IE72462B1 - Pesticides - Google Patents

Pesticides

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Publication number
IE72462B1
IE72462B1 IE288189A IE288189A IE72462B1 IE 72462 B1 IE72462 B1 IE 72462B1 IE 288189 A IE288189 A IE 288189A IE 288189 A IE288189 A IE 288189A IE 72462 B1 IE72462 B1 IE 72462B1
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IE
Ireland
Prior art keywords
alkyl
radical
substituted
phenyl
formula
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IE288189A
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IE892881L (en
Inventor
Helmut Zondler
Adolf Hubele
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Ciba Geigy Ag
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Publication of IE892881L publication Critical patent/IE892881L/en
Publication of IE72462B1 publication Critical patent/IE72462B1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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-aminopyrimidine 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 14 ingredients or the compositions for controlling pests, especially plantdestructive microorganisms, preferably fungi.
The pyrimidine compounds according to the invention have the general formula I 8K >R? ^_Z N— .Ra (I) wherein: Rx is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-C5alkyl, C1-C5alkyl substituted by the radical OR5 or by the radical SR5, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is hydrogen, C^-C^alkyl, Cx-C4alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SR5, C3-C6cycloalkyl or C3-Cecycloalkyl mono- to tri-substituted by Cx-C4alkyl or by halogen; R4 is halogen, Cx-C3alkyl, C^-C^haloalkyl, C^-C^alkoxy or C^-Cjhaloalkoxy; Rs is hydrogen, C1-C5alkyl, Cx-C5alkenyl, Cx-C5alkynyl or the radical (CH2)n-X-Cx-C3alkyl ; R7 is the group -KH2, Rs ~N=Z or .Z’· Hj. 1 R8 is hydrogen, Cx-C3alkyl or C1-C3haloalkyl; R9 is hydrogen, C^-Cgalkyl, C^-Cjalkyl substituted by hydroxy, OR12, SR12 or by N{R12)2, C3-C6cycloalkyl, cyclopropyl substituted by SR12, C3-C10alkenyl, C1-C3haloalkyl, 1-, 2- or 3-pyridyl, ___ Z , « V — fc* Z \ or . \/x \/ · Re 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 - 2 carbon atoms in ths alkyl radical; RX1 is hydrogen, Cj-Cgalkyl, C3-C5alkenyl, C3-C5alkynyl or cyanoalkyl 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 1 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, CH2CH2Sr, C2C15, CH2Br, CHBrCl etc., preferably CF3. Depending on the number of carbon atoms indicated, cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl 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 nonharmful 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 - 3 acid, p-toluenesulfonic 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, benzoates, etc. of the elements of the second min 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 any 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 I (Substituents) R3 is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, Cj-Cgalkyl, C1-C5alkyl substituted by the radical ORS or by the radical SRs, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C1C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is Cx-C^alkyl, C1-C4alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SR5, C3-Cecycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen; R4 is halogen or C1-C3alkyl; Rs is hydrogen, C1-C5alkyl, C3-Csalkenyl, C3-Csalkynyl or the radical (CH2) jj-X-C^-C^alkyl,- Rg 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 δ '30 carbon atoms; r7, R10, rx1, r12 ar,-' Z are as defined under formula I and halogen is preferably fluorine, chlorine or bromine. X is oxygen or sulfur; and n is l to 3.
Group 2 (Subs t i tuent s) Rx is phenyl or phenyl mono-substituted by halogen; R2 is hydrogen, C^-Cgalkyl, Cj.-Cgalkyl substituted by OR5, C3-C6cyeloalkyl, C3C6cycloalkyl mono- to tri-substituted by Cx-C4alkyl or by halogen, C3C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is Cx-C4alkyl, CxC4alkyl substituted by halogen, cyano or by ORS, C3-C6cycloalkyl or C3-Cseycloalkyl substituted by methyl; R5 is hydrogen or C1-C2alkyl; R9 is hydrogen, Cx-C5alkyl, C3-C6cycloalkyl, C3-C5alkenyl, C1-C3haloalkyl, Re and Rg, 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, chlorine or bromine.
Group 3 (Substituents) Rx is phenyl or phenyl mono- to tri-substituted by R4; R2 is hydrogen, C1-Csalkyl, Cx-Csalkyl substituted by the radical ORS or by the radical SR5, C3-C6cyeloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C1-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is Cx-C4alkyl, Cx-C4alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SR5, C3-C6 cycloalkyl or C3-C6cycloalkyl monoto tri-substituted by Cx-C4alkyl or by halogen; R4 is halogen, C1-C3alkyl, C1-C2haloalkyl, Cx-C3alkoxy or Cx-C3haloalkoxy; R5 is hydrogen, Cx-C5alkyl, C3-C5alkenyl, C3-Csalkynyl or the radical (CH,)n-XC1-C3alkyl; R7 is -NH2; 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, Cx-C5alkyl, Cx-C5alkyl substituted by the radical OR5 or by the radical SRs, C3-Cscycloalkyl, C3-Cecycloalkyl mono- fo tri-substituted by Cx-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is Cx-C4alkyl, Cx-C4alkyl substituted by halogen, cyano or by the radical ORS or by the radical SRs, C3-C6cycloalkyl or C3-Cecycloalkyl monoto tri-substituted by Cx-C4alkyl or by halogen; R4 is halogen; R5 is hydrogen, C1-Csalkyl, C3-C5alkenyl, C3-C5alkynyl or the radical (CH2)n-X-Cx-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 hydrogen, Cx-C5alkyl, Cx-Csalkyl substituted by the radical ORS or by the radical SRs, C3-C6cycloalkyl, C3-Cscycloalkyl mono- to tri-substituted by Cx-C4alkyl or by halogen, C2-C5alkenyl, C2-C5alkynyl or the formyl radical; R3 is C1-C4alkyl, C^-C^alky! substituted by halogen, cyano or by . the radical OR5 or by the radical SR5, C3-C6cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by Cx-C4alkyl or by halogen; Rs is hydrogen, C3> C5alkyl, C3-C5alkenyl, C3-C5alkynyl or the radical (CH2)jj-X-Cj-C^alkyl; X is oxygen or sulfur; and n is 1 to 3.
Group S (Subst i tuents) Rx is phenyl or phenyl mono-substituted by chlorine or by fluorine; R2 is C^-Cgalkyl, or is C^-Cjalkyl substituted by OR5, C3-C6 cycloalkyl, 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, C^-C^haloalkyl, C3-C6cycloalkyl or C3-C6cycloalkyl substituted by methyl; and R5 is hydrogen or Cx-C2alkyl.
Especially preferred are those compounds of groups 5 and S wherein R3 is: methyl, fluoromethyl, chloromethyl, bromomethyl, C3-C6 cycloalkyl or methoxymethyl.
The following groups of individual substances are preferred: Group 1 (Compounds) N-(4-fluoromethyl-0-cyclopropylpyrimid-2-yl)-ϊί-phenylhydrasine; N- (4-methyl-δ-cyclopropylpyrimid-2-yl) -N-m-fluorophenylhydrazine; N-(4-methyl-δ-cyclopropylpyrimid-2-yl)-N-p-fluorophenylhydrazine ; Group 2 (Compounds) N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4,6-di25 methylpyrimid-2-yl)-N-phenylhydrazine; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenylhydraz ine; ' Group 3 (Compounds) N-(4,6-dimethylpyrimid-2-yl) -N-phenylpropionaldehyde hydrazone; • N-(4,6-dimethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N- (4-methyl-6-methoxymethylpyrimid-2-yl) -N-phenylisobutyraldehyde hydrazone; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4-methyl- 6 -cyclopropylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N- (4-methyl-6-cyclopropylpyrimid-2-yl) -N-phenyl-n-hutyraldehyde hydrazone; W-(4-methyl-δ-cyclopropylpyrimid-2-yl)-M-phenylisohutyraldehyde hydrazone; N- (4-methyl-δ-cyclopropylpyrimid-2-yl)-N-pheny1trichloroacetaldehyde hydrazone; N-(4-methyl- 6 -cyclopropylpyrimid-2-yl)-N-p-fluorophenylacetaldehyde hydrazone; N-(4-methyl- 6 -cyclopropylpyrimid-2-yl)-N-p-fluorophenylisobutyraldehyde hydrazone; W-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-m-fluorophenylisobutyraldehyde hydrazone; N-(4,S-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4,S-dimethyIpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4,S-dimethylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-isohutylhydrazine; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N- (4-methyl-6-methoxymethylpyrimid-2-yl) -N-phenyl-N' -n-propylhydrasine; N- (4-methyl-6-methoxymathylpyrimid-2-yl) - N - pheny 1 -N' -dimethylhydrazine; N-(4-methyl-b-cyclopropylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N- (4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-isohutylhydrazine; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-phenyl-N'-diethylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-methyl-N'-ethylhydrazine; N-(4-methyl-e-cyclopropylpyrimid-2-yl)-N-p-fluorophenyl-N' -ethylhydrazine; N- (4-methyl-e-methoxymethylpyrimid-2-yl) -N-m-fluorophenyl-S' -isopropylhydrazine; The compounds of formula I are prepared as follows: Process (a) Reaction of a pyrimidine derivative of formula 11 (II) \-Z Rs with a phenylhydrazine derivative of .he formula III Rj-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, preferably chlorine, the radical SO2R6 or N®(CH3)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 R1-R3 are as defined under formula I.
Process (b) 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 wNH2 M:c=0 Ηχο Rs Re R (IV) (V) (VII) in any desired solvent, in the presence of an acid and at temperatures of -20° to 120°C, preferably 10° to 50°C, Rx-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 Na2SO4, can also be used. In the case of the reaction of derivative (IV) 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 ,R?.
Rx. s \ / wr R? Rj Bednctip: stednctipz (vxi) .Rs Rl4~\nJ» N"" \ as CKRa(R*) (1 using a reducing agent, for example borohydride etherates, NaBH4, NaCN3H3 or LiAlHtl, 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 nickel, platinum, pallamium or rhodium.
Process (d) Reductive alkylation of a pyrimidine hydrazine derivative of formula IV Ra A SH- S (IV) 'Ra with an aldehyde or ketone of formula V in the presence of a reducing agent, for example borohydride etherates, 10 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, preferably 10° to 40°C.
Process (a) Alkylation of a pyrimidine hydrazine of formula IV or VIII with an alkyl 1 5 halide RoHal (IV) X=Rs: \ Rj CHR0(R?) (VIII) . Hal R Hal o Z it >3 O 9 ( XX) Rz i *< / \ s‘ H CHRg(Ri) (X) in an inert solvent, in the presence of a base and at temperatures of 0°-S0°C, preferably 10°-40°C, Ro being C1-C4alkyl. Other suitable alkylating agents are dialkyl sulfates.
In processes (a-e) described above, R-^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.
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 with /J-diketones to form 2-hydroxypyrimidines which are subsequently reacted to form 2-halopyrimidines as follows: H2N. \ =0 Especially phosphorus oxychloride or phosphorus oxybromide may be used as halogenating agents.
Another possible method of obtaining the 2-halopyrimidines of formula II is to prepare them by way of the 2-aminopyrimidines. The 2-aminopyrimidines are obtained by known methods (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962), then diazotised, and converted by the Sandmeyer process into the 2-halopyrimidines. The 2-amino-pyrimidines are obtained, for example, by condensing 0-diketones with guanidine in the following manner. 1) NaNO2/H The pyrimidine derivatives of formula II in which Y is SOj-Cj-C^alkyl or SO2aryl 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 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 IX Y- in which Y is halogen or SO2-R6 and R6 is Cx-C4alkyl or aryl and R2 and R3 are as defined under formula I, are known.
The hydrazine derivatives of formula XXI are knovm or can ba prepared by methods known to the person skilled in the art.
EP-A-270111 describes 2-anilinopyrimidine 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 X 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 Ascomycer.es class (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and the Oomycetes class (e.g.
Phytophthora, Pythium, Plasmopara). 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 effective 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 and fodder beet); 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); lauracaae (avocados, cinnamonium, 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 applicationpromoting 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 I, 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 Jcnown 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, atomising, 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, 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 dioctyl phthalate, aliphatic hydrocarbons 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 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 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 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 comprising mixtures of surfactants.
Both so-called water-soluble soaps and water-soluble synthetic surfaceactive 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 alkylsulfonares.
The fatty alcohol sulfonates or sulfates are usually in the form of 10 alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cg-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 2sulfonic [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 dibutyl20 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 30 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 2q polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene 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 IS 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 polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are in particular quaternary ammonium salts which contain, as M-substituent, at least one C8-C22alkyl radical and, as further substituents, unhalogenated or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methy3.sulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(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 X, 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 % 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 more detail without limiting it. 1. Preparation Examples Example 1.1: 2-hydroxy-4-mathvl-6-cyclopropyIpvrimidine hydrochloride (starting material) Λ H0Z HC1 S.O g (0.10 mol) of urea and 12.6 g (0.10 mol) of cyclopropylbutane-1,3dione are dissolved at room temperature (~20°C) in 35 ml of ethanol and 15 ml of 32 % 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 S0°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: CbH10N2O*HC1 (MW: 186.64) % calc. % found c 51.48 51.47 H 5.94 5.97 N 15.01 15.15 Cl 18.99 18.89 - 18 Example 1.2: 2-chloro-4-methyl-a-cvclopropylpyrimidine hydrochloride (starting material) ft «ζν'γί 52.8 g (0.24 mol) of 2-hydroxy-4-methyl-S-cyclopropylpyrimidine hydrochloride are introduced into a mixture of 100 ml of phosphorus oxychloride and 117 g (0.79 mol) of diethylaniline and stirred; the exothermic reaction slowly begins, the temperature rising from room temperature to S3 °C. The batch is then heated ia an oil bath for 2 hours at 1OO-11O°C internal temperature. After cooling to room temperature, the mixture is poured, with stirring, into a mixture of ice-water and methylene chloride. After one hour, the organic phase is separated off in a separating funnel and is washed neutral with NaHCO3 solution. After removing the solvent, 115.4 g of crude product comprising 2-chloro-4methyl-S-eyelopropylpyrimidiae and diethylaniline are obtained. Chromatographic separation using silica gel and a mixture of 25 % of 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~eyclopropylpyrirnidine in the form of a colourless oil.
Example 1.3: 2-amino-4-diethoxvmethvl-6-cvclopropylpyrimidine (starting material) γ— I ¥ f. β A H;)/ XCH(OCjHs)2 74.8 g (0.42 mol) of guanidine r^rbonate and 74.1 g (0.35 mol) of 4-cyclopropyl-2,4-dioxobutyraldehyde diethyl acetal are boiled for 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 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-formyl-g-cyclopropylpyrimidine (starting material) \ / 70.3 g (0.30 mol) of 2 -amino-4-diethoxymethyl- 6 -cyclopropylpyrimidine are dissolved in 340 ml of 32 % aqueous hydrochloric acid and cooled 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 gal, eluant 30 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: C0H7ClN2O (MW: 182.61) % calc. 52.6 52.6 3.9 4.1 .3 14.8 Cl 19.4 18.7 Example 1.5 : 2 - chloro- 4 - hydroxymethyl - 6 - cyclopropylpyrimidine (starting material) II .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 horohydride. 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 i£-recrystallised from a mixture of 20 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: C8H9C1N2O (MW: 184.63) % calc. % found c 52.04 52.05 H 4.91 4.90 M 15.17 15.27 Cl 19.20 19.28 Example 1.6: 2-chlpro-4-hydroxymethyl-6-cvclopropvlpyrimidine methanesulfonate (starting material) II C1' XCH;OSO2CHj 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 parts of hexane) to give 13.6 g of the pure substance. M.p. 64-66°C.
Analysis: C9H11C1K2O3S (MW: 262.71) % calc. % found C 41.15 41.32 H 4.22 4.33 N 10.66 10.56 Cl 12.20 12.16 - 7"» <*W Λ Example 1.7: -chiorο-4-fluoromethyl-6-eye1opropylpyrimidine (starting material) \ / ΐ .// \ y H C1Z V XCH2F 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 fluoride and 0.8 ml of 18-crown-6 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.
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 10.25 Cl 19.00 18.50 Example 1.8: 2 -chloro-4 -methvl-S (starting material) \77 c/ XCHi 76.4 g (0.47 mol) of 2-amino-4-methyl-5-(2-methyIcyclopropyl)pyrimidine, produced by boiling guanidine carbonate with acetylmethyl-2methylcyclopropyl ketone in ethanol, are dissolved in 536 g of 32 & 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 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 and 80 parts of hexane as eluant to give 32.2 g of the pure substance; refractive index n^' = l. 5334 .
Analysis: CgH^ClI^ % calc. % found c 59.18 59.IS H S.07 5.15 N 15.34 15.25 Cl 19.41 19.20 Example 1.9: 2-(g-phenvlhvdrazino)-4. a-dimethylpyrimidine (Comp. 1.12) CH3 I ' x CHj 4.77 g (0.033 mol) of phenylhydrazine hydrochloride are suspended under nitrogen in SO ml of tetrahydrofuran, and 7.41 g (O.OSS 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 tvith ethyl acetate and water with the addition of a small amount of 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 55 parts of hexane gives 2.89 g of the pure substance which, after recrystallisation from nhexane, malts at 41-43°C.
Example 1.10: 2-(g-phenylhvdrazino)-4,6-dimethylpyrimidlne {Comp. 1.12) 7.06 g (0.035 mol) of 2-triraethylaramonium-4,6-dimethylpyrimidine chloride1 and 5.78 g (0.04 mol) of pheaylhydrazine hydrochloride are suspended in 50 ml of tetrahydrofuran, and a solution of 5.04 g (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 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-methyl-6-cvclopropylpyrimidin-2-yl)-N-phenvlhvdrazine (Comp. 1.4) 2.20 g (0.013 mol) of 2-chloro-4-methyl-6-cyclopropylpyrimidine and 1.S2 g (0.015 mol) of phenylhydrazine are dissolved in 20 ml of tetrahydrofuran. A solution of 2.02 g (0.018 mol) of potassium tertbutylate in 20 ml of tetrahydrofuran is added dropwise to this solution with cooling at 20-25°C. After 30 minutes, the starting pyrimidine can no longer be detected by thin Iyer 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 (SO.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 (65.3 % of the theoretical yield).
Analysis: C14H16N4 (MW: 240.31) % calc. % found 69.8 6.71 6.77 23.32 23.49 Example 1.12: M-(4-methyl-6-cvclopropvlpyrimidin-2-vl)-N-phenvIisobutvraldehvde hydrazone (Comp. 3.26) II II 6.25 g (0.026 mol) of JST— (4-methyl-6-cyclopropylpyrimidin-2-yl) -N-phenylhydrasine 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 (eluant: 72 % of hexane/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: C18H22N4 (MW: 294.40, % calc. % found 73.44 7.53 19.03 73.25 7.64 18.92 Example 1.13: M-(4-methvl-6-c_yclopropylpyrimidin-2-yl)-N-phenyl-N'isobutvlhydrazine (Comp. 4.8 7) \ Z* Y V \h, HNCH2CH(CHj)2 8.55 g (0.029 mol) of N-(4-methyl-6-cyclopropylpyrimidia-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/15 % 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-methoxvmethvlpyrimidin-2-vl)-N-phenyl-N'methvlhydrazine (Comp. 4.17) J ii ί ii z \z \ • y V CHzOCHj NHCH3 3.70 g (0.033 mol) of potassium tert-butylate are dissolved in 25 ml .if tetrahydrofuran dried with molecular sieves, 3.67 g (0.03 mol) of Nmethyl-N' -phenylhydrazine2 are added and a solution of 4.22 g (0.025 mol) of 2-chloro-4-methyl-6-methoxymethylpyrimidine in 30 ml of K. Kratzl, Monatshefte f. Chemie 89, 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: % 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: C14H18N4O (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-dimethvlpyrimidin-2-yl)-N-phenvl-N'-methvlhydrazine (Comp. 4.1).
CHj s Y i ii γ/γ V > SHCHj CHj 4.03 g (0.02 mol) of 2-trimethylammonium-4,6-dimethylpyrimidine hydrochloride3 are stirred with 3.05 g (0.025 mol) of N-methyl-N'phenylhydrazine under nitrogen in 30 ml of anhydrous tetrahydrofuran, and a solution of 3.36 g (0.03 mol) of potassium tert-hutylate in 15 ml of tetrahydrofuran is added dropwise at room temperature. The batch is left overnight at room temperature to complete the reaction and is extracted with water and ethyl acetate, the solvent is removed and the crude product is purified by column c' (eluant: 70 % Of hexane/30 % of ethyl substance in the form of an oil. Analysis: Ci3H16N4 % 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. IS : N-(4.S-dimethylpyrimidin-2-yl)-N-phenvl-M1dimethylhvdrazine (Comp. 4.13).
CH3 N(CHj)2 3.42 g (0.015 mol) of N-(4,6-dimethylpyrimidin-2-yl)-N-phenylhydrasine 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, and 1.33 g (0.018 mol) of sodium cyanoborohydride 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 (46.4 % 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-cvclopropylpyrimidin-2-vl)-N-phenyl-Ν' methyl-N'-isobutylhydrazine (Comp. 4.102) 4.55 g 0.0153 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenylN'-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 (O.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.
Analysis: Ci9H26N4 (MW: 310.45) % found % calc. c 73.51 73.94 H 8.44 8.58 5 N 18.05 17.93 Table 1: Compounds of formula Comp. No. 3ϊ Rg Ra physical constant 1.1 CeHs H ch3 5 1.2 4—CF aCgBsi CSa ch3 1.3 4-r-C&Hfc 3 H a.P.129-131°C 1.4 CgHs CS3 - •m.p. 45-46°C 1.5 CaHg c(ch3)3 CH2OCH3 1.6 C6H5 ch2och3 ' m.p. 37-38°C 10 1.7 c&h5 ch3 CH2OCH3 m.p. 6O~61°C 1.8 c5b5 CH2OC2H5 C(CHs)3 1.9 CsHs CH2OCH(CH3)C2Hs ch3 1.10 3?4-(C2'd5O)2-C&H3 CHa Cn2OC2Hs 1.11 CsHs CHs CKjOC2H5 15 1.12 CsBs CHa ch3 m.p. 41-43°C 1.13 4-CH3O~C6Hu C(CH3)3 CH2OC2Hs 1.14 CgHs ch3 CHCI2 1.15 3,5-Cl2~C6h3 ra3 CH2OC2Hs 1.16 3»5-Cl2--Csrh ch3 ch3 ,-m.p,154-156°C 20 1.17 3.5CX2— Cth3 c(ch3)3 ch2oc2h5 1.18 3,5-Cl2"C6H3 - CH3OCH3 1.19 3,4"(C2H5O)2~C5H3 CH2OC2H5 c(ch3)3 1.20 4-CH3O~C6Hi. CHj ch3 m.p. 90*-92°C 1.21 4-CH3O~CsH& ch2oc2h5 ch3 25 1.22 3,4-(C2HsO)2~CsH3 ! / \ CH; ->CH3 1.23 C6H5 ch3 ch2och2ch=ch2 1.24 4-Ch3~C6H«i ch3 CHa n^8 1 .604 Continuations Tabla 1 Comp. Wo. Rz Rs K3 physical constemt 1.25 A-OCfb-CeSk - CSgOCHa 1.26 3,5-Cl2-C6H3 ch3 CH20CB(CH3)C2Hs 1.27 4-001} CHs O320CH(CHs)C2H5 1.28 2-Br-CsHi. ch3 ch3 ffl.p. 55-57°C 1.29 3,5~C12~C«S3 Ο320Ο32Ο3«Ό32 CHs 1.30 4-CB3O-CsBfe c(ch3)3 ch2och3 1.31 3,5~Cl2-C6H3 oj3 OSC12 1.32 3~C1-C5H^ ch3 CHS ».p. 47-48°C 1.33 3s4-(c2I!sO) 2 "CsH3 CHs CH20CH(CH3)C2Hs 1.34 4—CH3O—CsB% ch3 CHgOCH3 1.35 3,4-(C2a5O)2-C6H3 c(ch3)3 Cjsa g 0C£i 3 1.36 3,5~C1z-C6B3 CHs CHjOOh 1.37 2,4,6-Cl3-C6H2 ch3 03 3 s.p.150152eC 1.38 3s4(C2H5O)2-C6H3 ch3 03 2 003 3 1.39 3?5~Cl2-C6Si3 CH 2 OCH 2 OCH CH3 1.40 C6Hs CH 2 OCH z OCH 03 3 1.41 4-CH3O-CsHfe CH 2 OCH 2 OCH 03 3 1.42 35S-(CF3)2-CgB3 CHs 03 3 sa.p. 88 "90°C 1.43 Cells CHsOOis Oi2OCH3 1.44 Cells ch2sch3 03 3 1.45 CsHs ch3 ch(och3)2 1.46 CeHs ch3 O3(0C2Hs)2 >ation: Table 1 Mi R·» Ms physical constant CsBs Ol Z Y \ / at C3j 4-Br—C$Hi* CHs cab a.p..92-93°C C6Sts CH3 Cyelo—CsHx1 c6h5 L»a« 3 CF2Cl CsHs - CF3 c6h5 ® ~\J - c6h5 - CF2C1 3~CH3-C6H<. CH3 CH3 a.p. 72-73°C C6Hs C2H5 - nJ5 1.6063 C6H5 CH3 lit nJ0 1 .6072 CsH5 CH(CH 3)2 - CsHg CH2OCH3 CF 3 C 3 *3 5 - CH(OCH3>2 CsHs CH2OCH 3 CH2CH(CH3)2 C&H5 CHO - CsH5 CH2OCH3 Φ ~zi Z \i Cha - C S £) CH2CH2CH3 CH2OCH3 CsHs CH(CKia) 2 CH2OCH3 A-r-CsHfc ch3 —^|\sb n^ 1.5883 CsH5 CH 2 OH 9> - cion: Table 1 Ri Rz r3 physical constant GsHs (CHabCHs CH2OCH3 G&Hs C2H5 CHzOCHj a»* 1.5923 CgHs CB2OCH3 cl » \l Erf 5 Jf3 3 CB2OCH3 CF 2 ci CjHs - CH2C1 C&Hs CB2OCB3 CB(OGSh)2 Λ-F-CsHfe CB3 gh3 a.p. 78-79eC 4-Cl-CeH., ch3 ch3 a.p.Wl-lOFc 4-r-CsHfe ch3 C2JS5 ,,3 5 -j cypo 1 CsBs - CHC12 e C6H5 - CH2Br CsH5 CHsOCnj CT2CF3 CSHS - ch2f 1.61 50 CjHs CSi(CH3)C2H5 CH2 OCH3 C5H5 CHO CH2OCH3 CsH5 (CH2)3Cii3 zi \l CsHs (CHabGBa zi \l C3H5 - CH(CH3)C2H5 c&h5 61 - CH2CB(CH3)2ZC1 C5H5 cib · j s / \ 4—CF 3— CsHi, ch3 CH2OCH3 4~Br~C6Hi» CHj CH2 OCH 3 ation: Table 1 Rj Rx Rj CgHg CgHs CgHg A-CHj-esBii Cg B g 2-CTj-CgHfe CgHs C g£3 5 CsHs ch2oh z" —b® CHZOCHj CHjOCHs CH(OC2B5)2 ch3 CHj CHj 4-Cl-CsHb CHj &-Cl-3-CF3-CgB3 CHj 3-CHj—CgHfc CHj 3-F-CgHit Caa 3-CF j—CgHii CH2OCH3 3-Cl-CgH^ CHzOCBj 3-F—CgHii CHgOCHj i-F-CgsU CH20CHj 4-Cl-CgHfc CHj CHgOCHj Cx2C?3 Cfi2Cl CHa ch2och3 Cl. ZC1 z \ CHj qhz CHO CHzOCHj CH2OCH3 CHzOCHj CH(OCzHg)z CHj CHj CHj CHj Continuation: Table 1 Comp. Mo. Ri Ra Ra physic®! constant 1.107 CsS?5 Gas CH20H 1.108 4-F-CeHi, ch3 - m.p. 93-95’C 1.109 C$JKs CS2OCH3 GH23r 1.110 CsBa CJ83 CHgCl 1.111 A~ei~3-cF3-ess?3 - CSI3 1 1 17 J. a a Λ ft» CsHs CH2OCH3 CHj? 1.113 Csns - 1.114 Cf 5 ch3 CH23r 1.115 GgHg CH3 CB2F 1.116 & C(CH3)3 c(ca3)3 1.117 C6Hs (CH2)tCH3 CHa 1.118 c&h5 C2H5 CgHs 7.5923 1.119 CH3 C2H5 7 .5953 1.120 C$is 5 CHj OCH 1.121 CsMs CH3 OCCH3 1.122 3-F-GsHfc Cis 3 - a.p. 41-42°C 1.123 3~F-C6Hi. yj \l CH2F 1.124 3-T-CsHt ch3 β „Z| «-ra3 nJ* 1.5943 1.125 CeHs s 1.126 CsHs CH2CH2CH(CH3)2 CH3 Continuation: Tabla 1 Comp» Ho. Bi Ra Ra physical constant 1.127 4-F-C6EU C’Ug C2H5 nJ3 1.5743 1.128 4— Γ—C&Hit CH2OCH3 - a.9. 56-’57°C 1.129 3-F-CcHi, ch3 CHa m.p. 6O"62°C 1.130 *k «wm <- n CHa Cans nJ® 1 .5373 1.131 3-F-CeHi, CHaOCHa - 1»5373 1.132 CsH5 CH3 CF3 nJ* 1.5543 1.133 1.134 4-F-CsHfe 2-F-CsBfe CHaOCHa CH 3 C;iH5 Γ&2- WSA 3 ml* Ί .5733 D nJ- ί .5353 1.135 2~T-C&H& CHa CH2OCH3 nJ3 1 .5773 1.136 2-F-CsHfe CBs nj ~ nJ7 1.5811 1.137 4-F-C6Hu CaHs IS -(1 ® nJ2 1.5813 1.138 3_Ί?_Γ,ρί C2H5 "<ί nJ3 1 . 5394 1.139 C$ns CH2CH2CH3 CHaCHaCHa n23 1.5743 1.140 3-F-CsHfe CHzCH2CH3 CHaCHaCH3 *>J3 1.5533 1.141 2-F-Ce.Hu -’(jXCHa β CHa nJ* 1 „ 5854 1.142 CeHs m.p. 75-77°C Tabla 2: Compounds of formula Comp. Bo. Rg R3 V Y constant 2.1 CHO - Cl •γ5 1.5503 2.2 t-butyl CBgOCsrSs Cl 2.3 CHj CH2OCH(CHj)CaH5 Cl 2.4 ch3 CH2OC2HS Cl 2-5 CHj CHC12 Cl 2.6 CH3 CH2OCH2CH®CH2 Cl 2.7 CH3 CH2OCH2CSCH Cl 2.8 CHaOCH3 GHgOGSa Cl 2.9 CHjOCHj - Cl •λ $ S -a C O Λ ‘75 '-b3^s 2.10 CHa CH(OCHa)2 Cl 2.Π CHa CH(OC235)2 Cl 2.12 CHa CTsCl Cl 2.13 CH2OCH3 CFa Cl 2.14 CH(OC2Hs)2 - Cl oil 2.15 n-propyl CHaOCH3 Cl 2.16 iso-propyl CHaOCH3 Cl 2.17 n-butyl CHa OCH a ci 2.18 CH2OCH3 C2B5 Cl 1„5064 2.19 CH2OCH3 CH(OCBa)a Cl 2.20 CHgOCHa CFaCFa Cl 2.21 CH2OH CHgOCHa Cl 2.22 CHiOCHj CHa Cl Cl 2.23 CHaOCH3 CHa? Cl 2.24 CHj CBaOCHs SO2CH3 Table 3s Compounds of formula A\ Si— r/ Rs Comp. Ho. Rs R j Rs Rs physical constant 3.1 3.2 3.3 3.6 3.5 3.6 3.7 (S’ 0 5 * υ 3.9 3.10 3.11 3.12 3.13 3.14 3.15 3.18 c6h5 CsHs C e H s Crib CsHs C 6 H 5 CeH s C fills Cs H s 3-F-CfiHt, Ceils A-HOg-Crib . Crib CsHs C j H 5 C ® ii 5 CHj CHj CHj CHj CHj gh3 CHj CHj CHj CHj CH j Cg (I s CHj Gib CHj CHj CFj CFj CHj cyclo-Cjib cyclo-CjHs CHj CHgOCHj cyclo-CjHs CjHs CHgOCHj Ciij Crib n-Cj H; cyclo-CjHs cyclo-CjHs eye I®-C j II s ii H H II H ii H H CHj CHj Crib H e — a Z V ~ g e \ / ί — Θ CHj CHj CHj 2-CHj-CsH., CgHs CHj CHj Crib crib Crib n-Cjib CHj CHj CHj n-C3H7 CHj CHj β < 5 \/ 3 CHjOCHj m.p.J83-19OeC m.p.117-113°C m.p.l37-138°C m.p.103-105’C m.p. 46-69°C m.p. 51-53°C n‘* 5.5882 ly nJ? I.W8 y η*1 I.S830· D nV 1.5982 D ι GJ <1 i Tabla 3: (continuation) COHip. Ri Rg r3 Rs Rsr physical constant 3.17 4-CnG-CsiH CSi 3 cyclo-CjHs H (CfbhCfi 3.18· is-C'FjO-Csfh Cfh cyclo-CjHs H CHj 3.19 3-r-CsHij CHj CHgOCHj H C(CHj)j ra. p.104-106’C 3.20 3-F CsiU CH j CHgOCHj H CgHg m.p. 95-97®C 3.21 ft-CHjO-Cslh ch3 CHj. H CjHs m.p. 81-82eC 3.22 6-CHj-CsHf. (CHj)jC CHj H Π-CjHy 3.23 6-CHj-CsHt, n-CjHy n-Cjfly H C-jH®, 3.26 CsHs C2il5 C}Hs H Cgii$ 3.25· C«Hs CHj CHj H (CHj)2CK B.p, 83-86°C 3.26 CsHs CHj cyclo-CiHj H (CHjhCH m.p. 53-55°C 3.27 CiHs Cl!j-C»C cyclo-CjHj H CHj 3.28 3F-C$fh CH 3 cyclo—CjH5 cyclc-CjlH CHj 3.29 4 F-C A CH 3 cyclo— CjHj CHj ;CFj. 3.30 4-(CHj)yCH-Cefh CHj CHj Cgfh CHj 3,31 C$H j ch3 CHj -(CHj)5- 3.32 2-r-CeIh CHj n—CjHy -( Cf h) fc- 3.33 A-I-CsJH CHj CHj Cifls H 3.36 4-1-CA cyclo-CjHs CHj. (CHj)gCH H 3.35 cyclo-CjHs CHj CHjCH=CH- . H m.p.121-122°C 3.36 c&iu cyclo-CjHs CHj CFj CHj H 3.37 C(H& CHj CHjCBYW=h- CHj H 3.3S C&lis C(CHj)j C(CHj)j (CHj)iCH H 3.39 C J il s C(CHj)j C(CHj)3 CgHj CHj 3.40 CjBj CHj cyclo-CaHs H CCIj ra.p.139-141"C Table 3; (continuation) Comp. Ri Rg Rj Ra R? physical constant 3.41 C s II s CHj CHj Cfi^ ^SCiij H m.p. 94-96°C 3.42 CsHs CHj CHj H BrCHj 3.43 CsHs CHjOCHj CHj Z-CHj-CsIb H m.p.l43-145°C 3.44 CgHj CHj cyclo-CjHs 2-CHj-CtH^ H m.p.1O7-1O9°C 3.45 C5H5 CHj eyclo-CjHj 2-F-Cdb CHj 3.46 CjHs CHj n-CsHi j 3-CHjO-Cefb CHj 3.47 C8Hs CHj CHj Cells H m.p.l30-14O°C 3.40 4-{CIb)sCH-C6ih CHj CHj -(CHj) j- 3.49 4—Br-C®H CHj CHj H HOX / ΐ SS s / \ _e s m. p. '155—2 56 °C 3.50 4-F-Ciiit, cyclo~CjHs CHj CHj H m.p.162-164°C 3.51 4-F-CsHt, cyclo-CjHs CHj CHj CHj 3.52 4-F-CsHi, cyclo-Cjiij CHj (C1Ii)2CH i! m.p. 58-60°C 3.53 CgH& CHj CHj H MCHjhH-CsIb 3.54 C j H s CHj CHj ΪΪ 4-CK-CgHt, 3.55 C c H s CHj CHjOCHj H 2-OH-CeH if 3.56 C6Hj CHj CHj H 2,3-Cls-C6Hi m.p.221-222°C 3.57 CgH§ CHj CHj H CHi=CH- 3.58 C6Hs CHj CHj -CH=CHCHiCH2CH2- 3.59 CgHj CHj cyclo-CjHs -CH=CHCibCth- 3.60 Celle CHj CHj CHj h- i GJ Tablo 3? (continuation) Comp. Ri Rs Rs 3.SI CtH5 CHs cyclo-CjHj 3.62 Ceils CHs cyclo-CjHs 3.63 3,5-(CF3) 2-Cs1Ij CHs CHs 3.54 CeiJg CHs cyclo-CsHs 3.55 Cgils CHs cyclo-CjHs 3.55 Ceils CHs cyclo-CsHs 3.6? Ceils CHs cyclo-CsHs 3.58 • Ceils CHs CHjOCHs 3.69 Ceils CHs CHs 3. 70 Ceils CHs eyclo-CjHs 3.71 CtH5 CHs CHs 13.72 C&H g CHs Gils 13.73 Cell:. CHs cyclo-CsHj 3.74 C $ ii s CHs CHzOCHj 3.75 CeHs CHs cyclo-C jils 3. 76 Ci H# CHs cyclo-CsHs Rs Rs physical constant CHs CFs CFs CFs Cjlis H nJ* 1.4990 ψΗ 3 H H CHj=C- 2-pyridyl H 3-pyrldyl H 4-pyridyl H s.p.155—456°Cz\z H z~\ ZV H a. ρ.Ί77-ί79°C CiijSCHjCHs S — « / \ — S 3 \ / θ— ί CJij Ceils CFj Cells Oils CHs CJhHiCHsh H >1 CflClj CSxs i Table 3: (continuation) Corap. Ri Ra R j Ra Rs physical constant 3. 77 ’ c6h> Cih CHj S — 3 / \ \ / £«—3 II 3.78 3~F-CsJh: CHjOCHj CHj H (CHj)jCH m.p. 83-84’C 3.79 C6Hs CKjOCHz CHj H (CIIj)zCH n’s 1.5673 u 3.80 C5Hs cyclo-CjHs CHj 2i3-Clj-CsHj H ro.p.,279-182’C 3.81 4-CFj-CsH% CHj CHj CHj. CHj 3.82 4-CFj-Cslh CHj CHj. H Cglij 3.S3 CgH s CHj CHj CH3(CHj)e H 3.84 CeHs CHj-C®C cyclo-CjHs ΪΪ CzKs 3.85 4—F-CeiL cyclo-CjHs CHj S —· 3 ¥ H m.p.l32-134’C 3.86 3-F-CjHii cyclo-CjHs CHj II β «— 3 / Μ β * S v m.p.11l-l12eC CHj 3.37 Cells CHjOCHj CHj CHj H m.p.112-114°C 3.88 Ceii5 CHj CHj cyclo-CjHs CHj 1.600 3.83 3-F-CsK-i CHj cyclo-CjHs If CHj m.p.114-116eC 3.90 3-F-CUh CHj cyclo-CjHs H CiHj 3.91 3-F-CjIh CHj cyclo-CjHs H n-Cjil7 m.p. 46-4 7°C 3.92 3-F-CsH^ CHj cyclo-CjHs H (CHj)2CH m.p. 45-46°C (continuation) Ri Ra Ra Re Rs physics! constant C a l·'! 5 CHa cycio-CaHs H -ch=ch2 A-F-CeH* CHj cycio-CaHs CzH5 H ai.p. 79-CO°C 4-F-CsHi, Cfh cyclo-CaHs n-CaH? H ra.p. SO-81 °C CsHs CHj cycio-CaHs B CBs\ ^SCHa kzx CeHs CHj cycio-CaHs CjH5 CHa 3-F-CdU CHj cycio-CaHs CHa CHa 3-F-CsBi, CHa cycio-CaHs CHa Cifis 3-F-Ceilfc CHj cycio-CaHs CHa CFa 4-F-CsHi, CHa cycio-CaHs CCla H 4—F-CeHfc CHa cycio-CaHs CH2OCH3 CHa C5H3 CHjOCib cycio-CaHs 11 1-nsphthyl m.p.12?-12S°C 3-F-Csi!U CHgOCHj CHa 11 2-pyridyl 3-F-CsHb cyclo-CaKs CHa CHaSCHgClh Ji 3-F-CsHfc cyclo-Calis CHa (CH 3) a C H m.p.104-I05eC C6Hs cyclo-CjHs CHa (CHa)sC H \ jn.p.iO{M02eC CeHs cycio-CaHs CHa H . Ϊ / s. V m.p. 90-92°C C6Hs cyclo-Calls CHa H cycio-CaHs CeHs CH3 CHa 2-pyridyI CHj CeHs CHa CH 3 CHa 2 4—Cl j "CsK 3 CeHs CHa CHa CHa (CihbCHj 3-F-CeiH CH3 CHiOCHj 4-pyridyl H m.p.190-192eC Table 3; (continuation) CoiTbp» Ri Rg Ra Rg R® physical constant 3.114 3.115 3.116 3.117 3.113 3.119 3.120 3.121 3.122 CjHs CeHs 3-F-CsiU CsHj CsHs Csiis' Ccih 3- F-CsHt, 4— F-Cclh CHj CHj Cll 3 cih CHj CHj CH3 Cih CHj Cih OCH 3 CHaOCHa CHaOCHa Cih OCH 3 Cih CIhCCih Cih ClhCCHa 3 - 11 -S~x_ γ cih CHa 11 H H H II H 2,3-C12-C£Hj H H n-CjHy C m.p.135-136eC a.p.121-122°C m.p.A44-145eC 1.5756 m.p. 73-74°C m.p,100-101 °C njj5 1 .5860 m.p. 47-48°C m.p. 2?-I28°C Table A; Compounds of formula RxK Rs ©R{sx) Comp. Rs Rg Rj Rj © Ri i physical constant 4.1 CgHs CHj CHj H CHj. nV 1.5953 D 4,2 CsJis CHj CHj H C2ib 4,3 C6Hs CHj CHj H CHrCH=CH2 4,4 C s il s CHj Cfij H n-Cjib nl* 1-5740 3J 6.5 CSH s cyclo-CjHj CHj H CHjCbCK 4,6 4-CHjO-Crib CHj CHj ii zch2- S' —5 y v V n-CsHii 4.7 Cpis CHj - cyclo-CjHs H nV 1.6150 β 6,8 3,4-{CH3)i-CsHj CHj CHj Cii8- V H Table 4: (continuation) Comp. Rs Rz R j Rs ¢. Ri s physical constant /CHg- 4.9 4-CFs-CjHt, CHs CHs s ' s V CHs 4.10 3-F-CsiU CHs cycio-CsHs n-CjH? 51 3 ϊ’ί 7 n*>7 1.5510 4.11 GUIs CHsOCHs CHs CihC(CHsb -Η 'e—r H 4.12 CeH5 CHj. OCH j CHs H 4.13 CeHs CHs CHs CHj CHj n’s 1.5673 D 4.14 Ceils CHj CHs CsHsCHi- H m.p. 56-57°C 4.15 Calls CHs cyclo-CjHs ^-CHs- ΈΗ H 4.16 4—F-Csilii CHs cyclo-CsHs / \-CHs- \h H m.p. 83-84°C 4.17 Cells CHsOCHJ CHs H CHs 1.5793 4.13 Cr.ii5 CH2OCH3 CHs CHjCH^CHCHs- H 4.19 Calls CH2OCHs CHs CFjCIh H 4.20 C 6 H s CHgOCHs CHs n-CsH? H n" 1.5635 Table 4; (continuation) Comp. Rj Ra Rj Rj o Ru 1 physical constant A. 21 CsHS CHzOCHj CHj Ϊ II H7 XOH 4.22 4-F-Cslltt CHj cyclo-CjHs CgHs H nl* '1.5693 D 4.23 3-Sr-CsHs CHj cyclo-CjHs n-C%Hs CHj 4.24 2-Cl-4-CFi-CcHj CHj CHj CHj. Czils 4.25 C$H j CgHj CHj H ' CH j 4.26 C s H s n-CjHs CHj H CHj 4.27 C$ils CH(CHj)i CH(CHj)z H CHj 4.20 CgHs CHj C(CHj)j H CHj 4.29 CeHs CzHj CzHj H CHj 4.30 CSK5 CHj CHjOCHj il 4.31 4-F-CsHft CHj CHj Czils Cjllsn?i 1 . 5533 IJ 4.32 4-F-CslU CHj CHj CHj H m.p. 57-59 C 4.33 CsHs CHj CHj CHzCCIj H 4.34 Cglis CHj CHj s' H 4.35 CgHs CHj CHj (Ciij)jCH 11 4.36 CsHj cyclo-CjHs CHj (CHj)zCH H 1.5772 4.37 CjHj cyclo-CjHs CHj CzH&(CHi)CH- It 4.38 CjHs CHj CHj BrjCGHg- II 4.39 CeHs CHj CHj CHzCHzCH H 4.40 CeHs CHj CHj CHzCHzCH* ClkCHzCH 4.41 CsHs CHj cyclo-CjHs CikCHzCN CHzCHzCH (continuation) Rs Ra Rj Rso Rs ϊ physical constant C $ H $ CHj cyclo-C jHs CHjCHjCU H C a 115 CHj cyclo-CjHj cyclo-CeHii H m.p. 75-77°C C&Hj CHj cyclo-CjHs CgHs H n£jr 1.5830 CsH5 CHj cyclo-Csiis CHj H 1.5983 3-F-CaHis CHj cyclo-CjHs CHj H 1.5842 3-F-CjHm CHj cyclo-CjHs CjHs H nJ* 1.5778 4-F-CsIh CHj cyclo-CjHs C2ff5 H CsHs CHj CHj H cyclo-C®Hi i Cells CHj CHj ii / \ 1 (3 \ '/ C g H s CHj CHj H cyclo-CsH? m.p. 84-06aC CeIis CHjOCHj CHj CHjCCHj(CHj)CH- H 1.5565 C®Hs CHgCCHj CHj (CHjhHCHaCCHjjCH-J H 3-F-Cslh CHgOCHj CHj H (CHj)CHCHj 3-F-C6H„ CHjOCHj CHj H n-CjH? 3-F-CsH^ ClijOCHj CHj (CHjbCH ii nV 1.5450 4-I-CsHi, CHj CHj eass SO-ζ ).-011, ' s —s' H CsHs CHj cyclo-CjHs H cyclo-Csili i m.p. 75-77°C CsHs CHj cyclo-C j Ii 5 H ι -j · Tabla 4§ {continuation) I Comp. Rj Rs Rj Rjo Ri i physical constant 4 . SO. C$Sh CM* cyclo-CjHj H n-CjHy 4.61 C»ft$ CHj cyclo-Cjih H Cgih sn.p. 125-127’C 4,62 CgHs CHj cyclo-CjHs CFjCHz H 4.63 2-F-CsH·, CHj cyclo-CjHj DrjCCHs H 4.64 2-F-CsHi, C 2 ΪΪ 5 CHj ClaCHCih CHj ZCH FjC H 4.65 Cih cyclo-CjHs H 4.66 4-F-Cgfh CHj cyclo-Cjih H !>-?- * cih 4.67 4-F-Cjhh CHj cyclo-Cjfh H n-CjH? 4.63 4-F-CeHib CHj cyclo-CjHs H (CibhCHCHjnn 1.5595 4.69 CgHj CHj CH §QCH3 CHj CHj 4.70 C&lb CHj Cih OCH 3 n-CjH? n-Cjib n" 1.5483 4.71 C6Hj CHj CHjOCHj H CHj(CHj)y 4.72 Cgib CHj CH s OCH j. BrCHzCHO · H 4.73 C$Hj CHj CHjOCHj s —s y \ YY Yih- CHj H m.p. 67-S8°C 4.74 C ε H 5 CHj CHj H CgH5.(CH3)CH- n* J 1 „ 5638 D 4.75 Cjib CHj CHj CeH5(CFj)CH- H Table 4; (continuation) (continuation) Hi Rg Rj R j o ih i physical constant Csllj CHj cyclo-CjHs H Ah 1 ie e s Y \l ii ra.p. 67-60°C C&H j CHj cyclo-Cjfh »ς cih- H CA CHj cyclo-Cjfh if (CfbhCHCHa-nn* 1.5733 C ε H s Cfh cyclo-C jfig η CfljCH«CHCfh- CA CHj. cyclo-Cjfh CgHgCHg It 4-F-C6H% CHj cyclo-Cjfh n-C jfh n-C jih td3 1=5483 ϋ 3-F-CA CfhOCfh Cfh Jf CHj 3-F-CA CfijOCHj CHj H CA 3-F-CA CHjOCHg CH j ff n-C Uh 4—CF jO-Cjfh CfhOCHg CHj fi Caffs 4-CFjO-CA CHjOCHj Cih CHj CHj 4-1-CA Cfh cyclo-Cjfi® fi π-C jfh 4-1-CA Cfh cyclo-CjHj H (Cfh) a CECH g. C®H§ Cfh cyclo-Cjfh CHj CHj ηθ* 1.5813 CA Cfh cyclo-CjHs CA Caffs n,V 1.5762 ϋ CeHs Cfh cyclo-CϊΗ} Jf CHa-CHCKj- CA Cfh cycio-CjHa CHjSCfhCfhCfh H CA cfh cyclo-C j. Sh CHj CfhCH(Cifj) a n^a 1=5613 Table 4; (continuation) Comp. Ri Rg Rj Rio Ri i physical constant 4.103 Cells Ciij cyclo-C 3 ii 5 /\ / β 3 i I H 4,104 CsHs CgHs CHgOCHj H CHS np 1 /5753 CHj 4.105 C ell 5 CHj Ciij Clh«=C-CHi- 11 4.106 Cells cyclo-CjHs CHj CHjOClli(CIij)CH- CHj β 10 / Cells cyclo-CjHs Ciij CFjiClij )CH- CHj 4.10C Cells cyclo-CjHs Ciij (CFa)sCH- H 6.109 3-F-CsHt, n-C jit 7 n-CjH? 11 n-Cjll? 6.110 3-F-c6ih CHj ,/j \l '3 CHj CHj n" 1.5755 4.111 Ceils CHj - CHiC(CHj)j H m.p. j69-7O°C 2. Formulation Examples for liquid active ingredients of formula I (¾ per cent bv weight) 2.1. Emulsion concentrates a) b) c) active ingredient from Table 1 25 % 40 % 50 % calcium dodecylbensenesulfonate 5 % 8 % 6 % castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % 4 % cyclohexanone - 15 % 20 % xylene mixture 65 % 25 % 20 % Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
Solutions active ingredient from Table 1 ethylene glycol monomethyl ether polyethylene glycol (MW 400) N-methy1-2-pyrrolidone epoxidised coconut oil petroleum bensin (boiling range 150-190°C) (MW = molecular weight) a) % % b) c) d) 10 % 5 % 95 % % 20 % 94 S The solutions are suitable for application in the form of microdrops. 2.3. Granules active ingredient from Table 1 kaolin highly disperse silicic acid attapulgite a) b) % 10 % % % % The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. - 53 2.4. Dusts a) active ingredient from Table 1 highly disperse silicic acid talcum kaolin % % % b) % % % Ready-for-use dusts are obtained by intimately mixing onto [sic] carriers with the active ingredient.
Formulation, Examples for solid active ingredients of formula..^_(% = ge cent by weight). 2.5. Wettable powders a) active ingredient from Table 1 25 % sodium ligninsulfonate 5 % sodium laurylsulfate 3 % sodium diisobutylnaphthalenasulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly disperse silicic acid 5 % kaolin 62 % b) c) 50 % 75 % % % % 10 % % % 10 % % The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording 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 (4-5 moles of ethylene oxide) 3 % calcium dodecylbansanesulfonate 3 % castor oil polyglycol ethe. (35 moles of ethylene oxide) 4 % cyclohexanone 34 % xylene mixture 50 % Emulsions of any desired concentration can be prepared from this concentrate by dilution with water. 2.7, Dusts active ingredient from Table 1 talcum kaolin a) b) % g % % % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. 2.8. Extruder granules active ingredient from Table 1 10 % N-ligninsulfonate [sic] 2 % carboxymethylcellulose l % kaolin 87 % The active ingredient is mixed with the adjuvants, 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 % (W = molecular weight) The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. 2.10. Suspension concentrate active ingredient from Table 1 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % N-ligninsulfonate [sic] 10 % carboxymethylcellulose 1 % % aqueous formaldehyde solution silicone oil in the form of a 75 % 0.2 % aqueous emulsion water 0.8 % % • The finely ground active ingredient is intimately mixed with the adjuvants, giving 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 inaegualis on.apple shoots Residual protective action Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006 % of active substance) prepared from a wettable powder of the active ingredient. The treated plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 % relative humidity and stood in a greenhouse for a further 10 days at 20-24°C. Scab attack is evaluated 15 days after infection.
Compounds of the Tables exhibit good activity against Venturia {attack: less than 20 %). For example, compounds 1.79, 1.108, 1.122 and 4.45 reduce Venturia attack to 0 to 10 %. On the other hand, Venturia attack is 100 % on untreated but infected control plants.
Example 3.2. Action against Botrytis cinerea on apples Residual protective action Artificially damaged apples are treated by dripping onto the damaged areas a spray mixture (0.002 % or 0.02 % of active substance) prepared from a wettable powder or an emulsion concentrate of the active substance. The treated fruits are then inoculated with a spore suspension of the fungus and incubated for one week at high humidity and about 20°C. Evaluation of the fungicidal action of the test substance is made by counting the number of damaged areas that have rotted.
I Compounds of the Tables exhibit good activity against Botrytis (attack: less than 20 %). For example, compounds 1.4, l.S, 1.7, 1.12, 1.17, 1.48, 1.55, 1.5S, 1.S5, 1.68, 1.79, 1.104 , 1.108 , 1.118, 1.119, 1.122, 1.124 1.129, 1.137, 1.138, 3.5, 3.6, , 3.7, 3.8, 3 .10, 3.11, 3.25, 3.26, 3.35, 3.40, 3.50, 3.52, 3.78, 3.79, 4.1, 4.4, 4. 15, 4.17, 4.20, 4 > *45, 4 .56 / - 56 4.73, 4.74, 4.87 and 4.98 reduce Botrytis attack to 0 to 10 %. On the other hand, Botrytis attack is 100 % on untreated but infected control plants.
Example 3.3:. Action against Ervsiphae [sic] graminis in barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02 % of active substance) prepared from a wettable powder of the active ingredient. The treated plants are dusted with conidia of the fungus after 3-4 hours. The infected barley plants are stood in a greenhouse at about 22°C and the fungus attack is evaluated after 10 days.
Compounds of the Tables exhibit good activity against Erysiphae [sic] (attack: less than 20 %). For example, compounds 1.32, 1.56, 1.04, 1.122, 1.124, 3.5, 3.8 and 3.52 reduce the Erysiphae [sic] attack to 0 to 10 %. On the other hand, Erysiphae [sic] attack is 100 % on untreated but infected control plants.
Example 3.4: Action against Helminthosporium gramineum Wheat grains' are contaminated with a spore suspension of the fungus and dried. The contaminated grains are dressed with a suspension of the test substance prepared from a wettable powder (600 ppm of active ingredient based on the weight of the seeds). Two days later the grains are placed in suitable agar dishes and after a further four days the development of the fungus colonies around the grains is evaluated. Evaluation of the test substance is made according to the number and size of the fungus colonies. Compounds of the Tables inhibit fungus attack substantially (less than 20 % fungus attack).
Example 3.5: Action against Colletotrichum lagenarium on cucumbers Cucumber plants are grown for 2 weeks and are then sprayed with a spray mixture (concentration 0.002 %) prepared from a wettable powder of the active ingredient. 2 days later, the plants are infected with a spore suspension (1.5 >< 10s spores/ml) of the fungus and incubated for 36 hours at 23°C and high humidity. Incubation is then continued at normal humidity and approximately 22-23°C. The fungus attack which occurs is evaluated 8 days after infection. Fungus attack is 100 % on untreated - 57 but infected control plants.
Compounds of the Tables exhibit good activity and prevent the disease from spreading. Fungus attack is reduced to 20 % or less.
Example . 3_. 6 : Action against Puccinia craminis in wheat Wheat plants are sprayed 6 days after sowing with a spray mixture (0.02 % of active substance) prepared from a wettable powder of the active ingredient. After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100 % relative humidity and about 20°C and then stood in a greenhouse at about 22°C. Evaluation of rust pustule development is made 12 days after infection.
Compounds of the Tables exhibit good activity against Puccinia (attack: less than 20 %). For example, compound no. 3.10 reduces Puccinia attack to 0 to 10 %. On the other hand, Puccinia attack is 100 % on untreated but infected control plants.
Example 3.7: Action against Phvtophthora on tomato plants a) Residual protective action After a cultivation period of three weeks, tomato plants are sprayed with a spray mixture (0.02 % of active substance) prepared from a wettable powder of the active ingredient. The treated plants are infected 24 hours later with a sporangia suspension of the fungus. Evaluation of the fungus attack is made after the infected plants have been incubated for 5 days at 90-100 % relative humidity and 20°C. b) Systemic action After a cultivation period of three weeks, tomato plants are watered with a spray mixture (0.002 % of active substance based on the volume of the soil) prepared from a wettable powder of the active ingredient. Care is take that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a sporangia suspension of the fungus. Evaluation of the fungus attack is made after the infected plants have been incubated for 5 days at 90-100 % relative humidity and 20°C.
Compounds of the Tables exhibit good activity against Phytophthora (attack: less than 20 %) . For example, compounds 1.104, 1.122, 4.31 and 4.98 reduce Phytophthora attack to 0 to 10 %. On the other hand, Phytophthora attack is 100 % on untreated but infected control plants.

Claims (26)

1. CLAIMSι 1. Ά compound of the formula I Sss (ϊ) wherein.- R x is phenyl or phenyl mono- ¢0 tri-substituted by R 4 ; R 2 is hydrogen, C x -C 5 alkyl, C x -C 5 alkyl substituted by the radical OR 5 or by the radical SR S , C 3 -C 6 cycloalkyl, C 3 -C 6 eycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is hydrogen, C x -C 4 alkyl, C 1 -C 4 alkyl substituted by halogen, cyano or by the radical OR S or by the radical SR 5 , C 3 -C s cyclos.lkyl or C 3 -C 6 cycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen; R 4 is halogen, C x -C 3 alkyl, C x -C 2 haloalkyl, C x -C 3 alkoxy or C x -C 3 haloalkoxy; R s is hydrogen, C x -C 5 alkyl, C x -C 5 alkenyl, C x -C s alkynyl or the radical (CH 2 ) n -X-C x -C 3 alkyl; * ® iC ** 0 R 7 is the group -NH 2 , _ R 8 is hydrogen, C x -C 3 alkyl or C x -C 3 haloalkyl; R 9 is hydrogen, C x -C e alkyl, C x -C 3 alkyl substituted by hydroxy, OR X2 , SR X2 or by N(R X2 ) 2 , C 3 -C 6 cycloalkyl, cyclopropyl substituted by SR X2 , C 3 -C x0 alkenyl, C x -C 3 haloalkyl, 1-, 2- or 3-pyridyl, or R 8 and R 9 , together with the carbon atom in the radical R 7 , are a saturated or unsaturatad ring comprising 4 to 7 carbon atoms; R xo is CH(R 8 )R 9 , phenyl, C 3 -C 5 alkenyl, C 3 -C 5 alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R xx is hydrogen, C x -C 5 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 alkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R x2 is CH 3 or C 2 H 5 ; X is oxygen or sulfur; 2 is O, S, NH or NCH 3 ; and n is 1 to 3; including the acid addition salts and metal salt complexes thereof.
2. A compound of the formula I according to claim 1, wherein: R x is SO phenyl or phenyl mono- to tri-substituted by R 4 ; R 2 is hydrogen, C x C s alkyl, C x -C 5 alkyl substituted by the radical 0R 5 or by the radical SR 5 , C 3 -C s cycloalkyl, C 3 -C s cycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is C x -C 4 alkyl, C x -Chalky 1 substituted by halogen, cyano or by the radical OR S or by the radical SS 5 , C 3 -C s cycloalkyl or C 3 -C s cycloalkyl mono- to tri-substituted by C X “C 4 alkyl or by halogen; R 4 is halogen or C,-C 3 alkyl; R 5 is hydrogen, C x -C 5 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 alkynyl or the radical (CH 2 ) n -X-C x -C 3 alkyl; R g is hydrogen, C 1 -C 5 alkyl, C 3 -Cgeycloalkyl, C 5 -C s alkenyl, C 1 -C 3 haloalkyl; R 8 and Ht 9 , together with the carbon atom in the radical R 7 are a saturated or unsaturated ring comprising 5 or S carbon atoms; R 7 , R xo , R xx , R x2 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 1 according to claim 1, wherein: R x is phenyl or phenyl mono-substituted by halogen; R 2 is hydrogen, C x -C 5 alkyl, C x -C 5 alkyl substituted by OR S , C 3 -C s cycloalkyl, C 3 -C s cycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen, C 2 -C s alkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is C x -C 4 alkyl, C x -C 4 alkyl substituted by halogen, cyano or by OR S , C 3 -C s cycloalkyl or C 3 -C e cycloalkyl substituted by methyl; R 5 is hydrogen or C x -C 2 alkyl; R g is hydrogen, C x -C 5 alkyl, C 3 -Cgcycloalkyl, C 3 -C 5 alkenyl, C x -C 3 haloalkyl, R 8 and R g , together with the carbon atom in the radical R 7 , are a saturated or unsaturated ring comprising 5 or S carbon atoms; and R 7 , R xo , R 1X and R x2 are as defined under formula I.
4. A compound of formula I in claim 1, wherein: R x is phenyl or phenyl mono- to tri-substituted by R 4 ; R 2 is hydrogen, C x -C 5 alkyl, C x -C 5 alkyl substituted by the radical OR 5 or by the radical SR s , C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is C x -C 4 alkyl, C x -C 4 alkyl substituted by halogen, cyano or by the radical OR S or by the radical SR s , C 3 -C e cycloalkyl or C 3 -C 6 cycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen; R 4 is halogen, C x -C 3 alkyl, C x -C 2 haloalkyl, C x -C 3 alkoxy or C^-Cjhaloalkoxy; R s is hydrogen, C x -C 5 alkyl, C 3 -C 5 alkenyl, C 3 -C s alkynyl or the radical (CH 2 ) n -X-C x -C 3 alkyl; R 7 is -NH 2 ; X is oxygen or sulfur; and n is 1 to 3; including the acid addition salts and metal salt complexes thereof.
5. A compound of the formula I according to claim 4, wherein: R x is phenyl or phenyl mono- to tri-substituted by R.-; R 2 is hydrogen, Cj-Cgalkyl, Ci-C s alkyl substituted by the radical 0R 5 or by the radical SR 5 , C 3 -C 6 cycloalkyl, C 3 -C s cycloalkyl mono- to tri-substituted by 5 C,-C 4 alkyl or by halogen, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is C x -C 4 alkyl, C x -C 4 alkyl substituted by halogen, cyano or by the radical 0R 5 or by the radical SR s , C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl mono- to tri-substituted by Cj-C^alkyl or by halogen; R 4 is halogen; R s is hydrogen, C 1 -C s alkyl, C 3 -C 5 alkenyl, C 3 -C 5 alkynyl or the radical •j θ (CH 2 ) n -X-Ci-C 3 alkyl; X is oxygen or sulfur; and n is 1 to 3.
6. A compound of the formula I according to claim 1, wherein: R x is phenyl or phenyl mono- to tri-substituted by halogen; R 2 is hydrogen, C 1 -C 5 alkyl, C 1 -C 5 alkyl substituted by the radical 0R 5 or by the radical SR 5 , C 3 -C 6 cycloalkyl, C 3 -C s cycloalkyl mono- to tri-substituted by 15 Cj^-C^alkyl or by halogen, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl or the formyl radical; R 3 is C x -C 4 alkyl, C x -C 4 alkyl substituted by halogen, cyano or by the radical OR 5 or by the radical SR s , C 3 -C e cycloalkyl or C 3 -C 6 cycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen; R s is hydrogen, C x -C 5 alkyl, C 3 -C 5 alkenyl, C 3 -C 5 alkynyl or the radical (CH 2 ) n -X-C 1 -C 3 alkyl; 20 X is oxygen or sulfur; and n is 1 to 3.
7. A compound of the formula X according to claim 1, wherein: R x is phenyl or phenyl mono-substituted by chlorine or by fluorine; R 2 is C x -C 5 alkyl, or is C 1 -C 2 alkyl substituted by OR 5 , C 3 -C 6 cycloalkyl, C 3 -Cgcycloalkyl mono- to tri-substituted by C x -C 4 alkyl or by halogen, 25 C 2 -C 5 alkenyl, C 2 -C s alkynyl or the formyl radical; R 3 is C x -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by methyl; and R 5 is hydrogen or C x -C 2 alkyl.
8. A compound of the formula I according to claims 6 and 7, wherein R 3 is: methyl, fluoromethyl, chloromethyl, bromomethyl, C 3 -C 6 cycloalkyl or t>3 0 methoxymethyl.
9. A compound of formula I according to claim 1, 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-fluorophenylhydrazine; - 62
10. A compound of formula I according to claim 5 from the group: N-(4-methyl-6-eyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenylhydrasine; N-(4-methyl-δ-methoxymethylpyrimid-2-yl)-K-phenylhydrazine;
11. A compound of formula I according to claim 1 from the group: N-(4,6-dimethylpyrimid-2-yl)-M-phenylpropionaldehyde hydrazone; N-(4,6-dimethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methyl-δ-methoxymethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl) -K-phenylpropionaldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-n-butyraldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl) -W-phenylisobutyraldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyltrichloroacetaldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-p-fluorophenylacetaldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-p-fluorophenylisobutyraldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-m-fluorophenylisobutyraldehyde hydrazone; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-S'-dimethylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-H'-isobutylhydrazine; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; H-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazina; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-H-phenyl-N'-methylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-H'-isobutylhydrazine; N-(4-methyl-5-cyclopropylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-diethylhydrazine; N- (4-methyl-6-cyclopropylpyrimid-2-yl) -N-phenyl-N' - methyl-M -ethyl- S3 hydrazine; Ν-(4-methyl-S-cyclopropylpyrimid-2-yl)-N-p-fluorophenyl-N'-ethylhydrazine; N- (4-methyl~S-methoxymsthylpyrimid-2-yl) -N-m- fluorophenyl-N' - isopropyl hydrazine;
12. A process for the preparation of a compound of the formula ϊ according to claim l, which comprises a) reacting a pyrimidine derivative of the formula II M.— TO V, Z \ R? (XX) Rs with a phenylhydraz ine derivative of the formula III Rj-NH-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 SO 2 R s or N 9 (CH 3 ) 3 , R 6 is C x -C 4 alkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for R xo and R xx , and the latter and also R X ~R 3 are as defined under formula I, or b) reacting aldehyde or the removal a pyrimidine hydrazine derivative of formula IV with an ketone of formula V to form a compound of formula VII with of water Ri Ri c~o (TV) / R* Rs. R? (v) 'Ol (VJX) / '''Rj in any desired solvent, in the presence of an acid and at temperatures of -20° to 120°C, R x -R 3 and R 8 and R 9 being as defined under formula I, or 64 c) reducing & hydrazone derivative of formula VIj Kat aeduction Mm eee?, / S.Z \. CHR e (R*) (VII) («ΙΠ) 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 3b 6' % K - X v / Hs to reductive alkylation with an aldehyde or ketone of formula V R l5 “C--Jb (V) in the presence of a reducing agent, in an inert solvent and at temperatures of 0° to 50°C, 1q e) alkylating a pyrimidine hydrazine of formula IV or VIII with an alkyl halide R o Hal 3b Ri-S ‘(IV) \s. R Z \, \s O © (IX) - 65 Μ Ζ ft} «* IS / \„ A Rg R Kai o Y -s. CHRgiRs) ’ 1 v< A r chr®(r 9 ) (x) in an inert solvent, in the presence of a base and at temperatures of 0°”60°C, R o being C.-C^alkyl and ί^-Rg .in processes (a-e) described above being as defined under formula I.
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 1 according to claim 4. Ίθ
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 ll.
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 ll.
20. A method according to claim 18, which comprises controlling phytopathogenic fungi. - SS
21. A process for the preparation of an agrochemical composition according to claim 13, which process comprises intimately mixing at least one compound of formula 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.
24. 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.
IE288189A 1988-09-09 1989-09-08 Pesticides IE72462B1 (en)

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CH337188 1988-09-09
CH257989 1989-07-11

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AT (1) ATE140699T1 (en)
AU (1) AU626913B2 (en)
BR (1) BR8904485A (en)
DE (1) DE58909704D1 (en)
DK (1) DK170336B1 (en)
ES (1) ES2090045T3 (en)
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GR (1) GR3020621T3 (en)
HU (1) HU207998B (en)
IE (1) IE72462B1 (en)
IL (1) IL91556A (en)
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Publication number Priority date Publication date Assignee Title
DE3881320D1 (en) * 1987-09-28 1993-07-01 Ciba Geigy Ag PEST CONTROL.
EP0388838B1 (en) * 1989-03-22 1996-01-10 Ciba-Geigy Ag Parasiticide
JPH0859628A (en) * 1994-08-26 1996-03-05 Sumitomo Chem Co Ltd Production of pyrimidine derivative

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* Cited by examiner, † Cited by third party
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IL38815A0 (en) * 1971-03-05 1972-04-27 Ciba Geigy Ag Iodoethynyl compounds,their manufacture and their use
JPS55151570A (en) * 1979-05-15 1980-11-26 Takeda Chem Ind Ltd Pyrimidine derivatives, their preparation and antimicrobial for agriculture
DE3441935A1 (en) * 1984-11-16 1986-05-28 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING 2,4-DIHYDROXYPYRIMIDINES
JPH0784445B2 (en) * 1986-12-03 1995-09-13 クミアイ化学工業株式会社 Pyrimidine derivatives and agricultural and horticultural fungicides
US4929726A (en) * 1988-02-09 1990-05-29 Georgia State University Foundation, Inc. Novel diazines and their method of preparation
EP0388838B1 (en) * 1989-03-22 1996-01-10 Ciba-Geigy Ag Parasiticide
DE4017460A1 (en) * 1989-10-10 1991-04-18 Bayer Ag New substd. sulphonyl-amidino hydrazone(s) - are defoliants, desiccants and weed killers

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NZ230592A (en) 1992-02-25
AU4119289A (en) 1990-03-15
FI894212A0 (en) 1989-09-06
EP0358609A3 (en) 1990-10-10
GR3020621T3 (en) 1996-10-31
ATE140699T1 (en) 1996-08-15
EP0358609A2 (en) 1990-03-14
IL91556A0 (en) 1990-04-29
JPH02115174A (en) 1990-04-27
IE892881L (en) 1990-03-09
BR8904485A (en) 1990-04-24
HU207998B (en) 1993-07-28
EP0358609B1 (en) 1996-07-24
FI894212A (en) 1990-03-10
IL91556A (en) 1994-01-25
PT91648B (en) 1995-05-31
DK444189D0 (en) 1989-09-08
HUT51604A (en) 1990-05-28
FI98914C (en) 1997-09-10
PT91648A (en) 1990-03-30
DE58909704D1 (en) 1996-08-29
DK444189A (en) 1990-03-10
DK170336B1 (en) 1995-08-07
AU626913B2 (en) 1992-08-13
ES2090045T3 (en) 1996-10-16
FI98914B (en) 1997-05-30
JP2832544B2 (en) 1998-12-09

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