DD282685A5 - PROCESS FOR THE PREPARATION OF NEW 2-ANILINOPYRINDIDE DERIVATIVES - Google Patents

Abstract

The invention relates to a process for the preparation of novel 2-anilino-pyrimidine derivatives of the formula I, 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 C1-C3-haloalkoxy; R3 is hydrogen, C1-C4-alkyl; or C 1 -C 4 -alkyl substituted by halogen, hydroxy or cyano; Cyclopropyl or cyclopropyl substituted by methyl and / or halogen up to three times identically or differently; R 4 is C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl which is up to three times identically or differently substituted by methyl and / or halogen; which possess valuable microbicidal and insecticidal properties. The new active ingredients can be used in crop protection for the prevention of infestation of crops by phytopathogenic microorganisms or pest insects and to combat these Schaedlinge. Formula (I) {2-Anilino-pyrimidine Derivative Preparation; microbicide; Insecticide; Schaedlingsbekaempfungsmittel; Plant protection}

Description

Process for the preparation of novel 2-anilinopyrimidine derivatives Field of application of the invention

The present invention relates to a process for the preparation of novel 2-anilinopyrimidine derivatives and to agrochemical compositions which contain as active ingredient at least one of these compounds. The invention also relates to the preparation of said agents and the use of the active substance or the agent for controlling pests, especially of harmful insects and plant-damaging microorganisms, preferably fungi,

Characteristic of the known state of the art

N-pyrimidinylaniline compounds are already known. Thus, in published European patent application 0 224 339 and DD patent 151 404 compounds having an N-2-pyrimidinyl structure are described as being effective against plant-damaging fungi. However, the confessed compounds have not been able to fully satisfy the demands made in practice on sis.

Object of the invention

The novel i-anilinopyrimidine derivatives prepared according to the invention differ in a characteristic manner from the known compounds by the introduction at least

2 8 26 8 p

-Ia-

a cycloalkyl-Reetee and other substituents in the anilinopyrimidine structure, whereby in the new compounds sine unexpectedly high fungicidal activity and insecticidal activity is achieved.

They bind at room temperature stable oils, resins or solids, which are characterized by valuable microbicidal properties and can be used in the agricultural sector or related fields preventively and curatively for the control of plant-damaging microorganisms. The active compounds produced according to the invention are not only distinguished by excellent insecticidal and fungicidal activity at low application concentrations, but also by particularly good plant compatibility.

Explanation of the essence of the invention

The present one. The invention has for its object to produce new compounds with respect to the prior art improved fungicidal and insecticidal activity with good plant tolerance.

According to the invention, compounds of the general formula Z are prepared

R ₁ / H

in which mean:

R ₁ and R _{2 are} independently hydrogen, halogen ι C ₁ -C 4 -alkyl, C ₁ -C 9 -halogenoalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ - Haloalkoxy ·, R ₃ hydrogen, Cj-Сд-Аікуі; or by halogen, hydroxy

or cyano substituted C ₁ -C ₄ -alkyl; CyclopropyJ. or cyclopropyl which is up to three times the same or differently substituted by methyl and / or halogen;

^R 4 is Cj-Cg-cycloalkyl or by methyl and / or halogen to

triply identical or differently substituted C ₃ -C ₆ -

cycloalkyl; including her home-made additional and Metallialzkomplexe.

Under alkyl itself or as Beetandteil another substituent, such as haloalkyl, alkoxy or haloalkoxy, depending on the number of named Kohlenstoffatorae be understood, for example, methyl, ethyl, propyl, butyl, and their isomers, such as. B * isopropyl, isobutyl, tert-butyl or d-butyl, halogen, also called shark, is fluorine, chlorine, bromine or aod. Haloalkyl and haloalkoxy simply refer to perhalogenated radicals, such as. Bt CHCl ₂ , CH ₂ F, CCl ₃ , CH ₂ Cl, CHF ₂ , CF ₃ , CH ₂ CH ₃ Br, C ₂ Cl ₅ , CHBr, CHBrCl, etc., preferably CF ₃ . Cycloalkyl is depending on the number of said carbon atom z. As for cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Apart from the free compounds of the formula I, their addition salts with inorganic and organic acids and their complexes with metal salts are also prepared.

Salts prepared according to the invention are in particular addition salts with harmless inorganic or organic acids, for example hydrohalic acids, eg. Hydrochloric, hydrobromic or hydroiodic acid, sulfuric acid.

2 8 2 6 θ 5

acid, phosphoric acid, phosphoric acid, nitric acid, or acids such as acetic acid, trifluorofluoric acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluene aiuli fumaric acid, methanesulfonic acid, salicylic acid, p-Aminosalicyclic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalene-dlsulfonic acid.

MetaUealz complexes of formula t consist of the underlying organic molecule and an inorganic or organic metal aaa, such as the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicyclates, bonoates, etc. of the second main group elements calcium and magnesium and the .ritten and fourth main group vie aluminum, tin or lead, and of the first to eighth preferred Mebengruppe such as chromium, manganese, Elsen, cobalt, nickel, copper, zinc, etc. are the transition group elements of the 4th period. The metals can be present in the different valencies. The metal complexes can occur mononuclear or polynuclear, ie they can contain one or more organic molecular moieties as ligands.

An important group of plant fungicides and insecticides are those of formula I in which Ri and R.? Mean hydrogen.

A particular group are the following compounds of the formula I in which R] and Rz independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C] -Cz -hilo-haloalkyl, CfCj-methoxy or СС-Сз -Naіоветіаікохут Ri hydrogen , C] -Ci, -alkyl or by halogen or cyano-substituted C ι -Ci, -alkyl ', vmd

t is Cj-Ce-cycloalkyl or substituted by methyl or halogen.

The following active substance groups are preferred owing to their outlined microbiciria, in particular plant fungicides, activity:

2Q 26B S

GRU p pe 1л: Compounds of formula wherein:

Ri and Rg independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, halogenoethyl, methoxy, ethoxy or halomethoxy; Ri is hydrogen, methyl, methyl substituted by fluorine, chlorine, bromine or cyano; Ethyl, eicylated by fluorine, chlorine, bromine or cyano; n-propyl otlsr век.-butyl;

Ri ₁ Cj-Cr, cycloalkyl or substituted by methyl, fluorine, chlorine or bromine Gj-Cs-cycloalkyl.

Among the compounds mentioned above, those represent a particularly preferred group in which Ri = R;> = hydrogen (= group Iaa).

Group Ib: compounds of the formula I ₁ in which Ri and R; u! are each hydrogen, chlorine, bromine, methyl, ethyl, Trifluoromethyl, methoxy, ethoxy or fluoromethoxy; R] is hydrogen, methyl, substituted by fluorine, chlorine or cyano Methyl, ethyl or n-propyl; R 1, C 1 -C 4 -cycloalkyl or C ₃ -C 12 -substituted by methyl or chlorine Cycloalkyl.

Among the compounds mentioned above, those represent a particularly preferred group in which Ri = R.2 ³ Was3erataff (= group lob).

Ic. Compounds of the formula. I, in which mean: R] and R ₂ independently of one another hydrogen, chlorine, methyl, methoxy, Ethoxy otier trifluoromethyl; R _{1 is} hydrogen, methyl, ethyl or trifluoromethyl; Rit cyclopropyl or by methyl or "chloro substituted CycJopropyl.

Among the compounds mentioned above, those which are particularly preferred are those in which R.sub.1.sub.10 R.sub.1.sup.13 is hydrogen (= I.sub.10 group).

- Group Id: Compounds of the formula I ₁ in which

Ri hydrogen ·, Rs and R] are independently hydrogen or methyl; Ri, cyclopropyl or methyl-substituted cyclopropyl. Group 2a: compounds of the formula I, in which Rj and Rj independently of one another hydrogen, halogen, Ci-Cj-alkyl, Halomethyl, Ci-Cj-alkoxy or Cj-f.j-Halogenalkoxyj Ri is hydrogen, Ci-Ci ₍ -Alky1, substituted by halogen or hydroxy Cj-Ca-ATkyl; Сусіортнуі or by methyl and / or halogen up to

trisubstituted by identical or different cyclopropyl;

Ri, Ca-Cft-cycloalkyl or by methyl and / or halogen up to three times

identical or different substituted Cj-Cii-cycloalkyl.

Among the compounds mentioned above, those represent a particularly preferred group in which R 1 is R = water (= group 2aa).

Group 2b: compounds of the formula t, in which Ri and R ?. independently of one another hydrogen »fluorine, chlorine, bromine, methyl, Trifluoromethyl, methoxy or difluoromethoxy; R] is hydrogen, Сі-Сз alkyl, substituted by halogen or hydroxy

Сі-Сг-Аілуі; Cyclopropj ¹ or by methyl and / jder Kalogen to zudreifach identical or different substituents cyclopropyl;

Ri, Cj-C ~ ~ Cyclaalkyl or by methyl and / or halogen up to three times

identical or different substituted Cj-Cii-

Among the compounds mentioned above, those represent a particularly preferred group in which R 1 is R 2 ^e waterBtofi (= group 2bb).

Group 2c: compounds of the formula I ₁ in which

Ri and Rj independently of one another are hydrogen, fluorine, chlorine, methyl, trifluoroethyl, methoxy or difluoromethoxy;

- fi -

R] hydrogen, Сі-Сз-Аікуі; halogen or hydroxy-substituted C 1 -C 6 -alkyl; Cyclopropyl or substituted by methyl and / or halogen up to three times identically or differently substituted cyclopropyl; Ri ₁ Cj-Сб-Сусіоаікуі or substituted by methyl and / or halogen up to three times the same or differently substituted Ci-Cu-cyclaalkyl.

Among the compounds mentioned above, those represent a particularly preferred group in which R | => R;> = hydrogen (= group 2cc).

Group 2d: Compounds of the formula I, in which Ii and R2 are hydrogen; Rj Ci-Ci-alkyl, substituted by fluorine, chlorine, bromine or hydroxy Methyl; Cyclopropyl, substituted by methyl, fluorine, chlorine or bromine cyclopropyl; Ri ₁ Cj-Ci, -cycloalkyl or by methyl and / or fluorine, chlorine, bromine up to

trisubstituted by identical or different substituents C3-Ci, -Cycloalkyl.

Among the most preferred single substances are e.g. to name: г-Рпепуіаяііпо - ^ - іпе ^ уі-б-сусіоргоруі-ругітігііп (Compound No. 1.1..) Z-phenylamino-A-ethyl-ö-cyclopropyl-pyritnidin (Compound No. 1.6..) of 2-Phenjlamlno-4 -methyl-6- (2-methylcyclopropyl) -pyrimidine (comp. no. 1.14) Z-Phenybimino- ^ ö-bieCcyclopropynpyrimidin (comp. no. 1.236) of 2-Phenylaaino-4-iiydraxymethyl-6-cyclopropylpyrimidine (comp. no. 1:48) of 2-phenylamino-4-flu0rmethyl-6-cyclopropyl-pyriinidin (Ver. no. 1.59) 2-phenylamino-4-hydroxymethyl-6- (2-raethylcyclopropylJ-pyriinidin (comp. Mr. 1.13)

2-Phenylamino-4-methyl-6- (2-fluorocyclopropyl) -pyriniidine (Comp # 1.66) 2-Phenylamino-4-methyl-6- (2-chlorocyclopropyl) -pyrimidine (Comp # 1.69) 2- Phenylamino-4-ethyl-6- (2-difluorocyclopropyl) -pyrimidine (Comp No. 1.84)

? -Pheiiylamiivo-4-fluoromethyl-6- (2-fluorocyclopropyl) -pyrimidine (Comp No. 1.87)

2-phenylamino-4-fluoromethyl-6- (2-chlorocyclopropyl) -pyriinidine (Comp # 1.94)

2-phenylamino-4-fluoromethyl-6- (2-methylcyclopropyl) -pyriinidine (Comp # 1,108)

2-Phetiylamino-4-ethyl- <i- (2-methylcyclopiopyl) - {iyrimidln (Compound No. 1Л31..) Of 2- (p-Fliiorphenylaraino) -4-methyl-6-cyclopropyl-pyriinidin (Compound No. 1.43..

The compounds of formula I are prepared by adding 1. a phenylguanidine salt of Formal На

"V-v JM = * e

· *> -KH- <A ⁰ UIa)

or the parent guinidine of formula Hb

'Γ

"2

with a carillon of formula III

KH;

R _{3 is} C-CHs-C-

! -R., Uli)

without solvent or in an aprotic, preferably in a protic solvent at temperatures of 60 ^b C to 160 ° C, preferably 60 ⁰ C to 110 ⁰ C, or

2. in a multi-stage process: 2.1 urea of formula IV

with a diketone of formula III

R 3-C-CH ig-C-Ri ₁

(Iv) Hi

(III)

in the presence of an acid in an inert solvent at temperatures of 20 ⁰ C to UO ⁰ C, preferably 2O ⁰ C to 40 ^e C, гиг reaction brings and to a pyrimidine compound of the formula V

Μ- · "

HO- <> (V)

cyclized and

2.2 the OH group in the resulting compound of formula V further with excess POHaLi in the presence or absence of a solvent at temperatures of 50 "C to 110" C, preferably at the Rückfluusteraturatur of POHaI), exchanged with halogen

Hai {^ · IVIl

wherein Hal in the above formulas is halogen, especially chlorine or bromine, and

2.3 the obtained compound of the formula VI further with an aniline compound of the formula VII

H ₂ N- <2 x <VII)

depending on the process conditions either

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

b) in the presence of an acid in an inert solvent at temperatures of 60 "C to 120 ^u C, preferably 80 ^v C to 100" C, or

3. in a two-step process: 3.1 a guanidine salt of formula VIII

8th

IH г

JIH г

HjN-C A

(VIII)

with a diketone of formula III

R С-С-Сгг-H-Ri ₁ (HD

a) without solvent at temperatures of 100 "C to 160" C, preferably 12СГС bia 15D-C, or

b) in an inert solvent at temperatures from 30 "C to 140" C, preferably from 60 "C to 12O ⁰ C,

to a pyriridine compound of the formula IX

cyclized and

3.2 the compound of the formula IX obtained with a compound of the formula X.

Y-t Z * < ^X)

with elimination of HY in the presence of a proton acceptor in aerobic solvents at temperatures of 30 "C to 140" C ₁ preferably 60 ° C to 120 "C, wherein in the formulas II to X, the substituents Ri to Ru the under formula I have given meanings, A is an acid anion and Y is halogen, or else

4. in a multi-step process: 4.1a) thiourea of formula XI

- ίο -

s = cr (Xu

with a diketone of the Foreel IJI

,, (IIIJ

in the presence of an acid in an inert solvent at temperatures of 20 "C to H (TC, preferably 20 ^u C to 6O ⁰ C, the reaction brings to a Pyrimidinvertoindung the formula

HS-Α) · _ШІ)

cyclized and their alkali metal or alkaline earth metal salt with a compound of formula XIII

ШИ)

where Rs is Ci-Cg-alkyl or unsubstituted or substituted with halogen and / or Ct-Ci.Alkyl Вепгуі and Z means kogen, ζυ a Pyrimidinverbindting the formula XIV

RIS(У (XIV)

implements, or

b) an isothiuronium salt of the formula XV

^ C-SR ₅ ΑΘ (XV)

with a diketone of the formula III, preferably in a protic solvent, at temperatures of 20 ^u C to 140 ⁰ C, preferably at 20 "C to 80" C, brings to reaction and also passes to a Pyrimiditwerbindung the formula XIV and

2 R 2 л β S

-u

4.2 the obtained compound of the formula XTV with an oxidizing agent, e.g. with a Persäuro, г «the Pyrimidlnverbindung of the formula XVI

oxidized and

4.3 the compound of the formula XVI obtained with a formylaniline of the formula XVII

* ^ -NHCHO (XVII)

 / "

in an inert solvent in the presence of a base as proton acceptor at temperatures between -30 "C to 120 ⁰ C z of a compound of formula XVIII

R,> ^Rl

5C (XVIII)

implements and

4.4 the obtained Yerbinduitg the formula XVII of hydrolysis in.Gegenwart a base, for example alkali hydroxide, or an acid, for example hydrogen halide or sulfuric acid, in haters or aqueous solvent mixtures, such as aqueous alcohols or dimethylformamide, at temperatures from WC to 11O "C, preferably 30 ^ü C to 6O ^- C, wherein in the formulas XI to XVIII, the substituents Ri to Ri have the meanings given under formula I, and A represents a Sa'ureanion and Y is halogen.

Compounds deT formula I, in which Rj represents the СНгОН-Gxuppe, can be prepared in special methods by

2 8 2 6 θ S

- 12 -АЛЛ the guanidine salt of Forwel Ha · * ^ -NH-C ^ Α ^Θ (Ha)

i; ^NHA

or the guanidine of the formula lib

 f; -NH-cf (iib)

with a ketone of formula XIX

i, (XIX)

wherein Rt is C ₁ -Ci ₁ -alkyl, in a Aratiechen solvent or without solvents at temperatures of 40 ⁰ C to 160 "C, preferably 60" C to 110 ^u C, to a pyrimidine compound of the formula XX

CH (ORrJ ₂

. 4 "- ·. л-:

implements and

Al.2 the acetal of the formula XX obtained in the presence of an acid, for example hydrohalic acid or sulfuric acid, in water or aqueous solvent mixtures, for example with solvents such as alcohols or dimethylformamide, at temperatures of 20 ⁰ C to 100 ⁰ C, preferably 3O ⁰ C to 60 ⁰ C, to Pyrimidinaldehyd the formula XXI

R, / ^CH0

C \ / ^NH C> ^(XXI)

hydrolyzed and

A1.3, the resulting compound of formula XXI is hydrogenated with elemental hydrogen using a catalyst or reduced with a reducing agent such as sodium borohydride to the corresponding alcohol XXII

CH-OH ίπ ⁴ R,

А2.1 the gu.mtdinsalz of the formula Ha or the guanidine of the formula Hb with a diketone of the formula XXIII

R ₇ OCH ₃ -C-CH ₃ -C -RI ₁ (XXIII)

in which R7 is benzyl substituted or unsubstituted or halogen or Cj-Cd-alkyl, in a protic solvent or solvent without solvent at temperatures of AO "C to 160 ^u C, preferably t>O" C to INTC, to a pyrimidine compound of formula XXIV

Rl / MiOR-,

• j * ^ - KK-(У (XXIV)

fen

Translates and In this through

A2.2 hydrogenation in a solvent, preferably an aprotic solvent, for example dioxane or tetrahydrofuran, with a catalyst such Palladiun-charcoal, preferably Raiwy nickel, b "i temperatures of 2Q ^U C to 90" C, bevorsugt 50 "C to 90 "C, the rest of CHjORy is converted into the radical CH ₂ OH; or

A3.1 the guanidine salt of the formula Ha or the cuanidine of the formula Hb with a diketone of the formula XXV

-C-CHs-C-R ".

(XXV), ReOCH ₂ -

wherein Ra is C ₁ -Co-AllCyI, Cj-Co-alkenyl or roono-substituted or substituted by halogen or Ci-Ci, alkyl benzyl, in a protic solvent or without solvent at temperatures of 40 ^e C to 160 "C, preferably 60 "C to 110" C to a pyrimidine compound XXVI

8 268

CH ₂ OR,

· *; -NH- ζ ; ·

X ^ν

implements and

A3.Я with the obtained compound of formula XXVI an ether cleavage with a Halogenwasserstoffsäui't, preferably hydrobromic acid, or a lewis acid such as aluminum halide (eg AlCl ₁ ) or Bochalogenid B (HnI)] (г.B. BBr, or BCIj) in aprotic solvents, for example hydrocarbons or halogenated hydrocarbons !!, at temperatures from -80 ^v C to 30 "C, preferably -70 * C to 20" C, is carried out.

Compounds of formula I in which Rj represents the CHaHaI group can be prepared by reacting a compound of formula XXII with phosphorus halide or thionyl halide in the presence of tertiary bases, e.g. Pyridine or triethylamine, in inert solvents, at temperatures of 0 ^u C to 110 ^u C., preferably from ^{0 0} C to 80 * C, reacted.

Compounds of Fornel I, in which Rj is the CH'F group, can be prepared * by reacting a compound of formula XXVII

ι; ν

wherein X is chlorine or bromine, with potassium fluoride, preferably lyophilized potassium fluoride, in the presence of catalytic amounts of calcium fluoride or a crown ether, eg lo-crown-6-ether, in aprotic solvents such as acetonitrile, at temperatures of 50 ⁰ C to 160 "C. react in a pressure autoclave.

A further process for the preparation of compounds of the formula I in which R _{3 is} the CHjF group consists in the fluorination of a compound of the formula XXII with N, N-diethylaminosulfur trifluoride (= DAST)

?. 8 2 6 8 p

in aprotic solvents such as dichloromethane, chloroform, tetrahydro · '! ran or dioxane, at temperatures from 0 C "C bi» iOO ^u C, IO preferred "hie S (TC.

Also in the above formulas XVIII to XXVIII have Ri, Ri unri Ii, the for Form ··! I mean meaning.

In the processes described, the following salt residues are suitable for the compounds of the formulas Ha and VIII for the acid anion a ", for example: carbonate, hydrogen carbonate, nitrate, halide, sulfide, and hydrogen sulfide.

In the process described above, in the case of the compound of the formula XV for the acid anion A ~, the following salts are used, for example: halide, sulfates or hydrogensulfate.

By halide are in each case fluorine, ChlüTid, bromide or iodide, preferably Broraid or Chlovid, au understand.

As acids mainly inorganic acids, e.g. Halogenated acids, for example fluoric acid, hydrochloric acid or hydrobromic acid, and sulfuric acid, phosphoric acid or nitric acid, but suitable organic acids such as acetic acid, toluene sulphonic acid and the like can be used.

As proton acceptors serve e.g. inorganic or organic bases, such as alkali metal or alkaline earth compounds, e.g. the hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium, and also hydrides, e.g. Sodium hydride. As organic Baaen selen beispielsveioe tertiary amines such as triethylamine, triethylenediamine, called pyridine.

Ir _{1 to} the methods described above, in adaptation to the respective reaction conditions, for example, the following solvents in addition to the 2.T. be used mentioned.

г 8 г б 8 ь

-Ib-

Halogenated hydrocarbons, in particular, chlorohydrocarbons, such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylnchloride, dichlorobutane, chloroform, chloronaphthalene, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorocarbon, 1,2-dichloroethane, 1,1-dichlorocethanol, cia-dichloroethylene, chlorhenzene, fluorobenzene, lignin, dichlorobenzene, dibromobenzene, chlorotoluene, trichlorotoluene; Ethers, such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-butyl ether, di-isocyanate, diisoamyl tetur, tert-butyl ether, anisole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether , Tetrahydrofuran, dioxane, thioanisole, dichloro diethyl ether; Nitrohydrocarbons, such as nittromethane, nitroethane, nitrobenzene, chloronitrobenzene, 1-nitrotoluene; Nitriles such as acetonitrile, butyronihril, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, such as heptane, hexane, octane, nonane, cymene, benzene fractions within a boiling point of 70 ° C to 19O ⁰ C, cyclohexane, methylcyclohexane, decalin, petroleum ether, ligroin, trimethylpentane, such as 2,3,3- Trimethylpentane; esters, such as ethyl acetate, acetoacetic ester, isobutyl acetate, amides, eg formamide, methylformamide, dimethylformamide, ketones, such as acetone, methyl ethyl ketone; alcohols, in particular lower aliphatic alcohols, such as, for example, methanol, ethanol, n-propanol, isopropanol and the isomers the butanols; gb _w just fall and water mixtures of gp;. ia; inten solvents and diluents are also suitable.

Analogous methods of synthesis to the production methods described above are published in the literature.

As references are mentioned: Method 1 : A.Kreutzbergcr and J.Gillessen, J. Heterocyclic Chem. 22,

101 U985).

Method 2, step 2.1: 0. Stark, Ber.Dtsch.Chein.G48.42, 699 (1909); J. Haie, J. Am. Chem. Soc. 36, 104 (1914); G. N. Kosolapoff, J.Org.Chem.26,

1895 U561). Study 2.2: St. Angerstein, Her.Dtsch.Chem.Ges.34,

3956 (1901); G.M. Kosolapoff, T.Org.Chcm.26, 1895 (1961). Stage 2.3:

28

MPV Bcarland and OFW МсОтіѳ, O.Chem.Soc. 1951 «1218; T. Mateukewa and K. Shirakuwa, O. Pharm. Soc.Oapan 71, 933 (1951); Chen.Abstr. 46, 4549 (1952).

Method 3 ; A. Combes and C. Combes, Bull.Soc.Chem, (3), 7, 791 (1892); WO Hale and FC Vibrans, O.Ani.Chem.Soc. 40, 1046 (1918).

The described production processes including all partial steps are part of the present invention.

The following compounds which are used as intermediates in the preparation of the compounds of formula 1 are new:

1) compounds of the formula

N-

in which mean:

R _{0 is} halogen or R ₅ SO ₃ -! R _{3 is} hydrogen, C ₁ -C ₄ -alkyl; or substituted by halogen, hydroxy or cyano, C ₁ -C ₄ alkyl; Cyclopropyl or cyclopropyl substituted by methyl and / or halogen up to three times or differently substituted cyclopropyl;

R _{4 is} C ₁ -C ₆ -cycloalkyl or C ₃ -C ₆ -cycloalkyl which is up to three times identical or differently substituted by methyl and / or halogen; and

R _{5 is} C 1 -C 8 -alkyl or unsubstituted or substituted by halogen and / or С-Сд-Лікуі benzyl. As halogen

28 268 p

- 17a -

substituents R, chlorine and bromine are preferred,

Я) Compounds of the F ліеі XXI

CHO

Ж4 -NH- »f\ (XXI)

in which mean:

- 18 -

Rj and Rs independently of one another are hydrogen, halogen, Cj-Cj-alkyl, Ci-Cj-HaLogenalkvl, Ci-Cj-alkoxy or Ci-C ₃ haloalkoxy; Ri, Ci-Cfi-cycloalkyl or by methyl and / or halogen up to three times identically or differently substituted Cj-Ce-cycloalkyl.

Überschnchnnderweise has now been found that compounds of formula I for practical needs very favorable biocidal spectrum for controlling insects and phytopathogenic microorganisms, in particular fungi, have. They have very beneficial curative, preventive and in particular systemic properties and are used for the protection of numerous crops. With active compounds of the formula I, the occurring pests can be contained or destroyed on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of different useful crops, whereby later-growing plant parts e.g. spared from phytopathogenic microorganisms.

Compounds of formula 1 are e.g. effective against the phytopathogenic fungi belonging to the following classes! Fungi iraperfecti (especially BotrytiH, also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basiomycetes (e.g., Rhizoctonia, Hemileia, Puccinia). In addition, they act against the class of Ascomycetes (e.g., Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes Iz.B. Phytophthora, Pythium, Plasmopara). Me compounds of formula I can also be used as mordants for the treatment of Seatgut (fruits, tubers, grains) and plant cuttings to protect against fungal infections and occurring in ErdW-r phytopatViogene fungi. In addition, compounds of the formula I are active against noxious insects, e.g. against cereal pests, in particular rice pests.

The invention also relates to the compositions containing as active ingredient component compounds of formula I, in particular plant protection agents, as well as their use in the agricultural sector or related fields.

In addition, the present invention also envisages the preparation of these agents, which is characterized by the intimate mixing of the active substance with one or more substances or substance groups described herein. Also included is a method of treatment of plants which is characterized by application of the novel compounds of formula I or of the new agents.

As target crops for the plant protection use disclosed herein, for example, the following plant species apply in the context of this invention: cereals (wheat, barley, rye, oats, Rei corn, sorghum and related species); Beets (sugar and fodder beets); Pome, stone and berry fruits (apples, pears, plums, oak, almonds, cherries, peanuts, kim and blackberries); Legumes (beans, lentils, peas, soybeans); Oelku doors (rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); Cucumbers (squash, cucumbers, melons); Fiber plants (cotton, flax, hemp, jute); Citrus fruits (oranges, lemons, grapefruit, mandarins); Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel family (avocado, cinnamonium, 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 the formula 1 are usually used in the form of compositions and can be added simultaneously or successively with other active ingredients to the surface or plant to be treated. These further active ingredients may be fertilizers, trace element mediators or other preparations which influence plant growth. Selective herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations may also be used together with optionally further carriers customary in formulation technology, surfactants or other application-promoting additives.

Suitable carriers and additives may be solid or liquid, and are useful in the art of formulation, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

2β 268

- 20 -

A preferred method for applying an active ingredient Formal I or an agrochemical composition containing at least one of these active ingredients iat the application to the foliage. (Foliar application). The application sequence and application rate depend on the pressure of the affected pathogen. The active ingredients dec formula I can also enter the plant through the root system via the earth bath. Isyatemische effect) by impregnating the location of the plant with a liquid preparation or introducing the substances in solid form into the soil, e.g. in the form of granules (soil application). In water rice crops, ma granules of this type can be added to the flooded rice field. The compounds of the formula I can also be applied to seed grains (coating) by either soaking the grains in a liquid preparation of the active ingredient or coating them with a solid preparation.

The compounds of the formula I are used here in unchanged form or preferably together with the auxiliaries customary in formulation technology. For this purpose, they are expediently processed, for example, into emulsion concentrates, spreadable pastes, directly sprayable or verdi'innbaren solutions, dilute emulsions, wettable powders, soluble powders, dusts dusting, granules by encapsulation in eg polymeric substances in a known manner. The application methods such as spraying, nebulizing, dusting, scattering, brushing or its are the same uie the type of gown chosen according to the objectives and the given circumstances. Favorable expenditure margins are generally from 50 g to 5 kg of active substance (ai) per ha, preferably from 100 g to 2 kg ai / ha, in particular from 200 g to 600 g ai / ha.

The formulations i. the compositions, preparations or compositions containing the active substance of the formula I and, where appropriate, a solid or liquid additive are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with diluents, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

28 268 p

- 21 -

Suitable solvents are: Aromatic hydrocarbons, preferably the fractions Co to Cj2, e.g. XyIolgemisehe or substituted naphthalenes, phthalic acid esters such as dibutyl or Dioctylphthalat, aliphatic hydrocarbons such as Cyclohexaii or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monoBiethyl- or F.thylether, ketones such as cyclohexanone, strongly polar solvents, such as N Methyl 2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, z. for dusts and diapergable powders, wetden are used in the shelf natural minerals, such as calcite, talc, kaolin, montmorilotiit or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or finely divided, ductile polymers. As granular, adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite, as non-sorptive carrier materials, e.g. Calcite or sand in question. In addition, a variety of unnatural materials of inorganic nature, in particular dolomite or crushed plant residues can be used.

Special advantageous application-promoting additives, which can lead to a large reduction in the application rate, are also natural (animal or vegetable) or synthetic phospholipids from the series of cephalins and Lee1 thine, which are obtained, for example, from soybean кяпп.

Depending on the nature of the active ingredient of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also Tenaidgemische to understand.

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

- 22 -

Ale Seifon is the Alknll, Erdalkali- or BegebenenfaIls "ubetituierten ammonium salts of higher fatty acids CCje-Cn)» as г.B. the Na or K salts of OqI or stearic acid, or of natural fatty acids, e.g. B. can be obtained from coconut or tall oil. Further, the fatty acid methyllaurine salts Eu are also mentioned.

More often Bog. synthetic surfactants, in particular alkyl sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkyl sulfonates.

The fatty alcohol sulfonates or sulfates are typically present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the Na or Ca salt of lignosulfonic acid, of dodecylsulfur acidurea or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This subheading includes the salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. The sulfonated benziridoazole derivatives preferably contain 2-sulfanyl groups and a fatty acid residue having 8-22 C atoms. Alkylarylsulfonates are e.g. the sodium, calcium triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates, e.g. Salts of Vhosphor-bonsäureesters a p-nonylphenol (A-14j-F.thylenoxyd adduct in question.

Suitable nonionic surfactants are primarily 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 8 to 20 carbon atoms in the (aliphatic) carbonyl radical and from 6 to 18 carbon atoms in the alkyl radical of the alkylphenols ,

Further suitable nonionic surfactants are water-soluble polyethylene glycol adducts containing 20 to 250 ethylene glycol ether groups and polyethylene oxide adducts containing from 10 to 100 ethylene glycol ether groups, on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol nitroglycerin.

28 208

- 23 -

etoffatoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol units.

Examples of nonionic surfactants which may be mentioned are nonylphenolpolyetlioxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide end-products, tribiitylpheiioxppolyethyleneethanol, polyethylene glycol and octylphenoxypolyetlioxyethanol.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan triL'eate.

In the cationic surfactants ei ea is mainly to quaternary ammonium salts containing as N-substituent at least one alkyl radical having 8 to 22 carbon atoms and as further substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfate, e.g. the stearyltrimethylammonium chloride or the benzyldU2-chloroethyl) ammonium bromide.

Other surfactants commonly used in formulation technology are known to the person skilled in the art or can be taken from the relevant specialist literature.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95 X, active ingredient of the formula I, 99.9 to 1 %, in particular 99.9 to S %, of a solid or liquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.

While almond products tend to be more concentrated, the end user typically uses diluted funds.

The compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

2 8,268

- 24 -

AusfOhrungsbeispiele

The following examples are for closer. Explanation of the invention without limiting the same.

1. Manufacturing overview

Example 1.1 Preparation of 2-phenylamino-4-methyl-6-cyclopropylpyriroidine

NH-

.ГУ

.CH ₃

(Verb no. 1.1)

IO g (51 mmol) of phenylguanidi.n-hydrogencarbo:> at and 9.7 g (77 mmol) of 1-cyclopropyl-lfS-butanedione are heated with stirring to 110 ⁰ U for 6 hours »with the onset of coal • ijxicientwicklung with progressive reaction time decreases. After cooling to room temperature, the dark brown emulsion is mixed with SO ml of diethyl ether «washed twice with 20 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The residual dark brown Dl (13A g) is purified by column chromatography over silica gel (diethyl ether / toluene 5/3). After evaporation of the eluent mixture, the brown Dl is brought to crystallization and recrystallized from diethyl ether / petroleum ether at 30 - 50 ⁰ C. There are obtained half brown crystals. Melting point: 67-69 ⁰ C; Yield: 8.55 g (38 mmol) (= 74.5 % of theory ).

28268

- 24a -

Example 1.2: Harvesting of 2-anilino-4-forroyldjLethyl « acftal-6-cyclopropyl »pvrimidin

CH (OC ₂ Hg) ₂ Jf ^ i - NH

11.7 g (59.2 mmol) of phenylguanidine-bicarbonate and ІЗіЗ g (62.2 mmol) of 1-cyclopropyl-S-forrayldiathylac-val-1-propanol in 40 ml of ethanol are refluxed with stirring for 5 hours! the carbon dioxide evolution decreases as the duration of the biscuitation progresses. To

the Ahkiihlen to room temperature, the dark brown emulsion with 80 ml of U is: ^ thylethec added, washed twice with} .e 'iO ml of water, dried, filtered over sodium sulfate and the solvent evaporated. IJsa remaining dark brown OeI U 7 g) is s'aulenchronuitograpMsch on kieselgcl (toluene / ethyl acetate: 5/2). After the Ahdampfon of Laufmittoigemisches remains a red-brown OeI with dom refractive index η '* ί], 58ΐ3. Yield: 15 g <* 8 mmol; 81.1 % of theory).

Example 1. І Production of З-АпШпо- гаѵі-б-сѵсіоргор у і-ругі-mlain

^ ^ - (verb Mr. 2.1)

  - ·

I /

12,3 g (39,3 mmol) of г-АпШпа-й-ги -.- туЫіеіпуіасеіаі-б-сусіоргоруі-ругітпі-din, 4 g (39,4 mmol) conc. Hydrochloric acid and 75 ml of water werc.en heated with intensive stirring for 14 hours at 50 ° C -j'.id after addition of 2 g (19.6 mmol) of lance. Hydrochloric acid stirred for a further 24 hours at this temperature .. After cooling to room temperature fourden to the beige-colored suspension added 50 ml of ethyl acetate and neutral with 7 ml 3Ω% sodium hydroxide solution ordered. The ethyl acetate solution is then separated, dried over sodium sulfate, filtered and the solvent evaporated. For purification, the brownish-colored solid is recrystallized in the presence of activated carbon from 20 ml of isopropanol. The yellowish crystals melt at 112 - 114 ⁴ C. Yield 7.9 g (33 mmol: 84 % of theory).

Example UAt nuclear division of 2-Апі11ио - 4-пѵДтохѵтеЬпѵ1-6 ~ сѵс1орсору1-pvrimidin

'vy "~ ^Щ - ч у' tVetb. St. 1.48)

ix *

- 26 -

а) Ум 14.1 g (59 шМоі) 2-anilino-4-fori "YB6-cyelopiOpyl-pyrlinidin in 350 of absolute methanol in 15 minutes with stirring hei room temperature 2.3 g (60 mmol) of sodium borohydride are added in portions, wherein The reaction mixture is warmed to 28 ° C. with evolution of the product, and after 4 hours it is acidified by adding dropwise 10 ml of concentrated hydrochloric acid, 120 ml of sodium bicarbonate solution are added dropwise, and then diluted with 250 ml of water.The separated precipitate is filtered off , dried, largely dissolved in 600 ml of diethyl ether in normal heat, treated with charcoal and filtered, and the clear filtrate is concentrated to the point of turbidity, diluted with petroleum ether, and the pale yellow crystalline powder is filtered off, mp 123-125 ° C. Yield : 10.8 g (hb, 8 mmol, 75.9% of theory).

b> 5.9 g (23 »mol) of 2-anilino-4-methoxyniethyl-6-hydroxypropyl-1-pyridine, prepared from phenylguanidine and 1-cyclopropyl-3-methoxy-1,3-butanedione are dissolved in 2» l of ml Dichloromethane was dissolved and cooled to -68 ° C. To the salmon-colored solution 6.8 g (27 mmol) of boron tribrony were slowly added dropwise within half an hour, then the cold bath removed and stirred for 2 hours at room temperature The precipitated crude product is filtered off from ISO g ice water and re-crystallized from methanol using activated charcoal, the pale yellow crystals melting at 124 ° -6 ° C. Yield: 4.7 g (19.5 mol, 84.7 % of theory).

Example. 1 × 5: Preparation of 2-phenylamino-4-hydroxypropyl-6-lyclopropylpvimidine

• ^ ^ -NH-(_ S (Verb no. 1.4)

To 12 g (5t) mmol) of 2-phenylavine3-4-hydroxymethyl-6-cyclopropylpyri.iidi.n and 0.4 % (50 mmol) of pyridine in 350 ml of diethyl ether within 15 minutes, 15.6 g (75 mmol) of thionylbroroid in 50 ml of diethyl ether added dropwise with stirring. After stirring for 2 h at room temperature, another 0.4 g (50 μl) of pyridine are added and refluxed for 5 hours. After cooling to room temperature, 200 ml of water

- 27 -

is added and by dropwise addition of H 2 ml of saturated Natriumhydroßencarbonat-Lbaiing the pH value 7 is adjusted. After separation, the Üiethylethorphase is washed twice with 100 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The remaining brown OeI is purified by column chromatography on silica gel (toluene / chloroform / diethyl ether / petroleum ether (bp 50-70 ^u C): 5/3/1/1). After evaporation of the Uufmittelgemisches the yellow OeI is diluted with diethyl ether / petroleum ether (bp 50 - 70 ⁰ CJ and in the cold for crystallization g.-brings.) That yellow crystal powder melts between 77 »5 - 79.5 ° C. Yield: 9.7 g (32 mmol, 64 % of theory).

Example l.b Preparation of 2-phenyl-amino-u-fluoro-ethyl-6-cylcl-propyl-p-tri-widin

/ H ₂ F · '- NH-' · · (Compound No. 1.59)

I /

a) 3.9 g (12.8 mmol) of Z-phenylamino-u-bromomethyl-o-cyclopropyl-pyrimidine, 1.5 g (26 mmol) of spray-dried potassium fluoride and 0.3 g (1.33 mmol) of 18-Crown ~ (i-ether is refluxed in 50 ml of acetonitrile for 40 hours, and 0.75 g (13 mmol) of potassium fluoride is then added and heated for 22 hours to complete the reaction, a further 0.75 g (13 mmol) of spray-dried potassium fluoride and 0.1 g (0.38 mmol) of 18-Crnwn-6 ~ added ether and heated under reflux for a further 24 hours · After cooling to room temperature, the suspension with 150 ml of diethyl ether, washed three times with 20 ml of hater, over Dried sodium sulfate, filtered and the solvent evaporated The remaining brown OeI is purified by column chromatography on silica gel (toluene / chloroform / diethyl ether / petroleum ether (bp 50-70 "C): 5/3/1/1).) After evaporation of the eluent the yellow OeI is diluted with 10 ml Potrolether (bp 50 - 7O ¹⁹ C) and crystallized in the cold. The yellow crystals melt at 48-52 ^D C; Yield: 2.1 g (8.6 mmol); 67.5% of theory

- 28 -

b) 6.1 g (37.8 mmol) of diethylaminosulfur trifluorole are added to a suspension of 9.1 (37.8 mmol) of 2-phenylaroino-A-hydroxymethyl-6-cyclopropylpyrimidine in 80 ml of dichloromethane with stirring over 1 hour slowly added dropwise in 15 ml of dichloromethane. After the addition of 50 ml of ice-water, 50 ml of 10% aqueous sodium bicarbonate are dissolved in vac. dripped. After completion of the CoMendioxydnnicklung the organic phase is separated and the aqueous phase extracted twice with 20 ml of dichloromethane. The combined dichloromethane solutions are washed with 15 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The residual black oil is purified by column chromatography on silica gel (toluene / chloroform / diethyl ether / petrolethar (bp 50-70 °), 5/3/1/1). After evaporation of the LaufiMttelgemisches the yellow oil with 20 ml of petroleum ether is added - diluted and te in the Ka "is brought to crystallization The yellowish crystals melting at between 50 - 52 * C Yield (b.p. 50 70 ⁰ C.). 4.9 g. (20.1 μmol; 5: % of theory).

Beis p iel 1.7: Preparation of 2-Hydroxy-u ~ Methyl-6 "CvcIoptqnvI p vr: imidtn HO · ^ * ·

6 g (100 mmol) of urea and 12.6 g (100 mmol) of 1-cyclopropyl-1,3-tandione are concentrated at room temperature in 35 ml of ethanol with 15 ml of conc. Hydrochloric acid added. After standing at room temperature for 10 days, the mixture is concentrated on a rotary evaporator at a maximum bath temperature of 45 ° C. The residue is dissolved in 20 ml of ethanol, after which the hydrochloride of the reaction product separates after a short time. 20 ml of diethyl ether are added with stirring, and the precipitated white crystals are filtered off and washed with an ethanol-diethyl ether mixture and dried. Concentration of the filtrate and recrystallization from an ethanol / diethyl chloride mixture: 1/2 give a further portion of hydrochloride , The white crystals melt> 230 * C. Yield: Hydrochloride 12.6 g (67.5 mmol, 67.5% of theory).

2 8 2 6 8 p

Example 1.81 Manufacture of Z

(Verb no. 3.1)

52.8 g (0.24 mol) of 2-hydroxy-4-ethyl-6-cyclopropylpyrimidine hydrochloride are added, while stirring at room temperature, to a mixture of 100 ml of 11.1 mol) of phosphorus oxychloride and g (0.79 mol) of diethylaniline, the temperature rising to 63 ° C. After heating for 2 hours on U (T), the mixture is cooled to room temperature and the reaction mixture is poured out onto an ice-water / methylene mixture while stirring The organic phase is separated off and washed with sat After evaporation of the solvent 116, A g CeI are obtained, which is composed of the reaction product and Diothyianilin, The separation of Disthylanilins and the purification of the crude reaction product is carried out by column chromatography over silica gel (hexane / ethyl acetate: 3 The colorless oil which crystallizes after a few days has a refractive index η '': 1.5419, yield: 35.7 g, 10.21 mol, 87.5 % of theory, melting point: 33-34 ° C.

Example 1.9 Preparation of 2- (m-fluorophanvlamino) -4-methyl-6-cyclopropyl -pyrimidine

• f ; -NH- ζ γ (verb »1.63)

A solution of 5.5 g (50 mmol) of 3-fluoroaniline and 9.3 g (55 mmol) of 2-chloro-4-ethyl-6-cyclopropylpyridine in 100 ml of ethanol is added with stirring to 5 ml conc. Saizsauιс brought to pH 1 and connect: 'heated under reflux for 18 hours. After cooling to room temperature, the brown emulsion is made alkaline with 10 ml of 30% ammonia, poured onto 100 ml Eiswaseer and extracted twice with 150 ml of diethyl ether. The combined extracts are washed with 50 ml of water, dried over sodium sulfate, filtered and the solvent evaporated.

8 26 8 5

- зо -

The remaining yellowish crystals are purified by dissolution of diisopropyl ether / petroleum ether (bp 50-7QT.). Pie wise crystals melt at 87 - 89 ° C; Yield 8.3 g (34 mmol, 68 % of theory).

The following compounds of the formula I can be prepared in this way or according to one of the methods given above.

- 31 -

Table 1: Compounds of the formula

_{1 year} ...

Verb 1fr. Rt H rj rn ► I Physical constant 1.1 H H CHj I i M.p. 67-69'C 1.2 2-Cl H CH ₃ \ I i 1.3 H H H \ I i Mp. 53-56 "C 1.4 H H -CHsBr \ Snip. 77.5 to 79.5 ° C 1.5 3-ca H CH 3 ~ \ Sap. 1O4-1Ü5 * C 1.6 H H -CjHs ^ / "\ September 42-45 "C 1.7 4-Cl H -CH ₃ \ Mp. 86-87 "C 1.8 H H -CH ₂ Sr 1.9 H -CH ^ Cl • \ Mp. 50-52 ° C

Оч Cb

- 32 -

Continuation: Table 1 H R * -CH ₃ R .. -У "I / И, Physical constant Verb.Nr. Ri H -CFj - <! Swp. S3-56 "C 1.10 4-CH ₃ H -Сзн7-П / H ₃ - <і / Нз - <і «- · _У \ 1.11 H H -CH ₂ OH ~ \ Mp. 44-46 "C 1.12 H H -CH ₃ Snip. lll'I13 "C 1ЛЗ H Ц. CHj / \ - · Mp. 73-74 * С 1.14 H H -CH ₂ CH ₃ OH ш Swp. 48-5Ü ° C 1.15 4-ОСНз H -CH ₂ Br 4 _У \ 1.16 H H -Сі, Н? -П 1.17 H H -CH ₂ OH dark brown OeI τι £: 1.5992 1.18 H 1.19 H

Ni Оч OO

Cl

e О X ^и ч Ч / X I i / * Ч M / ч к о X S У X CJ О ϊ! U ^ C о ч / I i M Ч / σ о .э ч / к и -η I ч / ^: но- ж I I -CH; ІП UO а  <ч С I ¹ I О " ¹ · "Я X I X X I te " и г " · «Ui X X __! ^ ¹ 33 σ \ • rt C " - » I -CH; о Со О R CF; ? , ^C α с. (Л X Ч / ά й О VO to * _# / ч _§ гч X CM - * I (N І І χ P • I ul Ч / Ч / * Ч ~? * f-I и •• ч * с < I I CS О OA О ·! X f Oi ' г-1 ^: но- S X X M ce ν * η X I · іЛ "  G H 1-1 г " 00 G μ et CM л г * "- · "I "1 > for

- 3ft -

Continuation: Table 1

Verb.Nr. R ₁ H R ₂ π, / \ > 'Physical' Constant » 1Л0 H H H -CvH ₉ tert. 1.31 H H H -CH; Sap. 50-52 "C 1:32 H 4-OCHFz H -CF ₃ 1:33 H H -CKi [I STNP. 89-91 "C 1:34 H H H I ϊ.35 H -CHjCl · - · \ -S Mp. 55-57 "C 1:36 H -CFs / \ 1:37 H -CHJ OeI n ^: 1.5763 1:38 H -C ₃ H ₅ • / \ _ «« 1:39 H -CHCl ₃ I / "-Jp. 56-58 "C t /

oo го о.

- 35 -

Continuation: Table 1

Verb.Nr. 3-Cl H Rs S-Cl H Ri -CH ₃ Ri ₁ у I t I Physical constant 1:40 H 3-OCiHs K 4-OC ₂ H ₅ -CHCl ₂ 1:41 H H H H -CH ₃ 1:42 4-CXJF ₃ H -CH ₂ OH ! · - · - <I Mp. 6L-65 "С 1:43 H H -chi • W - < 1:44 H H -CF ₃ / \ - < OeI ng: 1.5498 1:45 3-CPj 4-Cl -СНд \ Mp. 66-69 "C 1:46 -CH ₂ OH - ( ' 1:47 -CH ₂ CH 1:48 -CH ₃ Mp. 123-125'C 1:49 Mp 128-130 ⁰ C

- 36 -

Continuation: Table 1

Verb.Nr. Яг H H H H Rii A < I / CHj Physical constant 1:50 H H H H - < "! "\ 1:51 H H -CH ₂ CH ₂ OH Jy \ i I ' 1:52 H 4-Cl -CH ₅ -mm 4 I 1:53 3-Cl H CH, / Mp. 85-87 "C 1:54 H -CH ₃ \ S "p. 73-74-C 1:55 2-F -CH ₃ 1:56 H H 1:57 H

as ro

Ov OD

Continuation: Table 1 Ra H Лл -CH ₁ R ₁ , ί> \ I - <i / Physical constant Verb.Nr. Ri H -CH ₃ F I i - / ~ "\ Mp. 58-61'С 1:58 H * -CHJ CH, _y I ' L · m Mp. 48--52 "C 1:59 H H H 3 1.60 3-ci H -CK з P > 1.61 H H -CH ₁ 1.62 H H -CHJ / CH., ⁴ CH ₃ Mp. 87-89 "C 1.63 3-F 3-Cl -CH ₃ 1.64 H H -CH ₃ 1.6S 2-СНз H -CH; F Srap. 81-84 "С 1.66 H S "p. 63-65 ^u C 1.67 H

ГО / л CD

Continuation: Table 1

- 38 -

Verb.Nr. Ri R * rj -CH ₃ K. \ I i I i I Physical constant 1 Mp. 43-45 ⁴¹ C 1.68 2-Cl 5-CH ₃ -CHJ / I · - «X I · - · 1.69 H H -CHJ • / -, m \ 9 ^ шЛ I Sl September 67-69 "C 1.70 2-Br H -CH ₃ / \ 1.71 2-CH ₃ 4-Cl -CH ₃ -K 1.72 H H -CH ₃ - • m \ Mp. 64-66 "C 1.73 2-Cl 6-CH ₃ -CH-F 1.74 H H -CH ₃ F 1.75 H H -CHJ 1.76 3-Br H 1.77 H H •

- 39 -

Continuation: Table 1

Verb.Nr. H H -CH э Rk Cl щ, \ > / CH ₃ Physical constant 1.78 2-Cl 4-СНз -CH з _A • • I Mp. 51-53 "C 1.79 H H - <! • А W 1.80 H К -CH ₁ F -P OeX njij ": 1.6101 1.81 3-Cl 4-ϊ 1 • 1.82 H H -C ₃ H? -! 1.83 H H -CH ₃ 1.84 H H -CjH ₇ -I Snip. 81-84 ^M C 1.85

- 40 -

Continuation: Table 1

Verb.Nr. Ri Ks H -chi Ku \ I Physicnische Konstantρ 1.86 4-J H -CHjF _ / ~ \ I 1.87 H H -Ct ₁ Hi-II _ / ~ \ I i Mp. 63-65-C USS H H -CH ₃ i> \ P I 1.89 2-CH ₃ H -CaJb-i / I F 1.90 H H -CH ₃ - < OeI n £: 1.6074 1.91 H 5-Cl -CH ₃ - < Mp. 65-68 "C 1.92 2-CH ₃ H -CHJ - < \ / 1.93 H H -CHiF - < 1.94 H Mp. 48-5ü "C

JO OO

Continuation : Table .1

Verb.Nr. Ri rn Ri -chi Ri. t к - < ^ Br ⁴ Br ι / H ₃ Physical constant 1.95 2-OCHj S-Cl CH, _ / к ι ' 1.96 3-C 4-OCH -CH ₃ CHiOH / S Уфе, ; 1.97 H H -CH ₃ 1.98 H H -CH ч \ < 1.99 2-Br 4-Br -CH-F 1100 H H -CH ₃ < Mp. 38-41 ^M C 1101 3-CH ₃ H -Ci) H ₉ -H 1102 H H

- 42 -

Continuation: Table 1

Verb.Nr. 3-CHj R: R? -CH ₃ R ". I Physical constant 1103 H 4-Br -CjHt-п / ~ \ ⁴ Cl 1 1304 H H -CK ₃ H ^ 4 / Br ⁴ CH ₃ 1105 H H -CH ₂ CH ₂ OH / -4 / CH я 1106 2-C ₂ H ₅ H -CH ₃ Ы07 H H -CH ₂ F - < / CHj Ы08 H H H у Mp 55-57-C 1109 H H -С1Н7-П P \ / CHj - <! in O H

- 43 -

Continuation: Table І

Verb.Nr- Rt Ri H Ri -CHJ R " I ⁴ CH ₃ I I i Physical constancy 1111 3-C-Hs H -CH2F / \ - <n I 1 1ЛІ2 H H -chi / N 1113 H 5-Br -CH э / 4 Mp. 83-85 "C 1114 2-Br 4-Br -CH ₅ A 1115 2-CHi H -СцНч-sec. 1 I / - <! 1116 H 5-F -CHJ   * I I 1117 2-CHj H -CHJ 1118 4-C ₂ Hi H H 1119 H

- ftft -

Continuation: Table 1

Verb.Nr, H H Ri -CH ₃ Ri \1 Physical constant 1120 2-Вг 4-CHi -CH ₃ / H ₃ -φ », / ^Вг Mp. 5I-54 "C 1121 H H -CH ₂ F - < - <! 1122 К H -CF ₃ "• Чу I 1123 H H -CF ₃ - < 1124 2-C ₃ H ₇ -I H -CH ₃ * / \ 1125 H H -CH ₂ F \ 1126 H H -CH ₃ STNP. 44-47 "C 1127

© * · OO

Continuation: Table 1

Verb.Nr. Ri H Rs H - < Ri ₁ [I Physical «» Constant 1128 2-Cl 4-Br K, _{C /} . \ > Mp. 54-56 "C 1129 H H CH? - < I i 1130 H H -СцНч-sec 4 / H ₃ I ' 1131 4-C ₃ H ₇ -I H -C ₃ Hj / \ 1 I Mp. 57-59 "C 1132 2-OCH3 5-CHj -CH ₃ - < I 1 1133 H H -chi - < 1134 H H -CH ₃ 1135 3-CFj 5-CF3 -CHjCl K 1136 -CH ₃ A / \ 1

- 46 -

Posting: Table 1

Verb.Nr. Ri H Ru H Ri -CF ₃ R., Physical constant 1137 H H ь i 1138 2-CFj H -CH ₅ -. ' 4 * I 1139 H H И / \ Mp. 56-58 ^v C 1140 H H -CH ₃ ^ CHj I 1141 H H -CH ₂ Ci 1142 2-Cl 3-Cl -CH ₃ 1143 H H -C Hn-tert. - < 1.П4 K

- 47 -

Continuation; Table 1

Verb.Nr. H Ri H Ri -C ₃ Hs Ri, Physical constant 1145 2-CFj 4-Cl -CHJ - <i Mp. 55-6O "C 1146 2-Cl 4-Cl CH, 1Л47 H H -chi - <! 1148 H H -CH-Cl / Hj-u 1149 3-CFj H CH, 1150 K K -C, H9 tert. - <i Mp. 81 ~ 83 "C 1151 4-CF ₃ H -CH ₃ ~ чі 1152 2-Cl 5-CFj -CHJ - <! Mp. 60-62 "C 1153 - <!

OO fO Os. OO

Continuation: Table 1

Verb.Nr. Ri H Rs H Ri R '. ./ t / \ I i Physical (Constant * 1154 H H -CHiCJ / _ _p / I> SMP 63-66 ^w C 1155 2-Cl 5-Cl -CH ₃ -K • Mp. 99-109 ^M C 1156 H -CHJ 1157 H H -CH ₃ 1158 2-Cl 6-Cl -C; H ₅ M.p. 58-61 ^M C 1159 H H -chi 1160 H H Hi -C 1161 -CH ₃

to CO

RESTRICTION: Table 1

Verb.Nr. Ri H March H R ₃ R-. I _{/ R} r ⁴ CH, Physical constant 1162 2-OCH ₃ H -CH ₂ Cl / - · \ f t Mp. 55-57 "C 1163 H H -CH) / - · \ t 1164 H H -CHOCH ₃ CH ₂ Cl / - · 1165 2-F 3-F H -C 1166 H H -CH ₁ - · 1167 H H -C ₂ H ₅ ь \ 1168 H H -chi Нз _{С /} \ 1169 -CHiCl • _ / \ *

OO N3 CN CO

Continuation: Table 1

Verb.Nr. 3-OCH ₃ H rj -CH ₃ R-. t i Physical constant 1170 H H -CH ₂ Cl / - · / ^{C1 4} Cl I Mp. 47-50 "C 1171 2-CH ₃ 4-OCH ₃ -CH ₃ \ I i 1172 2-F 4-F -CH ₃ / - »\ I ' 1173 H H -CH ₂ CH ₂ CH ₂ Cl / - · \ / H ₃ 1174 H H -CH ₃ / - · / H ₃ ⁴ CH ₃ 1175 H H -CH ₂ Cl н _{зС /} \ / H ₃ 1176 2-OCHF ₂ H -CH ₃ J / • 1177 я / \

CXJ Ю CN CO

- 51 -

Continuation: Table 1

Verb.Nr. R. H March H R ₃ Ri ₁ / ^{cl 4} Cl • / ^{CI 4} Cl Physical constant 1178 H H -CH ₂ OH \ ⁴ Cl I / H ₃ ⁴ CH ₃ 1179 2-F 5-F H H ₁ C ₇ \ I i /: Нз 1180 H H -CH ₃ / \ OPI 1181 H H -CHiOH _ / / H ₃ 1182 H H -CH ₃ P \ i 1183 4-OCF ₂ CHF ₂ ff H -CHCJ ₂ * 1184 H H -CH ₁ I / - · \ 1185 -CH ₂ Cl •

CK OO

- 52 -

Continuation: Table 1

Verb.Nr. H H R2 H R3 H / H ₃ r I / H ₃ -CH ₃ rn I i Physical constant 1186 H 4-0CF ₂ CHClF H / \ I - · · \ / • ) 1 1187 H H H \ -CH ₃ T / \ / ^{cl 4} Cl I Oei 1188 2-F H -CH ₃ ь • 1189 H H -CH ₂ Cl P \ • - · · • 1190 4-ОС ₃ Н? -P H -chi / - · / - · \ 1191 6-F • / - · \ • \ I 1192 H «/ - · \ я 1193 H 1194

ro α- < co cn

- 53 -

Continuation: Table 1

Verb.Nr. Ri H R ₂ H H R ₃ \ t t ι Ru I i ⁴ cl > Physikalische Konfitante 1195 H H H -chi -CHJ \ 1196 H H 4-F .!> Y / \ s> \ 1197 4-OCF ₂ CHCl ₂ H / \ 1198 H H -chi _ / \ 1199 3-F -CClF ₂ / - · \ 1200 H -CH ₃ Щ / \ Oei 1201 3-OC ₂ H ₅ I _ / \ Mp. 68-7O ^u C 1202 I / - t \ «

OO Cn

Continuation: Table 1

Verb.Nr. Ri H R ₂ H R ₁ -CH ₃ ь I i Physical constant 1203 H H -CH ₂ Br / - · I i 1204 4-OCF ₂ CFCl ₂ H -CH ₃ - I i 1205 2-OCH ₃ 5-OCH ₃ -CH ₃ - < 1206 H H -CH ₂ OH -C 1207 H H -CClF ₂ 1208 H H -CH ₂ Br / \ 1209 2-OCH ₃ 4-OCH ₃ -CH ₃ 1210

- 55 -

Continuation: Table 1

Verb.Nr. R ₁ H R ₂ H R) / - · \ / H ₃ I / ^] / H ₃ -CH ₃ R ₁ , / I Physical constant 1211 H H -CH-Br -CH ₂ OH -CH-Br _ / \ I t Oe] 1212 H H / \ t / - · \ t CH ₁ -CH-CHCH ₃ \ I i 1213 H H T / \ Ζ 'ι 1214 H H P 1215 3-OCH ₃ 5-OCH 3 / \ 1216 H H _ / \ I / 1217 H H ι / \ • 1218 • / \ • Mp. A4-46 "C

OO

- 56 -

Location : Table 1

Verb.Nr. Ri R ₂ R ₅ -CH j R ». > Physical constant 1219 2-CH ₃ 3-CHj -CH ₂ OH / - · \ i 1220 H H / H ₃ - <! / \ ; 1221 H H CH ₃ -CH ₂ CHCH ₃ / \ / H ₃ 1222 H H -CH ₃ - / 1223 2-CHi 4-CH ₃ -CH ₂ Br - < 1224 H H - <! _ / * \ I / ^r 1225 H H -CH ₃ - <; 1226 2-CHi 5-CH ₃ •

ro ca to

Ch-CO

- 57 -

Continuation: Table 1

Verb.Nr. Ri H H -CH ₂ OH I i R, I i / ' ⁴ Cl Physi kaiische constant 1227 H H -CFpCFi CH, P] W • I i 1228 H H -CH ₂ OH -CH ₂ Br - # t i Mp. 50-52 "C 1229 H H / - · \ -CF ₂ CF) ?> - » I 1230 2-CH ₃ 6-CHi Ϊ / \ - * 1231 H H ζ \ 1232 H H - · \ 1233 H H / 1234 H, _{C /} \

- 58 -

Site : Table 1

Verb.Nr. Ri H R ₂ H Ri - * \ t ^/ Rk / H ₃ ~ "\ I i / H ₃ PhyfiJkalische constant H H / H ₃ • ~ \ I t - t \ ь * I i Cl 1235 3-CH ₃ 4-CH ₃ -CH ₃ 5} • > M.p. 58-6 ° C 1236 H H -CH ₂ OH \ Mp. 75-77 "С 1237 H H -CK ₂ Br F 1238 H H 1 Oei 1239 H H I t 1240 H H I 1241 1242

: Table 1

Verb.Nr. H March H Ri * R> \ l \ / H ₃ Physi cal constant 1243 H H -CH ₂ Br -chi \ I 1244 3-CH ₃ 5-СНз J} \ / - * \ H _{) C /} - · \ / 1245 H H / - * \ t / \ 1 · • 1246 3-F 4-СНэ -CH ₃ / \ OeI n ² ^ : 1, (> 232 1247 H H t / - - · \ I / - 4 \ i 1248 H H I / \ 1249 -CH ₂ Br

- 60 -

Post: Table 1

Verb.Nr. R ₁ R ₂ -CH 3 Ri. / \ I i 4, Physikali see constant 1250 2-OCHF ₂ 4-CH ₃ -CH ₃ < I Mp. 85-87 "C 1251 3-Cl 4-OCHF CH, < nf * 1.5898 1252 3-OCH ₃ 4-OCH ₃ -CH ₃ < Mp. 74-76 "C 1253 H H Mp. 97-99 "C

The following Tables 2, 3 and 4 exemplify intermediates of the present invention.

Table 2: Compounds of the formula

R14

Verb no. R ₁ R ₂ Ru f - · \ / H ₃ \ Physical constant 2.1 H H I ~ \ I Mp 112-114 ° C 2.2 H H » Mp 123-127 ° C 2.3 H H  - · \ I Mp. 87-90 "C 2.4 4-Cl H ~ \ 2.5 H H Mp. 128-132 ^U C 2.6 3-F H 2.7 4-F H

Table 3:

- 62 -

-О

2 8 26 3 p

Verb no. Hal R ₃ CH ₃ J-CH-CH ₃ I) / CH ₃ 1 I Physical constant 3.1 Cl -CH ₃ I i ~ \ \ Y ' 3 _. •> Mp. 33-34 "C 3.2 Cl -CH ₃ -CH ₃ - ft \ J / / CH ₃ * oil; n ^ : 1.5432 3.3 Cl -CH ₃ 3.4 Cl -CH ₃ O 3.5 Cl -CH ₃ 3.6 Cl -C ₃ H ₇ -I CH \ ~ \ 3.7 3.8 Cl Cl   - · \ -CH 3.9 Cl ~ \ - ♦ \ 3.10 br

- 63 -

8 268

Table 3: Continuation

Verb no. Hal R ₃ Ru < ~ \ ⁴ cl Physical constant 3.11 Cl H ⁴ Cl, CH ₃ I 3.12 Cl CL • I 3.13 Cl -CHCl ₂ I i 3.14 Cl -CH ₃ ~ \ 3.13 Cl -CH ₃ ~ \ 3.16 Cl -CH ₃ ~ \ 3.17 Cl -C ₂ H ₅ - a \ Mp. 32-35 "C 3.18 Cl -CF ₂ CF ₃ "\ 3.19 Cl -CH 3 3.20 br -CH ₃

Table 3: Continuation

Verb no. Hal R ₃ / H ₃ 1 ι Ru \ / -Cl > t Physical constant 3.21 Cl -C ₂ Hs -CH ₃ ~ \ \ r r ψ Note 28-ЗГС 3.22 Cl -CH ₃ -CH ₃ ~ \ 3.23 Cl -Ci ₄ Hq-sec. CH к 3.24 Cl -CH ₃ Snip. 42-45 ° C 3.25 Cl < j "\ 3.26 Cl ~ \ 3.27 Cl -CH ₃ ~ \ 3.28 Cl -CH ₃ ~ '\ 3.29 br ~ \ 3.30 br

- 65 -

23 268 5

Table 3: Continuation

Verb no. Hal R ₃ Ru / CH ₃ * \ ft ~ '\ Z ¹ - ft \ • J - ft \ / CH ₃ "" \ ⁴ CH ₃ ft ~ '\ \ ~ * \ I Physical constant 3.31 Cl -C ₃ H ₇ -n ~ \ \ I / \ ft 3:32 Cl -CH ₃ I i ft • 3:33 br -CcHs t 3:34 Cl -CF ₃ 3:35 br -C ₂ H ₅ 3:36 Cl -CH ₃ 3:37 Cl CH, 3:38 Cl -CH ₃ 3:39 Cl -CClF ₂ " 3:40 Cl 3:41 Cl -CH ₂ Cl 3:42 Cl -CH ₂ F 3:43 br • 3:44 br 3:45 Cl > -CH ₂ F -CH ₂ OH

Verb no. Hal -CH ₂ OH Ru Physical constant 3:46 br - / \

- 67 -

Table 4:

/ ^R3

RsSO ₂ - ^ ^ ·

Verb no. R Ri / H ₃ ι R ₁ * I Physical constant 4.1 CH ₃ -CH ₃ I i 4.2 CH ₃ -CH ₃ 4.3 С k H о -η -CH ₃ 4.4 CH ₃ -CH ₃ 4.5 -CH ₃ - · I \ l / H ₃ * 4.6 CH ₃ -CH ₃ 4.7 -CH ₂ - ^) -CH ₃ -CH ₃ 4.8 C ₂ H ₅ -CH ₃ 4.9 CH ₃ -CH ₃ ~ \ 4.10 CH ₃ - < ~ * \ Mp. 84-89 "C

- 68 -

2 3 2685

Table 4: Continuation

Verb no. Rs Ra R. / H ₃ ь ⁴ cl I і / H ₃ Physical constant 4.11 сн ₂ -. ('"') .- сі -CH ₃ ~ \ ~ '\ I ~ \ I 4.12 4.13 CH ₃ CH ₃ -CH ₃ -CH ₃ 4.14 CH ₃ -CH ₃ ~ * \ ä 4.15 C ₂ H ₅ -CH ₃ 4.16 CH ₃ -C ₂ H ₅ j "N Mp. 64-68 "C 4.17 C ₂ H ₅ -CH ₃ 4.18 C ₃ H ₇ -Ii -CH ₃ 4.19 CH ₃ -CH ₃ 4.20 C ₃ H ₇ n -CH ₃

- 69 -

2 5 2 6 8 5

Table 4: Continuation

Verb no. R ₅ R ₃ Ru • \    \ / H ₃ ~ \ ⁴ CH ₃ - · \ Physical constant 4.21 CH ₃ -CH ₃ • 4.22 _C3 H7 n -CH ₃ \ Z ¹ 4.23 CH ₃ -CH ₃ / H ₃ Z ¹ 4.24 CH ₃ -C ₂ H ₅ ⁴ cl 4.25 CH ₃ -CH ₃ / H ₃ • 4.26 C ₂ H ₅ -CH ₃ 4.27 CH ₃ -CH ₃ 4.28 CH ₃ -CH ₃ 4.29 CH ₃ Mp. 54-58 ^u C 4.30 С3Н7-П -CH ₃

2 3 2685

- 70 -

2. Formulation examples of liquid active ingredients of the formula I.

% = Weight percent) 2.1. Emulsion concentrates Active ingredient from the table Ca-dodecylbenzenesulfonate

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

Tributylphenoyl polyethylene glycol ether (30 moles of ethylene oxide) Cyclohexanone Xylene tallow

a) b) с) 25 % 40 % 50 % 5 % 8th % 6% 5% _ -

%

12 %

15% 25 %

4%

20 % 20 %

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

2.2. solutions

Active substance from the table Ethylene glycol monomethyl ether Polyethylene glycol MG 400 N-methyl-2-pyrrolidone Epoxidized coconut oil

Gasoline (boiling limit 160-190 "C) (MW = molecular weight)

b) 10%

70% 20 %

c)

1 % 94 %

d) 95%

5%

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

2.3. granules a) b) Active ingredient from Table 1 5% 10 kaolin 94 % - Highly dispersed silicic acid 1 У 1 / о - attapulgite - 90

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

28 26 3 5

a) b) 5 i / о 5 97%

- 71 -

2.4. Dusts · Active ingredient from the table of highly dispersed silicic acid talc

Kaolin - 90 %

Intimate mixing with excipients with the active ingredient gives ready-to-use dusts.

Formulation Examples for solid active ingredients of formula I ^(g% by weight)

2.5. Injection powder Active substance from the table Na lignosulfonate Na lauryl sulfate Na diisobutanolnaphthalenesulfonate

Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) Highly dispersed silica kaolin

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

2.6. Emulsion concentrate

Active ingredient from Table 1 10%

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

Ca-dodecylbenzenesulfonate 3 %

Castor oil polyglycol ether 4%

(35 moles of ethylene oxide)

Cyclohexanone 34%

Xylene mixture 50 %

a) b) c) 25% 50 % 75 5% 5% - - 5 - 6% 10 - 2% - 5% 10% 10 62% 27% -

- 72 -

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

2.7. dusts table 1 a) % b) Active ingredient from the 5 % 8th talc 95 - kaolin _ 92

Ready-to-use dusts are obtained by milling the active ingredient mixed with the carrier on a suitable mill.

2.8. Extruder granules

Active ingredient from Table 1 10%

N-lignosulfonate 2 %

Carboxymethylcellulose 1%

Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

2.9. Coated granules

Active ingredient from Table 1 3%

Polyethylene glycol (MW 200) 3%

Kaolin 94% (MW = molecular weight)

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

2.10. Suspension concentrate

Active ingredient from Table 1 40%

Ethylene glycol 10 %

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

N-lignosulfonate 10%

- 73 -

Carboxymethylcellulose 1 %

37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% strength

aqueous emulsion 0.8%

Water 32 %

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

3. Biological examples

Example 3.1: Action against Venturia inaequalis on apple shoots Residual-protective action

Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture prepared from spray powder of the active ingredient (0.006% active ingredient). After 24 hours, the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 % relative humidity and placed for a further 10 days in a greenhouse at 20-24 ° C. Scab infestation is assessed 15 days after infection.

Compounds from Table 1 show good activity against Venturia (infestation: less than 20%). For example, compounds Nos. 1.1, 1.6, 1.13, 1.14, 1.59, 1.66, 1.69, 1.84, 1.87, 1.94, 1.108, 1.126, 1.145, 1.158, 1.180, 1.200 and 1.236 reduced Venturia infestation to 10 %. By contrast, untreated but infected control plants have a Venturia infestation of 100%.

Example 3.2: Action against Botrytis cinerea on apple fruits Residual-protective effect

Artificially injured apples are treated by grafting a spray mixture (0.002% of active substance) prepared from spray powder of the active substance onto the points of injury. The treated fruits are then treated with a spore suspension of

2085

- 74 -

Inoculated mushroom and incubated for one week at high humidity and about 20 ^u C. In the evaluation, the rotted injury sites are counted and derived from the fungicidal action of the test substance.

Compounds from Table 1 show good activity against botrytis (infestation: less than 20%). For example, compounds Nos. 1.1, 1.6, 1.13, 1.14, 1.31, 1.33, 1.35, 1.48, 1.59, 1.66, 1.69, 1.84, 1.87, 1.94, 1.108, 1.126, 1.131, 1.145, 1.158, 1.180 and 1.236 reduced Botrytis Fall to 0 to 10%. By contrast, untreated but infected control plants show Botrytis infestation of 100 % .

Example 3.3: Action against Erysiphae graminis on barley a) Residual-protective action

Approximately Barley plants 8 cm in height are sprayed with a spray mixture (0.006 % active substance) prepared from spray powder of the active ingredient. After 3-4 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are placed in a greenhouse at about 22 ^U C and assessed the fungal infection after 10 days.

Compounds from Table 1 show good activity against Erysiphae (infestation: less than 20%). Thus, e.g. the compounds Nos. 1.1, 1.6, 1.13, 1.14, 1.35, 1.48, 1.59, 1.66, 1.69, 1.84, 1.87, 1.94, 1.108, 1.131, 1.158 and 1.236 the Erysiphae infestation to 0 to 10%. By contrast, untreated but infected control plants have an Erysiphae infestation of 100%.

Example 3.4: Action against Helminthosporium gramineum Wheat grains are contaminated with a spore suspension of the fungus and dried again. The contaminated grains are pickled with a suspension of the test substance prepared from spray powder (600 ppm active ingredient based on the weight of the seeds). After two days, the granules are placed on suitable agar dishes and after another four days the development of the fungal colonies around the granules becomes evident

2085

- 75 -

assessed. The number and size of the fungal colonies are used to assess the test substance. The compounds of the table prevent the fungal attack largely (0 to 10% fungal infestation).

Example 3.5 Action against Colletotrichum lagenarium on cucumbers Cucumber plants are sprayed after 2 weeks of cultivation with a spray mixture prepared from wettable powder of the active ingredient (concentration 0.002%). After 2 days, the plants are infected with a spore suspension (1.5xlQ ³ 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 approximately 22-23 ° C The occurrence of fungal attack is assessed 8 days after the infection, but untreated but infected control plants have a fungal attack of 100 % .

Compounds from Table 1 show good activity and prevent the spread of the disease infestation. The fungal infection is pushed back to 20 % or less.

Example 3.6. a) Contact effects against Nephotettix cincticeps and

Nile apivvate lugens (nymphs);

The test is carried out on growing rice plants. In each case 4 plants (14-20 days old) with a height of approx. 15 cm are planted in pots (diameter 5.5 cm).

The plants are sprayed on a turntable with 100 ml of an aqueous emulsion preparation containing 400 ppm of the respective active ingredient. After the spray coating has dried on, each plant is colonized with 20 nymphs of the test animals in the third stage. To prevent the cicadas from escaping, a glass cylinder open on both sides is placed over the populated plants and covered with a gauze lid. The nymphs are kept on the treated plant for 6 days until they reach the adult stage. The evaluation on percentage mortality takes place 6 days after the colonization. The test is carried out at about 27 "C, 60 % relative humidity and a lighting period of 16 hours.

2 8 2 6 3

- 76 -

b) Respiratory activity against Nilaparvata lugens (water) About 10 days old rice plants (about 10 cm high) are placed in a plastic beaker containing 150 ml of an aqueous emulsion preparation of the test compound in a concentration of 100 ppm, and finished with a plastic lid with holes. The root of the rice plant is pushed through a hole in the plastic lid into the aqueous test preparation. Then the rice plant is colonized with 20 nymphs of Nilaparvata lugens in the N 2 to N 3 stage and covered with a plastic cylinder. The test is carried out at about 26 ° C and 60% relative humidity with a lighting period of 16 hours. After five days, the number of killed test animals is compared to untreated controls. This determines whether the active ingredient absorbed through the root kills the test animals on the upper parts of the plant.

Compounds from Table 1 show a strong killing effect on rice pests both in test a) and b). The mortality rate is 80% or more. Compounds Nos. 1.1, 1.6, 1.14, 1.59, 1.66, 1.87, 1.94, 1.108 and 1.236 achieved almost complete kill (98-100%).

Claims (16)

claims 1} a phenylguanidine salt of the formula Ha · -NH С A ^ (На) NH ₂ 1. A process for the preparation of a compound of the formula I, ^R i "V RR ₂ У ³ (I) in which mean: R ₁ and R "independently of one another hydrogen, halogen, Cj-Cg-haloalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -haloalkoxy; R _{3 is} hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkyl substituted by halogen, hydroxy or cyano, cyclopropyl or cyclopropyl which is up to three times identically or differently substituted by methyl and / or halogen; R _{4 is} C 1 -C 6 -cycloalkyl or by methyl and / or halogen, up to three identical or different substituents, C, _-C - cycloalkyl, characterized in that 2-phenylamino-4-ethyl-6- (2-fluorobenzopropyl) pyrraidin, 2-phenylamino-4-methyl-6- (2-chlorocyclopropyl) -pyriroidine, 2-phenylamino-4-methyl-6- (2-difluorocyclopropyl ) -pyriniidine, 2-phenylamino-4-fluoromethyl-6- (2-fluorocyclopropyl) -pyrimidine, 2-phenylamino-4-fluoromethyl-6- (2-chlorocyclopropyl) -pyrimidine, 2-phenylaraino-4-fluoro-ethyl-6 (2-methylcyclopropyl) -pyriraidine and
2-phenylamino-4-ethyl ~ 6- (2 'nethylcyclopropyl) -pyrimidine. 2. The method according to claim 1, characterized in that a compound of the formula I is prepared, wherein R ₃
and R _{4 have} the meaning given and R ₂ and R _{2 represent} hydrogen * 2 8 26В 5 П - wherein Hal in the above formulas halogen means »and the compound of formula VI obtained further with an aniline compound of the formula VIZ R ₁ (VII) at 60 ^° C to 120 ^° C depending on the condition of the process either a) in the presence of a proton acceptor with or without solvent or b) in the presence of an acid in an inert solvent or 2) urea C is reacted with a diketone of formula III in the presence of an acid in an inert solvent at temperatures from 20 ⁰ C to 140 ⁰ and then at RückflußteiBp ° .ratur to a Pyrimidinverblndung of the formula V N /
HO- / 4 (V) cyclized, the OH group in the resulting compound with excess POHeI, in the presence or absence of a solvent at temperatures of 50 ⁰ C to 110 ⁰ C exchanged for halogen shark (Λ (VI) 2 8,268 or the underlying guana in the formula Eb Ѵч / с * ^{4 N} t-NH - C (Lib) with a diketone of formula III O O II Il R ^ · ^^ C "· CH- ⁱⁿ C" * "Rj () react with or without solvent at temperatures of 60 ⁰ C to 160 ⁰ C lftfct · or 3. The method according to claim 1, characterized in that a compound of formula I is prepared, in which mean: R ₁ and R independently of one another are hydrogen, halogen,
C ₁ -Cj-AlUyI, C ₁ -C 6 -halogenoalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -haloalkoxy; R _{3 is} hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkyl substituted by halogen or cyano; R _{4 is} Cj-Cg-cycloalkyl or C ₃ -C ₆ -cycloalkyl substituted by methyl or halogen. 3) a guanidine salt of formula VIII S ^mz ° Q H₂N -QT A ^ (VIII) with a diketone of formula III a) without solvent at temperatures of 100 ⁰ C to 160 ⁰ C, or b) in an inert solvent at temperatures of 30 ⁰ C to 140 ⁰ C to a pyrimidine compound of the formula IX R * Jt \\ ^R 4 cyclieiert, and the resulting compound with a compound 2685 tion with a compound of the formula X. Υ-\ Q (X) with elimination of HY in the presence of a proton acceptor in aprotic solvents at temperatures of
30 ⁰ C to 140 ⁰ C, wherein in the formulas II to X
the substituents R. to-J? _4, the meanings given under formula I have _f A ^ represent an acid anion and Y is halogen · 4. The method according to claim 3, characterized in that a compound of formula I is prepared, in which mean: 28 268 R ₁ and R independently of one another hydrogen, fluorine, chlorine, Bromine, methyl, ethyl, halomethyl, methoxy, ethoxy or halomethoxy; Я, hydrogen, methyl, ethyl, n-propyl or sec-butyl, or substituted by fluorine, chlorine, bromine or cyano Methyl, or ethyl; R _{4 is} Cj-Cg-cycloalkyl or by methyl, fluorine, chlorine or Bromine-substituted Cj-Cg-cycloalkyl. 5 * Process according to Claim 1, characterized in that a compound of the formula I is prepared in which mean: R ₁ and R "independently of each other hydrogen, fluorine, chlorine, Methyl, trifluoromethyl, methoxy or difluorothymethoxy Rj is hydrogen, C ₁ -C ₃ alkyl; by halogen or hydroxy substituted C 1 -C 4 alkylcyclopropyl or by methyl and / or halogen up to three times the same or different substituted cyclopropyl; R _{4 is} Cj-Cg-cycloalkyl or by methyl and / or halogen to triply identical or differently substituted C ₃ -C ₄ - Cycloalkyl. 6. The method according to claim 1, characterized in that a compound of formula I is prepared, in which mean: R ₁ and R _{2 are} hydrogen; R _{3 is} C ₁ -C ₃ alkyl, methyl substituted by fluorine, chlorine, bromine or hydroxy; Cyclopropyl, cyclopropyl substituted by methyl, fluorine, chlorine or bromine, R ₄ Cj-C ^ cycloalkyl or Cj-C ^ cycloalkyl substituted by methyl and / or fluorine, chlorine, bromine up to three times identically or differently. 7. The method according to claim 3, characterized in that a compound is prepared .selected from a-Phenylafflino- methyl-ö-cyclopropyl-pyrimidine, a-Phenylaraino- ^ ethyl-e-cyclopropyl-pyrimidine, 2-phenylamino-4 -methyl-6- (2-methylcyclopropyl) -pyrimidine and
2- (p ~ fluorophenylamino) -4-methyl-6-cyclopropyl-pyrimidine. 8. The method according to claim 1, characterized in that a compound is prepared, selected from 2-phenylamino-4 _t 6-bie (cyclopropyl) -pyrimidine, 2-phenylamino-4-hydroxymethyl-6 ~ cyclopropyl-pyrimidine, S-phenylamino - ^ - fluoromethyl-δ-cyclopropyl-pyriffiicline, 2-phenylamino-4-hydroxymethyl-6- (2-methylcyclopropyl) -pyrimidine, 9. A composition for controlling or preventing an infestation by harmful insects or microorganisms, characterized in that it contains as active component at least one compound of formula 1 according to claim 1, together with a suitable carrier material · 10. Composition according to claim 9, characterized in that it comprises as active component at least one compound of the formula I. 28268 -63- contains according to claim 2. 11. A composition according to claim 9, characterized in that it contains ale active component at least one compound of formula I according to claim 3. 12. Composition according to claim 9, characterized in that it contains at least one compound of the formula I as claimed in claim 4 as the active component. 13. Composition according to claim 9, characterized in that it contains as active component at least one compound of the formula I according to one of claims 5 to 8. 14. A method for controlling or preventing an infestation of crops by pest insects or phytopathogenic microorganisms, characterized in that applied as active ingredient a compound of formula I according to claim 1 to the plant, plant parts or their location. 15. The method according to claim 14, characterized in that ale active ingredient is applied a compound according to one of claims 2 to 8. 16. The method according to claim 14, characterized in that phytopathogenic fungi are combated.