 //

O-U CM

ω in \ K

Pi K I U

co K 39 K / K

U O O U co u

I N II ^ 39 CM

O x- 'K · —U x-M

1 — I m ro ro / rom

OcoK K K co ro ro KK

> oKCM NUKh K U CM

KKKKKKK K33KKOOO U v-x U U U n-x U K

rouoin in in in tn in

Pi 39 K K K K K K

m ro ro ro ro ro ro

O O ro ro OOOO rt n {J

i IKK i i i i i t "x-N ^ 1

0 O O O K OOOO æ ro ro O

r-4 rH O O ro ift r — I Η Η H ro E EC <H

U U N N η ro U E ^ U 0 U U π n U rommm ro OOti>,> iKKxa: 1 ΝΚ ^^^^ ΕΕίκκίΕκ e w w ^ aoouooc oooooauocuooo Ό cj o o cm t n t n m

Pi K 39 K

ro m ro o U U U O «n

co cm HI III X “\ X ~ N

x-n K U OOO toro

cocoin I 1 — li — li — I KK

CO CO CO CO CO K U Kcococococococococorouuu to U U CO

K K K K K U I cmKKKKKKKKK> o> o!> O K vxvxK

__UUUUU ^ C UUUUUUUUUU DUO u uuu 3 39

CD

- o

YY -3 3 Y · I

frt K 39 K m 3 K

In vd m m> K 39 U

U 'r-t U U -3 3 Q ID ID CM 3 3 3 +> Pi I I K K I U U »-3 x-n K 39 39

H O O> d u> o I I K 39 co 10 10 ID

Q co ro O U to ro to ID id K UUU

ni K P-ι I I K 39 K m in in (J U U m | I I min in in tn C. UUKhUUU Κ393933ΙΙ'-χ39Κ '- >> -> 33Κ 39 KK39

1 I I I I I I U) ID Μ 10 K Pm I CD I I I ID ID 10 IDiDlD

<f <t (O co <J- 4 <f UUQQtn <f <fUMst <tUU U UUU

ro --— 'll' Sj γόο σι oh cm co <ιοιθΓΜθοσθΗΜ (θ · ίιΛνθ oo cr \ o X SS r — I r — I t — 4 CM CM CM CM CMCMCMCMCMCMCOCOCOCOCOCOCOCO CO CO CO -d rQ OC ···· ·· ·········· ** · ··· - nj fb co co ro co co co co coocococococococococococococo co co co co El - 47 DK 170336 B1 - ooomo «a- o

vD \ Q O

^ 4 σ »i-» vd tn i ii

• ri (0 ^ tM CO

ro VO m> i nj. Ί k Ό α α α.

E ee 1/3 (Λ 10_ *.

Os Ρ3

I I

35 κ »

µ OS

S II O I

rt N N N

U I K pa s S3

35 «r S O K O O O I

--- cm rg - I - ΓΜ SK »3; O O r- \

o S S N

V_ / o o s • I II II o SK w

<a O O I

pi n l / l S s o o VJ ni \ / ^ • m nj / \ N tn rn 35 '

SS SKO

O-O K o o ^ s cn «

tt! K

* tn 0 o r-1 n m pi) m rn m tn m Q tn

K K S S S S S S S? ·> K

O O O o O O O O <·> o CM cn 10 ΙΛ «s s s tn tn m

0 O O

1 I I

o o o

ιΗ Η H

tn tn tn U O U rn tn tn m

35 35 35 f o S >> K S S S

o o O O O U O O O o jr

K

ml

+ j V

ns S

S - * -r ~

f * «/ -v CSC

H m tf o «c o s o o o iij m m o i i i m m cn in

Cl S Xn_ / Pm {»4 {USSK

^ I) I I Φ% £> Φ \ D

U CJ * 4- -4-4- ^ 4 O O U O

— .-- -. - ... ------------

'm "R. * ι-l (Μ Μ Or.Nf'OOO" O

S b Ϊ <5 <f ij ιΛιΛΛίΟιΠΛ VO

tO AND «.,«. »····

(d lpt) fO CO to tototorocoto CO

£ π I ---- 48 DK 170336 B1

0) S

X σ> to -a- • H cd “to 4J ^>) td ^

Hj cm Q

C

CM

O 'rH rH

Pi is is>. - »» ΐ ό A as

S I -ri -ri -H O

0-0 W U U w IM

II is is is Z IH «ror *) CM PU PW ro η n n U p xiii x dixxxn __uox u N w -J x o ooooo cd ro

Pi X

O · ** / \ 32 · · O! i Λ (/ 3 · i il) ifl m m S «\ / XX«

S tn n X · d d X

o o o xxxxo i oooxx ro mm mmmmm m mm

Pi XX xxxxx XXX

rj rj r) r) η n rt 'rn rt o oo ooooo o «o o

II I I I I I I X I I

00 ooooo o o o o i — li — i ι-H i — i i — j ri H 1 — iOiHi — i O O «o O O O O« «o« o o ^ 1 ^ 1 X ^! S X X X ^ is O O O o o o o o o ooooo

N

Pi n rt 1 * 1 r *) f *) i *) r *) ro ro ro ro ro ro r) XXX X X X X X X xxxxx o o o o o o o o o ooooo «m

+> V

id n M ^ ij Pi f * η. ° LU m m I mmmmm m mmmmm ^ xxm xxxxx x xxxxx mm * »mmmmm mmmovom

^ OOCO OOOOO O OOOOO

ro. .....

* iH rQ · fl \ 7j t, i — i fsj η »ϊ ιλ vo is O« - »rsicn ^ m ^ o λ i? 2 vøvovo vosovoxo Λ AND ··· · · · · · · · * ··· iu 1¾ <λ <n Λ η cn λ ro ro ro m ro ro m ÉH L. II I ι.ι n · .- —— · Ι ι »'" I ..— - - - 1 49 DK 170336 B1 _ - - -

You o o o o o U U

O 04 vO o o

«Ί CO (Π r— <i — I i-H Γ-- VO

m od r> * f-t γη »—t o γη <r <r

I VO I (i O t I I

mm cg ph cvj vd <· vo m ^ oo m r-i H · r-H <Τ <ί

fy r-H f-H pH »H

W + j. . .....

b> s (ΰ Thin 0. 0. Dλ- 0. 0 «O.

in? ηΗ Enfl e ε ε ^ οεεε HMU 0/3 C Vi Vi Vi c We Vi Vi o g g · g o o // \ m. u

ΓΊ ro. \ ΪΠ CVJ

/ -v / -s I a-U g j ^> pi ro tn ifl · / ιο ro ro g g <·> g g «-» sus

U U g n f «· g g γ» I U

__g w w u u g u_g_j_gu u u c ^ GO lT>

& φ X

* · / -S · rn / \ N // \ u

II U I S-S O

• · w · / i — 1

µ / mm / m (J

• g g · g g I g g U g U g I g UOgggg ro lA lf> ιΛ lf> ΙΛ

Pi g g g g g g m m m m m U U U U u

I I I I I

o o o o o

Η ιΗ Η Η H

m m m m m m m O m m m m 0 O O 0 g g g g g g g g g g g g g> i g

U U U U U U U 0 U U UUUUUO

N in in tf X X - ro r> fM <m O O O ro g g III I I g u u u o o o

O O IH H O

m m m m m m m m O O c \ j m m m m m g gg.gggg g g gggggg o uuuuuu O o ouuuou +> Ό £ £ rrt s s W rt tf tø VD tf tf tf tf tf tf • Mg g U U g g gggg

Lj ^ i I <0 vO vø iD vD tf

O u mm u o UUUU

Λ in I tn pv <e.g. tn in | In mmllll ϋ g g g U U g g g g g g g g g g g to f th | | tc tø I I tø tø 1 I I 1

U HU <3- <T O O -J CO UUHHHH

----0 -----——-———- * Ti $ · in oa οι γη n (O -i lt> vo mo o \ o η m uj hm r- r · oo to oo oo oo oo oo oo co ooo Λ AND ....... · ......

ro Em ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro

o o «Λ tj CM

O 1-1 O O ON

D 03 CO 1 r-c t-H

^ • 11 III

m On O <f O O

JJ f "CO O O on» S. ^ ^> 1 ιΰ α α α o. Ο * fe * ϋ ε ε ε ε ε W W ν> \ Λ We ro ΙΛ σ> a rH S3 «

Pi O> n «32

cm w -o Ο O

X \ / -ri I a)

O · W O

II / \ m 3s iH CM

a cm n η n 5 n m Pm Ο ”X

0 33 KSB «fe 331> ·« K U _ __i 3: a o-o uuuuauNaaa ο o w x a

CO N

.Pi 33 r-l r-i o> ·>.

n cm Ο Ο * Π "O

rv B m n vi * rt

B Ο ϋ y-vy- ^ W U

in m m η O t0 «« P *>

KO S Μ η nH n «S IS pW-mpK

<M | cm a X X Ο X 33001331 33 O C 33 UUOU'OOXO '~' wX <NO <t «*) in in in in in in in in in m

Pi 33 53 33 33 333333333333 Π (*) ro ro n ro po r> π ro OUOO OOOOOO "> 1 I I I I I I I I I S3

OOOO OOOOOO O

'—Ί' —i ι-Ί i — 1 i— (i — i r — I Η Η O

U U y O OOOOOO <-5 m m m m rn cn ro 3s is> n 3s isisisisisisXXXX 33333333

OOO O OOOO O OOOOO OOOO

m in in tn in

Pi S3 53 33 33 m ro m

"OOOO X I I I I

OOOOO Ο Η Η Η H

frames ro mmr-nmmmr \ iU (JU CJ "" "sxx x xxaxxxa>,>,>, fsxxx

__OOP O OOOOOOOOOO 0QOO

4J

flj r-t j 7 "« xa xxxxxxxx = π IfilD ιΟιβιβίΟΐβ ιβφιβ ^ ο oo ουοοϋϋοο 9

m mil m m I I I I I I I | | m m m m I

> - X is Pm X Kluhhfchhfefes ES33h

mil m mlllll I I I »o» m m I

„O <i <f o οηηη <ι · ί wnmo ooo ^ en - 1—- •

r | Oh. O ri N ιΛ ifl S O 'O ^ M

m 7J I, CO -a- in VO r ^ oOQNOOOOOOO O · —11-11-1 s p OC OnOnOn On Q \ CvOnhhhhhhh hh ^ h <ϋ fe and and and and some ones and some ones

Eh ---—- 51 DK 170336 B1 - _ ~ o o o U o O o cm ιΛ o · —i o oo

CM MJ- o o O oo CM

Q) I — I r— (m H O <f t— <

k> I f i— (I eo I I

Tn r-ι <1 m Cl O LO r- ~ r- ~ “* cm <r> r» o * st cm

Ή ro ιΗ Η M fH (H r-H

W 4J. . ·. .

Sn σ <0 «0 * ir> CL di« CL CL

£ rn b e «Q ε εcn, q ε ε to υο c co to c co co o tt! r> in ro fs. ✓— · * r- ts / -s SC w to S m

λ B S «** SB

u u c> u> o o I w w I I w __ffi_ns c o o c c u

CO

tf i S \ n • \ x I a-o • / n 35. U X 35 K 55 S 55 m tt! m ro ro to to 35 35 S 35 55 O u O ϋ O · - · o o o o o \ / tNJ CMNrtNrtN ·

35 35 35 35 35 35 S I

__O_u u u u u u u_ IS) 05 r) w µ n nj i ·} i * i n X X X X X X X 35 __O_U U OPEN u o

+ J

(tf

CO

ΓΗ -3- J · J ·

l-l Oh 35 XX

0 U5 ID ID

(H O O O

^ m I m m in a J | 33 fn K SC SC K Pn P-,

ιο I o Φ vii thø I I

ro O m o o O u f o »d- | —j · m n.> J0 \ D ΓΝ OO ^ o * -H es

Ψ (il, * “» Η H r-H r-H CVJ CM CM

1¾ Π Π r — I t — t i — i r — l r- (p-H rH i — I

(y 0 C · ····· gn ft, eo forocofocoeofo 52 DK 170336 B1 m M o u) \ o sr

X Os ΓΙΟ u ~ l LO

• h m j · _r tD + J 1-1 ^> ιΐβ w. *

N Ό cnj Q cm Q

__ C_C_

H

r-i fO

P = i s 0 35 *

Il ^ O 35 35 III 35 rt ϋ fl O 'Λ

ro 35 N O N O

B N s i si __o o u c u c a

ISLAND

H

S

mm »t * * r *" r * · · "* T * MM *** MM MM ΓΜ

fO

S

n rt n m n m

S S S S SK

__O o o u o o c

<D

I h

(5 (M in.)

£ S S

”M 0 h

Ή I

ISLAND

frt Ή 5i ro ro »o» o O ro S s s s s s i- s s o o υ o u o "> (M '- ......

MS · s 0) \ / ^ / H 1 '' «Ό · ^

Cl s 2 Λ - o • P fe «; in

M s O

O <n

fy i · - * ift tfl tA ιΑ ιΛ S

W 3535X35350

ςς v0 tø id tø vD I

·· o οουυο-a · M · ri-- S · Η X5 · Λ h {\ in <f iruo.

ιΰ h <f <j- -3- <r -} -3 E-i - 53 DK 170336 B1 υ o O ro -t ro in (U fH r- «od σ \ ro

ij in vo I n «VO

S m m cn m m "J - co - * H HJ. -Mf f— (lH i" l

CD

> 1 {tf. T «tn S * · *" m.

Éjfrt'cMQ csj P S «fl

. C C 00 C C

H

H

Pi

IN

33 m rj »n» n I g 33 c aa_a o π_a υ a g g

I I I I

o CM N CM CM

i-t ro 52 PC 52 «~ v v v s

«O I I I 5C

E · · · O

i-O / ^ \ ^ \ IIcmc «g w g · · \ g · Ng g g g m o II I I al a υ υ«

lg \ ^ g / ~% ^ / a fa I

c u ► o · · g υ υ c m tn in in g g g g ro ro * ro 0 υ o 1 i i o o o i — I «—I <—t

About mm O O mmmm J>, g gg> 1 rS g g g g o O ου u_o υ υ υ υ

(M

Pd K) r *) ro ro * ro m g g g g g g ου υ υ υ υ ο m m mcM CMm m m cmcmcmcm gg g g g gggg ου υ υ υ_υ υ υ υ

+ J

(ό WW ^ »Ρ gga jj ω ό η υ υ 'χ' lift tft ift ift I iftifttftift * W fl * g ggg pH gggg lift sftiftiø I« ft ift O ift co oo ο υ <r aoou ^ - i— l Λ · o --1 <\ i ro mother · * co is »o 0) P} -! t — l · - «rH r- <* —i '—1 <—I« -Η t-H Cs) n 0C ·· .. · · ....

(tt ptn -t <t · -t-Jt-i o- -3- «t <rl · * - DK 170336 Bl 54 oo co m σ \ <m <D cr \ mm r-, ¾ 10 mi r— 03 mm r- m -H fd “w + J -. ^ I> 1 KJ tn m Q. jr

P4 Ό n Q Μ QE * »W

C C ΙΛ__C_

H

x »x o o

CM CM

x s m m ου r> 33mnmmnX cmm

SNKSD3EE N XX

33 O O O O O O O U X X g X X X X X O O

n

o O X

c * C S O

X. island-

In XX m in X S X

«. O O X cm O O O

o> iH / '^ cmcmOXmnn

κ υ · · —O X X X

m µγ m O II | m m m O O O O

X O "X» n cm X · ΧΧΧ <*) ίΜΝΓΜ

~ I x cm X X \ // OO NUXXX

O CUXXXXX U O O · µ- 'v—- O P3 O O O

cn in a Λ XXX 33 fO ro * \ j * "* O O ^ *> 9

I I rt / —i I

O O X "> o

Ή i — I O X> »TJ

µ m t * i rt * nv _ / OE * · »i *> m» * i m ιό ρί m ro (j> 1 S *, XXXXwnXXX X X X X X X X> -.

o oooooou uou o o o o o o o o cm in in

X XX

JZ. Island Island

mm II

XX o o

in n O in Η H

<n η η H rj w cnX η η η η n U O n o w n

X XX N | XX cm XXX X X f, fnX X X X

0 o o o e e o u u QUO O OOOOOOU

<·>

X

m

9 V

Itf «

0] - »X

η λ x o * · *

£ X X 10 I XX

Η φ O o vd O o I i υ o lu I WiHminminm I 1 in inminmininm

v_, pLiiqoxxxxxXXXXXXXXXXX

1 II IC ΙΟ Φ O (fi II U3 vD ID ID OO Ifi \ 0 (0 <r cncviooouu sr * d · ooou υ uouu * 5T - i, I. "" '• r-t Π i π »«, i , c \ i ro ιλ vo n co σ \ h cm (n * ^ · ιΠΌΓ ^ οοσΝΟ »-« s Λ OS ^ ^ ^ ™ ^^^ nrtrtrtrt <.j (¾ fci -Mj- <j- <t - 3 -3 -3-3-3-3-3 · -3-3-3-3-3-3-3 B - 55 ^ DK 170336 B1 O ouooo r'-Of'icvjoo vo ui o O) r'- cicO'd-r · '. oo \ include "ij I co cri co r" im «3-1 7J; inm in in οι« 3 · m min jj ··> · · oo - - i' '

"J i — I. — I r — I! —L rH

Cl}> P · i * (ΰ Οι »λ o o m Di ^ _ * n Oi One rrH E nQ nQ mQ νΩ EcmQ m Q £ u__m c c c c wc _c m_ ri ri ri ri <M ri

rt g X 33 S

<j> in O v0 ου s υ ii υ n · i o o S o

rH rH ri m rH

o o s s o υ>,> o O I> 1 ggg π g g s o ug | - |> w> c g u s

X

i υ g ✓ *** O n

»Λ X

ri s "» υ ri OS'-4 and Om I ri ri g O ri M-r g g g g pi O O X CM O O 0-0

CM I O S3 CM

go W O CM / -i OHo in a O <r \ ro cMQgnrogg nm g ·

g> 1 CM g g CM CM gg O / N

OOO O O EAST gOOSS ^ -c S --- n in m m m m in lo * Λ in «ggggggg g g

m m ro m m m <n **> M

οοοοοου υ φ ..... ii i 0000000 o o

i— {rHHi-Hi-HHH rH rH

U0U U U UOfnmmtnmroro U V

> 1> 0> 0> 0 S> o>, ggggggg> 1> i ooo o o οοοουυυο o o

CM

g Π r * 1 Π (*} **} g g g s g o o o o o o o o foriro ro ro nrororofMCMCMCMCM ri ro ssssssssssxsss W * o o o o ooooooooo υ υ i «

® ri J-JJ- -3 J M

p Oo ggg ggg

Li «jD vO vD vd Φ vD

o ooo ooo n_i inmm m | || mininin ||| m m

C. gggg & MpH & HSgSSfctHtnS S

IDIDIØ 10 I || \ 6OlØl0 | l | ^

OOO O ci cn -3- o O O O m and m o O

sr ---——--- rj cMcn-a- m vo r »oocr> η m and o- m vo oo on q) Η h -3 · ^ · ^ · -3- -3- -3-- 3-HT mmmmmm mm X} AND ...............

(C) pL1 <3 3- <J- <3 * 3 3 · -3-3-3 ^^ -3-3- -3 "

Eh L ------------- 56 DK 170336 B1 uo mm oo oo u) σ \ oo vo m M mi vo rø mm r- m • h ns ^^^ m 4-i ^^ .

cti j. i * »0« ** »1x4 γμ Q n P S n Ω _g c_tn_c_

• I

CM S

w KO

W I O r- ^

Di I «X ^" K K O n 32

r- 0—0 r- cm c- K O

K I K λ K O v- 'tf) j rt rt tn V- / ift

0 · O X "O" X

1 / \ i o x i x "c K K K K --- C O C O X x_o_

* I

N

SS

Island Island

H CM O /

Pi CM X K * cm K O X c- O // \ ·>

KOKO X cm · \ K

o o o / \ "x I." - o m m cm m O cnO O · / lu IjHS «Kl K O« O O pH K · KKOCXX · x m m in ιΛ in tn mm

Pi KXX X KXX

p M M rt (*) i * 5 W 1 * 5 η u ϋ O O O O ^ ^ ^ * n {It I l l l S3 33 3 = 33 53 000 o o OOUOCJO o

f — I Ή «Η r-i pH Η H O O O O O

O (J U π · »o O 0 O cm cm cm cm cm tn 33 5C 33 33 33 23 33 οοϋϋ o o ooouuua o

CM

e <tn η η n £ m tn m tn rn rn mm <n rn

KXX ~ X X KXXXXX X X

0 o o o o_o oooooo o_o

+ J

(C

w +) (. (H Jt MC Λ Λ Λ

S T KXX KXX

\ j te vo vd tn tn tø 't-ι oooooo' w 'm in I I I I i i in m tn in m m 1 s t, h lin ^ s s: tD 10 I! 1 t I (Φ O Φ to Φ to ”o o cm cm -j · _ * 3_-3 -3 o o o o o o H · 0) Λ · n Jj b © CM CO« 3 tP! vD f-. CO Os O I — i CM CO -3 m λ S so so so so so so so so r— c- r-- r- r— -

Jv ΟΪΗ, ·· · · ·· «··· · · El W -3-3-3-3 -3 · -3 · -3-3-3 3 <f ~ 3- -3 -3 57 DK 170336 B1

fl, rrt fO

S £ N o λ vo oo to m m * H id '* 10 +> ^ ^

> i flJ

fcl Ό es, Q ~ Q

__C _ ^ _ C_

H

ri m I

«K N i

OK N

w o K

\ / υ

• in O.

/ \ as «

•-· NOW

S K KO PQ K

O CM

η K

a o.

K I I

o CM I N

N E N S

/ —S O SS u ro I O i

52 · «n · -“ 1 CO

o / \ nk / \ ”

K w --- o O K - · K

r ·) iD irt ιΛ

Cd K K K

ro m ro 0 o o

1 I I

O O O

.H r-l rM

mm m ro O U O

K K K K> o> o o o o o o o o

N

cd ry r *} n rt rt W ro

K K K K K K K

o o o o o o o s

-P

(0 co • P £ u «o 4-1 ιοιήΐηιηιηιηιη

asæasKKKK

^ φ to id ω tø • s' ooooooo Η Λ · (D MV-ι vo r- σι o --i cm p "> OC r» r- r-- oo oo oo oo g® ff4 -a- * 3 · -A · -a · -a · -a · -a · 58 DK 170336 B1 tn cn cn cvj tn m tn oo ri ko —iu P> oo N vo 70 mm mm Ή (O pi ri ri ri ri

ID -U

> ΐίβ Λ _ η _ ΗΛ β_

fVj rrt nQ nQ nOuP m Q

^ 0__e c_c c_c_ 1 t

NN N N

rn XX EC I / -n w CJ O O N rj (¾ 33 53 33 33 35 ou o ου N || n σ. NN K \ _ ^ /->.33 33 33 X / -n 033

ni Q m m j- i / l mm Ln π Q

X <·> O "33U33" 033 «33 n n

0331 33 n 1 n 33 i o SC «X X

X wQC OOCOOCwO O OXO

N

'1 X

N o

X N

O X

• O I o

rt · N

Cd // \ r- X

• · X o

I II n in W

J2 · · O rt π 32 ro λ

/ I X X N 33 X

• xx xxxxoxxo o xoo rt it> ιλ in m m m in in tn in in

X X XXX XXX X XXX

m r> m m rt rt rt rt η w n 0 ooo 0000000

1 III I I I I I I I I

o 000 0000000 r-i r-i r-i i — i i — i r — i i — i I — i I — i I — i I—!

O OOO mmmmmOOO O OOO

> ·> Jn ^ inXXXXXinE * ·. ^>, O υοο ουοουοοο o 000

N

x

N N N N N N

X X X X X

o o o o o 00000 η n rt rt rtnrtrtrtrtrtrt rt rt rt rt rt

X XXX XXXXXXXX X XXX

_ o o 00 00000000 o 000 «—n

4J

never id * «

Jj n> »+ * ri -» - »-». * O O ^ J ·

V-l X XXXXIIXX

O O ttttvøOO VØ

OOQQrtrtOO

m tn m I | | 1 tj-, pu, 1 | tn m m in m s sffiN sc sete «u> o \ c I! i I I i I l id o <0 «o ifi ^ O o O cnfOcn <r <i ^ <i-o Ό OUU 4 H ·

Λ1 o · O Ή M

JX 'P. so n co O - »CMCO ^ fiAvOr ^ cO σ> OOO

»Y HH Qo CO 00 ^ O-vO - '^ ONO'» ^^^ CJn * -h γ-η ih ίθ AND ................ - 59 DK 170336 B1 uo cn mo 0) mm r-

k / r- I

m m m cn 0J. vo Ή · β γη i-h ω-Ρ> | Π3 mn e

(iJn-S CM Q CM Q K

^ u C C w

H

H

Pi r **

B

PO

ro rj co U m 33 33 33 I 33 _ a o x ο υ g c o_a i 33 U <—n. m 1 I 33 33 ”> N U U I Λ

o 33 vn / -. É M

ιΗ Π Ο IM ΓΟ U 33

Pi \ B I B B ^ o • - * 0—0 O O ^ w / || O W m o • cm m m pH and cm \ 33 33 3-1 O 33 33

- · 33 ϋ O U ^ S O O

calm down

Pi 33 to O to 1 * «O Q 33 1-10 n ·; -; · ·: -; · O cm to ro to U \ / \ / 33 33 33 33 33 I · ·

O U U U U U C I_I

cm m u) m pi 33 33 33 to to to 0 u u 1 I! <"0 0 0 3 tn rH i — I pH to to 3 * toUUOO« m 33 cm 33 ϊ> ->> i I 33 33 a o a u u u c u_u

+ J

tn P ^ j- j- S-l pci 33 33 Π u> 10 m o o m to m m m m | | in K B KKWKPM n b u> m <n «η ιο« ο I I uo -¾4 o O OOOOCO c "> _ O_ ή. cn m m r ~ - oo on O t- <X ti, oo OOOOO ^ H on

r-H «—I r-H rH pH t ~ H rH r— <rH

<ti OS .. ......

t-ι 1¾ <t -3 · o · <t · <r o- -j -J_2 * _ 60 DK 170336 B1 2. Preparation Examples for Solids of Formula I (% - wt%) 2.1 Emulsion Concentrates a) b (c) 5 Active substance from Table 1 25% 40% 50%

Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5% -

Tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4%

Cyclohexanone - 15% 20%

Xylene blend 65% 25% 20%

From such compositions, by dilution with water, emulsions of any desired concentration can be prepared.

15 2.2 Solutions a) b) c) d)

Active substance from Table 1 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20% -

Polyethylene Glycol MV 400 - 70% N-Methyl-2-pyrrolidone - 20% 20 Epoxidized Coconut Oil 1 5%

Gasoline (boiling range 160-190 ° C) - - 94% (MV = mole weight)

The solutions are suitable for use in the form of very small droplets.

2.3 Granules a) b)

Active substance 5% 10%

Kaolin 94% High-dispersion silicic acid 1%

Attapulgite - 90% 30 The active substance is dissolved in methylene chloride and sprayed onto the support, after which the solvent is evaporated in vacuo.

61 DK 170336 B1 2.4 Powders a) b)

Active substance 2% 5% High-dispersion silica 1% 5% 5 Talc 97%

Kaolin - 90%

By thoroughly mixing the carriers with the active substance, ready-to-use powders are obtained.

Preparation Examples for Solids of Formula I 10 (% =% by weight) 2.5. Spray Powders a) b) c)

Active from Table 1 25% 50% 75%

5% 5% of lignin sulfonate

Na-lauryl sulfate 3% - 5% Na-diisobutylnaphthalenesulfonate - 6% 10%

Ootylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% - High-dispersed silicic acid 5% 10% 10%

Kaolin 62% 27% 20 The active substance is well mixed with the additives and ground well in a suitable mill. Spray powders are available which can be diluted with water to suspensions of any desired concentration.

2.6 Emulsion concentrate 25 Active substance from Table 1 10%

Octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3%

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 moles of ethylene oxide) 4%

Cyclohexanone 34%

Xylene mixture 50% DK 170336 B1 62

From this concentrate, emulsions of any desired concentration can be prepared by dilution with water.

2.7 Powders a) b) 5 Active substance from Table 1 5% 8%

Talc 95%

Kaolin - 92%

Ready-to-use powders are obtained as the active substance is mixed with the carrier and ground on a suitable mill.

2.8 Extruder Granules

Active substance from Table 1 10% N-lignin sulfate 2%

Carboxymethyl cellulose 1%

Kaolin 87% 15 The active substance is mixed with the additives, ground and wetted with water. This mixture is extruded and then dried in an air stream.

2.9 Coating Granules

Active substance from Table 1 3% 20 Polyethylene glycol (MV 200) 3%

Kaolin 94% (MV = mole weight)

The finely ground active substance is uniformly applied to the kaolin wetted with polyethylene glycol in a mixer. In this way 25 dust-free coating granules are obtained.

63 DK 170336 B1 2.10 Suspension concentrate

Active substance from Table 1 40%

Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6%

Sodium lignin sulfonate 10%

Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2% Silicone oil in the form of a 75% aqueous emulsion 0.8%

Water 32%

The finely painted active substance is thoroughly mixed with the additives. There is thus obtained a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

3. Biological examples

Example 3.1

Effect against Venturia inaequalis on apple shoots 20 Residual-protective effect Apple cuttings with approx. 10 to 20 cm long fresh shoots are sprayed with a spray liquid made of the active ingredient (0.006% active substance). After 24 hours, the treated plants are infected with a conidium suspension of the fungus. The plants are then incubated for 5 days at 90 to 100% relative humidity and placed for an additional 10 days in a greenhouse at 20 to 24 ° C. The scab attack is assessed 15 days after the infection.

Compounds from the tables show good effect against Ven-30 turia (attack: less than 20%). Thus, e.g. Compounds Nos. 1.79, 1.108, 1.122, and 4.45 Venturia attack to 0 to 10%. Untreated but infected control plants, on the other hand, have a Venturia attack of 100%.

Example 3.2

Effect against Botrytis cinerea on apple fruit 5 Residual protective effect

Artificially damaged apples are treated by dripping a spray liquid containing the active substance (0.002 or 0.02% active substance) into the damaged places. The treated fruits are then inoculated with a 10 spore suspension of the sponge and incubated for a week with high humidity and approx. 20 ° C. In the assessment, the damaged sites are counted with initial advice, and hence the fungicidal effect of the test compound is deduced.

Compounds from the tables show good effect against 15 Botrytis (attack: less than 20%). Thus, e.g. Compounds Nos. 1.4, 1.6, 1.7, 1.12, 1.17, 1.48, 1.55, 1.56, 1.65, 1.68, 1.79, 1.104, 1.108, 1.118, 1.119, 1.122, 1.124, 1.129, 1.137, 1.138, 3.5, 3.6, 3.7, 3.8 , 3.10, 3.11, 3.25, 3.26, 3.35, 3.40, 3.41, 3.50, 3.52, 20 3.78, 3.79, 3.79, 3.113, 3.115, 4.1, 4.4, 4.15, 4.17, 4.20, 4.45, 4.56, 4.73, 4.74, 4.87 and 4.98 Botrytis attacks to 0 to 10%. Untreated but infected control plants, on the other hand, have a Botrytis attack of 100%.

Example 3.3 Effect against Erysiphe graminis on barley a) Residual protective effect

Ca. 8 cm tall barley plants are sprayed with one of a spray powder containing the active substance produced spray liquid (0.02% active substance). After 3 to 4 hours, the treated 65 DK 170336 B1 plants are sprayed with conidia of the fungus. The infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is assessed after 10 days.

5 Compounds from the tables show good effect against Ery-siphe (attack: less than 20%). Thus, e.g. Compounds Nos. 1.32, 1.56, 1.104, 1.122, 1.124, 3.5, 3.8 and 3.52, the Erysiphe attack to 0 to 10%. Untreated but infected control plants, on the other hand, have an Erysiphe-10 attack of 100%.

Example 3.4

Effect against Helminthosporium gramineum

Wheat grain is contaminated with a spore suspension of the sponge and dried again. The contaminated grains are stained with a suspension of the test compound prepared from 15 spray powders (600 ppm active substance based on the weight of the seeds). After 2 days, the grains are placed on suitable agar dishes, and after another 4 days the development of fungal colonies around the grains is assessed. The number and size of the fungal colonies were used to evaluate the test compound. Compounds from the tables largely prevent the fungal attack (less than 20% fungal attack).

Example 3.5

Effect against Colletotrichum lagenarium on cucumbers 25 Cucumber plants are sprayed after 2 weeks of cultivation with a spray powder containing the active substance produced spray liquid (concentration 0.002%). After 2 days, the plants are infected with a spore suspension (1.5 x 10 5 spores / ml) of the fungus and incubated for 36 hours at 23 ° C and high humidity. The incubation is then continued at normal humidity and approx.

22-23 ° C. The occurrence of fungal infestation is assessed 8 days after the 66 DK 170336 B1 infection. Untreated but infected control plants have a 100% fungal attack.

Compounds from the tables have good effect and prevent the spread of the disease attack. The fungal attack is reduced to 20% or less.

Example 3.6

Effect against Puccinia graminis on wheat

Wheat plants are sprayed 6 days after sowing with one of 10 spray powders containing the active substance prepared spray liquid (0.02% active substance). After 24 hours, the treated plants are infected with an uredospores suspension of the fungus. After 48 hours incubation at 95 to 100% RH and approx. At 20 ° C, the infected plants are placed in a greenhouse at approx. 22 ° C. The assessment of rust bleaching occurs 12 days after infection.

Compounds from the tables show good effect against Puccinia (attack: less than 20%). Thus, e.g. compound # 3.10 The Puccinia attack 0 to 10%.

20 In contrast, untreated but infected control plants have a Puccinia attack of 100%.

Example 3.7

Effect against Phytophthora on tomato plants a) Residual protective effect 25 Tomato plants are sprayed after 3 weeks of cultivation with a spray powder containing the active substance produced spray liquid (0.02% active substance). After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. Assessment of the fungal attack occurs after 5 days of incubation 67 at 170 to 100% of the infected plants at 90 to 100% relative humidity and 20 ° C.

b) Systemic effect 5 Tomato plants are irrigated after 3 weeks of cultivation using a spray liquid containing the active substance (0.002% active substance based on soil volume), keeping in mind that the spray liquid does not come into contact with the above-ground plant parts. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungal attack is assessed after 5 days of incubation of the treated plants at 90 to 100% relative humidity and 20 ° C.

Compounds from the tables show good effect against 15 Phytophthora (attack: less than 20%). Thus, e.g. compounds Nos. 1,104, 1,122, 4.31, and 4.98 Phy tophthora attacks to 0 to 10%. Untreated but infected control plants, on the other hand, have a Phytophthora attack of 100%.

Claims (9)

68 DK 170336 B1 1. 2-Hydrazinopyrimidine derivatives, characterized in that they have the general formula I wherein R 1 represents phenyl or up to three times with R 4 substituted phenyl, R 2 hydrogen, C (1-5) alkyl, with the groups OR5 or SR5 substituted C (1-5) alkyl, C (3-6) cycloalkyl, with C (1-4) alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, C (2-5) -alkenyl, C (2-5) -alkynyl or formyl, R3 means hydrogen, C (1-4) -alkyl, with halogen, cyano or the groups OR5 or SR5 is substituted C (1-4) alkyl, C (3-6) -cycloalkyl or with C (1-4) -alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, R4 is halogen, C (1-3) alkyl, C (1-2) haloalkyl, C (1-3) alkoxy or C (1-3) haloalkoxy, R5 means hydrogen, C (1-5) alkyl, 0 (3-5) -alkenyl, C (3-5) -alkynyl or a group (CH2) n "x_c (1" 3) -alkyl · r8 r10 / / R 7 represents a group -NH 2, -N = C or -N 25 R 9 R 11 represents hydrogen, C (1-3) -alkyl or C (1-3) -halo-alkyl, R 9 means hydrogen, C ( 1-8) -alkyl, with hydroxy, OR 1 SR12 or N (R 2) 2 substituted C (1-3) alkyl, C (3-6) -cycloalkyl, with SR 12 substituted cyclopropyl, C ( 3-10) alkenyl. 69 DK 170336 B1 C (1-3) -haloalkyl, 1-, 2- or 3-pyridyl, v / v or V, Vx V 'or Rg and Rg together with the carbon atom of the group R7 means a saturated or unsaturated ring consisting of 4 to 7 carbon atoms, R10 is CH (Rg) Rg, phenyl, C (3-5) -alkenyl, C (3-5) -alkyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl group, R 1 represents hydrogen, C (1-5) alkyl, C (3-5) alkenyl, 0 C (3-5) alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl group, R 12 represents CH 3 or C 2 H 5, X means oxygen or sulfur, 15. means NH or NCH 3, and n means 1 to 3, including their acid addition salts and metal salt complexes. A compound according to claim 1, characterized in that R 3 is C (1-4) alkyl, with halogen, cyano or groups OR5 or SR5 substituted C (1-4) alkyl, C (3-6) -cycloalkyl or with C (1-4) -alkyl or halogen up to three times substituted C (3-6) -cycloalkyl, and R7 means -NH 2 Compounds according to claim 1, characterized in that R 3 is methyl, fluoromethyl, chloromethyl, bromomethyl, C (3-6) -cycloalkyl or methoxymethyl. A compound according to claim 1, characterized in that it is selected from: N- (4-fluoromethyl-6-cyclopropylpyrimidyl-2) -N-phenylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl) -2) -Nm-fluorophenyl-hydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Np-fluorophenyl-hydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenyl propionaldehyde hydrazone, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-isobutyraldehyde hydrazone, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-isobutyraldehyde hydrazone, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-propionic aldehyde hydrazone, N- (4-methyl-6-cyclopropylpyramidyl-2) -N-phenyl-propional-dehydhydrazone, N- ( 4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-n-butyral-dehydhydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-isobutyral-dehydhydrazone, N- (4-methyl -6-cyclopropylpyrimidyl-2) -N-phenyl-trichloro-acetaldehydhydrazon, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Nβ-fluorophenyl-acetaldehyde hydrazone, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Nβ-fluorophenyl-iso-butyraldehyde hydrazone, N- (4- methyl 6-cyclopropylpyrimidyl-2) -Nm-fluorophenyl-isobutyraldehyde hydrazone, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-N'-methylhydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-N'-dimethylhydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-N'-n-propylhydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenyl-N '-isobutylhydrazin, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-N'-methylhydrazine, N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-N'-n-propylhydrazine , N- (4-methyl-6-methoxymethylpyrimidyl-2) -N-phenyl-N '-dimethylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N'-methylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N'-isobutylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N'- dimethyl-hydrazine, Compound according to claim 2, characterized in that it is selected from: N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenylhydrazine, N- (4,6-dimethylpyrimidyl-2) -N-phenylhydrazine and N- (4-methyl-6-methoxymethylpyrimidyl) 2) -N-phenylhydrazine. N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N'-diethyl-hydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -N-phenyl-N'-methyl-N -ethylhydrazine, N- (4-methyl-6-cyclopropylpyrimidyl-2) -Np-fluorophenyl-N '-10-ethylhydrazine, N- (4-methyl-6-methoxymethylpyrimidyl-2) -Nm-fluorophenyl-N'-isopropylhydrazine . a Process for the preparation of a compound according to claim 1, characterized in that a) a pyrimidine derivative of formula II v - / -> v \ 3 is reacted with a phenylhydrazine derivative of formula III RX-NHNH-R (III) in the presence of a base in aprotic solvents at temperatures from -50 to 150 ° C, Y being halogen, a group SO2R6 or N® (013) 3, Rg being C (1-4) alkyl, phenyl or methyl or chlorine is substituted phenyl, and R has the meanings for Rjq ° ST R11r and these and R1-R3 have the meanings set forth in claim 1, b) a pyrimidine hydrazine derivative of formula IV is reacted with an aldehyde or ketone of formula V to compounds of formula VII under water decomposition • / 2 M β- \ Rb. Rv Ij-.f 5) · +) c = o -rb γ. (R3 R »\ 3 (IV) (V) (VID in a any solvent in the presence of an acid at temperatures of -20 to 120 ° C, wherein R1-R3 and Rg and Rg # have the meanings given in claim 1, c) a hydrazone derivative having formula VII Ri / N— \ / Χ ~ '\ Y>' w 5ί ^ · Κι «Γν> 10 s / \ chr8 (r9) (VII) (VIII) is reduced by a reducing agent in an inert solvent at temperatures from 0 to 50 ° C or by catalytic hydrogenation with catalysts; d) a pyrimidine hydrazine derivative of formula IV Rl; C> <IV) K3 is reductively alkylated with an aldehyde or ketone of the formula V 0 11 Rg-C-Rg (V) 73 in the presence of a reducing agent in an inert solvent at temperatures from 0 to 50 ° C, or e) a pyrimidine hydrazine of formula IV or VIII is alkylated with an alkyl halide RgHal J - C xN-V) · + R Hal - Ri- ¥ - (_) * kv \, Av \, 0 0 (IV) (IX) • _ _ /;> h \ A chr6 (r9) r CHRb ( R 9) o (VIII) (X) in an inert solvent in the presence of a base at temperatures of 0-60 ° C, where R0 is C (1-4) alkyl, and R1-R3, Rg and Rg at the above Methods 10 (ce) described have the meanings given in claim 1. A means for controlling or preventing an attack by harmful insects or microorganisms, characterized in that it contains as an active ingredient at least one compound according to claim 1 together with a suitable carrier material. An agent according to claim 7, characterized in that it contains as active ingredient at least one compound according to claim 2. Method for controlling or preventing an attack on cultured plants of harmful insects or phytopathogenic microorganisms, characterized in that as an active substance a compound according to claim 1 is applied to the plant, to plant parts or their habitat.