LT3874B - 2-aniline-pyrimidine derivatives - Google Patents

Description

in which

R ₁ and R ₂ independently of one another are hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;

R 3 is hydrogen, C 1 -C 4 alkyl, or substituted by halogen, hydroxy and / or cyano C 1 -C 4 alkyl; cyclopropyl or substituted up to three times the same or different with methyl and / or halogen cyclopropyl;

R 4 -C 3 -C 6 cycloalkyl or substituted up to three times the same or different with methyl and / or C 3 -C 6 halo cycloalkyl; has valuable microbicidal and insecticidal properties.

The new biologically active substances may be used for plant protection against phytopathogenic microorganisms or harmful insects and against these pests.

i

This invention relates to novel, biologically active 2-aniline-pyrimidine derivatives. · -.

where:

R ₁ and R ₂ independently of one another may be hydrogen, halogen, C _x -C ₃ alkyl, C _x -C ₂ haloalkyl, C _x -C ₃ alkoxy - or O 2 -O ₃ haloalkoxy;

R ₃ is hydrogen, C ₁ -C ₄ alkyl, or substituted with halogen, hydroxy or cyano, C _x -C ₄ acyl; cyclopropyl or up to 3 times identical or differently substituted with methyl and / or halogen cyclopropyl;

R ₄ - C ₃ -C ₆ cycloalkyl, or identically or differently substituted up to three methyl and / or halo-C ₃ -C ₆ cycloalkyl, as well as their addition acids, or their salts of the metal complexes.

Alkyl, either alone or as part of another substituent (e.g., haloalkyl, alkoxy or haloalkoxy), depending on the number of carbon atoms, may be methyl, ethyl, propyl, butyl, as well as their isomers such as isopropyl, isobutyl secondary or tertiary butyl. The halogen designated Hal may be fluorine, chlorine, bromine or iodine.

Halogenalkyl or haloalkoxy may be present in simple to perhalogenated residues such as CHO ₂ , CH ₂ F, CCl ₃ , CH ₂ Cl, CHF ₂ , CF ₃ , CH ₂ CH ₂ Br, C ₂ Cl ₅ , CH ₂ Br, CH Br etc. but best CF ₃ . Cycloalkyl may be, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, depending on the number of carbon atoms indicated.

N-pyrimidinyl anil compounds are known. Yes, DD application no. No. 0224339; 151,404 describes compounds having an N - 2 - pyrimidinyl structure and effective against plant - harmful fungi. However, the known compounds could not fully satisfy the requirements of practical use. The compounds of formula I of the present invention differ substantially from the known introduction of at least one cycloalkyl moiety or other substituents into the anilinopyrimidine structure resulting in an unexpectedly high fungicidal and insecticidal activity.

The compounds of formula I are stable oils, resins or solids at room temperature which differ in valuable microbicidal properties.

According to the invention, the salts are, in part, the addition salts of inorganic or organic acids, for example, hydrohalic acids, namely, hydrochloric, hydrobromic, sulfuric, phosphoric, nitric. acid or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propanoic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, acidic acid, benzosulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, or 1,2-naphthalenedisulfonic acid.

An important group is compounds of formula 1 wherein R _x and R ₂ are hydrogen. '

A particular group comprises compounds of formula 1 wherein R _x and R ₂ are independently hydrogen, halo, C ₁ -C ₃ alkyl, C _x -C ₂ haloalkyl, C _x -C ₃ alkoxy or C _x -C ₃ - haloalkoxy; R ₃ is hydrogen, C _x -C ₄ alkyl, or substituted with halogen or cyano C _x -C ₄ alkyl; and R ₄ -C ₃ -C ₆ cycloalkyl or substituted with methyl or halogen C ₃ -C ₆ cycloalkyl.

Other groups of biologically active substances are preferable because of their explicit microbicidal, partly fungicidal activity:

Group Ia: The compounds of Formula 1 wherein R _x and R ₂ are independently hydrogen, fluorine, chlorine, bromine, methyl, ethyl, halomethyl, methoxy, ethoxy or halomethoxy;

R ₃ is hydrogen, methyl substituted by fluorine, chlorine, bromine or methyl cyano; ethyl, or ethyl substituted by fluorine, chlorine, bromine or cyano; n-propyl or fluorobutyl;

R ₄ is C ₃ -C ₆ cycloalkyl or substituted with methyl, fluoro, chloro or bromo C ₃ -C ₆ cycloalkyl.

Among the compounds mentioned above, compounds of particular value are those wherein R ₁ = R ₂ = hydrogen / laa group.

Group lb: Compounds of formula 1 wherein R _x and R _? , independently of one another, are hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy. R ₃ is hydrogen, methyl substituted by fluorine, chlorine or methyl cyano; ethyl or n-propyl;

R ₄ is C ₃ -C ₅ cycloalkyl or substituted with methyl or chlorine C ₃ -C ₅ cycloalkyl.

Particularly valuable compounds among the above compounds are those wherein R ₁ = R ₂ = hydrogen / group 1bb /.

Group 1c: Compounds of formula 1 wherein R ₄ and R ₂ independently of one another are hydrogen, R ₃ is hydrogen, methyl, ethyl or trifluoromethyl; R ₄ is cyclopropyl or substituted with methyl or chloro cyclopropyl;

Particularly valuable among the above compounds are those compounds wherein R _: = R ₂ = hydrogen / Icc / group.

Group 1d: Compounds of Formula 1 wherein Rj is hydrogen; R ₂ and R ₃ are independently hydrogen or methyl;

R ₄ is cyclopropyl or substituted with methyl cyclopropyl.

Group 2a: Compounds of formula 1 wherein R ₄ and R ₂ independently of one another are hydrogen, halogen, alkyl, halomethyl, C ₁ -C ₂ alkoxy or C ₁ -C ₂ halogenoloxy;

R ₃ is hydrogen, C ₂ -C ₄ alkyl substituted with halogen or hydroxy C ₁ -C ₂ alkyl; cyclopropyl or substituted with methyl and / or halogen up to three times the same or different cyclopropyl;

R ₄ -C ₃ -C <5 -cycloalkyl, or C ₃ -C ₄ cycloalkyl, optionally or differently substituted up to 3 times with methyl and / or halogen.

Of particular interest among the above compounds are those compounds wherein R ₄ = R ₂ = hydrogen (group 2aa).

Group 2b: Compounds of formula 1 wherein R ₃ and R ₂ are independently hydrogen, · -fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or difluoromethoxy;

R ₃ is hydrogen, C ₁ -C ₃ alkyl substituted by halogen or hydroxy, C _Y -C ₂ alkyl, cyclopropyl or substituted up to three times the same or different by methyl and / or halogen cyclopropyl;

R ₄ -C ₃ -C ₆ -cycloalkyl or substituted up to three times the same or different with methyl and / or halogen C ₃ -C ₄ -cycloalkyl.

Of particular interest among the above compounds are those compounds wherein R _x = R ₂ = hydrogen (group 2bb).

Group 2c: Compounds of formula 1 wherein R ₄ and R ₂ are independently hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy or difluoromethoxy;

R ₃ is hydrogen, C _x -C ₃ alkyl substituted with halogen or hydroxy C ₁ -C ₂ alkyl; cyclopropyl or substituted up to three times with the same or different methyl and / or halogen cyclopropyl,

R ₄ -C ₃ -C ₆ -cycloalkyl or substituted up to three times the same or different with methyl and / or halogen C ₃ -C ₄ -cycloalkyl.

Among the compounds mentioned above, preference is given to compounds wherein R 1 R 3 = hydrogen (group 2 cc).

Group 2d: Compounds of Formula 1 wherein R ₃ and R _{2 are} hydrogen; R ₃ -C ₁ -C ₃ -alkyl substituted by fluorine, chlorine, bromine or hydroxyl methyl; cyclopropyl substituted with methyl, fluorine, chlorine or bromine cyclopropyl;

R ₄ -C ₃ -C ₄ -cycloalkyl or substituted with methyl and / or fluorine by chlorine, bromine up to three times the same or different C ₃ -C ₄ -cycloalkyl.

Examples of particularly valuable compounds are:

- phenylamino-4-methyl-6-cyclopropylpyrimidine (Compound 1.1);

- phenylamino-4-ethyl-6-cyclopropylpyrimidine (Compound 1.6);

- phenylamino-4-methyl-6- (2-methylcyclopropyl) pyrimidine (Compound 1.1);

- phenylamino - 4,6-biscyclopropylpyrimidine (Compound 1.236);

- phenylamino-4-hydroxymethyl-6-cyclopropylpyrimidine (Compound 1.48);

- phenylamino-4-fluoromethyl-6-cyclopropylpyrimidine (Compound 1.59);

- phenylamino-4-hydroxymethyl-6- (2-methylcyclopropylpyrimidine (Compound 1.13);

- phenylamino-4-methyl-6- (2-fluorocyclopropyl) pyrimidine (Compound 1.66);

- phenylamino-4-methyl-6- (2-chlorocyclopropyl) pyrimidine (Compound 1.69);

- phenylamino-4-methyl-6- (2-difluorocyclopropyl) pyrimidine (Compound 1.84);

- phenylamino-4-fluoromethyl-6- (2-fluorocyclopropyl) pyrimidine (Compound 1.87);

- phenylamino-4-fluoromethyl-6- (2-chlorocyclopropyl) pyrimidine (Compound 1.94);

- phenylamino-4-fluoromethyl-6- (2-methylcyclopropyl) pyrimidine (Compound 1.108);

- phenylamino-4-ethyl-6- (2-methylcyclopropyl) pyrimidine (Compound 1.131);

- (p-Fluorophenylamino) -4-methyl-6-cyclopropylpyrimidine (Compound 1.33).

Compounds of formula 1 are obtained

1. Phenylguanidine salt (Formula 11a)

R

R

11a or guanidine (Formula 11b)

R

NH

NH

11b Reacts with Diketone (Formula 111)

O

CH.

111 in solvent-free or aprotic, preferably protic, solvent at a temperature of 60 ° C to 160 ° C, preferably 60-110 ° C, or

2. In a multistage mode:

2.1. urea (formula IV)

O =

IV

reacting with diketone (formula III),

III in an acid-inert solvent at 20 to 40 ° C / preferably 20 to 40 ° C and cyclization to give the pyrimidine compound (Formula V)

In compound V and 2.2, in the resulting compound (V), the OH group is further substituted by an excess of halogenated POHal in the presence or absence of solvent at 50 ° to 110 ° C, preferably at the boiling point of POHal

in addition, Hal in the above formula is halogen, preferably chlorine or bromine, and

2.3. the resulting compound (Formula VI) is further reacted with the aniline compound (Formula VII)

depending on the mode variant or

(a) in the presence of a proton acceptor, such as an excess of an aniline compound (Formula VII) or inorganic alkali, with or without solvent, or

(b) in an acid-inert solvent at a temperature of from 60 ° C to 120 ° C, preferably from 80 ° C to 100 ° C, or

3. Two-way:

3.1. guanidine salt (Formula VIII) io

Cyclin VIII with Diketone (Formula III)

R-C - CH "- CR ³ II ² II

III

(a) without solvent at 100 to 160 ° C, preferably 120 to 150 ° C, or

b) in an inert solvent at 30 ° to 140 ° C, preferably 60-120 ° C, until a pyrimidine compound (Formula IX) is obtained

IX

3.2. the resulting compound (Formula IX) is treated with a compound (Formula X)

Y

X,

11th by splitting HY, in the presence of protons acceptor in aprotonic in solvent from 30 ° up to 140 ° C at temperature, preferably 60-120 ° C, without to in formulas Substitute II Ri-R ₄ has

A is an acid anion and Y is halogen, or

4. In a multistage mode:

4.1. a) Thiourea (Formula XI) _Z NH

S = C

XI

NH, reacting with diketone (Formula III)

C-CH

II

O

C - R. II ⁴ O

III in the presence of an acid in an inert solvent at a temperature of 20 ° C to 140 ° C, preferably 20-60 ° C, and cyclized to give the pyrimidine compound (Formula XII)

and its alkali or alkaline earth metal salt is acted upon by a compound (Formula XIII) (ZR ₅ )

XIII wherein R ₅ is C 1 -C ₈ alkyl or unsubstituted or substituted by halogen and / or C _x -C ₄ alkyl benzyl. and Z halogen until a pyrimidine compound (Formula XIV) is obtained for ₂ sec

XIV or b) Isothiuronium salt (Formula XV) ^H 2 ^N

C —SR _C

XV reacts with diketone (Formula in aqueous solvent, preferably from 20 ° C to 20-80 ° C also, Compound (Formula XIV) and

III), preferably protocols at 140 ° C until pyrimidine is obtained

4.2. oxidizing the resulting compound (Formula XIV) to an pyrimidine compound (Formula XVI) with an oxidizing agent such as an acid.

and 4.3. the resulting compound (Formula XVI) is treated with formylaniline (Formula XVII)

R

NH

XVII

CHO in an inert solvent with an alkali proton acceptor at -30 ° C to 120 ° C to give the compound (Formula XVIII)

Hydrolyzing the compound (XVIII) obtained in Formula XVIII and 4.4 in the presence of an alkali such as an alkali metal hydroxide or an acid such as a hydrohalic or sulfuric acid in water or a mixture of water and a solvent such as aqueous alcohols or dimethylformamide to 10 ° C. 110 ° C, preferably 30-60 ° C, and in addition, in Formulas XI to XVIII, R! - R ₄ has the meaning given in formula I, while A® is an acid anion and Y is halogen.

In Formula I, compounds wherein R ₃ is CH ₂ OH are obtained in a special manner.

A. 1.1 guanidine salt (formula Ha)

Ha

or guanidine (Formula Ilb)

Ilb acts with a ketone (Formula XIX) (R, O) _n CH-C-CH-C-R. 6 2 ,, 2 „4

O O

XIX, wherein R ₆ is C 1 -C 10, solvent-free alkyl at least 60-110 ° C (Formula XX), in a protic solvent or at 40 ° C to 160 ° C, to give a pyrimidine compound

and A 1.2 is obtained by hydrolysis to the pyrimidine aldehyde (formula XXI) in the presence of an acid such as halogen or sulfuric acid in water or in a mixture of water and solvent at a temperature of from 20 ° C to 100 ° C, preferably from 30 ° C to 60 ° C.

NH

CHO

N

The compound XXI and A 1.3 are hydrogenated with atomic hydrogen using a catalyst such as sodium borohydride to the corresponding alcohol (Formula XXII).

or A 2.1 guanidine salt (Formula Ha) or guanidine (Formula IIb) acts with a diketone (Formula XXIII)

R _? OCH ₂ - C - CH ₂ - c - r ₄

XXIII, wherein R ₇ is unsubstituted or substituted by halogen or C 1 -C 8 alkyl benzyl, in a protic solvent or solvent free from 40 ° C to 160 ° C, preferably 60-110 ° C, to the pyrimidine compound (Formula XXIV)

XXIV and A 2.2 hydrogenate in a solvent, preferably an aprotic solvent such as dioxane or tetrahydrofuran, with a catalyst such as palladium on activated carbon or preferably Renee nickel at 20 ° C to 90 ° C, preferably 50-90 ° C, CH ₂ OR ₇ converts the residue to a CH ₂ OH residue: either the A 3.1 guanidine salt (Formula Ha) or the guanidine (Formula Ilb) is treated with a diketone (Formula XXV)

0CH-- R _and C - CH - C -R.

2 n 2 ,, 4

II H XXV,

And wherein R ₈ is C ₁ -C ₈ alkyl, C ₃ -C ₆ alkenyl, or unsubstituted or substituted by halogen or C ₁ -C ₆ alkyl benzyl, in a protic solvent or solvent at a temperature of 40 ° C to 160 ° C, preferably 60 ° C to 60 ° C. 110 ° C until the pyrimidine compound (Formula XXVI) is obtained

XXVI and A 2/3 existing compound (Formula XXVI) performs an ether cleavage with halogenvandenilio an acid, preferably bromvandenilio acid, or a Lewis acid such as aluminum helogenidu (such as A1C1 ₃₎ or borhalogenidu (such BBR ₃ or BC1 ₃₎ in an aprotic solvent, such as solvents, or in halogenated hydrocarbons at -80 ° C to -30 ° C, preferably -70 ° C to -20 ° C.

Compounds of formula I wherein R ₃ is a CH ₂ -Hal group are prepared by reacting a compound of formula XXII with a phosphorus halide or thionyl halide in the presence of a tertiary base such as pyridine or triethylamine at an inert peak at 0 to 110 ° C, preferably 0- 80 ° C.

Compounds of Formula I wherein R ₃ is CH ₂ F - by Reaction of Compounds of Formula XXVII

XXVII wherein X is chlorine or bromine, with potassium fluoride, preferably lyophilized potassium chloride, in the presence of a catalytic amount of cerium fluoride or crown ether, for example 13 cr - 6 - ether, in an aprotic solvent such as acetonitrile at 50 ° to 160 ° C in an autoclave , under increased pressure.

Another process for the preparation of compounds of formula I wherein R ₃ is a CH ₂ F group is by fluorination of a compound of formula XXII with N, N -diethylaminothiotrifluoride (DEATT) in an aprotic solvent such as dichloromethane, chloroform, tetrahydrofuran or dioxane from 0 ° C to 100 ° C. temperature, preferably 10 ° -50 ° C.

In the formulas XVIII to XXVII above, the substituents R ₄ and R ₂ as well as R ₄ have the meanings given in formula 1.

In the described processes, the acid anion A @ in the compounds of formulas Ha and VIII could be the following salt residues: carbonate, hydroxycarbonate, nitrate, halide, sulfate or hydrosulfate.

In the foregoing methods, the compounds of Formula XV may contain, for example, the acid anion A®. the following salt residues: halide, sulphate or hydrosulphate.

The halides are fluoride, chloride, bromide or iodide, preferably bromide or chloride.

Preferred inorganic acids are, for example, hydrohalic acids, such as hydrofluoric, hydrochloric or hydrobromic acids, as well as sulfuric, phosphoric or nitric acids; however, suitable organic acids, such as acetic, toluene sulfuric acid and the like, may also be used. Proton acceptors include, for example, inorganic or organic bases such as alkali or alkaline earth metal compounds such as hydroxides, lithium, sodium, potassium, magnesium, calcium, strontium, barium oxides or carbonates, or hydrides such as sodium hydride. Examples of organic bases include tertiary amines such as triethylamine, triethylenediamine and pyridine.

The following solvents may be used in combination with the partially mentioned halogenated hydrocarbons, partially chlorinated hydrocarbons such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, trichloroethalene, trichloroethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, chlorotoluene, trichloro-toluene: ethers, such as ethyl, -butyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, cyclohexyl ether 3874B-ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole, dichloroethyl ether; hydrocarbon nitro-derivatives such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons: heptane, hexane, octane, nonane, cymol, gasoline fractions with vir. temp. 70 ° C to 190 ° C, cyclohexane, methylcyclohexane, decalin, petroleum ether, naphtha, trimethylpentane, 2,3,3-trimethylpentane; esters: atyl acetate, acetoacetic acid ester, isobutyl acetate; amides such as formamide, methylformamide; ketones such as acetone, methyl ethyl ketone; alcohols such as partially lower aliphatic alcohols, methanol, ethanol, n-propanol, isopropanol as well as butanol isomers; in some cases, so does water. Mixtures of these solvents and thinners should also be borne in mind.

Unexpectedly, compounds of formula 1 have been found to possess a very favorable biocidal spectrum for practical use in the control of insects and phytopathogenic microorganisms, in part fungi. They have very useful curative preventive and, in part, systemic properties and can be used to protect many crops. Thanks to the biologically active substances of formula (1) in various useful crops or parts of them (fruits, flowers, stems, tubers, roots), the resulting damage can be limited or eliminated, and even later parts of the plant remain protected against, for example, phytopathogenic microorganisms. .

The compounds of formula 1 are biologically active against phytopathogenic fungi of the following classes: Fungi imperfecti (Botrytis, Pyricularia Helminthosporium, Fussarium, Septoria, Cescospora, Alternaria) Basidiomyceten (Chizoctania, Hemilcia, Puccinia). In addition, they act against ascomycetes (e.g. Ascomyceten (Venturia, Erysiphe, Podosphaera, Monilinia, Uncinula) and omycetes (e.g. Phytophthora, Pytium, Plasmopara)). In addition, the compounds of formula 1 can be used as seed treatments. (fruits, tubers, cereals) and protection of plant stems against fungal infections, as well as against phytopathogenic fungi on the ground.

Formula 1 compounds are effective against harmful insects such as cereal pests, partially rice pests. The following examples illustrate the invention without limiting it.

1. EXAMPLES OF RECEIPT

EXAMPLE 1.1. Preparation of 2-phenylamino-4-methyl-6-cyclopropyrimidine

g (51 mmol) of phenylguanidine bicarbonate and 9.7 g (77 mmol) of 1-cyclopropyl-1,3-butanedione are heated with stirring for 6 hours to 110 ° C with increasing carbon dioxide evolution. After cooling to room temperature, the dark brown emulsion is mixed with 50 ml of diethyl ether, washed twice with 20 ml of water each time, dried over sodium sulphate, filtered and the solvent is evaporated. The remaining dark brown oil (10.1 g) was purified by column chromatography over silica gel (diethyl ether: toluene 5: 3). After evaporation of the eluting liquid, the brown oil is crystallized and recrystallized from diethyl ether (petroleum ether, boiling point 30-50 ° C). Brown crystals are obtained. Melting point 67-69 ° C. Yield: 8.55 g (38 mmol) (74.5% of theory).

EXAMPLE 1.2. Preparation of 2-aniline - 4-formyldiethyl acetate-6-cyclopropylpyrimidine

11.7 g (59.2 mmol) of phenylguanidine bicarbonate and 13.3 g (62.2 mmol) of 1-cyclopropyl-3-formyldiethylacetal-1,3-propanedione in 40 ml of ethanol are heated with stirring to the boiling point of the phlegm, increasing carbon dioxide evolution for the reaction. After cooling to room temperature, the dark brown emulsion is mixed with 80 ml of diethyl ether, washed twice with 30 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The remaining dark brown oil (17 g) was purified by column chromatography over silica gel (toluene: ethyl acetate 5: 2). Evaporation of the eluent mixture left a reddish-brown oil, refractive index Ηθ °: 1, 5815

Yield: 15 g (48 mmol, 81.5% of theory).

EXAMPLE 1.3. Preparation of 2-anilino-4-formyl-6-cyclopropylpyrimidine (Compound 2.1)

CHO

12.3 g (39.3 mmol) of 2-aniline -4-formyldiethylacetal-6-cyclopropylpyrimidine, 4 g (39.3 mmol) of concentrated hydrochloric acid and 75 ml of water are heated under vigorous stirring at 50 ° C for 14 hours and 2 g (19 g) are added. (6 mmol) of concentrated hydrochloric acid was stirred at the same temperature for another 24 hours. After cooling to room temperature, 50 ml of ethyl acetate are added to the light brown suspension and neutralized by the addition of 7 ml of 30% sodium hydroxide. The ethyl acetate solution is then separated, dried over sodium sulfate, filtered and the solvent is evaporated. For purification, the brown solid was recrystallized from 20 mL of iso20 propanol by addition of activated carbon. The yellow crystals melt at 112-114 ° C.

Yield: 7.9 g (33 mmol, 84% of theory).

EXAMPLE 1.4. Preparation of 2-aniline-4-hydroxymethyl-6-cyclopropylpyrimidine (Compound 1.48)

CH ₂ OH

a) To 14.1 g (59 mmol) of 2-aniline-4-formyl-6-cyclopropyl35-pyrpyrimidine in 350 mL of absolute methanol was added 2.3 g (60 mmol) of sodium borohydride in portions with stirring at room temperature over 15 minutes. the reaction mixture is hydrogenated, heated to 28 ° C, and after 4 hours the reaction mixture is acidified by the dropwise addition of 10 ml of concentrated hydrochloric acid; add 120 ml of 10% sodium bicarbonate solution in drops and then dilute with 250 ml of water. The precipitate is filtered off, dried, completely dissolved in 600 ml of diethyl ether under heating, treated with activated carbon and filtered. Evaporate the clear filtrate until cloudy, dilute with light petroleum and filter off a light yellow crystalline dust: t. 123-125 ° C. Yield: 10.8 g (44.8 mmol, 75.9% of theory).

b) Dissolve 5, 9 (23 mmol) of 2-aniline -4-methoxymethyl-6-cyclopropylpyrimidine from phenylguanidine and 1-cyclopropyl-4-methoxy-1,3-butanedione in 200 ml of dichloromethane and cool to - 68 ° C. To the lightly colored solution, 6.8 g (27 mmol) of boron tribromide are slowly added dropwise over 30 minutes with vigorous stirring, then the cooling bath is removed and stirred for another two hours at room temperature. After addition of 150 g of ice water, the precipitated wet product is filtered off and recrystallized from methanol using activated carbon. The pale yellow crystals melt at 124-126 ° C. Yield

4.7 g (19.5 mmol), 84.7% of theory).

To 12 g (50 mmol) of 2-phenylamino-4-hydroxymethyl-6-cyclopropylpyramidine and 0.4 g (50 mmol) of pyridine in 350 mL of diethyl ether was added 15.6 (75 mmol) of thionyl bromide 50 ml of diethyl ether. After stirring for 2 hours at room temperature, another 0.4 g (50 mmol) of pyridine was added and heated to reflux for 5 hours. After cooling to room temperature, 200 ml of water are added, 140 ml of a saturated sodium bicarbonate solution are added and the solution is adjusted to pH 7. After separation of the diethyl ether phase, the mixture is washed with 100 ml of water twice, dried over sodium sulphate, filtered and evaporated. The residual brown oil is purified by column chromatography over silica gel (toluene: chloroform: diethyl ether: petroleum ether (boiling point 50-70 ° C): (5: 3: 1: 1). After evaporation of the elution mixture, the yellow oil is diluted with diethyl ether, light petroleum ether (boiling point 50-70 ° C) and set aside for cold crystallization The yellow crystalline dust melts at

77.5-79.5 ° C. Yield: 9.7 g -32 mmol (64% of theory).

EXAMPLE 1.6. Preparation of 2-Phenylamino-4-fluoromethyl-6-cyclopropylpyrimidine (Compound 1.59) ^r ₂ ^F

a) 3.9 g (12.8 mmol) of 2-phenylamino-4-bromoethyl-6-cyclopropylpyrimidine, 1.5 g (12.8 mmol) dried by sublimation of potassium fluoride and 0.3 g (1.13 mmol) of 18 -charge-6 ether is heated in 50 mL of acetonitrile for 40 hours to reflux. 0.75 g (13 mmol) of potassium fluoride are then added and the mixture is heated for 22 hours. 0.75 g (13 mmol) of potassium fluoride, dried by sublimation, and 0.1 g (0.38 mmol) of 18-crown-6-ether are added again to complete the reaction, and are further heated to reflux for 24 hours. After cooling to room temperature, the suspension is mixed with 150 ml of diethyl ether, washed three times with 20 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The residual brown oil is purified by column chromatography over silica gel (toluene: chloroform: diethyl ether: petroleum ether (boiling point 50-70 ° C): (5: 3: 1: 1). After evaporation of the elution mixture, the yellow oil is added to 10 ml. pet25 rol ether (boiling point 50-70 [deg.] C.) and standing for crystallization. The yellow crystals melt, 48-52 [deg.] C. Yield 2.1 g (8.6 mmol), 67.5% of theory).

b) To a suspension of 9.1 g (37.8 mmol) of 2-phenylamino-4-hydroxymethyl-6-cyclopropylpyrimidine in 80 mL of dichloromethane is slowly added 6.1 g (37.8 mmol) of diethylaminothiotrifluoride in 15 mL of dichloromethane. After adding 15 ml of ice water, 50 ml of 10% aqueous sodium bicarbonate solution are added dropwise. After the evolution of carbon dioxide, the organic phase is separated off and the aqueous phase is extracted twice with 20 ml of dichloromethane. The combined dichloromethane solutions were washed with water (15 mL), dried over sodium sulfate, filtered and the solvent evaporated. The remaining black oil is purified by column chromatography over silica gel (toluene: chloroform: petroleum ether, boiling 50-70 ° C: (5: 3: 1: 1). After evaporation of the elution mixture, the yellow oil is diluted with 20 ml of petroleum ether (boiling water). 50-70 ° C) and allowed to crystallize cold The yellow crystals melt at 50-52 ° C.

Yield: 4.9 g (20.1 mmol, 53% of theory).

EXAMPLE 1.7 Preparation of 2-hydroxy-4-methyl-6-cyclopropylpyrimidine in pu

HO g (100 mmol) urea and 12.6 g (100 mmol) 1-cyclopropyl-1,3-butanedione are stirred at room temperature in 35 ml of ethanol and 15 ml of concentrated hydrochloric acid. After 10 days of storage at room tempeLTLT 3874 B, evaporate in a rotor evaporator at a maximum bath temperature of 45 ° C. The residue is dissolved in 20 ml of ethanol and the hydrochloride of the reaction product is cooled very rapidly. After stirring, 20 ml of diethyl ether are added, the white crystals which precipitate are filtered off and washed with a mixture of ethanol and diethyl ether and dried. Evaporation of the filtrate and recrystallization of the residue from ethanol / diethyl ether (1: 2) afforded additional hydrochloride. The white crystals melt above 230 ° C. The yield of hydrochloride was 12.6 g (67.5 mmol, 67.5% of theory).

EXAMPLE 1.8 Preparation of 2-Chloro-4-methyl-6-cyclopropylpyrimidine (Compound 3.1)

52.8 g (0.24 mmol) of 2-hydroxy-4-methyl-6-cyclopropyl-pyrimidine hydrochloride are added under stirring at room temperature to 100 ml (1.1 mol) of phosphorus oxychloride and 117 g (0.79 mol). addition of diethylaniline and raising the temperature to 63 ° C. After heating for 2 hours to 110 [deg.] C., it is cooled to room temperature and the reaction mixture is stirred with ice-water / methylene chloride. The organic phase is separated and washed with neutral sodium bicarbonate aqueous solution until neutral. Evaporation of the solvent gave 116.4 g of an oil consisting of the reaction product and diethylaniline. The separation of diethylaniline and purification of the urea reaction product is carried out by column chromatography over silica gel with hexane: diethyl acetate): (3: 1). The colorless oil which crystallized after several days had a refractive index n ^ ⁵ 1.5419. Yield: 35.7 g (0.21 mol, 87.5% of theory). Lyd. t. 33-34 ° C.

EXAMPLE 1.9 Preparation of 2- (m-Fluorophenylamino) -4-methyl-6-cyclopropylpyrimidine (Jung.1.63)

A solution of 5.5 g (50 mmol) of 3-fluoroaniline and 9.3 g (55 mmol) of 2-chloro-4-methyl-6-cyclopropylpyrimidine in 100 ml of ethanol is stirred and added to 5 ml of concentrated hydrochloric acid and acidified to pH 1 with it is heated immediately at the boiling point of phlegm for 18 hours. After cooling to room temperature, the brown emulsion is basified with 10 mL of 30% ammonia to an alkaline reaction, poured into 100 mL of ice water and extracted twice with 150 mL of diethyl ether. The combined extracts were washed with 50 mL of water, dried over sodium sulfate, filtered and the solvent evaporated. The remaining yellow crystals are purified by recrystallization from a mixture of diisopropyl ether, petroleum ether (boiling 50-70 ° C). The white crystals melt at 87-89 ° C. Yield 8.3 g (34 mmol, 68% of theory).

EXAMPLE 1.10. Preparation of 2- (p-fluorophenylamino) -4-methyl-6-cyclopropylpyrimidine (Compound 1.33)

24.8 g (0.115 mol) of 4-fluorophenylguanidine bicarbonate and 17.5 g (0.138 mol) of 1-cyclopropyl-1,3-butanedione in 150 ml of methanol are heated with stirring for 24 hours at the boiling point of phlegm, with the addition of a certain amount of carbon dioxide. time clearly decreases. The resulting dark brown clear solution is treated with activated carbon, filtered and the filtrate is evaporated on a rotor evaporator to a crystalline mass separation and poured into 500 ml of water with stirring. The precipitated crystals are filtered off, washed with a small amount of cold ethanol, dried and recrystallized from a mixture of diisopropyl ether and petroleum ether (50-70 ° C). The pale brown crystals melt 89-91 ° C.

EXAMPLE 1.11 Preparation of 2-Phenylamino-4-methyl-6- (2-methylcyclopropyl) pyrimidine (Compound 1.14)

62.2 g (0.3 mol) of 95% phenylguanidine bicarbonate are placed in 300 ml of isopropanol and, with stirring at 124 ° C, heated to the boiling point of the phlegm (78 ° C), and a light brown suspension is formed. 42.1 g (0.3 mol) of 1- (2-methylcyclopropyl) -1,3-butanedione are added dropwise over 40 minutes and vigorous carbon dioxide evolution begins. At the end of the dropwise addition, the reaction mixture was heated for 6 hours under stirring at reflux temperature and 200 ml of isopropanol was distilled off when the external temperature dropped. Without further heating, at an internal temperature of 60 ° C, with stirring, slowly add 100 ml of water to a brown solution which slowly begins to cloud with the addition of water. After stirring at room temperature for 12 hours, cool for one hour to + 5 ° C and then for two hours to + 3 ° C. The precipitate formed is filtered off from the crystals, washed with 40 ml of cold isopropanol / water (1: 1) and the white crystals are dried.

Melting point 73-74 ° C. Yield: 51.4 g (0.215 mol; theoretical yield: 75.3%).

EXAMPLE 1.12

Preparation of 2-phenylamino-4-ethyl-6-cyclopropylpyrimidine (Compound 1.6)

NH

g (0.2 mol) of phenylguanidine in 200 ml of dimethylformamide is stirred at room temperature with 6 ml of acetic acid. After heating to 50 ° C, 28 g (0.2 mol) of 1-cyclopropyl-1,3-pentadione are added dropwise with stirring over half an hour and the mixture is heated to 150 ° C for another two hours. After cooling to room temperature, the solvent was evaporated in vacuo and the dark brown reaction mixture was poured into 500 ml of water with stirring. After adjusting the pH to 9 with a small amount of dilute sodium hydroxide (NaOH), the aqueous phase is extracted twice with 150 ml of diethyl ether, the combined extracts are washed with 200 ml of water and dried over sodium sulphate, filtered and the ether is evaporated. The remaining oil is distilled in a deep vacuum. Vir. t. 125-129 ° C / IIIa. The yellow oil hardens after a while: m.p. t. 42-45 ° C.

For full validation of the claimed compounds, the applicant shall provide additional physical data for the following units:

Jung.

1.55 1.82 melt. t. 51-53 ° C m.p. t. 79-81 ° C

EXAMPLE 1.13

Preparation of 2- (4-fluorophenylamino) -4-methyl-6-cyclopropylpyrimidine (Compound 1.33)

NH

CH

g. (30 mmol) of 2-chloro-4-methyl-6-cyclopropylpyrimidine are dissolved in 50 ml of absolute methanol and 3.3 g (30 mmol) of 4-fluoroaniline are stirred at room temperature. At an oil bath temperature of 8590 ° C, the mixture was heated to reflux for 19 hours immediately after stirring. After cooling, dropwise over half an hour into 300 ml of water containing 1.2 g (30 mmol) of sodium hydroxide. Light brown crystals settle very quickly, which are suctioned for one hour and rinsed with water. Drying gives 6.8 g (28 mmol) of yellowish crystals, melting at 89-91 [deg.] C., yield 93.3% of theory.

EXAMPLE 1.14.

Preparation of 2-methylmercapto-4-methyl-6-cyclopropylpyrimidine

CH

To 69.5 g (0.25 mol) of 5-methylisothiourea sulfate and 41 g (0.5 mol) of anhydrous sodium acetate in 375 µl of acetic acid are added 63 g (0.5 mol) of 1-cyclopropyl dropwise over 10 minutes at room temperature. -l, 3-butanedione and immediately thereafter heated at reflux for 14 hours. After cooling to room temperature, the product is filtered off and the product is then washed with acetic acid. The filtrate is evaporated on a rotor evaporator and the remaining brown oil is poured into 600 ml of water with stirring. After double extraction with 200 mL of methylene chloride, the extract is evaporated on a rotary evaporator and the remaining oil is distilled in a deep vacuum. Vir. t. 81-82 ° C. Yield: 64.8 g (0.36 mol), yield 72% of theory.

EXAMPLE 1.15

Preparation of 2-methylsulfonyl-4-methyl-6-cyclopropylpyrimidine (Compound 4.1)

Dissolve 2 g of methyl 2-methylmercapto-4-methyl-6-cyclopropylpyrimidine (100 g) in acetic acid (100 ml) and add 30 g of hydrogen peroxide (30 g) (0.25 mol) in 1 hour with stirring at 0 ° C. One hour after completion of the dropwise addition, the reaction mixture was heated to 70 ° C for 2 hours, cooled to room temperature and poured into 800 ml of water with ice stirring. The precipitated white crystals are filtered off and dried, m.p. t. 74-76 ° C.

EXAMPLE 1.16

Preparation of 2- (4-chlorophenylamino) -4-methyl-6-cyclopropylpyrimidine (Compound 1.7)

Cl

15.5 g (0.1 mol) of 4-chloroformanilide in 300 ml of toluene are stirred at room temperature with 4.4 g (0.11 mol) of a 60% dispersion of sodium hydride. After heating to 100 ° C for 1 hour, cool to room temperature and add 20.1 g (0.095 mol) of 2-methylsulfonyl-4-methyl-6-cyclopropylpyrimidine over 1 hour with stirring. After stirring for 5 hours, the mixture is washed with 100 ml of water, the toluene solution is dried over sodium sulphate, filtered and the solvent is evaporated. The brown precipitate was dissolved in 300 ml of ethanol and stirred at room temperature for 10 minutes with 60 ml of 10% aqueous sodium hydroxide solution and stirred for 3 hours at room temperature. After evaporation of the ethanol, the residue is poured into 300 ml of water with stirring and extracted three times with 50 ml of diethyl ether each time. The combined extracts were washed with 30 ml of water, dried over sodium sulfate, filtered and the ether evaporated. The remaining dark brown oil was purified by column chromatography over silica gel (eluent: toluene: chloroform: diethyl ether): (4: 2: 1). After evaporation of the eluting mixture, the yellowish oil is crystallized, triturated with petroleum ether (50-70 ° C). The pale yellow crystals melt at 86-87 ° C.

In an analogous manner, the following compounds may be obtained: See Table 1.

EXAMPLE 1.17: Preparation of 2-phenylamino-4-methyl-6-cyclopropylpyrimidine phosphate

g (18 mmol) of 2-phenyl-4-methyl-6-cyclopropylpyrimidine in 250 ml of absolute diethyl ether was added dropwise over 10 minutes at room temperature with 2.19 g (19 mmol) of 35% ortho-phosphoric acid (ga). ). The white precipitate formed is filtered off and rinsed with 20 ml of absolute diethyl ether. The white crystals melt at 188-191 ° C. Yield: 5.6 g (17.3 mmol = 96% of theory).

EXAMPLE 1.18: Preparation of 2-phenylamino-4-methyl-6-cyclopropylpyrimidine nitrate

g (53 mmol) of 2-phenylamino-4-methyl-6-cyclopropylpyrimidine in 180 ml of absolute diethyl ether are stirred in drops at room temperature and 5.81 g (60 mmol) of 65% nitric acid (ca. ). The resulting white precipitate was filtered off with nuLT 3874 B and further washed with 20 ml of absolute diethyl ether. The white, slightly brownish crystals melts at 151-153 ° C with decomposition. Yield: 14.7 g (52 mmol = 96% of theory).

The following additional salts are prepared analogously to 1.17 and methods:

1.18 in the examples

• HCI • H_SO. 2 4 • 1/2 H_SO. 2 4

Lyd. t. 151-154 ° C

Lyd. t. 183-185 ° C

Lyd. t. 200-202 ° C

BIOLOGICAL EXAMPLES

EXAMPLE 3.1. Effect against Veutuvia inaegualis on apple shoots (Resident protective action).

Apple shoots with young shoots sprayed with a spray liquid of 10-20 cm length, made from a wetting powder of biologically active substance (0.006% active ingredient). After 24 hours, the treated plants were inoculated with a suspension of fungal spores. Plants were placed in an incubator for 5 days at 90-10-0% relative humidity and then stored for 10 days at 20-24 ° C in a greenhouse. Scabies lesions were evaluated 15 days after infection.

the compounds in the table show good efficacy against Veutuvia (less than 20% damage). Thus, compounds: 1.1, 1.6, 1.13, 1.14, 1.33, 1.48, 1.59, 1.63, 1.66, 1.69, 1.84, 1.87, 1.94, 1.108, 1.126, 1.131, 1.145, 1.158. 1,180, 1,200, 1,236, 1,254 and 1,255 reduce Veutuvia lesion to 0-10%. Untreated but infected Veutuvia control plants were 100% infected.

EXAMPLE 3.2. Effect against Botrytis cinerea on apple trees.

Residently - protective action.

Artificially damaged apple trees were treated in such a way that a spray liquid made from a biologically active compound (0.002% active ingredient) wetting powder was applied to the affected areas. The treated fruits were immediately infected with a suspension of fungal spores and kept in high humidity air for about a week at about 20 ° C. The rotten lesions were counted and the fungicidal activity of the test substance was calculated.

The compounds in the Table show good efficacy against Botrytis (less than 20% damage). For example, compounds: 1.1, 1.4, 1.6, 1.9, 1.13, 1.14, 1.17, 1.31,

1.33, 1.35, 1.48, 1.54, 1. 58, 1.59, 1.62, 1.66, 1.69, 1.74, 1.82, 1.84, 1.87, 1.94, 1.108, 1.126, 1.131, 1.142, 1.145, 1.152, 1.166, 1,173, 1,180, 1,192, 1200, 1.236, 1.247, 1.254, 1.255 and 1,256 reduced Botrytis

lesion up to 0-10%. The untreated infected control plants were 100% affected by Botrytis.

EXAMPLE 3.3. Effect against Frysiphae graminis in barley

(a) Resident - protective action.

Barley plants were sprayed with a spray liquid prepared from a biologically active substance (0.006% active ingredient) wetting powder about 8 cm high. After 3-4 hours, the treated plants were pollinated with fungal spores. Infected barley plants were placed in a greenhouse at about 22 ° C and fungal lesions were evaluated after 10 days.

The compounds in the Table show good efficacy against Erysiphae (lesion less than 20%). For example, compounds: 1.1, 1.3, 1.13, 1.14, 1.33, 1.35, 1.46, 1.59, 1.63, 1.66, 1.69, 1.84, 1.87, 1.94, 1.108, 1.131, 1.158, 1.236, 1.254, and 1.255 reduced Erysiphae to 010%. . Untreated infected control plants were 100% damaged.

EXAMPLE 3.4. Effect against Helmin thosporium gramineum. The wheat grains were soaked in a suspension of benign spores and dried again. The soaked grains are treated with a suspension of a wetting powder of the test substance (600 ppm active substance by weight of seeds). Two days later, the grains were placed in certain agar plates and four days later, the spread of the fungal colony around the grain was evaluated. The amount and size of the fungal colony evaluated the test substance. The compounds in the table strongly inhibit fungal injury (0-10% of lesions).

EXAMPLE 3.5. Effect against Colletotrichum lagenarium on cucumber.

After germination, the cucumber plants are sprayed with a spray of a biologically active substance (concentration 0.002%) within 2 weeks with a wetting powder. Two days later, the plants were inoculated with a fungal suspension (1.5x10 spores / ml) and placed in an incubator for 36 hours at 23 ° C and high humidity. The incubator was then maintained at normal humidity and at a temperature of about 22-23 ° C. Fungal injury was evaluated 8 days after infection. Untreated but infected control plants were 100% fungal inoculated.

The compounds of the table showed good efficacy and stopped the spreading of the disease. Fungal injury was reduced to 20% and less.

EXAMPLE 3.6.

(a) Contact action against Nephotettix cincticeps and Nilaparvale lugeus (Nymphen)

The test was carried out on sprouted rice plants. For this purpose, pots (5.5 cm in diameter) were planted respectively with 4 plants about 15 cm tall (14-20 days).

Plants were sprayed on a rotating plate with 100 ml of a prepared aqueous suspension containing 400 ppm. relevant biologically active substances. After the spray layer had dried, 40 plants tested in the third stage of development were planted on each plant. To prevent the spread of cicadas, plants with caterpillars on each side were surrounded by an open cylinder and covered with a metal mesh. After 6 days, the nymphs reached the stage of adult insect development on the treated plants. Percent destruction assessment was performed 6 days after nymph challenge. The test was performed at a temperature of approximately 27 ° C, 60% relative humidity, and a lighting period of 16 hours.

(b) Systemic action against Nilaparvate lugens (water). Rice plants, approximately 10 days old (height 10 cm), were placed in plastic beakers containing 100 ppm of aqueous test biologically active substance. concentrations of emulsions and were covered with a plastic cap with a hole. The roots of the rice plant were placed through a hole in the plastic lid into the prepared test solution. The rice plants were then planted with 20 Nilaparvate lugens nymphs (caterpillars) of the 2nd and 3rd stages of development and covered with a plastic cylinder. The test was performed at approximately 26 ° C and 60% relative humidity with a 16-hour illumination period. After 5 days, the number of test animals destroyed was evaluated relative to the untreated controls. In this way, it was found that the biologically active substance, which enters the root, destroys the test animals on the upper parts of the plants.

The compounds from Table 1 showed strong killing effects on rice pests in both test a) and test b). The degree of destruction is 80% and above. With compounds

1.1. 1.6, 1.14, 1.59, 1.66, 1.87, 1.94. 1,108 and 1,236 achieved near complete destruction (98-100%). The results obtained clearly demonstrate the high fungicidal activity potential inherent in all salts of the compounds of formula 1.

Fungicidal activity tests on various pathogens have been performed to demonstrate the superiority of the Formula 1 compounds over structural analogues. The compounds of the formula used represent all compounds and exhibit pronounced fungicidal activity for all compounds of formula 1.

In addition to their fungicidal properties, the compounds of formula 1, as exemplified in Example 3.6, exhibit improved insecticidal activities.

Proof of the activity of salts of the compounds of formula 1

1. Salts of compounds

A)

B)

C)

D)

2. Tests:

2.1. Action against Botrytis cinerea on apples.

Artificially damaged apples are treated by the application of a ready-to-spray wetting powder (0.02%, 0.006%, 0.002%, 0.006% of the active substance) on the lesions.

The treated fruit is infected with a suspension of fungal spores and kept in an incubator at high humidity of 20 ° C for a whole week. The evaluation is done by calculating the putative lesion sites and deriving the fungicidal activity of the test substance.

Comparatively treated but infected control plants show 100% damage to Botrytis.

2.2. Action against Veuturia inaegualis on apple shoots. Apple shoots with fresh shoots 10 to 20 cm long are sprayed with a spray of a biologically active substance wetting powder spray (0.02%, 0.006%, 0.002%, 0.0006% active substance).

After 24 hours, the treated plants are infected with a fungal suspension. The plants are then incubated for 5 days at 90-100% relative humidity and kept in a greenhouse at 20-24 ° C for another 10 days. Scabies lesion is assessed 15 days after infection.

Comparatively, untreated but infected control plants show 100% lesion in Veuturia.

3. Rating scale

Rating * Activity,%> 95 (full operation)

30-95 (acceptable performance)

Rating * Activity,%

50-80 (malfunction) <50 (no malfunction) * Intermediate score is the mean value of several test results.

Results

The compound-salt Assessment / Test 2.1 2.2 dose (m.d.) 200 60 20th 6th 200 60 20th 6th A 1 1 1 2 1 1 1 2 B 1 1 1 2 1 1 1 2 C 1 1 1 1 1 1 1 1 D 1 1 1 1 1 1 3 1

Description of the test

Comparison of the activity of biologically active substances in this application with equivalents of the prior art

1. Compound / PS / 5-16701 / 1 + 2 / E / x ₂

Jung. 1.1

Jung. 1.14

Jung. 1.59

Jung.1.33

Jung. 1.63

DD-151404 Jung. 1

DD-151404 Jung. 35

DD-151404

Jung. 34

F

El-224339 Jung. 37

El-224339 Jung. 36

2. Test run

2.1. Effect against Botrytis cinerea on apples.

Artificially infected apples are treated by applying a spray of a wetting powder (0.002% active ingredient) made of the active substance on the lesion. The treated fruits are then infected with a fungal spore suspension and incubated throughout the week at high relative humidity and around 20 ° C. The evaluation shall include the calculation of the lesions affected by decay and the conclusion to be drawn regarding the fungicidal action of the test substance.

In comparison, untreated but infected control plants show 100% damage to Botrytis.

2.2. Effect against Veuturia inaegualis on apple shoots.

Apple tree stems with fresh shoots of 10-20 cm are sprayed with a spray of a moisturizing powder made from biologically active substance (0.006% of active substance 3874 B). After 24 hours, the treated plants are infected with a conidia fungal suspension. The plants are incubated for 5 days at a relative humidity of 90100% and kept for 10 days in a greenhouse at 20-24 ° C. Scabies lesions are evaluated 15 days after infection.

By comparison, untreated but infected control plants show 100% lesion in Veuturia.

2.8. Effect against Erysihae graminis on barley.

About 8 cm of barley plants are sprayed with a spray of a biologically active substance with a wetting powder spray (0.006% active ingredient). After 3-4 hours, the sprayed plants are pollinated with fungal conidia. Infected barley plants are kept in a glasshouse at a temperature of approximately 22 ° C and, after 10 days, are evaluated for fungal damage.

By comparison, untreated but infected control plants show 100% erysiphae damage.

3. Rating scale

Rating * Activity,%> 95 (full operation)

80-95 (Acceptable Performance) 50-80 (Underperformance) <50 (No Effect) * Intermediate score is the average of several test results

4. Results

The compound Assessment / Test 2.1 2.2 2.3 Χχ 1 1 1 X ₂ 2 2 1 x ₃ 1 3 1 x ₄ 1 3 2 x ₅ 1 1 1 Yi 8th 9th 9th y ₂ 9th 9th 9th Y ₃ -c 9th 9th Y ₄ 9th 9th 9th Y ₅ 9th 9th 9th

* was not performed.

table. Compounds of Formulas

m -P c Π3 -P ω U 0 O 0 O o · LD 05 O 0 LT) O p 0 o> kO r- ι-1 kO m | 1 o 1 tn • d) r- CO o kO LT) r- c r- • H • H -P pi + J -P N Ό Ό Ό Ό • H ί> 1 ί> Ί > 1 > 1 r — J i-1 i-1 »—1 (L '\ 77' i \ / * i i \ z * i '\ / * i u ro tf m ro CQ <o CH CH X O 1 CH (N (X ac cc X ac ϋ 1-1 i-1 r-l CL K u I E U l CM co p 2 i-1 CM tn * κΓ tn N t-1 T-1 ϊ — 1 i-1 1-1 > CL

table (continued)

Physical constant melts 42-45 ° C melts 86-87 ° C melts 50-52 ° C melts 53-56 ° C 'Sr cd * \ / i \ z * i x \ Z * ° i m X O \ _e \ / i * \ / 'i v 7 ' i m IT) 2d CM O 1 CQ 2d u 1 M m CM 2d u 1 i-i u CM 2d o 1 m X o 1 co Pu O 1 CM 2d 2d 2d X X X r-4 X 2d l-1 o 1 2d X n X o X No. kO 00 ΟΊ o t-1 , —I r — 1 N > CM i-1 i-1 l-1 t-1 r ~ ( ϊ — 1

table (continued)

Physical constant melts 44-46 ° C melts 111-113 ° C melts 73-74 ° C melts 48-50 ° C et m z i "\ \ z 'i z i \ z * I / \ i i \ z 'i T * O \ \ / 'i m ie c 1 r- X m O X o <N X o 1 ΓΟ X o 1 ro X o X o OJ X o OJ X u 1 o m CM X u 1 OJ X X X X X X i-l et X X X ro X o o X X . No. CM rH CO r "t 1-1 tn <—1 kO <—1 r- i-1 For example, t-1 i-1 i-1 <—1 1-1 , —1

table (continued)

Physical constant dark brown oil np ⁴ : 1.5992 melts 33-36 ° C (X \ / 'I z '\ j i \ z i \ z * i m re o \ \ z ' « 1 To j \ Z * i z \ i i \ z 'i m & c 1 σ> re U 1 re o Oops re u 1 m re u re M m f'J re o 1 M m Thu, re o 1 04 (X re re re re re re tn X OJ r— < X re re U o re re re S-l 2 00 σι i-1 o CM I-1 CM OJ CM co CM N > CM t-1 i-1 1-1 t-1 i-1 i-1

table (continued)

(ΰ + J C + J (0 . 6002 u u i-1 o o C Lf) 00 o ΧΓ CM Q 05 05 1 • Q) c r- 05 05 C w • H 3 'ΓΊ + J u -H ω N -H Ό Ό • H t- ( r — I > 1 > 1 3 <—1 1-1 (Z Z * \ / \ / \ * \ / * * '\ Z * / T> —-- g \ / z * ί i S 1 1 \ / 1 1 Ϊ i i I + J Z q o CM m ro m cee rO z z t-l fk □ =; Z u υ u cn z o | 1 1 1 u 1 CM Oops cc z Z z z z M <£ z z Z m 1 z z rr Ct Z LD <o r- 00 05 CM CM CM CM CM CM N rH i-1 r—) i-1 1-1 x-1 > CM

table (continued)

fO -P c 03 -P (f) u u - u o o C CM t-1 r- o LD | cn l LO 1 - (U O ΟΊ LO LO 00 LO c • H _{t 4} 3Z 4-J 4-) 4J -H N Ό Ό t • P > 1 > 1 > 1 1- ( 1-1 1-1 o3 • / \ • ---___ * » / \ \ z i '\ Z' i o-- X \ / o-- 1 i t 1 • · i '\ Ύ i -P d) P ro m ro o OJ n 4-> 33 fu 33 Cb U U O 33 33 UH 1 1 1 U J ^ r o 1 Oops Cd 33 33 33 33 33 33 r-H cb 33 33 33 fu 1 33 33 'tr M S O «—1 CM 00 u0 m CO ro ro CO 00 N r-1 i-i i-1 i-1 T-1 i— ( > CLi

table (continued)

Γ “1

Physical constant oil n ^ ⁵ : 1.5763 Melting point 56-58 ° C oh \ / i i t. -—. g \ / i i \ / i i i * \ / 'i n (Z m O 1 m oh o 1 m oh CM O 1 (M i-1 O oh o 1 n Oops o 1 CM i-1 U CM oh u 1 CM X oh oh oh r 1 5-C1 oh ι-I Pi □ i CM 2 oh o o 1 oh oh 3-Cl oh M 2 N > CU kO m tA 1.37 1.38 1.39 1.40 i-1 sr τ-1

table (continued)

Physical constant melts Mp 63-65 ° C oil n ^ ⁵ : 1.5498 melts 66-69 ° C X nr- · = \ ⁷ i z \ • * \ z i \ .z ' i i \ z 'ί to i \ z 'i m d m X u 1 X o CM X u 1 m X u 1 m X o 1 m X u 1 X o CM X o 1 CM X X m X (N O o X X X X X m X Cs] U o 1 co X rd (xj U O 1 X With X OJ m LD kO θ ' 'ΧΓ N > CU t-1 t — i 1 - 1 T - i (—1 I-1

table (continued)

f + J c Π3 -P ω O o LO CM o 0 o CO - U 0 C r- o I 00 CO 03 1 -ω CM CN LO co C • r4 P P P -H « N Ό Ό Ό • H > 1 > 1 fc-i 1-1 i— | i-1 E \ z ' • - · \ / i i • · \ z i '·' * · χ \ z \ z " * • 'l « • 1 1 1 1 1 i E m Oops E o CM E O m E U 1 E E O CM E U CM E n E U 1 1 O 1 • —l i-1 CM E o J E E E u 1 N ¹ ST Cm r-i cF E O E E E u 1 CO E M Z 03 05 O ϊ — l CN CO E m m LO N i-1 T-1 i-1 ϊ — 1 i-1 , —1 > E

table (continued)

Physical constant melts 73-74 ° C melts 51-53 ° C melts 58-61 ° C. oh / * Oj— · 1 \ / 'I X O \ / 1 —F \ / m oh m X o 1 ΓΩ al u 1 rn al o 1 al n al u 1 ΓΜ al x al al X 1 — I oh x 2-F al al X M Z N > CU 1.54 1.55 1.56 1.57 1.58

table (continued)

rO 4-> C rO 4-> ω c O o CN o o cr> O Λί LO J co 1 ω co r- co c • H X 4-1 4-1 • H N TS Ό Ή > 1 >, tui 1-1 1-1 m X X X O CJ \ z \ z \ z The ^z P \ z / * i i (P- · 1 i CJ— · 1 you m co co co m CM X O 1 X X X X et O 1 X o 1 o 1 o 1 CO CM X X o | X X X X £ X 1-1 o 1 X X 3-F X co M 2 04 o rH CM cn Ν ' LT) co CO co CO co N —1 i-1 1-1 1-1 I-1 , —1 > Pj

table (continued)

rO + J C rC -P ω O o O 0 O 0 C m cn o 00 1 CO 1 co 44 1 ω i-1 co r- 00 co co • H 44 -P -P -P N Ό T3 • H > 1 i-1 1-1 i-1 ck X O \ \ z • \ z P - <-. \ z \ z 1 i 1 i i i m m t-l cn m m CO rc rc ac o 1 rc rc rc ck o 1 u 1 u 1 u 1 o 1 cn l-1 rc CM (X u l rc rc u rc rc m LT) cn X l-1 P t-1 Ck o rc rc o 1 rr ffl 1 CN CN CN P 2 LD CO r- 00 cn O CO co co co r- N 1-1 <—1 i-1 , -1 t-1 l-1 > CP

table (continued)

rO P C (0 P m c O o CO O o tn - O to | • = tr p 1 • ω M ⁴ cn to c • H p P P • r | • N Ό Ό • l — f ✓h (j-l 1-1 «—1 X i i \ Z i \ / i \ / i P \ Z o-. 1 l- \ Z Λ-. 1 \ z i m m re X [J-I m m X x X X X o 1 u 1 u 1 U 1 u 1 o 1 i-i X! C-J (X O l U X X X to m OC 1-1 M p? u X o 1 X X CQ 1 CN CN cn C-I 2 1-1 CM m LT) co r- r- r- r ~ r- N t-1 1-1 t - t t-1 1-1 r > X

table (continued)

Physical constant melts 79-81 ° C melts 81-84 ° C O o kO 1 co kO -P Ό 1-1 * \ / * i o- · 1 \ / i rc o \ ___ \ / * i \ s i X \ __ \ / • 1 m n K u 1 Ή 1 r- X m O 1 ΓΩ X O 1 Ή 1 r- 2 m O 1 m X u 1 X 04 X o 1 CM (X 4-F X X X X X 1-1 (Z 3-C1 X X X 4-J X M 2 , 82 .83 .84 .85 kO CO Γ- ΟΟ N > d, t-1 1-1 1-1 I-I , - ( 1-1

table (continued)

Physical constant melts 51-53 ° C i-1 o r — 1 kO t — f cm Q C cn 3 • m (D • H l-1 tk Z P3_. 1 * \ ___ * \ / « 1 / i r — 1 Γ— < Oh o \ z '\ Z' yeah u \ / o- * o j X co i ΓΟ you o 1 co you o 1 i t-l (N 2 O 1 CM & X! ΓΟ X o 1 'TT X you , - < m X 2-C1 L- you you o 2 N > O-i Γ Γ , —1 1.78 1.79 1.80 1.81

table (continued)

Physical constant Γ- Ο co i-1 CM Q c ω n Π Φ • H i-1 Π5 melts 65-68 ° C & r ~ f \ / O— · i \ / ' i • - 1 - - «· i r— <r— ( CJ o \ / __ \ / i * · \ z i / \ i i «· \ z yeah o X ΓΩ od c σι X U 1 m X o 1 • H 1 r- X m O 1 f} 2 o 1 ro X O 1 ro X o 1 CN 2 X X 2 l-1 u 1 m X 0? χ ΓΟ 2 o 1 CM X χ: m K o 1 CM X S-l 2 N > 00 00 ί — 1 o 00 i-1 O o 1-1 1-1 οί , -1 CM O ϊ — l co o I-1

table (continued)

Physical constant melts 48-50 ° C r-l O N \ / i \ / ί \ / i z-1 f-1 O O \ / \ / 'O— · m I X k. u f '\ s' i CO C \ l 2 O 1 co o 1 m X u 1 2 O (N o CN X o 1 m X u 1 m X u 1 CN 2 5-Cl (* Ί 2 o o 1 X X 4-Br i r — S. X 2 cn 2 O O 1 CM 3-C1 X X 2-Br s-i 2 N > X 1.94 1.95 1.96 1.97 1.98 1.99

table (continued)

Physical constant melts 38-41 ° C melts 51-52 ° C 'ΪΓ CL U * \ s i '\ Z i X o \ \ / i \ / • 1 • “t * —f u u \ y * \ S o- · X M X i ΟΊ (L CM 33 O 1 n 33 O 1 C 1 <r> 33 ΜΓ U 1 m 33 O 1 c 1 r- 33 n U 1 m 33 O 1 <N & K 33 33 4-Br 33 33 i-1 CL 33 fO 33 U 1 co 33 m 33 O 1 co 33 33 s-i 2 N > CL 1.100 1.101 1.102 1.103 1.104 Lf) O i-1 i-1

table (continued)

Physical constant melts 55-57 ° C OS m : c o , * \ / Ϊ \ / i 4 * » re u \ x ' i u \ / (O-- 1 X o \ ___ \ z i i m od re o CN re o CN re o 1 m re o 1 h CN re u 1 re c 1 re m O 1 m re o 1 CJ Cd X re re re re re rH ce ac m re (N U 1 Csl re re re cn re CN U 1 m For example, No. 1.106 1.107 1.108 1.109 1.110 i-1t-1t-1 t-1

table (continued)

Physical constant melts 83-85 ° C «Tr oh r- | <-n X X Oh u \ / \ / i f — i M * \ y ' i . i '\ Z * i • X / ' o— · 1 i m (X Uj CM X o 1 m X o 1 Pd X o 1 m X u 1 + J o O 1 σ \ X O 1 m X U 1 CM & X X i 5-Br 1_. 4-Br X Uj 1 LO t-1 Pi X X 2-Br m X O 1 CM X ΓΩ Χί o 1 CM S-i Z N > (X 1.112 1.113 1.114 1.115 1.116 1> <-1 i-1 I-1

table (continued)

Physical constant melts 51-54 ° C X \ p ' i t- • \ __ * \ / ' i r. * d X X O CJ p / i \ z 'i / -T '-i o o \ / O— · m J X Uh m \ \ Z * i m & x ' CJ 1 X no U 1 ^ε Η0- X CM X u 1 m X o CM X X X co X O J KT X X X LO X CM O 1 X X 2-Br X X Sq Z N > X 1.118 1.119 1.120 1.121 1.122 co 04 r - 1 i-1

table (continued)

sort of 4-> C <e 4-> OT u o c o o o Γ kO sr 1 uo I c Lf) H Λ! • 4-1 Ή 4-> N H Ό Ό > 1 > ί 1-1 1-1 X rH O • —1 \ • U • ——- * · _e z \ \ \ z \ z \ z * z * • * \ z * * \ z ' 1 i o- · o— · i m J m | 1 x: X co CO CM co co cd -CF -CH 2 U 1 -CH \ z 'i 2 U 1 S-l CM 2 2 2 2 2 m 1 'T -H 1 r ~~ 1-1 rH X 2 2 CO 2 2 2 O I o | CM CM S-l 2 LT) 2> Γ 00 ΟΊ CN CM CM CM CM CM t — i t-1 5 — ί t-1 , —1 1-J N > t-1 1-1 1-1 i-1 1-1 i-I 2

table (continued)

Physical constant melts 57-59 ° C Oops \ / o- · J X rn X o \ ___ \ / ' i \ / i t U \ ___ \ z o- · m 1 X \ / 1 m oh M C (U 1 σι 2 O 1 LT! X CM U 1 m OC U 1 cn OC o 1 07 OC o 1 1-1 o (M OC o 1 CJ X OC OC m OC O 1 ID OC OC 1— (oh 2 □ c H 1 Γ- ΟΟ cn O 1 cn OC O o 1 CM OC OC M S N > Pu 1.130 1.131 1.132 1.133 1.134 LO CO i-1 x-1

table (continued)

Physical constant melts 56-58 ° C X i \ / 1 M i * \ / * i * —1 CJ \ y ' i o X O \ \ 7 om | X cd X m X O 1 Cd {-D U 1 m X CM U 1 m X U 1 X m X O 1 CM cd X o X X X X X LT) X rd X o | X X rd you U | X X 00 04 M X . 136 . 137 . 138 . 139 . 140 1-1 c — I For example, I-1 I-1 t-1 t-l I-1 t-1

table (continued)

Physical constant melts 55-60 ° C re Ή \ / O— <i \ / i -X / O—- 1 <-1 u \ / i \ / 'I \ / * i m oh 1-) o CN re o 1 m ac o 1 -P ω P o 1 cn re o 1 cn re CN U 1 cd ac ω 1 n re u 1 cn Pd ac 3-C1 re re 4-C1 <-1 u 1 n ¹ f — s re re 2-Cl re re cd O 1 CN <—1 o 1 CN For example, No. 1.142 1.143 1.144 1.145 1.146 Γ i-1 <—1

table (continued)

oh -P (U -P ω u o c o o o co C \ l 34 00 kO | • o t-1 o c 00 kO • H 34 • -P • H + J N Ό Ό X > 1 kO 1-1 r — H sr X X u \ \ / P-r— · 1 X / cq— · * \ / * X S. o- · 1 i ro 1 | I p) i-i d) m (J m P co co co X CN X -P X X et o 1 -CH o l 1 Os o 1 u 1 X u 1 CO CN ie X X X X X X o 1 m co co r-1 k X et X X o X u O 1 co CM n 2 00 <Ti o i-1 Cs] CO 'ΌΓ X X LT) X • i-l — — 1 ϊ — 1 T-1 i-1 , —1 N > t-1 t-l i-1 —1 T - t I-1 Cu

table (continued)

sort of -P c sort of P ω c o o o O O o o kO o P kO i-1 kO 1 o m Λ co c kO σι LO • H λ; • • * • H P P P N • • Ό Ό Ό X £> ί >, > 1 1-1 1 r-1 T X X \ · —1 r — 1 Oh u \ z \ .z ' \ z 'o- · / ' \ / * \ / * \ / 1 m | I i • X 1 1 Γ0 1-1 u CM m 2C co ΣΧ ro K in X C \ 1 u 1 ro K X X o o o u u 1 1 1 1 1 1-1 1-1 CM X X X u I X X O l LO kO Ή l-1 r- X n o 1-1 xf X X o 1 X o 1 CM O CM 'TT u LO kO r- co στ LO LD LO LO LO LO r - j t — I i-f t-1 1-1 i-1 N > i-i i-1 i-1 I-1 i-1 1 - Vol X

table (continued)

Physical constant i melts 55-57 ° C i 1_ X Z o- · 1 1-. t- . '\ / Oj '—I u \ z ' i \ / ' i \ z 'i u « * \ Z * I m m X (N O 1 to X O 1 l-1 u CM X u 1 m X u 1 1-1 u OJ X u CM X u CM X u 1 X CM & X X X X X X r-1 X X X X Γ0 X o o X X CM M 2 .160 , 161 CM kO t-1 .163 .164 10 kO For example, t-1 —1 <—1 t-1 I-1 ΐ — 1

table (continued)

constant O 0 kO U o O LO I Φ LO θ ' c to • H dd • + J -H + J N Ό Ό 6th > Ί > 1 i-1 Γ — I CL k · X P \ z ° 1 = 5 \ \ Z \ Z P -, - » \ z o— · * \ / * * \ 7 / ' I j ♦ i X 1 m 1-1 m 33 m o m m K OJ 33 OJ 33 CL u 33 O 33 O 1 O 1 O 1 1 OJ CL [-LJ 1 33 33 33 33 m n r— ( CL 2 1 33 33 33 -OCH CN CO M kO r- 00 cn o 2-1 kO kO kO kO Γ « r-1 t-l i-1 i-1 t-1 N > ϊ — f t-l , —I t-1 1-1 CL

table (continued)

Physical constant melts 73-73.5 ° C E U · O K z * \ z * o- · P * \ z ' i i m X o \ \ z ' i co co X X U c_> \ / b-- \ z o— · <o I X X o \ \ s 1 ro (X l-1 o CN E U 1 ΓΟ E O 1 ro E U 1 1-1 o CN E O CN E O CN E O 1 00 E U 1 1-1 o CN E U 1 CM & E co G o 1 Ν ' 4-F E E E £ E co E O 1 CN 2-F E E E For example, No. 1.171 1.172 1.17 3 1.174 1.175 kO> r ^- 1 ΐ — 1

table (continued)

fC -P c sort of -P ω u c 0 o ΟΊ p; r- -Φ C c r- • H • • H pi N • • H d bu > 1 1-1 τΓ X <* »/ O u υ \ _Z_ O CJ \ Z r − tr − 1 ^υ \ z ° X X ω u N Z \ / i. \ z o- · tn | \ Z o— · m j \ z ' U \ Z * X— · X X 1 1 1 x X ro ro tf o CN aa co tf o CN ro X X o x u X u 1 u 1 1 o i 1 CN tf P 1 X x ac X X LT) CM tf m [p X o x aa 1 X X o CM CM P r- 00 05 O t — i CM r ~ Γ 00 co 00 1-1 r "1 Γ — t 1-1 rH N > i-1 l-1 ΐ — 1 —1 i-4 t-1 X

table (continued)

you + J r- C o ~ (C o + J ω 1-1 c II o 44 CM Q £ C • <1> C W • H P 44 • m -H Φ N • H • H 1— f t-l m n · ck (* » rO x X o o \ \ z \ \ z i \ y P \ Z «- · 1 \ / i \ 7 P-r- · 1 \ z fl --- 1 ro X l-1 CJ 1-1 m o \ m o rc CM • - · ck 3C o rc X \ z \ z o 1 1 u 1 i P - <- · 1 CM Pd rc rc ac rc ac ac CM 2 rc u <—1 ck rc CM t-l ac rc ac rc U o I P 2 CO LO CO r- 00 00 00 00 co 00 00 τ-'1 t ^- 1 i-1 t-1 I-1 t-1 M > 1-1 I-1 t - t Ϊ — t I-1 T-1 CP

table (continued)

Physical constant melts 135-137 ° C & · —1 4-4 U o \ Z / «- · 1 \ z * i • z \ • « \ / i \ x ' i A \ / u— · 1 \ / i m co X u 1 m X u 1 1-1 o CM X o 1 n X o 1 <*> X u \ * \ z * i r-> X o 1 CM & X X X 6-F X X i-1 X X X r-4 o X u X o o 1 3 X 2-F X c 1 r ~ X co U o 1 'T M S i .189 .190 .191 .192 .193 ΟΊ i-1 For example, T - t —1 5 - l i-1 i-1 i-1

table (continued)

Physical constant O o C \] 1 r — 1 <T> -P 1-1 T Pi / ' o— · 1 <-1. U; O \ z / * U- · 1 f- “t u \ \ z ' i * \ z ' i ac o \ ___ '\ _Z' i \ / i m '\ 7ž * (L * - · 1 m X U 1 '\ 7 /' P-r- · 1 ΓΌ X u 1 co X u 1 CM (X X X X X X E-1-1 1 t-1 Pi X X X <N 1-1 o X u <M t-l ω o 1 X Pp 1 co o 2 N > O-i 1.195 _ 1.196 1.197 1.198 1.199 o o CN 1-1

table (continued)

sort of p) c - rc -P o ω c o. O o r- 1 3Z -d) co <o c • P JZ P • P N Ό • P fu > 1 I-1 cb Vi U \ z \ z P \ z ' \ z \ z ' z * • PO— · pLr- · 1 i 1 1 i i CM P Uh m cn CQ m ΓΊ m i-1  33 33 CM 33 33 cb u O U 33 U U o 1 1 1 O 1 1 1 cn 33 CM cd 33 33 33 33 33 U O LO CM (—1 LT) U re K 33 i-H cb 33 CM U o 33 33 O CM t-l u o 1 U. 1 CM co o ^ r p l-1 CM CO 'tr m <Ώ o O o o O O CM CM CM CM CM CM N > 1-1 i-1 <—1 T-1 i-1 1-1 O-l

table (continued)

(U -P r- c r- · <u o P LO • c t-1 o II λ: o CM Q -φ c c • H ω Oops 3 • H 'ΓΎ N Φ • H • H l-L | ι-1 Π3 'Χ X m M X o \ \ z ' \ / V o- · • · \ z * \ 7 * / ' Ρ3— · 1 t 1 i i I X X cu S-l ο S-l o t- | m ΓΌ \ m m cu t-1 cu K cu X X u X O \ ζ X u 1 o 1 o 1 1 ί u 1 C7 X cu & X X X o o X X co X rH X X X X u o X X CM S-l r- 00 CTs O ι-1 CM o o o r-1 t ^- 1 ι-1 CM CM CM CM CM CM N > i-1 5-1 1-1 I-1 , —1 <—1 X

table (continued)

Physical constant o o 1 -P > 1 <—1 X \ / 'X ~ · 1 > —H O * \ z ' i o \ * \ z ' i \ z 'i u. \ Z i \ z * i m X c - t O v i X o CM X o 1 m X O \ • ll · \ / i m X o 1 M m (N X o 1 07 X u 07 X X - u U CM X U 1 CM X X X 07 X o o X X LT) r — H X X X X re X o o X X Λ M 2 .213 .214 .215 .216 .217 00 i-I CM For example, i-1 i-1 1 - Vol ! —1 T - t X

table (continued)

Physical constant (Z i \ \ / i out i 30th O \ \ / i i • a i m m z o 1 z o CM Z o 1 m z o \ / * i m Z o co x Z - U U CM z u 1 CO z o 1 M m CM Z u 1 CM n Z O 1 CO z z z co Z u 1 z p? co Z u 1 CM z z z cn z u 1 CM z For example, No. 1.219 1.220 1.221 1.222 1.223 χτ CN CN i-1

table (continued)

Physical constant melts 50-52 ° C X \ ___ \ s i i: Λ— · 1 \ / i '—N. / O-1 cX / O-- 1 m Dd i m X o 1 X o CM X u 1 cd pE- | O CM ώ O t X o CM X u 1 * \ Z i CM Cd X m X U 1 to X X X X pT X CO X u 1 Csl X X X X For example, No. 1.225 1.226 1.227 1.228 1.229 o ro CN T ^- 1

Table (continued) t — I

Physical constant melts 122-123 ° C m.p. 58-60 ° C melts 75-77 ° C X \ / 'i U \ i <- » X o \ / i <—I «-Η Oh o \ y \ / O '· m | X rn X O \ __ \ / i i cd n X U 1 With m CM X o 1 rd li o CM O 1 \ / · 1 CM X o \ z * i '\ Z * i Cs] (X m X U 1 kO X X X X X i-1 X m X o 1 Csl X X X X X For example, No. 1.231 1.232 1.233 1.234 1.235 1.236

table (continued)

constant α o t "4 O? —1 - • φ c 1 00 07 H -H N 4-> • H {j-i Ό > 1 Ά O * Pi m X • —i o CJ _φ _ \ \ \ z i \ / 2- · 1 \ z 2— · 1 '\ Z * i \ z ' 2- · 1 A / u— · 1 2 n r — X m o m CJ 07 2 CM CM \ Pi U 1 2 2 • - • - • - » O 1 O 1 \ z i \ z i \ z i P7 <M 2 O | 2 2 2 2 2 07 2 Pi O 2 2 2 2 2 Λ sm 2 00 07 O X-1 CN 00 m n N ¹ sr • CN CN CN CN CN CN N > x-1 i-1 1-1 X-1 X-1 x-1 n.

table (continued)

p CM C CO - (ΰ OJ -P CD ω * - u G r ^- 1 0 o • · 00 to r- CM Q 1 -Φ c LO G r ~~ ω λ: P • 'ΓΊ P N Φ • H Ό Uj i-1 ί> Ί f i-1 m • T 1 * - < • —t 1 X X U u CJ CJ U \ z \ z \ \ z o—- \ z \ z \ / m | m I i I X X 1 P CQ m m m CM • - - -. - · X X X X <-r \ Z o \ / J u u 1 O— * 1 1 1 1 m m X X oh X X o I X o I LO m X Uh X X u X I 1 co ro M co LO <o θ ' M ¹ M ¹ CM OJ OJ CM OJ • • « « • > t - t i-1 t-1 <—1 t-1

table (continued)

Physical constant melts 85-87 ° C oil n ^, ⁵ : 1.5898 O o CD Γ I 'ΧΓ Γ- -P r — i o o cn cn 1 Γ cn P Ό £> 1 <—1 ^ r (k t *. r-1 \ Λ O \ l \ z * \ z * \ / \ z '\ / i i i i i i M CQ CN cd Cd Cd rd cd I with with re with c4 \ z re u u u u i o 1 1 1 J 1 CN CN Oops re re cd re u 1 OCHF re o O 1 with 1 funds re u o l-1 «—F you re re u 1 co 3-0C re CN o 00 O k-1 CN CO Z N ¹ 'ΚΓ LD LT) UO m • CN CN CN CN CN CN N > 1-i - ( <—I I-1 1 — i I- ( CM

table (continued)

-P P -P ω CJ O 0 r- o c o o o o O , —1 i-i λ: CO 1 O) 1 LT) 1 • d) CTi O ΟΛ c r- »—1 CO Ή λ: « • • H P P P N • • • H n Ό Ό Pi > 1 X X rp 1-1 <—1 <- » X X X o o \ \ \ / i \ / i \ z 'i ro ro ro ro X X X X u 1 u 1 u 1 X ώ X 1 X LD r ^- 1 X X P X co co M 'ST LO kO LT) LT) LO CM CM CM N > 1-1 1-1 i-f

50% of lethal dose (LD ₅₀ )

Compound No. LD ₅₀ md The organism being tested 1.28 200 Erysiphae graminis 1.31 200 Erysiphae graminis 1.45 200 Erysiphae graminis 1.201 200 Erysiphae graminis 1.236 60 Erysiphae graminis

Claims (9)

DEFINITION OF INVENTION 1. 2-Anilino-pyrimidine derivatives of the formula I: R Wherein R ₃ and R ₂ each independently represent hydrogen, halo, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ haloalkoxy; R ₃ is hydrogen, C ₁ -C ₄ alkyl or substituted by halogen, hydroxy or cyano by C ₁ -C ₄ alkyl, cyclopropyl or substituted up to three times the same or different by methyl and / or halogen cyclopropyl; R ₄ - C ₃ -C ₆ -cycloalkyl or substituted up to three times in the same or different positions with methyl and / or halogen C ₃ -C ₆ -cycloalkyl, or salts thereof, showing biological activity. Compound of formula 1 according to claim 1, characterized in that R ₃ and R ₄ have the meanings indicated and R _x and R ₂ are hydrogen. Compound of formula 1 according to claim 1, characterized in that R 1 and R ₂ independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₂ -haloalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -haloalkoxy; R ₃ is hydrogen, C ₁ -C ₄ alkyl, or substituted with halogen or cyano C ₁ -C ₄ alkyl; R ₄ is C ₃ -C ₆ -cycloalkyl or substituted with methyl or halogen C ₃ -C ₆ -cycloalkyl. A compound of formula 1 according to claim 3, wherein R ₁ and R ₂ independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, halomethyl, methoxy, ethoxy or halomethoxy; R ₃ is hydrogen, methyl, ethyl, n-propyl or fluorobutyl; or substituted by fluorine, chlorine, bromine or cyano methyl or ethyl; R ₄ is C ₃ -C ₆ -cycloalkyl or substituted with methyl, fluoro, chloro or bromo C ₃ -C ₆ -cycloalkyl. A compound of formula 1 according to claim 1, wherein R ₃ and R ₂ independently of one another are hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy or difluoromethoxy; R ₃ is hydrogen, C ₁ -C ₃ alkyl substituted by halogen or hydroxy, C ₁ -C ₂ alkyl; cyclopropyl or substituted up to three times the same or different with methyl and / or halogen cyclopropyl; R ₄ is C ₃ -C ₆ -cycloalkyl or is substituted up to three times the same or different by methyl and / or halogen C ₃ -C ₄ -cycloalkyl. 6. A compound of the formula 1 as claimed in claim 1, wherein R ₄ and R ₂ are hydrogen; r ₃ - C ₁ -C ₃ alkyl substituted by fluorine, chlorine, bromine or hydroxyl methyl; cyclopropyl substituted with methyl, fluorine, chlorine or bromine cyclopropyl; R ₄ -C ₃ -C ₄ -cycloalkyl or substituted up to three times with the same or different methyl and / or fluorine, chlorine, bromine C ₃ -C ₄ -cycloalkyl. 7. A compound according to claim 3, which is selected from the group consisting of: 2-phenylamino -4-methyl-6-cyclopropylpyrimidine, 2-phenylamino -4-ethyl-6-cyclopropylpyrimidine, 2-phenylamino -4-methyl-5- (methylcyclopropyl) pyrimidine, 2- (p-Fluorophenylamino) -4-methyl-6-cyclopropylpyrimidine. 8. A compound according to claim 1, which is selected from the group consisting of: 2-phenylamino -4,6-bis (cyclopropyl) pyrimidine, 2-phenylamino -4-hydroxymethyl-6-cyclopropylpyrimidine, 2-phenylamino -4-fluoromethyl-6-cyclopropylpyrimidine, 2-phenylamino -4-hydroxymethyl-6- (2-methylcyclopropyl) -piperidine; rimidine, 2-phenylamino -4-methyl-6- (2-fluorocyclopropyl) pyrimidine, 2-phenylamino -4-methyl-6- (2-chlorocyclopropyl) pyrimidine, 2-phenylamino -4-methyl-6- (2-difluorocyclopropyl) pyrimidine nas 2-phenylamino-4-fluoromethyl-6- (2-fluorocyclopropyl) pyrimidine, 2-Phenylamino-4-fluoromethyl-6- (2-chloro-isopropyl) pyrimidine, 2-phenylamino-4-fluoromethyl-6- (2-methylcyclopropyl) pyrimidine, 10 2-Phenylamino-4-ethyl-6- (2-methylcyclopropyl) pyrimidine.