IE892881L - Pesticides - Google Patents

Abstract

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

Description

The present invention relates to novel substituted 2-asninopyr imidine derivatives of formula I below. It also relates to the preparation of those compounds and to agrochemical compositions that contain at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the active ingredients or the compositions for controlling pests, especially plant-destructive microorganisms, preferably fungi.

The pyrimidine compounds according to the invention have the general formula I > R? (I) wherein: % is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-C5alkyl, C1-C5alkyl substituted by the radical 0R5 or by the radical SR5, C3-C6eye1oalky1, C3-C6cycloalkyl mono- to tri-substituted by Cj^-C^alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is hydrogen, C^-C^alkyl, C1-C4alkyl substituted by halogen, cyano or by the radical 0R5 or by the radical SR5, C3-Cecycloalkyl or C3-Cgcycloalkyl mono- to tri-substituted by C^-C^alkyl or by halogen; R4 is halogen, C^-C^alkyl, C1-C2haloalkyl, C1-C3alkoxy or Ci-C^haloalkoxy; Rs is hydrogen, C1-C5alkyl, C1-C5alkenyl, Ci-C^alkynyl or the radical (CH2)n-X-C1-C3alkyl; /R® Jfc»o R7 is the group -NH2, or ^ N,,' R8 is hydrogen, C1-C3alkyl or C1-C3haloalkyl; Rg is hydrogen, C^-Cgalkyl, C1-C3alkyl substituted by hydroxy, 0R12, SR12 or by N{R12)2, C3-CGcyclo-alkyl, cyclopropyl substituted by SR12, C3-C10alkenyl, C1-C3haloalkyl, X-, 2- or 3-pyridyl, _ / S or \ . * *■ u> « • \/N \/ ' Rg and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 4 to 7 carbon atoms; R10 is CH(R8)R9, phenyl, C3-Csalkenyl, C3-C5alkynyl or cyanoalkyl having 2 or 3 72462 carbon atoms in the alkyl radical; R1X is hydrogen, Cj-Cgalkyl, C3-C5alkenyl, C3-C5alkynyl or cyahoalkyl having 2 or 3 carbon atoms in the alkyl radical; R12 is CH3 or C2HS; X is oxygen or sulfur; Z is 0, S, NH or NCH3; and n is l to 3; including the acid addition salts and metal salt complexes thereof.

Depending on the number of carbon atoms indicated, alkyl by itself or as a constituent of another substituent, such as haloalkyl, alkoxy or haloalkoxy, is to be understood as being, for example, methyl, ethyl, propyl, butyl or pentyl and isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, haloalkyl and haloalkoxy are mono- to per-halogenated radicals, for example CHCl2, CH2F, CC13, CH2C1, CHF2, CF3, CH2CH23r, C2C15, CH2Br, CHBrCl etc., preferably CF3. Depending on the number of carbon atoms indicated, cycloalkyl is, for example, eyelopropy1, cyclobutyl, cyclopeatyl or cyclohexyl.

The compounds of formula I are oils, resins or solids that are stable at room temperature and are distinguished by valuable microbicidal properties. They can be used preventively or curatively in the agricultural sector or related fields for controlling plant-destructive microorganisms. The active ingredients of formula I according to the invention, while requiring only low application concentrations, are distinguished not only by excellent insecticidal and fungicidal activity but also be particularly good plant compatibility.

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

Salts according to the invention are especially addition salts with non-harmful inorg. lie or organic acids, for example hydrohalic acids, e.g. hydrochloric, hydrobromic or hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, or organic acids, such as acetic acid, trifluoroacetic 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-toluanesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybensoic acid or 1,2-naphthalene-disulfonic acid.

Metal salt complexes of formula I comprise the basic organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benssoates, etc. of the elements of the second main group, such as calcium and magnesium, and of the third and fourth main groups, such as aluminium, tin or lead, and of the first to eighth sub-groups, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, etc.. The subgroup elements of the 4th period are preferred. The metals may be present in amy of the various valencies attributed to them. The metal complexes may be mononuclear or polynuclear, that is to say, they may contain one or more organic molecular components as ligands.

Important groups of plant fungicides are compounds of formula I in which the symbols have the following meanings: Group 1 (Substituents) Ra is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-C5alkyl, C1-C5alkyl substituted by the radical 0RS or by the radical SRs, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C^-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C1-C4alkyl, C1-C4alkyl substituted by halogen, cyano or by the radical 0R5 or by the radical SR5, C3-C6cycloalkyl or C3-C6cycloalkyl mono- 'co tri-substituted by C1-C4alkyl or by halogen; R4 is halogen or C1-C3alkyl; Rs is hydrogen, C1-C5alkyl, C3-Csalkenyl, C3-C5alkynyl or the radical (CH2) jj-X-C^-C^alkyl; R9 is hydrogen, C1-Csalkyl, C3-C6cycloalkyl, C5-C5alkenyl, C1-C3haloalkyl; RB and Rg, together with the carbon atom in the radical R7 are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; R7, R10, R11, R12 an-' Z are as defined under formula I and halogen is preferably fluorine, chlorine or bromine. X is oxygen or sulfur; and n is 1 to 3.

Group 2 (Substituent s) Rx is phenyl or phenyl mono-substituted by halogen; R2 is hydrogen, - 4t ~ Cj-Cgalkyl, C1~C5alkyl substituted by 0RS, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C,-C4alkyl or by halogen, C3-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is Cj-C^alkyl, Cx-C4alkyl substituted by halogen, cyano or by ORs, C3-Ceeye 1 oalkyl or 5 c3-C5eycloalkyl substituted by methyl; R5 is hydrogen or Cj-C^alkyl; R9 is hydrogen, Ci-C5aiky!, C3-C6cycloalkyl, C3-C5alkenyl, C1-C3b.aloalkyl, Re and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 5 or S carbon atoms; and R7, R10, RX1 and R12 are as defined under formula I and halogen is preferably fluorine, -| o chlorine or bromine.

Group 3 (Substituents) Rx is phenyl or phenyl mono- to tri-substituted by R.,- R2 is hydrogen, C1-Csalkyl, C1-Cseilkyl substituted by the radical 0R5 or by the radical SR5, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by 15 C1-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C1-C4alkyl, Cx-C4alkyl substituted by halogen, cyano or by the radical 0R5 or by the radical SRs, C3-C6cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen; R4 is halogen, C1-C3alkyl, C1-C2haloalkyl, C1-C3alkoxy or Cx-C3haloalkoxy; R5 is 20 hydrogen, C-^Cjalkyl, C3-C5alkenyl, C3-Csalkynyl or the radical (CH2)n-X-Ci-^alkyl; R7 is -KH2; X is oxygen or sulfur; and n is 1 to 3; including the acid addition salts and metal salt complexes thereof.

Group 4 (Substituents) Rx is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, 25 C1-C5alkyl, C1-C5alkyl substituted by the radical OR5 or by the radical SRs, C3-C6cycloalkyl, C3-C6cycl oalkyl mono- to tri - subs ti tuted by C1-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C1-C4alkyl, C^-C^alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SRS, C3-C6eycloalkyl or C3-C6cycloalkyl mono-3 0 to tri-substituted by C1-C4alkyl or by halogen; R4 is halogen; R5 is hydrogen, Cj-C5alkyl, C3-C5alkenyl, C3-C5alkynyl or t!-=. radical (CH2)n-X-Ci-C3alkyl; X is oxygen or sulfur; and n is 1 to 3.

Group 5 (Substituents) Rx is phenyl or phenyl mono- to tri-substituted by halogen; R2 is 3 5 hydrogen, C1-C5alkyl, C1-Csalkyl substituted by the radical ORs or by the radical SRS, C3-C6cycloalkyl, C3~Cscycloalkyl mono- to tri-substituted by Ci-C^alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C^-C,,alkyl, C^C^ alkyl substituted by halogen, cyano or by the radical ORs or by the radical SR5, C3-C6cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen; Rs is hydrogen, Cx-C5alkyl, C3-C5alkenyl, C3-C5alkynyl or the radical (CH2)n-X-C1-C3alkyl; X is oxygen or sulfur; and n is 1 to 3.

Group 6 (Substituents) R1 is phenyl or phenyl mono-substituted by chlorine or by fluorine; R2 is Cj-Cgalkyl, or is Cj-Cjalkyl substituted by OR5, C3-C6eye 1 oalkyl, C3-C6cycl°alkyl mono- to tri-substituted by C1-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C1-C4alkyl, C2-C4haloalkyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by methyl; and R5 is hydrogen or C1-C2alkyl.

Especially preferred are those compounds of groups 5 and S wherein R3 is: methyl, fluoromethyl, chloromethyl, bromomethyl, C3-C6cycloalkyl or methoxymethyl.

The following groups of individual substances are preferred: Group 1 (Compounds) N-(4-f luoromethyl-6-cyclopropylpyrimid-2 -yl)-N-phenylhydrazine; N- (4 -methyl - S - eye 1 opropylpyrimid- 2 - y 1) -N-m- f luorophenylhydrazine ; N-(4-methyl-6-eye1opropylpyrimi d-2-yl)-N-p-fluorophenylhydrazine; Group 2 (Compounds) N-(4-methyl-6-eyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4, S-di-methylpyrimid-2-yl)-N-phenylhydrazine; N-(4-methyl-6-methoxymethyl-pyrimid-2-yl)-N-phenylhydraz ine; Group 3 (Compounds) N-(4,S-dimethylpyrimid-2-yl) -N-phenylpropionaldehyde hydrazone; N-(4,6-dimethylpyrimid-2-yl) -N-phenylisobutyraldehyde hydrazone; N- (4 - methyl - 6 - rae t hoxyme t hy Ipy r imi d-2-yl) - N - phenyl isobutyral dehyde hydrazone; N- (4 -methyl-6 -methoxymethylpyrimid-2 -yl) -N-phenylpropionaldehyde - s - hydrazone; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N- (4 -methyl - 6 - cyclopropylpyrimid- 2 -yl) - N - phenyl -n-butyra1 dehyde 5 hydrax one; N-(4-methyl-S-cyclopropylpyrimid-2-yl)- N -phenylisohutyra1dehyde hydrazone; N- (4 -methyl - 6 - cyclopropylpyrimid- 2 -yl) -N-phenyl triehloroacetaldehyde hydrazone; 1 0 n-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-p-fluorophenylacetaldehyde hydrazone; N- (4 -methyl - 6 - cyclopropylpyrimid- 2 -yl) -N-p- f luoropheaylisobutyraldehyde hydrazone; N- (4 -methyl - S - cyclopropylpyrimid- 2 -yl) -N-m- f luoropheaylisobutyraldehyde 1 5 hydrazone; N-(4,S-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrasine; N-(4,S-dimethylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N- (4, S-dimethylpyrirnid-2-yl) -N-phenyl-N' -n-propylhydrazina; K-(4,S-dimethylpyrimid-2-yl)-N-phenyl-N'-isohutylhydrasine; 20 N- (4-methyl-6- methoxymethylpyrimid-2- yl) -N-phenyl-N' -methylhydrazine; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-M-phenyl-M'-n-propylhydrasine; N- (4-methyl-S-methoxymethylpyrimid-2-yl)-N-phenyl-N' -dimethylhydrazine; N- (4 -methyl - S - cyclopropylpyrimid-2 -yl) -N-phenyl -N' -methylhydrazina; N- (4-methyl-6-cyclopropylpyrimid-2-yl) -N-phenyl-N' -isobutylhydrazine; 25 N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N- (4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-diethyIhydrasine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-methyl-N'-ethyl-hydrazine; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-p-fluorophsnyl-N'-ethyl-3 0 hydraz ine; N- (4-methyl-S-methoxymethylpyrimid-2-yl)-N-m- fluorophenyl-N'-isopropyl-hydrazine; The compounds of formula I are prepared as follows: Process (a) Reaction of a pyrimidine derivative of formula II N_.

/ \ / \ Rs (II) with a phenylhydrazine derivative of the formula III R1-NH-NH-R (III) in the presence of a base, in an aprotic solvent and at temperatures of -50°C to 150°C, preferably -30° to 80°C, wherein Y is halogen, 5 preferably chlorine, the radical S02R6 or 1^(013)3, R6 is C^-C^alkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for R10 and Rxl, and the latter and also R^Ru are as defined under formula I.

Process (b) 1 0 Reaction of a pyrimidine hydrazine derivative of formula IV with an aldehyde or ketone of formula V to form a compound of formula VII with the removal of water R2 . /R2 fyj— IB J^IIB R« (I¥) (V) (VII) '' */ ^ in any desired solvent, in the presence of an acid and at temperatures 15 of -20° to 120°C, preferably 10° to 50°C, Ri-R3 and R8 and Rg being as defined under formula I.

Azeotropic distillation or molecular sieves can be used to remove the water from the reaction mixture. During agents, for example CaCl2 or Na2S04, can also be used. In the case of the reaction of derivative (IV) * 20 with an aldehyde, the removal of water from the reaction mixture can often be dispensed with.

Process (c) Reduction of a hydrazone derivative of formula VII .H?, Es Rl. yN~'\ /J~"\ Re Badactipa_ Hj— M— ^ ^ ^C~h K—" HM Ti®" R ? R j \ K. s \ V VrffaR tjl ( R 'Jj ) (VII) (VIII) using a reducing agent, for example borohydride etheratas, NaBH4, NaCNBH3 or LiAlH4, in an inert solvent, for example suitable alcohols, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures of 0° to 50°C or by catalytic hydrogenation using catalysts, for example 5 nickel, platinum, pallamium or rhodium.

Process (d) Reductive alkylation of a pyrimidine hydrazine derivative of formula IV ,Ra X—• » v f V (IV) / 5H= 7«»- Ra with an aldehyde or ketone of formula V R0-i-R* in the presence of a reducing agent, for example borohydride etherates, 10 NaBH6, KaCHBH3 or LiAlH4, in an inert solvent, for example suitable alcohols, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures of 0° to 50°C, preferably 10° to 40°C.

Process (a) Alkylation of a pyrimidine hydrazine of formula IV or VIII with an alkyl 1 5 halide RoHal M -S v J&3 (IV) R Hal <3 rt\-/ /v v a: ii »i © o (IX) M / 2 R, —V—- v + R Hal Rx-$~< / ■N-. -• f K naj. «»» v v "\ x"\, /\ ' " CHRaCRo) R0 CHR«>(R«) (VIII) (X^ in an inert solvent, in the presence of a base and at temperatures of 0°-S0°C, preferably 10°-40°C, R0 being C1-C4alkyl. Other suitable alkylating agents are dialkyl sulfates.

In processes (a-e) described above, Ri-Rg are as defined under formula I.

In the processes described, it is possible, if necessary, to use both inorganic and organic bases, for example the following: the hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium or, alternatively, hydrides, for example sodium hydride, and alcoholates, for example potassium tert-butylate, and tertiary amines, such as triethylamine, triethylenediamine or pyridine.

Solvents and diluents that may be used as reaction media in conformity with the particular reaction conditions are, for example, the following: aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; N,N-dialkylated amides, such as dimethylformamide; and also mixtures of such solvents with one another. ~ 10 - The pyrimidine derivatives of formula II in which Y is halogen can be prepared according to known methods (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962).

An often-used method of synthesis consists in the condensation of urea 5 with /j-diketones to form 2-hydroxypyrimidines which are subsequently reacted to form 2-halopyrimidines as follows: / R^ =0 =0 h?n, \ - =0 R^ \ / a> V R 3 \ s J -OH / 'V &3 -It \ s' Especially phosphorus oxychloride or phosphorus oxybromide may be used as halogenating agents.

Another possible method of obtaining the 2-halopyrimidines of formula II 10 is to prepare them by way of the 2 -avninopyrimidines. The 2-amino- pyrimidines are obtained by known methods (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962), then diasotised, and converted by the Sandmeyer process into the 2-halopyrimidines. The 2-amino-pyrimidines are obtained, for example, by condensing /3-diketones 15 with guanidine in the following manner. / =0 =0 HN. 1 c-nhj Ra X / ,© \ Rj -nh2 1) NaN02/H 2) Hal0/Cu@ \ \ R^ \ -n®j The pyrimidine derivatives of formula II in which Y is S02-C1-C4alkyl or S02aryl are obtained according to known methods by oxidising the corresponding alkyl or aryl mercaptopyrimidines, whose preparation is likewise known (see D.J. Brown, The Pyrimidines, Interscience 20 Publishers, 19S2).

Apart from the condensation of the corresponding diketones as described above, pyrimidines of formula II in which the radical R3 is haloalkyl can also be prepared by reacting the hydroxyalkyl derivatives with phosphorus halide or thionyl halide in the presence of tertiary bases in inert solvents.

Some of the intermediates of formula XI ,n- V-.' n v Ej (II) in which Y is halogen or S02-Rg and Rg is C1-C4alkyl or aryl and R2 and R3 are as defined under formula I, are known.

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

EP-A-270111 describes 2-ani1inopyrimidine derivatives having fungicidal properties. Phenylhydrasone derivatives which are used in agriculture against microorganisms are known from EP-A-019450.

Surprisingly, it has been found that the compounds of formula I have, for practical application purposes, a very advantageous biocidal spectrum for the control of phytopathogenic microorganisms, especially fungi. They have very advantageous curative, preventive and, in particular, systemic properties, and can be used for protecting numerous cultivated plants. With the active ingredients of formula I it is possible to inhibit or destroy the pests which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected, for example, from attack by phytopathogenic microorganisms.

The compounds of formula I are effective, for example, against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (especially Botryitis, and also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). They are also effective against the Ascomycet.es class (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and the Oomycetes class (e.g.

Phytophthora, Pythium, piasmopara). The compounds of formula I can also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic fungi which occur in the soil. In addition, compounds of formula I are affective against insect pests, for example against pests on cereals, especially rice.

The invention also relates to compositions containing as active ingredient compounds of formula I, especially plant-protecting compositions, and to their use in the agricultural sector or related fields.

The present invention further embraces the preparation of those compositions, which comprises intimately mixing the active substance with one or more substances or groups of substances described herein. The invention furthermore relates to a method of treating plants, which comprises applying the novel compounds of formula I or the novel compositions.

Target crops for the plant-protecting use within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops); beet (sugar beet arid fodder best); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil crops (oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa, groundnuts); cucurbits (pumpkin, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, sweet peppers); lauraceae (avocados, cinnamoniunt, camphor) , or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, Musaceae and natural rubber plants as well as ornamentals.

The active ingredients of formula I are normally applied in the form of compositions and can be applied to the area or plant to be treated, simultaneously or in succession, with further active ingredients. These further active ingredients can be fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting additives customarily employed in the art of formulation.

Suitable carriers and adjuvants can. be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

A prepared method of applying an active ingredient of formula J., or an agrochemical composition which contains at least one of these active ingredients, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen. However, the active ingredients of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid formulation, or by applying the substances in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granulates may be metered to the flooded rice field. The compounds of formula I may, however, also be applied to seeds (coating) either by impregnating the seeds with a liquid preparation of the active ingredient, or coating them with a solid preparation.

The compounds of formula I are used in unmodified form or, preferably, together with the assistants conventionally employed in the art of formulation. For this purpose they are advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulations in e.g. polymeric substances. As the nature of the compositions, the methods of application, such as spraying, avomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active substance (a.s.) per hectare, preferably from 100 g to 2 kg a.s./ha, in particular from 200 g to 600 g a.s./ha.

The formulations, i.e. the compositions, preparations or mixtures comprising the active ingredient of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in a known manner, e.g. by intimately mixing and/or grinding the active ingredients with extenders, 5 e-g- solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions C8 to C12, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioccyl phthalate, aliphatic hydrocarbons 10 such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl [sic] ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable 15 oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally ground natural minerals such as calcite, talcum, kaolin, montmorilonite [sic] or attapulgite. In order to improve the physical properties it is also possible to add highly disperse silicic acid or 2q highly disperse absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic [lacuna] nature can be used, e.g. especially dolomite or 25 pulverised plant residues.

Depending on the nature of the active ingredient of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term surfactants will also be understood as 30 comprising mixtures of surfactants.

Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22) , e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin [sic] salts.

More frequently, however, so-called synthetic surfactants are used, especially alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.

The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22-alkyl radical, alkyl also including the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates prepared from natural fatty acids. Also included are the salts of sulfates and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic [sic] acid groups and one fatty acid radical having 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutyl-naphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of a p-nonylphenol/(4-14)-ethylene oxide adduct.

Non-ionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 3 0 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol units [sic].

Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylsne sorhitan, e.g. polyoxyethy1ene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationie surfactants are in particular quaternary ammonium salts which contain, as M-substituent, at least one C8-C22alkyl radieal and, as further substituents, unhalogenated or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benssyldi (2-chloroethyl) ammonium bromide.

Further surfactants customarily employed in the art of formulation are known to the person skilled in the art or can be taken from the relevant specialist literature.

The agrochemical preparations usually contain 0.1 to 99 % by weight, especially 0.1 to 95 % by weight, of an active ingredient of formula I, 99.9 to 1 % by weight, especially 99.9 to 5 % by weight, of a solid or liquid auxiliary, and 0 to 25 % by weight, especially 0.1 to 25 rs by weight, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute compositions.

The compositions may also contain further additives such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for achieving special effects.

The following Examples serve to illustrate the invention in snore detail without limiting it. 1. Preparation Examples Example 1.1: 2 - hydroxy- 4 -methvl - 6 - cvc 1 oproavl'ovr imidine hydrochloride (starting material) 6.0 g (0.10 snol) of urea and 12.S g (0.10 mol) of cyclopropylbutans-1,3-dione are dissolved at room temperature (~20°C) in 35 ml of ethanol and 15 ml of 32 rs aqueous hydrochloric acid. After standing for 10 days at room temperature, the solution is concentrated using a rotary evaporator at a bath temperature of maximum 45°C. The residue is dissolved in 20 ml of ethanol; after a short time, the product begins to separate out in the form of the hydrochloride. 20 ml of diethyl ether are slowly added with stirring, the product is separated from the solvent by filtering off with suction and is washed with a mixture of diethyl ether and ethanol and dried at 60°C in vacuo to give 7.14 g (38.2 % of the theoretical yield) of 2-hydroxy-4-methyl-6-cyclopropylpyrimidine hydrochloride. The filtrate is concentrated and, after recrystallisation from 10 ml of ethanol and 20 ml of diethyl ether, a further 5.48 g (29.2 % of the theoretical yield) of substance are obtained.

Analysis: C8H10N20*HC1 (MW: 186.64) HC1 % calc. % found C 51.48 51.47 H .94 .97 N .01 .15 CI 18.99 18.89 Example 1.2: 2-chloro-4-methvl-5-cvclopropvlpvrimidine hydrochloride (starting material) ci' V'\(j 52.8 g (0.24 mol) of 2-hydroxy-4-methyl- S -eyelopropylpyrimidine hydrochloride are introduced into a mixture of 100 ml of phosphorus 5 oxychloride and 117 g (0.79 mol) of die thy1ani1ine and stirred; the exothermic reaction slowly begins, the temperature rising from room temperature to S3°C. The batch is then heated in an oil bath for 2 hours at 100-110°C internal temperature. After cooling to room temperature, the mixture is poured, with stirring, into a mixture of ice-water and 10 methylene chloride. After one hour, the organic phase is separated off in a separating funnel and is washed neutral with NaHC03 solution. After removing the solvent, 11S.4 g of crude product comprising 2-chloro-4-methyl-S-eyclopropylpyrimidine and diethylaniline are obtained. Chromatographic separation using silica gel and a mixture of 25 % of 15 ethyl acetate and 75 % of hexane as eluant affords 35.7 g (89.4 % of the theoretical yield) of pure 2-chloro-4-methyl-6-eyelopropylpyrirnidine in the form of a colourless oil.

Example 1.3: 2-amino-4-diethoxvmethvl-6-cvclopropvlpvrimidine (starting material) ~\~s" i ¥ f. © (9 'V NCH(0CJHS)2 74.8 g (0.42 mol) of guanidine -^rbonate and 74.1 g (0.35 mol) of 4-cyclopropyl-2,4-dioxobutyraldehyde diethyl acetal are boiled for 10 hours in 250 ml of ethanol. The batch is then concentrated using a rotary evaporator and the residue is extracted with water and ethyl acetate. After evaporating the ethyl acetate, 79.2 g of crude product 25 remain which are recrystallised from hexane to give 70.4 g (85.8 % of the theoretical yield) of the pure substance. M.p. 77~78°C.

Example 1.4: 2 - chloro- 4 - fortnvl - 6 - cvclopropvlpvrimidine (starting material) i a ciy v ncho 70.3 g (0.30 mol) of 2-amino-4-diethoxymethyl-S-cyclopropylpyrimidine are dissolved in 340 ml of 32 % aqueous hydrochloric acid and cooled to -25°C using dry ice. A solution of 40.9 g (0.59 mol) of sodium nitrite in 80 ml of water is then slowly added dropwise at -20 to -25°C, nitrogen evolving and a solid product separating out. After 2 hours the cooling means is removed. The mixture is allowed to rise to room temperature and is extracted with ethyl acetate. The extract is dried with sodium sulfate and the solvent is removed to give 21.9 g of crude product in the form of an oil. Further purification by means of column chromatography (silica gel, eluant 3 0 parts of ethyl acetate and 70 parts of hexane) affords 16.1 g of the pure substance in the form of a colourless liquid.

Refractive index n^5 = 1.5603.

Analysis: CBH7C1M20 (MW: 182.61) % calc. % found C 52.6 52.6 H 3.9 4.1 N 15.3 14.8 CI 19.4 18.7 Example 1.5: 2 -chloro-4-hvdroxvmethvl -6-cvclopropvlpvrimidine (starting material) ¥ ii Cl'V"N ch2oh .4 g (0.084 mol) of 2-chloro-4-formyl- S -cyclopropylpyrimidine are dissolved in 125 ml of methanol and reduced by the addition of 1.6 g of sodium borohydride. The batch is concentrated and extracted with ethyl acetate and the solvent is removed using a rotary evaporator to give 14.5 g of crude product which is'-recrystallised from s. mixture of 2 0 ml of toluene and 20 ml of cyclohexane. The yield of the pure compound is 13.7 g (88.4 % of the theoretical yield); m.p. 102-104°C.

Analysis: C„K9C1N20 (MW: 184.63) % calc. % found C 52.04 52.05 H 4.91 4.90 N 15.17 15.27 CI 19.20 19.28 Example 1.6: 2-chlpro-4-hvdroxvmethvl-6-cvclopropvlpvrimidine methane-sulfonate (starting material) i x ? ij C1' XCH:0S02CHj 9.5 g (0.05 mol) of 4-hydroxymethyIpyrimidine and 5.7 g of triethylamine are placed in 150 ml of tetrahydrofuran, and a solution of 6.5 g of methanesulfonic acid chloride in 30 ml of tetrahydrofuran is added dropwise with cooling. Triethylamine hydrochloride separates out immediately and is filtered off with suction. Concentration yields 14.7 g of crude product which is chromatographed in silica gel (25 parts of ethyl acetate and 75 pares of hexane) to give 13.S g of the pure substance. M.p. 64-S6°C.

Analysis: C9H11C1N203S (MW: 262.71) % calc. % found C 41.15 41.32 H 4.22 4.33 N 10.66 10.56 CI 12.20 12.16 «■& ^ Example 1.7: 2 -chloro-4-fluoromethvl-6-c vc1oaropvIpvrimi dine (starting material) I 1 11 ciy v nch2F 13.4 g (0.05 mol) of methanesulfonate are boiled under reflux for 5 hours in 70 ml of propionitrile with 9.4 g (0.16 mol) of potassium 5 fluoride and 0.8 ml of 18-crown-S as catalyst. Removal of the solvent and subsequent extraction with water and ethyl acetate gives a crude product which is purified by column chromatography (silica gel; 15 parts of ethyl acetate and 85 parts of hexane). The yield of the pure compound is 7.5 g (78.6 % of the theoretical yield); m.p. 37-39°C. 10 Analysis: C8H8C1FN2 (MW: 186.62) % calc. % found C 51.49 51.73 H 4.32 4.45 N 15.01 14.90 F 10.18 10.26 CI 19.00 18.50 Example 1.8: 2-chloro-4-mechvl-S-(2-methvlcvclopropvl)-pyrimidine (starting material) qij / f N» c/ V NCHJ 76.4 g (0.47 mol) of 2-amino-4-methyl-S-(2-methylcyclopropyl)-20 pyrimidine, produced by boiling guanidine carbonate with acatylmethyl-2- methylcyclopropyl ketone in ethanol, are dissolved in 536 g of 32 I hydrochloric acid and cooled to -25°C. 2 g of copper powder are then added and a solution of 71.4 g (1.03 mol) of sodium nitrite in 200 ml of water is added dropwise at -25 °C over a period of 3 hours during which 25 nitrogen an nitrous gases evolve. The mixture is then allowed to rise to room temperature and extracted with ethyl acetate, and the extracts are washed with water and dried with sodium sulfate. After removing the solvent, 27.7 g of crude product remain as residue which is purified by chromatography on silica gel with a mixture of 20 parts of ethyl acetate 5 and 80 parts of hexane as eluant to give 32.2 g of the pure substance; refractive index rip'1 » l. 5334 .

Analysis: CSH11C1ISJ2 % calc. % found C 55.18 59.IS H 6.07 5.15 N 15.34 15.25 CI 19.41 19.20 Example 1.9: 2-(a-phenylhvdrazino)-4.a-dimethvl-ovrimidine (Comp. 1.12) J N'. i ■ ,CH3 I / \ h2n—s—v / CH i 4.77 g (0.033 mol) of phenylhydrasine hydrochloride are suspended under 15 nitrogen in 60 ml of tetrahydrofuran, and 7.41 g (0.06S mol) of potassium tert-butylate are added. A solution of 5.59 g (0.030 mol) of 2-methylsulfonyl-4,S-dimethylpyrimidine in 15 ml of tetrahydrofuran is then added dropwise at 25°-35°C. After 2 hours, the mixture is extracted with ethyl acetate and water with the addition of a small amount of 20 acetic acid at pHS. After drying the organic phase with sodium sulfate and removing the solvent using a rotary evaporator, 5.88 g of crude product are obtained. Chromatographic purification using silica gel and a mixture of 35 parts of ethyl acetate and S5 parts of hexane gives 2.89 g of the pure substance which, after recrystallisation from n-25 hexane, melts at 41-43°C.

Example 1.10: 2-(of-phenvlhvdrazino)-4.6-dimethvlnvrimidine {Comp. 1.12) /\ 1 " ch3 v N=< I / \ HjN N "v // s'< ch3 7.06 g (0.035 mol) of 2-trimethylaramonium-4,6-dimethylpyrimidine chloride1 and 5.78 g (0.04 mol) of pheaylhydrasine hydrochloride are suspended in 50 ml of tetrahydrofuran, and a solution of 5.04 g 5 (0.045 mol) of potassium tert-butylate in 25 ml of tetrahydrofuran is added dropwise under a nitrogen atmosphere. The exothermic reaction is maintained at 5°-10°C by cooling. When the mixture has warmed to 20°C, it is extracted with ethyl acetate and water and the extract is dried with sodium sulfate. After concentration, 5.9 g of crude product are 10 obtained which is purified by column chromatography (silica gel, eluant mixture of 25 parts of ethyl acetate and 75 parts of hexane) to give 3.94 g of the pure substance.

Example 1.11: N-(4-methvl-6-cvclopropvlpvrimidin-2-vl)-N-phenvl-hvdrazine (Comp. 1.4) " • chi I M i 3 ^ /"N- HJN—A—'t » . v xj 2.20 g (0.013 mol) of 2-chloro-4-methyl-6-cyclopropylpyrimidine and 1.62 g (0.015 mol) of phenylhydrazine are dissolved in 20 ml of tetrahydrofuran. A solution of 2.02 g (0.018 mol) of potassium tert-butylate in 20 ml of tetrahydrofuran is added dropwise to this solution with cooling at 20-25°C. After 30 minutes, the starting pyrimidine can '20 no longer be detected by thin 1 yer chromatography. The mixture is then extracted with water and ethyl acetate. After removing the ethyl acetate using a rotary evaporator, 3.13 g of crude product are obtained which are purified by column chromatography on silica gel (eluant: 35 % of 1 W. Klotzer, Monatshefte f. Chemie .87, 131 (1956) ethyl acetate/65 % of hexane). 2.83 g of the purified product are obtained (90.2 % of the theoretical yield) which are recrystallised from a mixture of 8 ml of n-hexane and 1 ml of cyclohexane, affording 1.62 g of the substance (m.p. 46°C). The mother liquor is concentrated and is recrystallised again to give a further 0.42 g of product (m.p. 45-4S°C). The total yield of the recrystallised product is 2.04 g (S5.3 % of the theoretical yield).

Analysis: CX4H16N4 (MW: 240.31) % calc. % found C 69.8 69.81 H 6.71 6.77 N 23.32 23.49 Example 1.12: £3- (4-methyl-6-cvclopropvlpvrimidin-2-vl)-M-phenvliso-butvraldehvde hydrazone (Comp. 3.26) \ / i /\ i n i ii n==chch(ch3)2 6.25 g (0.026 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-i?-phenyl-hydrasine and 2.25 g (0.031 mol) of isobutyraldehyde are dissolved in 30 ml of methanol, producing a slightly exothermic reaction. After standing for two hours at room temperature, the solvent is removed using a rotary evaporator to give 7.8 g of crude product in the form of a viscous oil of which 3.2 g are purified by column chromatography on silica gel (elua.nt: 72 % of nexane/18 % of ethyl acetate/10 % of methanol). The yield is 2.92 g of the pure substance having a melting point of 53-55°C. This corresponds to a yield of 93 % of the theoretical yield in terms of purification of all of the crude product.

Analysis: C18H22M4 (MW: 294.40) % calc. % found C 73.44 73.25 H 7.53 7.64 N 19.03 18.92 Exam-pie 1.13: N- (4-rnethvl-6-cvclopropvlPvrimidin-2-vl) -N-phenvl-N' -1sobucvlhvdrazine {Comp. 4.87) i ■/\ i/"N 1 l'l ^ f| HNCH2CH(CH3)2 8.55 g (0.029 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-isobutyraldehyde hydrazone are dissolved in 30 ml of methanol and 2 ml of glacial acetic acid. 2.14 g (0.029 mol) of sodium cyanoborohydride are then added in portions with stirring. The reaction proceeds exothermically; the temperature is maintained at 10-15°C by cooling. After 1 hour, the batch is worked up by extraction with ethyl acetate and water and the organic phase is concentrated using a rotary evaporator to give 8.5 g of crude product. Purification by column chromatography on silica gel (eluant: 85 % of hexane/I5 % of ethyl acetate) affords 7.6 g (89 of the theoretical yield) of an oil having having a refractive index of n^5 = 1.5733.

Analysis: C18H24N4 (MW: 296.42) % calc. & found C 72.94 72.90 H 8.16 8.21 N 18.90 18.83 Example 1.14: N-(4-methvl-6-methoxvmethvlpvrimidin-2-vl)-N-phenvl-N'-20 methvlhvdrazine (Comp. 4.17) S N v/ x I ll ? .1 v Y'Vwh. nhch 3 3.70 g (0.033 mol) of potassium tern-butylate are dissolved in 25 ml .if tetrahydrofuran dried with molecular sieves, 3.67 g (0.03 mol) of N-methyl-N'-phenylhydrazine2 are added and a solution of 4.22 g (0.025 mol) of 2-chloro-4-methyl-6-methoxymethyIpyrimidine in 30 ml of 2 K. Kratzl, Monatshefte f. Chemie 8jJ, 83 (1958) anhydrous tetrahydrofuran is added dropwise under nitrogen at -20°C to give a yellow-brown suspension which is gradually allowed to rise to room temperature. After 4 hours, the batch is extracted with water and ethyl acetate and the crude product is isolated by evaporating the solvent and purified by column chromatography on silica gel (eluant: 65 % of hexane/35 % of ethyl acetate). The pure product is obtained in the form of an oil having a refractive index of n§4 = 1.5793.

Analysis: C14H18N40 (MW: 258.33) % calc. % found C 65-09 65.08 H 7.02 7.09 N 21.69 21.05 Example 1.15: N- (4.6-dimethvlpvrimidin-2-vl)-N-phenvl-N'-methvlhydrazine (Comp. 4.1).

Analysis: Cl3H16N4 far calc. % found C 68.40 68.01 H 7.07 7.09 N 24.54 24.13 3 W. Klotzer, Monatshefte f. Chemie 87. 131 (1956) Example 1.16: N-(4.6-riirnethvlPVrimidin-2-vl)-N-ahenvl-W-dime thvlhvdra z ine (Comp. 4.13). n(chj)* 3.42 g (0.01S mol) of N- (4,6-dime'chylpyrimidin-2-yl) -H-phenylhydrazine are dissolved in 20 ml of methanol together with 3.28 g (0.042 mol) of 38 % formaldehyde and 2 ml of glacial acetic acid, arid 1.33 g (0.018 mol) of sodium cyanobo r ohydride are added in portions at approximately 5°C. The reaction proceeds exothermically and is complete after one hour. The batch is extracted with ethyl acetate and water and the solvent is removed using a rotary evaporator to give 3.25 g of crude product which is purified by chromatography using silica gel and a mixture of 76 % of hexane, 19 % of ethyl acetate and 5 % of methanol to give 1.80 g (45.4 % of the theoretical yield) of the pure substance in the form of an oil; n£5 = 1.5673.

Example 1.17: N-(4-methvl-6-cvclopropvlpvrimidin-2-vl)-N-phenvl-N'- 4.55 g 0.0153 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-N'-isobutylhydrazine are dissolved with 1.45 g (0.0184 mol) of 38 % formaldehyde in 25 ml of methanol and 2 ml of glacial acetic acid, and 1.24 g (0.C'68 mol) of sodium cyanoborohydride are added in portions at 10°C. The reaction proceeds exothermically and, after one hour, the mixture is extracted with water and ethyl acetate. After removing the solvent, 4.95 g of crude product are obtained which is purified by column chromatography on silica gel (eluant: 85 % of hexane/15 % of ethyl acetate) to give 4.4 g of an oil; refractive index n^0 = 1.5613. methvl-N'-isobutvlhvdrazine (Comp. 4.102) Analysis; C,9H26N4 (MW: 310.45) % calc. % found C 73.51 73.94 H 8.44 8.58 N 18.05 17.93 Table l: Compounds of formula Ji hsn 1 "n*,./ * V Cosap.

Mo, hi hz Ha physical constant: 1.1 1.2 1.3 CsHs 4-cf3C«hI. 4-F-CsHu h cha H ch3 ch3 h w.p.!29-131°C 1.4 CgBs ch3 -ch3 1.23 1.24 c»hs 4-chj-cshfc ch3 ch3 ch t och s ch=ch g ch:, T^8 1.604 Continuation' Table 1 Cosnp.

Ha S3 physical Ho. constant i .25 A-OCHa'-Cf.E.i - CH3 3 a.p. 55-57°C 1.29 3„5-Cl2-Csn3 CHzOCHgCH^CHg CHs 2.30 4-GHaO-CcB* C(GH3)i CIaOCH3 1.31 3,5-Cl2-CsHa GH3 CUClg 1.32 3-Cl~C&Hi. vH 3 CH3 47"4S°C 1.33 394—(C2H5O)2—C5H3 w£a 3 cagoch(Cl«3)CgHs 1.34 4—CI13 O—C s H CHa GH 2 OCH 3 1.35 3,4-(C2HsO)2—C5H3 c(ch3)3 CH2OCH3 1.36 3 s 5~Clg—C5B3 CHsOCH3 1.37 2,4,6-Cl3-C6h2 CHS CHa ss.p.1 50-152°C 1.38 3,4-(C2H50)2-C6H3 CB 3 CM2OCH3 1.39 3,5—Cl2~CsH3 CHgOCHgDsCH CH 3 1.40 C&Hs ch 2 och 2 c^ch ch3 1.41 4~CH30~C6H* CH2OCH2C*CH ch3 1.42 3 s 5™ ( cf 3 ) 2~c.>b3 cha ch3 m.p. 88 -90°C 1.43 cglls CI2OCH3 ci! 2 och 3 1.44 C5HS CH2SCH3 ci 3 1.45 cshs CHa cb(och3)2 1.46 CsHs CHa CH(0C2Hs)2 M O tn (_n ft-* ft-J W J—« M t—J »—> 9-J w *-* 9—9 O C 0 t « a e • « • • ® 9 « • » t • » 0 0 0 G\ c* ON o-v ON U* tyi Ui K/i Cn Ln in i> * B o\ %> UJ «vj S"^ o VO CO C7\ Ln U) M o \Q CO vj O Is n o o n o o O o n O u> O n o n n o (?» £>2 V9 4^ n «r o w ) c» o 232 O <2*1 4P 9* IS M <*v£ C>« r sr O a O o n o ! n O O I i 1 I in Surf Cue-J &e« w< &2'-5 & s !52 S N 3 9 e W /-N *» m o M / \ •w rv 6fl (uii) / \, / \ / \ /\ o o a &% O o o O Ifl g ■■«■■ 8 3 i i i S 9 9 o Sic o o o o o \ / Si frf a ftir-3 WJ &IT^ a&« Is* o n a •3 u» >*✓ a w w Ui w &L> Sr-jl 6®'? Si2j p U ie& t t o o ak.1 I o o | 1 1 n 1 O n o 3 3 &s &td e a? 6 0 s g Hi n / \ / \ hi / \ / \ M n / \ / \ / V O / \ irt o o s i i.— e o o o o *sj ? O 3 —1-» | a 0 Swl 0>i^ 8rj? 6d4 / o o iil o w \ w ]im£ s«^ «A9 %ti o sti /—\ 6TJ1 o o D3 1>) o w &«4 km ca> w id \«/ u £ti 4*1 N jp«f JsS , p , p B B o "0 i-fia HM e 0 o 5J' © vs >p £5 9 9 ft —& _t rt h« Q> VO (W O ln fvi 9 P> © j rt o <1 v£5 03 *»3 u> u> lj w 0 9 o o Continuations Table 1 Comp • Ri *2 rj physical Ho. constant 1.67 CsHs (CH2)iCH3 CH2OCH3 1.68 CSHS Cjhs CH2OCH3 n** 1 .5923 1.69 CsHs CH2OCH3 J}\ \l ® J) 1.70 C s H s CH2OCH3 CF 2 CI 1.71 CsHs - - Continuations Table 1 Co S3p.

Ri E2 r* physical Ho. constant 1.107 c&ji5 CH3 CH2 OH 1.108 4-f-cf,hfc CM 3 - Eg A\.

Nfcs.^ physic®! constant 2.1 2.2 2.3 2.4 2-5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 2.20 2..21 2.22 2.23 2.24 cbo t—btstryl ch3 CH3 cm 3 ch3 ch3 chaoch3 chgoch3 ch3 ch3 ch3 ch2och3 ch(ocahs)2 n-propyl Aso^propyl n-bwtyl ch2och3 CH2OCH3 ch 2och 3 cha oh CHxOCHj chaoch3 chj _/ \_ CH20C2B5 CH2OCE(CH3)C2H5 CH2OC2H5 CHCI2 ch %och2 ch®ch2 CH2OCK2CraCK CHzOC3j -4 J6 l) I ■ 3,3 ®3t i*l 1 1 - 5064 Table 3s Compounds of formula 3 /* Hi /=»n R,S / y==g nh—' R* Ra Comp. Ho.

Rs R j R3 Rs physical constant 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 C 6 H s C s H $ CsHs CsHs ■CsHs CsHs CgH$ CsHs CHj CHs CHs CHj CHs CHs CHs CHj CFj CF j CHj cyclo-CjHs cyclo-CjHs CHj CHjOCHJ cycIo-CjHs H H !) H H H H H 2-CH3-CsH<, CtHi CHj CHj C?Hj CjHs C1H1 n-CjHy m.p.J 83-190°C m.p. in-118°C m.p.l37-13B°C n.p.l03-105°C m.p. 46-49°C m.p. 5i-53°C ni s |. 5862 I#' 3.9 3.10 CsH$ 3-F-CgHt, CHj CHS CiHs CH jOCH j CHj CHj CHj CH t nf * I .£6'78 D 3.11 C(KS CH j CIS 3 CjHs CHj n" 1.5830 D 3.12 4-H02-CsH(, .

CjHs CjHs H n—C 3II7 3.13 CSH5 CHj 1j-C3H7 / V — 3 t \ / CHj 3.14 CsHs Clh cyclo-CjHs CHs CHs njj* 1.5982 3.15 C s H s CHs cycIo-C jllg, CHj /\ 1 \/ a 3.18 C 5 H 5 CHS cyclo-CjHs CHs CH.3OCH3 i I U) <1 i Tabl®3? (continuation) Ccsap8 Ri Rg Rj Kg Rj physical constant' 3.17 ^-CFjO-CeHii CHj cyclo-CjHs H (CHj)jCH 3.18 G-CFjO-CsHt, CHj cyclo-CjHs H CHj 3,19 3-r-CeHe, CH 3 CH3OCH) H C(CHj)j is. p. 104-10S°C 3.20 3-r CsHj, CHj CHgOCHs H CtMg m.p, 95-97°C 3.21 4-CHjO-CsHi ch3 CH3 H Cillj m.p. 81—02°C 3 = 22 4-CHj-CsK* (CH j)jC CHj H n-CjHy 3.23 ft-CHj-CtHti n-CJH7 n-CjHy H CjHs 3.26 CsHs CgHs CjHs H ' C g'Si s 3.25 CgHs CH» CHj H (CHj)sCH R>.p, 83-84°C 3.26 CsN5 CHi cyclo-CjHs H H m.p.121-!22°C 3.36 C»Hs cyclo-CjHs CHj CFj H CHj 3.37 CsHs CHs CHj CH\^V H CHj 3.38 CsHs C(CH3)3 C(CHJ)j (CHj)ICH H 3.39 Cells C(CH 3)3 C(CHj)j CgHj CHs 3« ftO C$H$ CHj cyclo-CjHs H CClj ra.p.139-1°C to o cn Ln ^ W W ^4 W (,4 US 9 9€u)inu © » 45* &* 4>» a %« ch <«rs 45" w o a a o O o o o 4E* £?* ■e* MB *B*3 SC W«4 SE a ^ *« << DA *~74 ■-*-- **"s **T° EE & w teT ««9 W &>9 fe3 us «M O O n (M ft-i M« M ta («> M ted 4si t-rf M H a o O O a 1 1 1 o o a w> tea «e» HSM e2e w» CW a oaaaaaaaaa ss ^ fed O ^ U ^ 10 ^ ^ <-d M O 0 a 1 s a « o o O 3 O o O O 83 I ^ s s h. o a n » w «-> £«> SO o t- I I ^ a a M «rJ f-r" HgB <*n ti-J a ft r o rt /s s w n II 1 fTf ci o e-M t-*n V O a biH *jW l««fl CVSt I O O SS 6*3 ^ O O 3S a f-O M w ss o—a o «^> 0» 6-^l a f-£| I I a o ^9 \ /i*Z «99 ss 0-"I «^o at v-»* O / \ ^3 o ig» I } M o S a a O se n «*■ C* ^ B^3 e» a 6-9" K3 / ^ / \ fa •e 3 s? B 3 a g 13 « <» « ® o a « •o ■s •a •o ■o ■tJ ■« lT5 e « Q A 0 ® o » £S3 u iSi t—* f—« >»* u* Q 42* vd M ea ■ i t/3 | c» 1 ***3 UJ | l 1 1 fo i I &—» 1 1 1 1 P=ss •»»■> va N} o G% U9 O js- OH £SJ 0 Cf^ o Q O a O <1 a 0 o o o n a O n o o [t3 o M! &n 6:i f? H- m O » S3 fT - 6£ - Table 3; (continuation) Rj Rg 21 J Us physical constant 3.61 3.52 3.53 3 c 54 3.55 3.56 3,5? CiH» C6Hs 3,5-(CF3)2-C6Hj C&Hj Cells C j; H s C&Hg, CHs CHj CHj CHj CHJ CHj CHj cyelo-Cslls cyclo-CjHs CHj. cyclo-CjHs cyclo-CsHs cyclo-CjHs cyclo-CjHs CHs CFj CjlU H H K H CFs CFs 11 sp!|. CH»«C- 2-pyridyl 3-pyridyl 4-pyridyl n[» 1.4990 3, S3 C & H s CHJ CHtOCH) H / V /V/ 0 ■fa. p. 155-156°C 3.69 C©H % CHj CHj it -® —8». / % *' 8 'V H n.p.177-179°C 3. 70 CsHs CHs cyclo-CjHs CHiSCHiCHs 3,71 C$Hs CHj CHj / S — (3 s \ / CHi 3.72 3.73 3. 74 3.75 3.75 C$i?§ CtHs CsHs C*i|9 CU 3 CHj C Hi CHj CHj CHa cyclo-CjHj CHsOCHj cyclo-CjH$ cyclo-CjHj C6Hs C6Hs CHs.

H H CFj CHs CHf»(CHj)s CHCli CBrj ■ Table 3 : (continuation) Comp .

Ri &2 Rj R@ Rg physical constant 3. 77 * CgHj CH3 CHi /~\ — <3 9 \ / K 3.78 3.79 3-F-CjHii CsHs CHjOCHi CHsOCH? CHj CHj H H (CHj)jCH (CHi)iCK m.p. 83-8'*°C 1.5673 3° 80 3.81 3.82 3= S3 3.8 A CsHs 4-CFj-CtH* 4-CFj-CjH* CsH s C$H$ cyclo-CjHs CHs CHj CH j CHs-CssC CHj CHs CHj.

CHs cyclo-CjHs 2i3-Cl2~C*Hj CHj.

H CHj(CHj)t H H CHj CgHs H CjKj us. p.,3 79-182°C 3.85 U—F-CjHt cyclo-CjHs CHj Y H m.p.l32-136 °C 3.06 3-F-CjHfs cyclo-CjHs CHj H 9mm I / s — a' \ \/ m.p.111—i12°C 3.87 3.88 CtHs CsHs CHiOCH j CHj CHj CHs CH3 cyclo-CjHs CHs H CHj m.p.112-1! 4°C nj* 1.600 3.89 3.90 3.91 3.92 3-F-CsHii 3-F-C&1U 3-F-CsHii 3—F-C a H\ CH j CHs CHj CHs cyclo-CjHs cyclo-CjHs cyclo-CjHs cyclo-CjHs H H H H CHj CjHS n-CjHt (CHi)iCH m.p.114-116"C m.p. 46-47°C m.p. 4 5-46°C Table 3: (continuation) Comp.

Ri Rs R Q Rg physical constant 3.93 " 3.96 3.95 3.96 3.97 3.98 3.39 3.100 3.10! 3.102 3.103 3.104 3.105 3.106 3.107 CgHs 4-F-CSHss 4-F-CSH., CsHs C<;Bs 3-F-CsHtj 3-F-CsHii 3-F-CsKi, 4-F-CsHi, 4-F-CsHfe CsHi 3-F-CsHfe 3-F-CsHb 3-F-CeHfc CsHs CHj CHj CHs CHj CHj CHs CHs CHs CHs CHs CH2OCH3 CHgOCHj cyclo-CjHs cyclo-CjHs cyclo-CjHs cyclo-CjHs cyclo-CjHs cyclo-CjH$ cyclo-CjHs cyclo-CjHj cyclo-CjH$ cyclo-CjHs cyclo-CjHs cyclo-CjH$ cyclo-CjKs cyclo-CjHs CHs CHs CHs CHs H CzHs n-CsH? H C j H 5 CHs CHj CHs CCls CH2OCH3 H H CHiSCHgClh (CH 3)j C (CHj),C -CH=CH2 H H 0h^ ^SCHj L/n CHj CHs C2H5 CF 3 H CHj 1-nephthyl 2-pyridyl H H H \ m.p. 79-CO°C m.p. 00-81°C m.p.127-128°C xn.p. 104-I05°C n.p.l00-102oC 3.108 CsHs cyclo-CjHs CHj H / \ V m.p. 90-92°C 3.109 3.110 3.111 3.112 3.113 CsHs CSHs C8Hs CsHs 3-F-CsJH cyclo-CjHs CHs CHj CHs CHs CHs CHs CHs CHs CHjOCHs H 2-pyridyl CH 1 CH j 4-pyridyl cyclc-CsHs CHj 2,4-Clj-CsSis (CHa)?CHj H m.p.190-192°C i •i* to I tH Ai m C u m 4-> go m ^ c ^ o CX U © H £SS £*3 El O o 0 o vo CO 1 8A o o o CM 0* £ o 0 6A •4? o 00 o 9 —5 W «0 U o €3 €S.3 a &0144 _ 0< Oo ® <5*9 (C5 u w «W £3 ° e is c js s e g s «o O I 0 1 0 1 e u o o w w I o u c 0 1 c o •w o y \ 5 I J&-U X. / o u o t> o o <5 Ifl P) «*» C-V, [»*-« u o o «* *5» O o Q u 32 «£ t£> «£» Q o O 1 twft tn &f» 1 1 Kfefl 5C Ri r$ Rj ^5® ( R11 physical corsstant 4»1 CsHs CHj CHj 11 CHj. n" i.5983 D 4.2 CsHs CHj CHJ H CiHft 4. 3 C & H s CHJ CHa h CHsCH=CH-| 4, 4 0 o! j s CHJ CHj H n-CjHy n" 1,5740 u 4. 5 Cji1?•> cyclo-CjHs CHj h CHjCbCH 4.6 4-CKjO-CsHij chs CHJ M /CHs- s-5. n-CsHi1 4.7 Cj,s!s chs cyclo-CjH$ / s 9 e V yCH 2 - 8_s H nls 1.61 so 1) 4.8 3,MCH3)s-C«H3 CHs chs y \ V h Table 4: (continuation) Comp, 1U Ra Rj Rt c Ri % physical constant ^CHs- 4.9 4-CF j-CsHi( CHs CHj v CHj 4.10 3-F-CsHt, CH 3 cyclo-CjHs S n-CjH? 51—'C 3 H 7 n^; 1 .5510 4.11 Csil$ CHjOCH3 CHj CH2C(CHj}j H 4.12 4.13 ■CsHs CgHs CHaOCHj CH3 CHj CHs /=H\ \ CHj H ■ CHj njj5 1 o 5673 4.14 CsHs CHa CHj CsHsCH a- ■3 9 H isi.p. 56-57°C 4=15 CsHs CHj ■cycio-C jH s \ y~ch~ \H H 4.16 4.17 4-F-Cs Hij CgHs ch3 CHjOCHj cyclo-CjHs CH j / v_C H,- ira H H CHj m.p. 03-04°C 1.5793 4, IS 4.19 4.20 CsHs CsHs CsHs CH2OCH3 CHaOCH3 CHgOCH3 CHj CHj CHj CHjCH-CHCHj-. CFjCHi n-CjH? H H H njjs 1 .5635 Tabls 4 l (continuation) Comp.

Ri Rj Hi 0 Ri 1 4.21 CsHs CH2OCHj CHj i ll H \ /\ntI OH 4.22 4-F-CsHti CHj cycio-CjHs CaHs h 4.23 3-Br-CeH* CHj cyclo-cjhs n-c<,h$ CHs 4 o 24 2-Cl-4-CFj-CeHj CHj CHj CHj.

CjHs 4.25 C(Hs CgHs CHj H < CHj 4.26 CsH$ n-CjHs CHj H chj 4.27 c$h§ CH(CBj)t CH(CHj)i H CHj 4.20 cshs CHs C(CH3>j H CHj 4.29 C s H s CjHJ c1h5 fl CHj 4.30 CjKs CHa CHsOCHj H ^s—£Hz 0 4.31 4-F-CjHfe CHj CHj cahs C «H» 4.32 4-F-CjHi, CHj CHj CH j H 4. 33 CsHj CHj CHj CHjCClj H 4.34 /~\ „ „ H CgHj CHj CHj \ ^*—9hch s s •• a 4.35 C5H5 CHj CHj (CHj)jCH H 4.36 C.j Hj cyclo-CjHj CHj (CHj)jCH 11 4.37 csh^ cyclo-CjHs chj CgHs(CHj)CH- H 4.38 cshs CH» CHj SrjCCHj- h 4.39 cshs CHj CHj CHjCHaCH H 4.40 Cells CHj CHs CHzCHaCK* CHjCHaCN 4.41 CSHS CHj cyclo-CjHs CHaCHaCN CHsCHjCH physical constant nf.1 1 .5593 D •b. CTl n»* 1 .5533 ra?p. 57-59°C n® * 1 . 5772 D TabI® 4 (continuation) Comp« Rs R 2 Rs Ri i physical constant 4.42 4.4 3 4. k 4 C $ H 5 C $ H 5 C&Hj CHj CH3 CHj cyclo-CjHs cyclo-CjHs cyclo-CjHs CHiCHiCN cycio-CsHii CjHs K H H m.p. 75-77°C njjf 1 . 5830 4.45 C gH 5 CHj cyclo-CjHs CHj H „» -j t 5933 4.46 3-F-CjH* CHj cyclo-CjHj CHj H niE 1 .5842 u 4.47 4.48 4® 49 3-F-CtHt, 4-F-CsHn CsHs CHa CHj CHj cycio-CjH$ cyclo-CjHs CHj CjHs C2Hs(CHj)CH H H H cyclo-C®Hii i S 8 Hp3, 1 .5778' 4.50 CsHs CHi CHj if / \ — s e \ V ®—. r 4.51 4.52 4.53 4.54 4.55 4.56 CsHs C®Hs CtHs 3-F-CsH* 3-F-CtH* 3-F-CsH's CHj CHjCCHj CHaCCHj CHgOCHj CHjOCHj CHjOCH3 CH3 CHj CH 3 CHs CH j CH3 H CHJCCH2(CH3)CH-(CH j)jKCH 2(CH 3)CH- H H (CHj)aCH cyclo-C$H» H 3 H (CHj)CHCHJ n-CjH7 H m.p. 04-068C n}* 1 .5565 n*} 1 .5450 D 4.57 4-I-CjHi, CHj CHj esi H 4.58 C s H 5 CHs cyclo-CjHs H cyclo-CjHii m.p. 75-77°C 4.59 CsHs CH3 cyclo-CaHj !>-gr ?■ H Tabla 4% (continuation) 1 Comp.

III Its Rj Ri o ; Ri i physical constant u. SO. 4 0 SI 4.62 4. S3 4. 64 4.65 C$Hs C«Ks 2-F-C$Hi 2-F-C$H)j 4-r-C$K!, CHs CHj CHs CHj CjHs CHj cyclo-CjHs cyclo-CjHs cyclo-CjHs cyclo-CjHs CHj cyclo-CjHs H H CFjCHi DrsCCHg CIiCHCHJ CHj ^CH FjCT n-CjH? Cells H H H H m.p.l25-127°C 4.66 4.67 4.68 4.69 4-F-CfiHv 4-7-CsKt 4-7-CsHt :C £. JI s CHj CHs CHj CHj cyclo-CjHs cyclo-CjHs cyclo-CjHs CHsOCHj IS H H CH j \ gII ^ Cfij n-CsH? (CHj)iCHCHj CHj „j» 1.5595 4.70 C £. ii 5 CHj CH?OCH3 n-CjHy n^CjHy nM 1.5483 4.71 4.72 Cells C 6II g CHj CHj CHjOCH3 CH a OCH j H BrCHiCHO • CHj(CH«)7 H 4.73 C(Hj CHj CBfOCHj y \ \y/ \ih- H m.p. 67-6®°C 4.74 CsHs CHj CHj CHj H C2Hs(CHj)CH- n' i „ 5638 1) 4.75 CHj CHj C«Hs(CFi)CH- H Tabls 4; (continuation) Comp.

Ri Rg Rs Hi 0 Ri i pftysical constant js /CHs J • 4.78 C«Hs CHj CHj H • CHj- 4.77 CtHs CHs CHj (CHj)iCHCHg H nO 1.5623 4.70 CsHj CHi CHj K chi- s n" 1.6175 D 4.79 C e H s CHj CHj 3 [/-CHj- 9 I! 4 <00 Ct*v CHs CHj CFjCHf- H •'<.81 CsHs CHj cyclo-C3H$ CHj C] H$ 1.5803 4.82 C'Hs CH3 cyclo-CjHj H firjCCHj- 4.03 C £ H 5 CHj cyclo-CjHs 9 |^j—CHf— CHai H 4, M CsHs CH j cyclo-CsHs H t !l 9 9 NCHt- m.p. 62-63°C i VO I Tabls hi (continuation) Corap.

Ri Ri Pvj Ri 0 Rx i physical constant k, as CsHs CHj cyclo-CjHs H 2t-\ A /CHs" %r t> f IE Si 8 Y sci 4i m.p. 67-60°C 4.05 C&Hs CHj cyclo-C jHs H 6.87 6.08 ft. 09 h. 90 CeKft C e H s CeHj 4-F-CeH* CHj CHs CHs. CHa cyclo-CjHs cyclo-CjHs cyclo-CjHs cyclo-CjHs H H C6H5CH2 n-CjH?

Claims (26)

CLAIMS i

1. A compound of the formula 1 /Rg 8, Rss» V (I) r/ nh- ( lis wherein: Rx is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-C5alkyl, Ci-Cgalkyl substituted by the radical 0R5 or by the 5 radical SRS, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen, C3-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is hydrogen, C1-C4alkyl, C1-C4alkyl substituted by halogen, cyano or by the radical 0RS or by the radical SRs, C3-Cseyclos.lkyl or C3-C6cycloalkyl mono- to tri-substituted by Ci-C4alkyl or by halogen; R4 10 is halogen, C1-C3alkyl, (^-Cjhaloalkyl, C1-C3alkoxy or Ci-C3haloalkoxy; Rs is hydrogen, C1-C5alkyl, Cj-C^alkenyl, C1-Csalkynyl or the radical (CH2)n-X-C1-C3alkyl; /^B Ri o R7 is the group -D3H2, -NbC or _«/ \ » R?j ^ , e, e> Rs is hydrogen, C1-C3alkyl or C^-C^haloalkyl; R9 is hydrogen, C-j^-Cgalkyl, 15 C1-C3alkyl substituted by hydroxy, OR12, SR12 or by N(R12)2, C3-C6cyclo- alkyl, cyclopropyl substituted by SR12, C3-C10alkenyl, C1-C3haloalkyl, 1-, 2- or 3-pyridyl, .-v V or / v. . vN V * R8 and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 4 to 7 carbon atoms; R10 is 20 CH(R8)R9, phenyl, C3-C5alkenyl, C3-C5alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical ; R13_ 2.S hydrogen, C,-C5alkyl, C3-C5alkenyl, C3-C5alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R12 is CH3 or C2H5; X is oxygen or sulfur; Z is O, S, NH or NCH3; and n is 1 to 3; including the acid addition salts and metal 25 salt complexes thereof.

2. A compound of the formula I according to claim 1, wherein: R, is - so - phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-Csalkyl, C1-C5alkyl substituted by the radical 0R5 or by the radical SR5, C3-Cscycloalkyl, C3-Cscycloalkyl mono- to tri-substituted by Cj-C^alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is 5 Cj-C^alkyl, Cx-Chalky 1 substituted by halogen, cyano or by the radical ORs or by the radical SR5, C3-Cscycloalkyl or C3-Cscycloalkyl mono- to tri-substituted by C, ~C4 alkyl or by halogen; RA is halogen or C,-C3alkyl; R5 is hydrogen, C^-Cgalkyl, C3-C5alkenyl, C3-Csalkynyl or the radical (CH2) n-X-C1-C3alkyl; R9 is hydrogen, C^-C^alky!, C3-C6eycloalkyl, 10 C5-Csalkenyl, C1-C3haloalkyl; R8 and R9, together with the carbon atom in the radical R7 are a saturated or unsaturated ring comprising 5 or S carbon atoms; R7, R10, Ri;l, R12 and Z are as defined under formula I; X is oxygen or sulfur; and n is 1 to 3.

3. A compound of the formula I according to claim 1, wherein: Rx is 15 phenyl or phenyl mono-substituted by halogen; R2 is hydrogen, C1-C5alkyl, C^Cgalkyl substituted by OR5, C3-Cscycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by Cj-C^alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C^-C^ alkyl, C1-C4alkyl substituted by halogen, cyano or by OR5, C3 -Cscycloalkyl or C3 - C6cycloalkyl substituted by 20 methyl; R5 is hydrogen or C;i-C2alkyl; Rs is hydrogen, C1-Csalkyl, C3-C6cycloalkyl, C3-C5alkenyl, C1-C3haloalkyl, Rs and Rg, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; and R7, R10, R1X and R12 are as defined under formula I. 25

4. A compound of formula I in claim 1, wherein: Rx is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-C5alkyl, C^-Cgalkyl substituted by the radical OR5 or by the radical SRS, C3 -Cgcycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C^-C^alkyl, 3 0 C1-C/jalkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, C3-C6cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by C^-C^. alkyl or by halogen; R4 is halogen, C1-C3alkyl, Cx-C2haloalkyl, C1-C3alkoxy or C1-C3haloalkoxy; Rs is hydrogen, C,-Csalkyl, C3-C5alkenyl, C3-C5alkynyl or the radical (CH2) n-X-C1-C3alkyl; R7 is -NH2; X is oxygen 3 5 or sulfur; and n is 1 to 3; including the acid addition salts and metal salt complexes thereof. - 61 -

5. A compound of the formula I according to claim 4, wherein: Rx is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, Ci"Csalkyl, Ci-Csalkyl substituted by the radical 0RS or by the radical SR5, c3-Cgcycloalkyl, C3-Cscycloalkyl mono- to tri-substituted by 5 Ci-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is Ci-C-alkyl, Cj^C^alkyl substituted by halogen, cyano or by the radical 0RS or by the radical SRs, C3-C6cycloalkyl or C3-Cscycloalkyl mono- to tri-substituted by Cj-C-alkyl or by halogen; is halogen; R5 is hydrogen, C^Cgalkyl, C3-C5alkenyl, C3-C5alkynyl or the radical 1 q (CH2)n-X-C1-C3alkyl; X is oxygen or sulfur; and n is 1 to 3.

6. A compound of the formula I according to claim l, wherein: % is phenyl or phenyl mono- to tri-substituted by halogen; R2 is hydrogen, C1-C5alkyl, C1-C5alkyl substituted by the radical 0R5 or by the radical SR5, C3-C6cycloalkyl, C3-C5eyeloalky 1 mono- to tri-substituted by 15 C!-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C^^-C^alkyl, C1-C4alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SRs, C3 - C6cycloalkyl or C3-Cgcycloalkyl mono- to tri-substituted by C^-C^alkyl or by halogen; Rs is hydrogen, Ci-Csalkyl, C3-C5alkenyl, C3-C5alkynyl or the radical (CH2)n-X-C1-C3alkyl; 20 X is oxygen or sulfur; and n is 1 to 3.

7. A compound of the formula 1 according to claim l, wherein: Rj is phenyl or phenyl mono-substituted by chlorine or by fluorine; R2 is C1-C5alkyl, or is C1-C2alkyl substituted by ORs, C3-C6cycloalkyl, C3-Cgcycloalkyl mono- to tri-substituted by C1-C/.alkyl or by halogen, 25 C2-C5alkenyl, C2-Csalkynyl or the formyl radical; R3 is C1-C4alkyl, C1-C4haloalkyl, C3-Cgcycloalkyl or C3-Cgcycloalkyl substituted by methyl; and R5 is hydrogen or Cj^-Cjalkyl.

8. A compound of the formula I according to claims 6 and 7, wherein R3 is: methyl, fluoromethyl, chloromethyl, bromomethyl, C3-Cgcycloalkyl or 1.3 0 methoxymethyl.

9. A compound of formula I according to claim l, from the group: N-(4-fluoromethyl-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-m-fluorophenylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-p-fluorophenylhydrasine; - 62 -

10. A compound of formula I according to claim 5 from the group: N-(4-methyl- 6 -cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4,6-di-mathylpyrimid-2-yl)-N-phenylhydrasine; N-(4-methyl-S-methoxymethyl-pyrimid-2-yl)-N-phenylhydrazine; 5

11. A compound of formula I according to claim 1 from the group: N-(4,S-dimethylpyrimid-2-yl)-N-phenylpropionaldehyde hydra2one; N-(4,6-dimethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methyl-S-methoxymethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; 1 0 N-{4-methyl-S-methoxymethylpyrimid-2-yl)- N -phenylpropionaldehyde hydrazone; N-(4-methyl-S-cyclopropylpyrimid-2-yl)- N -phenylpropionaldehyde hydrazone; N- (4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-n-butyraldehyde 15 hydrazone; N-(4-methyl- S -cyclopropylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyltrichloroacetaldehyde hydrazone; 20 N-(4-methyl- S -cyclopropylpyrimid-2-yl)-N-p-fluorophenylacetaldehyde hydrazone; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-p-fluorophenylisobutyraldehyde hydrasone; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-m-fluorophenylisobutyraldehyde 2 5 hydrazone; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4,S-dimethylpyrimid-2-yl)-N-phenyl-H'-n-propylhydrazine; N-(4,S-dimethylpyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; 3 0 N-(4-methy1-6-methoxymethyIpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N- (4-methyl-S-methoxymethylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4-methyl™ S-methoxymethylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N- (4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-isobutylhydrasine; 3 5 N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl- 6 -cyclopropylpyrimid-2-yl)-N-phenyl-N'-diethylhydrasine; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-methyl-N'-ethyl- - S3 - hydrazine; N- (4 -methyl - S - cyclopropylpyrimid-2 -yl) -N-p-£ luoropheayl -H' -ethyl-hydrazine; N- (4-methyl~S-msthoxymethylpyrimid-2-yl) -K-m-fluorophenyl-N' -isopropyl-hydrazine;

12. A process for the preparation of a compound of the formula I according to claim l, which comprises a) reacting a pyrimidine derivative of the formula II J*? Y_y \ cn) w Rs with a phenylhydrazine derivative of the formula III I^-KIH-NH-R (III) in the presence of a base, in an aprotic solvent and at temperatures of -50°C to 150°C, wherein Y is halogen, the radical S02Rs or ISP5 (CH3) 3, R6 is Ci-C4alkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for R10 and R11# and the latter and also Ri-R3 are as defined under formula I, b) reacting a pyrimidine hydrazine derivative of formula IV with an aldehyde or ketone of formula V to form a compound of formula VII with the removal of water a Jig Ji—. Ra J* ^ n u. v x r pb—- • Ri « *" T C-—W «, A ®>»dv TV ✓ V5 / 0 / —C=*l sis:» R f (TV) (V) (VII) in any desired solvent, in the presence of an acid and at temperatures of -20° to 120°C, Rj-Rj and R8 and R9 being as defined under formula I, or - 64 - c) reducing a hydrasone derivative of formula VI] .Ri .Ri R H- Rev 3educdpn Rj—»—' c~if *=-' n\ R? \$ \ CKR«(a») (VII) O'lXI) using a reducing agent, in an inert solvent and at temperatures of 0° to 50°C or by catalytic hydrogenation using catalysts, d) subjecting a pyrimidine hydrazine derivative of formula IV R-p / * SH :>?«=-' Es to reductive alkylation with an aldehyde or ketone of formula v Rb-?-R» in the presence of a reducing agent, in an inert solvent and at temperatures of 0° to 50°C, -JO e) alkylating a pyrimidine hydrazine of formula IV or VIII with an alkyl halide R0Hal _ /■ . "v Hi—ff—"• .. V Ih:v-( ° N» / ■», R a *vj "j o (TV) (IX) - 65 - R, /Rz R<—S-•• - + R Hal /*

13. A composition for controlling or preventing attack by insect pests 5 or destructive microorganisms, which composition contains as active ingredient at least one compound of formula I according to claim l together with a suitable carrier.

14. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 4. 10

15. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 9.

16. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 10.

17. A composition according to claim 13, which contains as active 1 5 ingredient at least one compound of formula I according to claim 11.

18. A method of controlling or preventing attacks on cultivated plants by insect pests or phytopathogenic microorganisms, which comprises applying to the plant, parts of the plant or the locus thereof, as active ingredient, a compound of formula I according to claim 1. 20 is.

19.A method according to claim 18. .which comprises applying as active ingredient a compound according to any one of claims 2 to 11.

20. A method according to claim 18, which comprises controlling phytopathogenic fungi. - S0 -

21. A process for the preparation of an agrochemical composition according to claim 13, which process comprises intimately mixing at least otis compound of fonnula I according to claim 1 with suitable solid or liquid adjuvants and/or surfactants. 5

22. A compound according to claim 1, substantially as hereinbefore described and exemplified.

23. A process for the preparation of a compound according to claim 1, substantially as hereinbefore described and exemplified. 10

24. A compound according to claim 1, whenever prepared by a process claimed in claim 12 or 23.

25. A composition according to claim 13, substantially as hereinbefore described and exemplified.

26. A method according to claim 18, substantially as 15 hereinbefore described and exemplified. F. R. KELLY & CO., AGENTS FOR THE APPLICANTS.