NZ230592A - 2-substituted-1,3-diazine derivatives, preparatory processes, intermediates and pesticidal compositions - Google Patents

2-substituted-1,3-diazine derivatives, preparatory processes, intermediates and pesticidal compositions

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Publication number
NZ230592A
NZ230592A NZ230592A NZ23059289A NZ230592A NZ 230592 A NZ230592 A NZ 230592A NZ 230592 A NZ230592 A NZ 230592A NZ 23059289 A NZ23059289 A NZ 23059289A NZ 230592 A NZ230592 A NZ 230592A
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New Zealand
Prior art keywords
radical
substituted
alkyl
phenyl
halogen
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NZ230592A
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Helmut Zondler
Adolf Hubele
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Ciba Geigy Ag
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Publication of NZ230592A publication Critical patent/NZ230592A/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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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

New Zealand Paient Spedficaiion for Paient Number £30592 230592 NO DRAWINGS ^ n ~ I - A Priority Da!o(s): J '.A.....' J.
Compel* Spjriliosiicn ... } els?:: htlrr j . i. fL .1 ....V, .-i-V. /.\.s „ , r-o 1LHY-£] 0 * * * 2 5 FEB 1992 P;«b!icoiio'i 8: — \ - f~ - P.O. Joiifoo"1, f*.3: '.w.w.'v Cl.tss. Cunt /v\yri i-.V. I C-P?l U ^6^v,:. :V I Wiv;?/ kk.. .V: -lU^UV^.,' Patents Form Ko. 5 f. ■' ?' - r- f CEV NEW 2EALAKD PATENTS ACT 1953 J COMPLETE SPECIFICATIok' PESTICIDES j^WE• CIBA-GEIGY AG, a Swiss Corporation of Klybeckstrasse 141, 4002 Basle, Switzerland, hereby declare the invention, for vhich it/Ve pray that a patent may be granted to ny^/us, and the method by vhich it is to be performed, to be particularly described in end by the following statement: (followed by Page la) 230 5 9 2 - la- -17200/1+2/- Pesticides The present invention relates Co 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 compounds or the compositions for controlling pests, especially plant-destructive microorganisms, particularly fungi.
The pyrimidine compounds according to the invention have the general formula I Rlv >-< > (I) R? Rj wherein: Ri is phenyl or phenyl mono- to tri-substituted by Ri,; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical OR5 or by the radical SR5. Ca-Cscycloalkyl, C3~C6cycloalkyl mono- to tri-substituted by Ci~Ci,alkyl or by halogen, C2-Csalkenyl, Cj-Csalkynyl or the formyl radical; R3 is hydrogen, Ci-Ci,alkyl, Ci~Ci,alkyl substituted by halogen, cyano or by the radical ORs or by the radical SR5, Cj-Cecycloalkyl or Cj-Cjcycloalkyl mono- to tri-substituted by Cj-Cualkyl or by halogen; Rt, is halogen, Ci~C3alkyl, Ci-C2haloalkyl, Ci-Caalkoxy or Ci-Cahaloalkoxy; R5 is hydrogen, Ci-Csalkyl, C3-Csalkenyl, Cj-Csalkynyl or the radical (CH2)n-X-Ci-C3-alkyl; yRa yRi0 R7 is the group -NH2, —N=C or —; R9 Ri 1 Rs is hydrogen, Ci~C3alkyl or Ci-C3haloalkyl; R9 is hydrogen, Cj-Csalkyl, Ci~C3alkyl substituted by hydroxy, 0Ri2» SR12 or by N(Ri2)2t C3-C6cyclo-alkyl, cyclopropyl substituted by SRi 2, C3-C1oalkenyl, Ci-C3haloalkyl, (followed by Page 2) * 2 3 0 5 phenyl, phenyl mono- to tri-substituted by halogen, Cj-Cjalkyl, Ci-Cj-alkoxy, Ci-Cshaloalkoxy, Ci-Cjhaloalkyl, hydroxy, nitro, cyano, amino or by dime thylamino, 1- or 2-naphthyl, 1-, 2- or 3-pyridyl, / • — • • — • • • or • * : vx v Re and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising A to 7 carbon atoms; Rio is CH(Rg)R9, phenyl, Cj-Csalkenyl, Cj-Cjalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; Ri1 is hydrogen, Ci-Csalkyl, C3-Csalkenyl, Cj-Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R12 is CH3 or C2H$; X is oxygen or sulfur; Z is 0, S, NH or NCHj; and n is 1 to 3; including their acid addition salts and metal salt complexes.
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, iso-butyl, 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 CHCI2, CH2F, CCI3, CH2C1, CHF2, CF3, CHzCH2Br, C2C15, CH2Br, CHBrCl etc., preferably CFj. 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 compounds of formula I according to the invention, when used in low concentrations, are distinguished not only by excellent insecticidal and fungicidal activity but also by particularly good plant compatibility. 2 3 0 5 The invention relates both to the free compounds of formula I and to their addition salts with inorganic and organic acids and to their complexes with metal salts.
Salts according to the invention are especially addition salts with non-harmful inorganic or organic acids, for example hydrohalic acids, for example hydrochloric, hydrobromic or hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid or organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, £-toluenesulfonic acid, methanesulfonic acid, salicylic acid, ^-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalene-disulfonic acid- Metal salt complexes of formula I comprise the fundamental organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloro-acetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc. of the elements of the second main group, such as calcium and magnesium, and of the third and fourth main groups, such as aluminium, tin or lead, and of the first to eighth sub-groups, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, etc.. The sub-group 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 1 (Substituents) Ri is phenyl or phenyl mono- to tri-substituted by Ri,; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical OR5 or by the radical SRs, C3-C6cycloalkyl, Cj-Cgcycloalkyl mono- to tri-substituted by Ci-Ci,-alkyl or by halogen, C2-Csalkenyl, C2-Csalkynyl or the formyl radical; R3 -I* - 2 30 5 9 2 is Cj-Cualkyl, Ci-Cualkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, Cj-Cecycloalkyl or Cj-Cscycloalkyl mono- to tri-substituted by Ci-Cualkyl or by halogen; Ri, is halogen or Ci-Cjalkyl; Rs is hydrogen, Ci-Csalkyl, C3-Csalkenyl, Cj-Csalkynyl or the radical (CH2) -X-Cj-Cjalkyl; R9 is hydrogen, Ci-Csalkyl, C3-C6cycloalkyl, Cj-Cs~ alitenyl, Ci-Cjhaloalkyl, phenyl or phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; Re and R9 , together with the carbon atom in the radical R7 , are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; R7, Rio, R11, Ri2 and Z are as defined under formula I and halogen is preferably fluorine, chlorine or bromine, X is oxygen or sulfur; n is 1 to 3.
Group 2 (Substituents) Ri is phenyl or phenyl mono-substituted by halogen; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by OR5, Cj-C6cycloalkyl, C3-C6cyclo-alkyl mono- to tri-substituted by Ci-C<,alkyl or by halogen, Cz-Csalkenyl, C2-Csalkynyl or the formyl radical; R3 is Ci-Ci.alkyl, Ci-Cualkyl substituted by halogen, cyano or by ORs, C3-C6cycloalkyl or C3-C&cycloalkyl substituted by methyl; Rs is hydrogen or Ci-C2alkyl; R9 is hydrogen, Ci-Csalkyl, C3~C6cycloalkyl, C3-Csalkenyl, Ci~C3haloalkyl, phenyl or phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; Rb and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; R7, Rio, Ri1 and Ri2 are as defined under formula I and halogen is preferably fluorine, chlorine or bromine.
Group 3 (Substituents) Ri is phenyl or phenyl mono- to tri-substituted by RwI R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SRs, C3~C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by C1-C1,-alkyl or by halogen, C2"C$alkenyl, C2-Csalkynyl or the formyl radical; R3 is Ci-Cualkyl, Ci-Cualkyl substituted by halogen, cyano or by the radical OR5 or by the radical SRs, C3-C6cycloalkyl or C3-C&cycloalkyl mono- to tri-substituted by Ci-Csalkyl or by halogen; Ri, is halogen, Ci~C3alkyl, Ci~C2haloalkyl, Ci-Csalkoxy or Ci-C3haloalkoxy; Rs is hydrogen, C1-C5- #» 2305 92 alkyl, Cj-Csalkenyl, Cs-Csalkynyl or the radical (CH2J^-X-Ci-Cjalkyl; R7 is -NH2; X is oxygen or sulfur; n is 1 to 3; including their acid addition salts and metal salt complexes.
Group A (Substituent.«) Ri is phenyl or phenyl mono- to tri-substituted by Ru; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical OR$ or by the radical SRs, C j-C6cycloalkyl, Cj-Ctcycloalkyl mono- to tri-substituted by C1-C1,- alkyl or by halogen, C2-Csalkenyl, Cj-Csalkynyl or the formyl radical; R3 is Ci-Ci,alkyl, Ci-Ci,alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, Cj-Cfccycloalkyl or Cj-C&cycloalkyl mono- to tri-substituted by Ci~Ci,alkyl or by halogen; Ri, is halogen; Rs is hydrogen, Ci-Csalkyl, Ca-Csalkenyl, Cj-Csalkynyl or the radical (CH2) -X-Ci-Cjalkyl; X is oxygen or sulfur; n is 1 to 3. n ~ Group 5 (Substituents) Ri is phenyl or phenyl mono- to tri-substituted by halogen; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SR5, Cj-C6cycloalkyl, Cj-C&cycloalkyl mono- to tri-substituted by Cj-Cwalkyl or by halogen, C2-Csalkenyl, C2-Csalkynyl or the formyl radical; Rj is Ci~Ci,alkyl, Ci-Cualkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, C3-Cscycloalkyl or C3-Ctcycloalkyl mono- to tri-substituted by Ci-Ci,alkyl or by halogen; Rs is hydrogen, Cj-Csalkyl, Cj-Csalkenyl, Cj-Csalkynyl or the radical (CH2) -X-C1-C3- n alkyl; X is oxygen or sulfur; n is 1 to 3.
Group 6 (Substituents) ^ Ri is phenyl or phenyl mono-substituted by chlorine or by fluorine; R2 is Ci-Csalkyl, or is Ci-Cjalkyl substituted by ORs, Cj-C&cycloalkyl, C3-C6-cycloalkyl mono- to tri-substituted by Ci-Csalkyl or by halogen, C2-C5-alkenyl, C2~Csalkynyl or the formyl radical; R3 is Ci-Cualkyl, Ci-Cuhalo-alkyl, C3-C6cycloalkyl or C3~C6cycloalkyl substituted by methyl; Rs is hydrogen or Ci-Cjalkyl. 2 30592 Especially preferred are compounds of groups 5 and 6 wherein Rj is: methyl, fluoromethy1, chloromethyl, bromomethy1, Cj-C^cycloalkyl or methoxymethy1.
The following groups of individual compounds are preferred: Group 1 (Compounds) N-(4-fluoromethy1-6-cyclopropylpyrimid-2-yl)-N-phenylhydrasine; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-m-fluorophenylhydraz ine; N-(4-me thy 1-6-cyc lopropy lpy rimid-2-yD-N-ji-f luorophenylhyd r azine; Group 2 (Compounds) N-(4-methy1-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4,6-di-methylpyrimid-2-yl)-N-phenylhydrazine; N-(4-methyl-6-methoxymethyl-pyrimid-2-yl)-N-phenylhydrazine; Group 3 (Compounds) N-(4,6-dimethylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4,6-dimethylpyrimid-2-y1)-N-phenylisobutyraldehyde hydrazone; N-(4-methy1-6-methoxymethy1pyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenyl-propionaldehyde hydrazone; N-(4-methy1-6-cyclopropylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4-methy1-6-cyclopropylpyrimid-2-yl)-N-phenyl-n-butyraldehyde hydrazone; N-(4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-( 4-methyl-6-cyclopropylpyriniid-2-yl)-N-phenyltrichloroacetaldehyde hydrazone; N-(4-methyl-6-cyclopropyl~ pyrimid-2-yl)-N-£-fluorophenylacetaldehyde hydrazone; N-(4-methy1-6-^ eyelopropylpyrimid-2-yl)-N-£-fluorophenylisobutyraldehyde hydrazone; N-(4-methyl-6-eyelopropylpyrimid-2-yl)-N-m-fluorophenylisobutyraldehyde hydrazone; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4,6-di-methylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4,6-dimethyl-pyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; N-(4-methyl-6-methoxymethyl-pyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4-methy1-6-methoxymethy1-pyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4-methyl-6-methoxymethyl-pyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methyl-6-cyclopropy1- ~. 2305 92 pyriroid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4-methy1-6-cyclopropyl-pyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; N-(4-methy1-6-cyclopropy1-pyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methy1-6-cyclopropy1-pyrimid-2-yl)-N-phenyl-N1-diethylhydrazine; N-(4-methy1-6-cyclopropy1-pyrimid-2-yl)-N-phenyl-N'-mer'nyl-N'-ethylhydrazine; N-(4-methy1-6-cyclo-propylpyrimid-2-yl) N-^-fluorophenyl-N'-ethylhydrazine; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-m-fluorophenyl-N'-isopropylhydrazine.
The compounds of formula 1 are prepared as follows: Process (a) Reaction of a pyrimidine derivative of formula II /*■ v-f > with a phenylhydrazine derivative of formula III rj-nh-nh-r (iii) in the presence of a base, in an aprotic solvent and at temperatures of -50° to 150°C, preferably -30° to 80°C, wherein Y is halogen, preferably chlorine, the radical SOzRt or N°(CHj)j, Rt is Cj-Cualkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for Rio and Rii, 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 /Rz /-z /~\ R<\ Rlv j. V-n —- t> . N.
J* \ Rb\ RlV ^ Ri-W—: + .c=o ——- r8v >-< kV< R/ "H2° >4 v. \3 Rs R (IV) (V) (VII) / 2 3 0 5 8 in any desired solvent, in the presence of an acid and at temperatures of -20° to 120°C, preferably 10° to 50°C, Ri-Rj and Re and R9 being as defined under formula I.
Azeotropic distillation or molecular sieves can be used to remove water from the reaction mixture. Drying agents, for example CaClz or NajSOi, , 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 using a reducing agent, for example a borohydride etherate, NaBHu, NaCNBHj or LiAlHi,, in an inert solvent, for example a suitable alcohol, tetrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures of 0° to 50°C or by catalytic hydrogenation using catalysts, for example nickel, platinum, palladium or rhodium.
Process (d) Reductive alkylation of a pyrimidine hydrazine derivative of formula IV reduction (VII) (VIII) (IV) with an aldehyde or ketone of formula V Rs-C—R9 (V) 2 30 5 in Che presence of a reducing agent, for example a borohydride etherate, NaBHu, NaCNBHj or LiAlHi,, in an inert solvent, for example a suitable alcohol, teCrahydrofuran, dioxane, ethyl acetate or toluene, at temperatures of 0° to 50°C, preferably 10° to 40°C.
Process (e) Alkylation of a pyrimidine hydrazine of formula IV or VIII with an alkyl halide R Hal o y + R Hal Rii-f' V AH2sN=< ° I R R R3 O O (IV) (IX) - "jsi CHReUs) R CHR0(R9) o (VIII) (X) in an inert solvent, in the presence of a base and at temperatures of 0°-60°C, preferably 10°-40°C, R being Ci~Ci,alkyl. Other suitable o alkylating agents are dialkyl sulfates.
In processes (a-e) described above, R1-R9 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.-butanolate, 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, 2 50 5 92 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 aceto-nitrile, propionitrile; N,N-dialkylated amides, such as dimethyl-formamide; 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 B-diketones to form 2-hydroxypyrimidines which are subsequently reacted to form 2-halopyrimidines as follows: Ra Ri Ri •=° H2N .=N ).=N •: + >=0 v OH < >-Hal >=0 H,/ W W R3 R} Ri There may be used as halogenating agents especially phosphorus oxychloride or phosphorus oxybromide.
Another possible method of obtaining the 2-halopyrimidines of formula II is to prepare them by way of the 2-aminopyrimidines. The 2-amino-pyrimidines are obtained by known methods (see D.J. Brown, The Pyrimidines, Interscience Publishers, 1962), then diazotised, and converted by the Sandmeyer process into the halopyrimidines. The 2-aminopyrimidines are obtained, for example, by condensing B-diketones with guanidine in the following manner. •=0 HNN /*-N\ ^ NaN02/H* /"~N\ + )C-NH2 ~ •( y- NH2 •( —Hal R/-=° 2) Hal0/Cu® /'=l/ K3 K3 R3 2 50 5 The pyrimidine derivatives of formula II in which Y is S02-Ci-Ci,alkyl or SCharyl 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, 1962).
Apart from the condensation of the corresponding diketones as described above, pyrimidines of formula II in which the radical Rj is haloalkyl can also be obtained 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 II ,-f> V\, in which Y is halogen or SO2-R& and Rt is Ci-C<.alkyl or aryl and Rz and R3 are as defined under formula I, are known.
The following groups of compounds of formula II are novel: 1. Compounds wherein R2 is Ci-Csalkyl or Ci-Csalkyl substituted by the radical ORs or by the radical SRs; R3 is Ci-Cualkyl substituted by halogen, cyano or by the radical OR5 or by the radical SRs; R5 is hydrogen, Ci-Csalkyl, C3-Csalkenyl, C3-Csalkynyl or the radical (CH2)n-X-Ci-Cjalkyl; X is oxygen or sulfur; n is 1 to 3; Y is halogen, preferably chlorine, or SO2R6; and R6 is Ci-Cualkyl or aryl, with the exception of the compounds 2-chloro-4-methyl-6-methoxymethylpyrimidine and 2-chloro-4-methyl-6-trichloromethylpyrimidine. 2. Compounds wherein R2 is hydrogen, Ci-Csalkyl or Ci-Csalkyl substituted by the radical OR5 or by the radical SRs'» R3 is C2_Csalkenyl or C2-CS-alkynyl; Rs is hydrogen, Ci-Csalkyl, C3-Csalkenyl, C3-Csalkynyl or the radical (CH2)n~X-Ci-C3alkyl; and Y is halogen. 2 3 0 5 9 The novel compounds of formula II form part of the present invention.
The hydrazine derivatives of formula III are known or can be prepared by methods known to the person skilled in the art.
Surprisingly, it has been found that the compounds of formula I have, for practical field 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. Uith the compounds 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 Botrytis, and also Pyricularia, Helminthosporium, Fusariunt, Septoria, Cercospora, Alternaria); and Basidiomycetes (e.g. Rhizoctoriia, Hemileia, Puccinia). They are also effective against the Ascomycetes 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. o u 5 The present invention further embraces the preparation of those compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the novel compounds of formula I or the novel compositions.
Target crops to be protected 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 plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds can be fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting adjuvants 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. 2 3 0 5 - u - A preferred method of applying a compound of formula I, or an agro-chemical composition which contains at least one of said compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula 1 can also penetrate the plant through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granulates may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing the active ingredient, or coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are for this purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with 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 ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.
The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants). * 2 30592 Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, 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 monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformaroide, 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 natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed 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 nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound 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 also water-soluble synthetic surface-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Cio —C22)» e.g. the sodium or potassium salts of oleic or stearic 2 3 0 5 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 salts.
More frequently, however, so-called synthetic surfactants are used, especially alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.
The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Ce-C22-alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutyl-naphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably 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 moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolyprop-ylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon 2 3 0 5 atoms in the alkyl chain, which adducts contain 20 to 2 50 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpoly-ethoxyethanols, 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 preferably quaternary ammonium salts which contain, as N-substituent, at least one Ce-Czzalkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)amnionium 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 compositions usually contain 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 to 1 % by weight, preferably 99.9 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably 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 formulations.
The compositions may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects. 230 5 9 2 The following Examples serve to illustrate the invention in more detail without limiting it. 1 . Preparation Examples Example 1.1: 2-hydroxv-4-methy1-6-cvclopropy1pyrimidine hydrochloride (starting material) fH3 /\ T II • HC1 6.0 g (0.10 mol) of urea and 12.6 g (0.10 mol) of cyclopropylbutane-1,3-dione are dissolved at room temperature (~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 60°C in vacuo to give 7.14 g (38.2 % of the theoretical yield) of 2-hydroxy-4-methyl-6-cyclopropylpyrimidine hydrochloride. The filtrate is concentrated and, after recrystallisation from 10 ml of ethanol and 20 ml of diethyl ether, a further 5.48 g (29.2 % of the theoretical yield) of the title compound are obtained.
Analysis: CbHioNzO-HCI (mol. wt.: 186.64) % calc. % found c 51.48 51.47 H .94 .97 N .01 .15 CI 18.99 18.89 2 3 0 5 Example 1.2: 2-chloro-4-methyl-6-cyclopropvlpyriroidine hydrochloride (starting material) fHj / ci' V'N<j 52.8 g (0.24 mol) of 2-hydroxy-4-methyl-6-cyclopropylpyrimidine hydrochloride are introduced into a mixture of 100 ml of phosphorus oxy-chloride and 117 g (0.79 mol) of diethylaniline and stirred; the exothermic reaction slowly begins, the temperature rising from room temperature to 63°C. The batch is then heated in an oil bath for 2 hours at 100-110°C internal temperature. After cooling to room temperature, the mixture is poured, with stirring, into a mixture of ice-water and methylene chloride. After one hour, the organic phase is separated in a separating funnel and is washed neutral with NaHCOj solution. After removing the solvent, 116.4 g of crude product comprising 2-chloro-4-methyl-6-cyclopropylpyrimidine and diethylaniline are obtained. Chromatographic separation using silica gel and a mixture of 25 % ethyl acetate and 75 % hexane as eluant affords 35.7 g (89.4 % of the theoretical yield) of pure 2-chloro-4-methyl-6-cyclopropylpyrimidine in the form of a colourless oil.
Example 1.3: 2-amino-4-diethoxymethy1-6-cyclopropylpyrimidine (starting material) \ / I f i V XCH(OC2H5)2 74.8 g (0.42 mol) of guanidine carbonate and 74.1 g (0.35 mol) of 4-cyclopropyl-2,4-dioxobutyraldehyde diethyl acetal are boiled for 10 hours in 250 ml of ethanol. The batch is then concentrated using a rotary evaporator and the residue is extracted with water and ethyl 2 3 0 5 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 title compound. M.p. 77-78°C.
Example 1.4; 2-chloro-4-formy1-6-cyclopropy1pyrimidine (starting 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 are then slowly added dropuise at -20 to -25°C, nitrogen evolving and a solid product separating out. After 2 hours the cooling means are removed and the mixture is allowed to rise to room temperature and is extracted with ethyl acetate. The extract is dried with sodium sulfate and the solvent is removed to give 21.9 g of crude product in the form of an oil. Further purification by means of column chromatography (silica gel, eluant 30 parts ethyl acetate and 70 parts hexane) affords 16.1 g of the pure title compound in the form of a colourless liquid. Refractive index (n]pS " 1.5603.
Analysis: CeHyClNzO (mol. wt.: 182.61) material) ci/ v ncho % calc. % found C 52.6 52.6 H 3.9 4.1 N .3 14.8 CI 19.4 18.7 2 3 0 5 Example 1.5: 2-chloro-A-hydroxymethy1-6-cyclopropy1pyrimidine (starting material) ,;T7' A ♦ • CI ' NK nCH2OH .4 g (0.084 mol) of 2-chloro-4-formyl-6-cyclopropylpyrimidine are dissolved in 125 ml of methanol and reduced by the addition of 1.6 g of sodium borohydride. The batch is concentrated and extracted with ethyl acetate and the solvent is removed using a rotary evaporator to give 14.5 g of crude product which is recrystallised from a mixture of 20 ml of toluene and 20 ml of cyclohexane. The yield of the pure title compound is 13.7 g (88.4 % of the theoretical yield); m.p. 102-104°C.
Analysis: C„H<>C1N20 (mol. wt.: 184.63) % calc. X found C 52.04 52.05 H 4.91 4.90 N 15.17 15.27 CI 19.20 19.28 Example 1.6: 2-chloro-4-hvdroxymethy1-6-cyclopropylpyrimidine methane-sulfonate (starting material) • ' • A • • Cl' V XCH20S02CH3 9.5 g (0.05 mol) of 4-hydroxymethylpyrimidine 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 immediately and is filtered off with suction. Concentration yields 14.7 g of crude product which is chromatographed on silica gel (25 parts ethyl acetate and 75 parts hexane) to give 13.6 g of the pure title compound. M.p. 64-66°C. 2 30 5 * Analysis: C,HuC1N203S (mol. ut.: 262.71) % calc. % found C 41.15 41.32 H 4.22 4.33 N 10.66 10.56 S 12.20 12.16 -<# Example 1.7: 2-chloro-4-fluoromethy1-6-cyclopropy1pyrimidine (starting material) • — I. I. • \ / « I f ciy 'v nch2f 13.4 g (0.05 mol) of methanesulfonate are boiled under reflux for 5 hours in 70 ml of propionitrile with 9.4 g (0.16 mol) of potassium 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 ethyl acetate and 85 parts hexane). The yield of the pure title compound is 7.5 g (78.6 % of the theoretical yield); m.p. 37-39°C.
Analysis: CbHbC1FN2 (mol. wt.: 186.62) % calc. % found C 51.49 51.73 H 4.32 4.45 N 15.01 14.90 F 10.18 10.26 CI 19.00 18.50 Example 1.8: 2-chloro-4-methy1-6-(2-methyIcyclopropy1)-pyrimidine (starting material) qi3 A Cl'' 'V nCH3 2 30 5 23 76.4 g (0.47 mol) of 2-amino-4-methyl-6-(2-methylcyclopropyl)-pyrimidine, produced by boiling guanidine carbonate with acetylmethyl-2-methylcyclo-propyl 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 and nitrous gases evolve. The mixture is then allowed to rise to room temperature, is 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 ethyl acetate and 80 parts hexane as eluant to give 32.2 g of the pure title compound; refractive index » 1.5334.
Analysis: C9H11CIN2 % calc. % found C 59.18 59.16 H 6.07 6.15 N 15.34 15.25 CI 19.41 19.20 Example 1.9: 2-(q-phenylhydrazino)-4,6-dimethylpyrimidine (Comp. 1.12) II CH3 )• N"< CHj 4.77 g (0.033 mol) of phenylhydrazine hydrochloride are suspended under nitrogen in 60 ml of tetrahydrofuran, and 7.41 g (0.066 mol) of potassium tert.-butanolate are added. A solution of 5.59 g (0.030 mol) of 2-methylsulfonyl-4,6-dimethylpyrimidine in 15 ml of tetrahydrofuran is then added dropwise at 25°-35°C and, after 2 hours, the mixture is extracted with ethyl acetate and water with the addition of a small amount of acetic acid at pH6. After drying the organic phase with sodium sulfate and removing the solvent using a rotary evaporator, 5.88 g of crude product are obtained which are subjected to chromatographic 2 3 0 5 purification using silica gel and a mixture of 35 parts ethyl acetate and 65 parts hexane to give 2.89 g of the pure title compound which, after recrystallisation from n-hexane, melts at 41-43°C.
Example 1.10: 2-(a-phenylhydrazino)-4■6-dimethyIpyrimidine (comp. 1.12) y \ N. N=-—"s CHj 7.06 g (0.035 mol) of 2-trimethylammonium-4,6-dimethylpyrimidine chloride* and 5.78 g (0.04 mol) of phenylhydrazine hydrochloride are suspended in 50 ml of tetrahydrofuran, and a solution of 5.04 g (0.045 mol) of potassium tert.-butanolate 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 ethyl acetate and 75 parts hexane) to give 3.94 g of the pure title compound.
Example 1.11: N-(4-methyl-6-cyclopropvlpyrimidin-2-yl)-N-phenyl-hydrazine (Comp. 1.4) T I. • • * ^ • 2.20 g (0.013 mol) of 2-chloro-4-methyl-6-cyclopropylpyrimidine and 1.62 g (0.015 mol) of phenylhydrazine are dissolved in 20 ml of tetrahydrofuran. A solution of 2.02 g (0.018 mol) of potassium tert.- * W. Klotzer, Monatshefte f. Chemie 87_, 131 (1956) 2 3 0 5 butanolate in 20 ml of tetrahydrofuran is added dropwise to this solution with cooling at 20-25°C. After 30 minutes, no further starting pyrimidine is detected by thin layer chromatography. The mixture is then extracted with water and ethyl acetate and, after removing the ethyl acetate using a rotary evaporator, 3.1 I g of crude product are obtained which are purified by column chromatography on silxca gel (eluant: 35 % ethyl acetate/65 % hexane). 2.83 g of the purified product are obtained (90.2 % of the theoretical yield) which are recrystallised from a mixture of 8 ml of n-hexane and 1 ml of cyclohexane, affording 1.62 g of the title compound (m.p. 46°C). The mother liquor is concentrated and is recrystallised again to give a further 0.42 g of that compound (m.p. 45-46°C). The total yield of the recrystallised compound is 2.04 g (65.3 % of the theoretical yield).
Analysis: CmHieNi, (mol. wt.: 240.31) % calc. % found C 69.98 69.81 H 6.71 6.77 N 23.32 23.49 Example 1.12: (N-(4-methy1-6-cyclopropylpyrlmidin-2-yl)-K-phenyliso- butyraldehyde hydrazone (Comp. 3.26) • ' —' • \/ /\ /\ I N T II 'VY'V\h, S=CHCH(CH j) i 6.25 g (0.026 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-hydrazine 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 % hexane/18 % ethyl acetate/10 % methanol). The 2 3 0 5 9 2 yield is 2.92 g of the pure title compound 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: CisHzzNi, (mol. wt.: 294.40) % calc. % found C 73.44 73.25 H 7.53 7.64 N 19.03 18.92 Example 1.13: N-(4-methyl-6-cyclopropvlpvrintidin-2-yl)-N-phenyl-N'-isobutylhydrazine (Comp. 4.87) • .i—ii i • \ / y\ /\ I II T II VyV^ HNCH2CH(CH3)2 8.55 g (0.029 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-isobutyraldehyde hydrazone are dissolved in 30 ml of methanol and 2 ml of glacial acetic acid. 2.14 g (0.029 mol) of sodium cyanoborohydride are then added in portions with stirring. The reaction proceeds exothermi-cally; 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 % hexane/15 % ethyl acetate) affords 7.6 g (89 % of the theoretical yield) of the title compound in the form of an oil having a refractive index of [n]^5 ■ 1.5733.
Analysis: C10H21.N1, (mol. wt.: 296.42) % calc. % found C 72.94 72.90 H 8.16 8.21 N 18.90 18.83 * 2 3 0 5 9 2 27 Example 1.14: N-(4-methyl-6-methoxymethylpyrimidin-2-yl)-N-phenyl-N'-methylhydrazine (Comp. 4.17) 3.70 g (0.033 mol) of potassium tert.-butanolate are dissolved in 25 ml of tetrahydrofuran dried with molecular sieves, 3.67 g (0.03 mol) of 2 N-methyl-N'-phenylhydrazine are added and a solution of 4.22 g (0.025 mol) of 2-chloro-4-methyl-6-methoxymethylpyrimidine in 30 ml of anhydrous tetrahydrofuran is added dropwise under nitrogen at -20°C to give a yellow-brown suspension which is gradually allowed to rise to room temperature. After 4 hours, the batch is extracted with water and ethyl acetate and the crude product is isolated by evaporating the solvent and purified by column chromatography on silica gel (eluant: 65 % hexane/35 % ethyl acetate). The pure title compound is obtained in the form of an oil having a refractive index of [n]^" * 1.5793.
Analysis: CiuHielUO (mol. wt.: 258.33) H C % calc 65.09 7.02 % found 65.08 7.09 21.05 N 21.69 Example 1.15: N-(4,6-diinethylpyrimidin-2-yl)-N-phenyl-N'-methylhydrazine (Comp. 4.1) K. Kratzl, Monatshefte f. Chemie 89, 83 (1958) 2 30 5 4.03 g (0.02 mol) of 2-trimethylamnionium-4,6-dimethylpyrimidine hydro-3 chloride are stirred with 3.05 g (0.025 mol) of N-methyl-N'-phenyl-hydrazine under nitrogen in 30 ml of anhydrous tetrahydrofuran, and a solution of 3.36 g (0.03 mol) of potassium tert.-butanolate in 15 ml of tetrahydrofuran is added dropvise at room temperature. The batch is left overnight at room temperature to complete the reaction and is then extracted with water and ethyl acetate, the solvent is removed and the crude product is purified by column chromatography on silica gel (eluant: 70 % hexane/30 % ethyl acetate) to give 3.09 g of the title compound in the form of an oil.
Analysis: CuHisNi, % calc. % found C 68.40 68.01 H 7.07 7.09 N 24.54 24.13 Example 1.16: N-(4,6-dimethylpyrimidin-2-yl)-N-phenyl-N'-dimethyl-hydrazine (Comp. 4.13) <|:h3 /\ I II T II X''y'V'nch, IHCH,), 3.42 g (0.016 mol) of N-(4,6-dimethylpyrimidin-2-yl)-N-phenylhydra2ine 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 % hexane, 19 % ethyl acetate and 5 % methanol to give 1.80 g (46.4 % of the theoretical yield) of the pure title compound in the form of an oil; [n]p5 = 1.5673. 3 W. Klotzer, Monatshefte f. Chemie 82, 131 (1956) 2 30 5 29 Example 1.17; N-(4-methy1-6-cvclopropylpyrimidin-2-yl)-N-phenyl-N'-methyl-N'-isobutylhydrazine (Comp. 4.102) 4.55 g (0.0153 mol) of N-(4-methyl-6-cyclopropylpyrimidin-2-yl)-N-phenyl-N1-isobutylhydrazine are dissolved with 1.45 g (0.0184 mol) of 38 % formaldehyde in 25 ml of methanol and 2 ml of glacial acetic acid, and 1.24 g (0.0168 mol) of sodium cyanoborohydride are added in portions at 10°C. The reaction proceeds exothernically 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 X hexane/15 % ethyl acetate) to give 4.4 g of the title compound in the form of an oil; refractive index [n]p° - 1.5613.
Analysis: C19H26N1, (mol. wt.: 310.45) H C % calc 73.51 8.44 % found 73.94 8.58 17.93 N 18.05 2 3 0 5 92 - Table I: Compounds of formula V\, Comp. No. ri rI r3 physical constant 1.1 1.2 1.3 CsHs 4-CF3c6HW 4-f-cSH.. h ch3 h ch3 ch3 H m.p.129-131°C 1.4 CSH5 ch3 _A \l m.p. 45-46°c 1.5 C6Hs c(ch3)3 ch2och3 1.6 c6h5 ch2och3 -<! m.p. 37-38°c 1.7 1.8 1.9 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 c6hs c6hs C6Hs 3.4-(c2h50)2-cth3 c6h5 c6h5 4-ch30-c6h..
C6hs 3.5-C1z-C6H3 3,5-Cl2-C6H3 3,5-Cl2-C6H3 ch3 ch2oc2h5 CH2och(CHJ)C2H5 ch3 ch3 ch3 c(ch3)3 ch3 ch3 ch3 c(ch3)3 ch2och3 c(ch3)3 ch3 ch2oc2h5 ch2oc2h5 ch3 ch2oc2h5 chci2 ch2oc2hs ch3 ch2oc2h5 m.p. 60-61°c m.p. 41-43°c m.p.154-156°c 1.18 3,5-Cl2-C6H3 A \l ch2och3 1.19 1.20 1.21 3,4-(c2h50)2-c6h3 4-CH30-c6hI« 4-CH30-c6hi. ch2oc2h5 ch3 ch2oc2h5 c(ch3)3 ch3 ch3 m.p. 90-92°c 1.22 3,4-(c2Hso)2-c6h3 A \l ch2och3 1.23 1.24 c6h5 4-ch3-c6h., ch3 ch3 ch2och2ch=ch2 ch3 n*0 1.604 2 30 5 9 2 Continuation: Table 1 Comp. No. ri r2 r3 physical constant 1 .25 4—OCH 3 — Cs hi, -<i CH:OCH3 1.26 1.27 1.28 1.29 1.30 1.31 1.32 1.33 1.34 1.35 1.36 1.37 1.38 1.39 1.40 1.41 1.42 1.43 1.44 1.45 1.46 3,5-Cl2-C6H3 4-OCHj 2-Br-CsH^ 3,5-Cl2-C6H3 4-CH30-C6Hi. 3,5-Cl2-C6H3 3-Cl-CsHu 3,4-(C2HsO)2-C6H3 4-CH30-C6Hw 3.4-(C2HSO)2-C6H3 3.5-C1z-CfcH 3 2,4,6-C1j-C6H2 3.4-(C2h50)2-C6hI 3.5-Cl2-C6H3 CSH5 4-CH30-C6Hi, 3,5-(CF3)2 ~C & H 3 c6h5 C6Hs CsHs C6Hs ch3 CHJ ch3 CHJOCH2CH=CH2 C(CH3)3 ch3 CH3 CHJ CHJ C(CH3)3 ch3 CH3 ch3 ch2 0ch2csch CH2OCH2CSCH ch20ch2c2ch ch3 chJoch3 CHzSCHs ch3 ch3 CH20CH(CH3)C2H5 CH20CH(chj)C2H5 ch3 ch3 ch20ch3 chc12 ch3 CH2OCH(CH3>C2H5 CH20CH3 CH20CH3 CH20CH3 ch3 ch2och3 ch3 ch3 CH3 CH 3 CH20CH3 ch 3 ch(och3)2 ch(oc2h5)2 m.p. 55-57°C m.p. 47-48°C m.p.150-152°C m.p. 88-90°c 230 5 92 Continuation: Table 1 Comp. ri r2 Rj physical No. constant 1 .47 cths • _ / \ \ / CH j 00 4-Br-C$Hi, CHj ch3 m.p. 92-93°C 1.49 CtHs CHj Cyclo-C6 H1j 1.50 CsHs CHj CF2C1 1.51 cths -<i • CFj 1.52 c6h5 • -<l • • A \l • 1.53 c6h5 • -<! CF2C1 1.54 3-CH3-C6Hfc CHj CHj m.p. 72-73°C 1.55 CsHs c2h5 —/i "\l • n^5 1.6063 1.56 c6h5 CHj • • n^° 1.6072 1.57 c6h5 CH(CHj)2 • y\ \l 1.58 CsH5 CH2OCHj CFj 1.59 c6h5 -<! CH(0CH3)2 1.60 C6Hs CH2OCHj ch2ch(ch3)2 1.61 C6H5 CHO -<i • 1.62 C6H5 ch2och3 a ci^! 1.63 C6H5 CHzCH2CH3 chzochj 1.64 C6Hs ch(ch3)2 CH20CHj 1.65 4-F-C6Hu ch3 -<jVCHj • n^5 1.5883 1.66 C6Hs ch2oh • #/l \l • 2305 92 Continuation: Table 1 Comp.
Ri Rz Rj physical No. constant 1.67 CsHs (CH2)JCHJ CH2OCHJ 1.68 1.69 C6H5 c6h5 c2h5 ch2och3 CH20CHJ _?>j \l 1.592 3 1.70 C&Hs ch2och3 CF2C1 1.71 c6h5 -<! ch2ci 1.72 c6h5 CH2OCH3 CH(OCHJ)2 1.73 4-F-C$HI, ch3 CHJ m.p. 78-79°C 1.74 4-Cl-CfcHw ch3 ch3 m.p.101-102°C 1.75 4-F-CiHi, ch3 c2h5 njj5 1 .5723 1.76 c6h5 -<i • chci2 1.77 c6h5 • — \ \l • CHzBr 1.78 CsHs CH2OCH3 CF2CF3 1.79 c6h5 -<! CHZF n^2 1.6150 1.80 c6h5 CH(CH3)C2H5 CH2OCH3 1.81 CtHs CHO ch2och3 1.82 CfcHs (CH2)3CH3 _a \l 1.83 c6h5 (ch2)2ch3 1 • / \ 1.84 C6Hs • -<l • ch(ch3)c2h5 1.85 c6h5 • — \ \l 4 /C1 • ch2ch(ch3)2 1.86 c6h5 C^3N* \l • 1.87 4-CF3-C6Hu ch3 CH2OCH3 1.88 4-Br-C6Hi, ch3 ch2och3 230 5 92 Continuation: Table 1 Comp.
Ri Rz R3 physical No. constant 1.89 C6Hs ch20h ch2och3 1.90 CsHs _A \l • CF2cfj 1.91 CeHs ch2och3 ch2ci 1.92 4-ch j-cehi, ch2och3 ch3 1.93 c5H5 CH(OC2hs)2 A \l n^s 1.5763 1.94 2-CF3-c6hu ch3 ch2och3 C^Cl • 1.95 C6Hs ch3 cc! 1.96 C&Hs ch3 cho 1.97 C6hs • — \ \l • -\l • 1.98 4-Cl-CeH.. ch3 ch2och3 1.99 4-Cl-3-CF3-C6H3 ch3 ch2och3 1.100 3-ch3-c6h.. ch3 ch2 0ch3 1.101 3-f-cshu ch3 ch(oc2h5)2 1.102 3-cf3-c6hu ch2och3 ch3 1.103 3-c1-c6hu ch2och3 ch3 1.104 3-f-C6Hi, ch2och3 ch3 n^ 1 .5863 1.105 4-f-C6hu ch2och3 ch3 m.p. 70-72°c 1.106 4-CI-cbHu ch3 _A \l • * 2305 92 Continuation: Table 1 Comp.
Ri Rz Rj physical No. constant 1.107 C6HS ch3 ch2oh 1.108 4-F-CSHu ch3 "<i m.p. 9 3-95°C 1.109 c6h5 CH2OCH3 CH2Br 1.110 C6Hs CHj CH2C1 1.111 4-C1-3-CF 3-CtHj 1 • / \ CH j 1.112 c6h5 CH2OCH3 CHZF 1.113 CeHs -<i • -<U"' • 1.114 C6H5 ch3 CH2Br 1.115 CtHs ch3 CH2F 1.116 CtHs C(CHj)3 C(CH 3)j 1.117 c6h5 (CHzKCHj CH j 1.118 C6hs c2h5 C2H5 n£5 1 . 5923 1.119 c6h5 ch3 C2H5 n^° 1.5953 1.120 CsH5 ch3 C=CH 1.121 CbH5 ch 3 C=CCH 3 1.122 3-F-C6H<, ch3 _A \l m.p. 41-42°C 1.123 3-F-CtHk • -•/l \l • CHZF 1.124 3-F-C6Hi. ch3 • _y\ n--ch3 n^ 1 . 594 3 1.125 c6h5 h A \l 1.126 CtHs CH2CH2ch(ch3)2 CH j Continuation: Table 1 2 3 0 5 9 2 Comp. No. ri r2 RJ physical constant 1.127 4-f-cth., CiHs C2hS rip5 1.5743 1.128 4-f-cfth., chjochj -<i • m.p. 56-57°c 1.129 1.130 3-f-cjhi, 3-f-cthi, chj chj CHj c2h5 ni.p. 60-62°c njj0 1 . 5873 1.131 3-f-c6hii CHjochj -<! rip5 1 .5873 1.132 1.133 1.134 1.135 c*h5 4-f-cshk 2-f-cths 2-F-C6Hs CHj CH2OCHJ CHj CHj cfj c2h5 ch j CH2ochj rip1* 1.5543 1 . 57 33 rip3 1 .5863 rip3 1 . 5773 1.136 2-f-cihi, CHj • /I — • 1 \l • n37 1.5811 1.137 4-f-CsHI, C2hs • A \l • r>pj 1.5813 1.138 3-f-c6hk c2h5 • /\ —— • 1 \l • rip3 1 .5894 1.139 1.140 c6h5 3-f-c&hk ch2CH2chj ch2ch2chj ch2ch2ch3 ch2ch2ch3 dp3 1.5743 np3 1.5633 1.141 2-f-csh!. -<N, • ch3 nj^ 1.5854 1.142 c6h5 H H m.p. 75-77°c 230 5 92 Table 2: Compounds of formula Y—• N« V\, Comp. No.
R2 Rj physical cons tant 2.1 2.2 2.3 2.A 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 2.20 2.21 2.22 2.23 2.24 CHO t-butyl CHj CHj CHj CHj CHj CH2OCHj CH2OCH3 CHj CHj CHj CH2OCHj CH(OC2H5)2 n-propyl iso-propyl n-butyl CH2OCHj CH2OCHj CH2OCHj ch2oh CH2OCH3 CH2OCHj CHj "\l CH2OC2Hs CH2OCH(CHj)C2Hs ch2oc2h5 chci2 ch2och2ch«ch2 ch2och2c=ch CH2OCHJ -<! CH(OCHj)2 ch(oc2h5)2 cf2ci CFj -<! CH2OCHj CH2OCHj CH2OCHJ C2Hs ch(och3)2 CF2CFj ch2och3 ch2ci ch2f CH2OCHj CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI S02CHj n^s 1.5603 n^s 1.5344 oil 1.5064 ) Table 3: Compounds of formula /*' p Rl\ ^ R8>=/-Vy Rs Kz Comp. No.
Ri r2 Rj Re Rs physical constant 3.1 3.2 3.3 3.a 3.5 3.6 3.7 3.8 C6H5 C6Hs C6Hs C6H5 c6h5 c6h5 c6h5 CsHs ch 3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 cf3 cf3 ch3 cyclo-CjHs cyclo-C3Hs ch3 CHzOCHj cyclo-CjHs H H H H H H H H 2-ch j-cshi, CzHs CHj CHj CzH5 CzH5 CzHs n-cjh7 m.p.188-190°c m.p.117-118°c m.p.137-138°c m.p.103-105°c m.p. 46-49°c m.p. 51-53°c 1 .5862 3.9 3.10 cshs 3-f-cshu ch3 ch3 CzHs CHzOCHj chj chj chj ch j n^" 1 . 5678 3.11 C6Hs ch3 ch3 CzHs chj n^j 1.5830 3.12 4-n02-c6hi, CzHs C2hs H n-C3H7 3.13 Csh5 ch3 n-c3h7 / \ _ • • \ / chj 3.14 CsHs ch3 cyclo-C3H5 ch3 CHj n£j 1.5982 3.15 CsHs ch3 cyclo-C3Hs ch j (> • 3.16 CsHs ch3 cyclo-C 3 H 5 ch3 ch2och3 r\o Ca| CD Ol Co IV> / \ V ^ () 9 Table 3: (continuation) Comp.
Ri r2 Rj Re R9 physical constant 3.17 4-cf30-c6hu CHj cyclo-CjHs h (ch3)2ch 3.18 4-cf30-c6hu ch3 cyclo-c3Hs h ch j 3.19 3-f-c6hi, ch3 ch20chj h c(chj)3 m.p.104-106°c 3.20 3-f-cfchi, ch3 ch2och3 h C2H5 m.p. 95-97°c 3.21 4-ch30-c6h^ ch3 ch3 H C2Hs m.p. 81-82°c 3.22 4-CH3-c6hu (chj)jc CHj h n-C jH7 3.23 4-CH3-c6hu n-CjH7 n-C3H7 h c2h5 3.24 c6h5 C2H5 c2h5 h c2h5 3.25 C6hs CHj CHj h (ch3)2ch m.p. 83-84°c 3.26 c6h5 CHj cyclo-CjHs h (ch3)2ch m.p. 53-55°c 3.27 C6hs chj-csc cyclo-CjHs h CHj 3.28 3f-c6h.. chj cyclo-CjHs cyclo-CjHs CHj 3.29 4f-c6h., ch3 cyclo-CjHs ch3 cf3 3.30 4-(ch3)2ch-c6h«, ch3 ch3 C2H5 CHj 3.31 c6h5 CHj ch3 -(ch 2)5 - 3.32 2-f-c6h.. chj n-CjH7 -(ch2)w- 3.33 4-i-ceh., CHj CHj cjhs h 3.34 4-i-cghu cyclo-CjHs ch j (chj)2CH H 3.35 c6h5 cyclo-CjHs ch j ch jch=ch— H m.p.121-122°c 3.36 c6h5 cyclo-CjHs ch j cfj chi H 3.37 c6h5 ch3 ch j CH\^iw h (l»i 2 CH J 3.38 c6h5 c(chj)j c(CHj)3 (chj)zch H 3.39 c6h5 c(ch3)3 c(chj)j C2Hs ch j 3.40 c6h5 ch3 cyclo-CjHs H CClj m.p.139-141°C ro 04 o en co f>0 4*' ( j 1 Table 3: (continuation) Comp. 3.41 3.42 3.43 3.44 3.45 3.46 3.47 3.48 3.49 3.50 3.51 3.52 3.53 3.54 3.55 3.56 3.57 3.58 3.59 3.60 ri c5h5 c5h5 c6h5 c6h5 c6h5 c6h5 c6h5 4-(CH3)2CH-C6HI, 4-Br-CeH.. 4-f-c6Hu 4-f-cthi. 4-F-CsH!, c6h5 c6h5 c6h5 c6h5 c6h5 c6h5 c6h5 c6h5 rz ch3 ch3 ch2och3 ch3 CHj ch3 ch3 ch3 CHJ cyclo-C3Hs cyclo-C3Hs cyclo-CjHs CHj CHj CHj CHj CHj CHj CHj ch3 r3 ch3 ch3 CHj cyclo-C3H$ cyclo-CjHs n-CsHi1 CH3 ch3 CHj CHj CHj CH3 CHj CH j CH2OCH3 CHj CHj CHj cyclo-CjHs CH3 Re R? physical constant CH^ /SCHj H m.p. 94-96°C H BrCH2 2-CH3-CtHw H m.p.l43-145°C 2-ch3-cihi, H m.p.107-109°C 2-f-C6hk CH3 3-chjo-cthw ch3 CsHs H m.p.138-140°c -(ch2) j- h / \ \_y nI m.p.255-256°C CH j H m.p.162-164°C CH3 CH3 (ch3)2ch h ....p. 58-60°C H 4-(CH3)2N-CsHW H 4-CN-c6Hw H 2-OH-CsH., h 2,3-Cl2-C6H3 m.p.221-222°C H ch2=ch- -CH=CHCH2CH2CH2- -ch=chch2ch2- —(ch2k- ro CM CD <_r? CO fS3 (1 x ts v Table 3: (continuation) Comp. ri r2 Rj Re Rs physical constant 3.61 3.62 3.63 3.64 3.65 3.66 3.67 c6h5 c6h5 3,5-(CF3)z-c6h3 C6hs c6h5 c6h5 C6Hs ch3 ch3 ch3 ch3 CHj ch3 ch j cyclo-c3H5 cyclo-C3Hs CHj cyclo-C3Hs cyclo-CjHs cyclo-CjHs cyclo-C3Hs chj cfj CzHs h h h h cf3 cf3 H ch3 ch2=c- 2-pyridyl 3-pyridyl 4-pyridyl n^s 1.4990 3.68 C6hs ch3 ch2och3 H y v 'V m.p.155-156°c 3.69 C6hs ch3 ch3 h y v 'V m.p.177-179°c 3.70 C6Hs ch3 cyclo-C3Hs ch3sch2chz H 3.71 C6Hs ch3 ch3 / \ — t • \ / ch3 3.72 3.73 3.74 3.75 3.76 c6hs c6hs C6hs c6Hs C6hs ch3 ch3 ch3 ch3 CHj ch3 cyclo-C3H5 CH2OCH3 cyclo-C3Hs cyclo-CjHs CsHs CsHs ch3 H h CFj ch3 ch2n(ch3)2 chci2 CBr3 rv> CM CD cjn CO ro o Table 3: (continuation) Comp.
Ri Rz Rj Rs R» physical constant 3.77 C6Hs CH j CHj / \ \ h 3.78 3.79 3-F-CsHu C6H5 CH 3OCH2 CH30CHz ch3 ch3 h H (CH3)zCH (chj)zch m.p. 83-84°C n^s 1.5673 3.80 3.81 3.82 3.83 3.84 CsHs 4-CF 3-C6Hu 4-CF3-C6H., CsHs CsHs cyclo-C3Hs CH3 ch3 ch3 ch3-c=c CH3 CH3 CH3 CH3 cyclo-C3Hs 2,3-Cl2-CsH3 ch3 H CH3(ch2)s h h CH3 C2Hs H CzHs m.p.179-182°C 3.85 4-F-CsHu cyclo-C3H5 ch3 • — » v.
Y h m.p.132-134°C 3.86 3-F-CsHi, cyclo-C3Hs ch3 H v m.p.lll-1120C 3.87 3.88 CsHs CsHs ch2och3 ch3 ch3 CH j ch3 cyclo-CsHs X H CH3 m.p.112-114°C n^ 1.600 3.89 3.90 3.91 3.92 3-F-C6H<, 3-F-C6Hu 3-F-CsHu 3-F-C6H<, CH3 CH3 ch3 ch3 cyclo-C3Hs cyclo-C3Hs cyclo-C3Hs cyclo-CaHs H h H H CH3 C2Hs n-C3H7 (CH3)zCH m.P.114-116°C m.p. 46-47°C m.p. 45-46°C ro 04 O en co ro O () Table 3: (continuation) Comp.
Ri r2 Rj 3.93 c6h5 ch3 cyclo-CiHs 3.94 4-f-c&hi.
CH3 cyclo-CjHs 3.95 4-f-cshi. ch3 cyclo-C 3 h5 3.96 c6h5 ch3 cyclo-CjHj 3.97 c6h5 ch3 cyclo-CjHs 3.98 3-F-C6Hu ch3 cyclo-C3Hs 3.99 3-F-C6Hu ch3 cyclo-CsHs 3.100 3-f-csh., ch3 cyclo-C3H5 3.101 4-f-c6hu ch3 cyclo-C shs 3.102 4-F-C6Hu ch3 cyclo-C3H5 3.103 c6h5 ch2och3 cyclo-C3h5 3.104 3-f-c6hu ch2och3 CH3 3.105 3-f-cth., cyclo-C3H5 CH3 3.106 3-F-C6Hu cyclo-C3Hs CH3 3.107 c6h5 cyclo-Cjhs CH3 3.108 c6h5 cyclo-C3Hs ch3 3.109 C6Hs cyclo-CjHs CH3 3.110 C6Hs ch3 CH3 3. Ill c6h5 ch3 ch3 3.112 c6h5 ch3 ch3 3.113 3-F-C6Hu ch3 ch2och3 - 43 Rs h c2h5 n-C jH7 h c2h5 ch 3 ch3 ch3 CCI3 ch2och3 h h CH3SCH2CH2 (ch3)3c (chj)3c H 2-pyridyl ch3 ch, 4-pyridyl R? -ch=ch2 h H / \ sch3 ch2 ch3 ch3 C2Hs cf3 h ch3 1-naphthyl 2-pyridyl h h h \ y v cyclo-C3Hs CH3 2,4-Cl2-C6H3 (CH2)7CH3 H physical constant m.p. 79-80 C m.p. 80-81°C m.p.127-128°C m.p.104-105°C m.p.100-102°C m.p. 90-92°C m.p.190-192°C rv> CM o en co ro o Table 3: (continuation) Comp. 3.114 3.115 3.116 3.117 3.118 3.119 3.120 3.121 3.122 ri c6h5 c6h5 3-f-c6h<, c6h5 C6Hs c6h5 c6h5 3-f-cshu 4-F-C6Hu Rz ch3 ch3 ch3 ch3 ch3 CHj ch3 CHj ch3 Rj ch2och3 ch2och3 CH20CHj CHzOCHJ CHj CH2OCHj CHj CH2OCH3 _/\ \l r8 H H H R, 2,3-Cl2-C6H3 H H n-CjH? C(CHj)j C(CHj)j n-C3H7 n-C3H7 C(CHj)j physical constant m.p.185-186°C m.p.121-122°C ir d.144-145°c n^ 1.5756 m.p. 73-74°C m.p.100-101°C n^5 1.5860 m.p. 47-48°C m.p. 27-128°C ro CM CD CJ1 CO ro Table 4: Compounds of formula vr> RioR(n)N SI— ( K2 Comp.
Ri Rz Ri RI o Rn physical constant 4.1 c6h5 ch3 ch3 H ch 3 njjj* 1.5963 4.2 c6h5 ch3 ch3 h CjH5 4.3 C6Hs ch3 ch3 h ch2ch=ch2 np" 1.5740 4.4 CsHs ch3 ch3 H n-C3H7 4.5 c6h5 cyclo-C3H5 ch3 H ch2och 4.6 4-ch30-c6hk ch3 CHj H n-CsHii /Hz- • — • 4.7 c6h5 ch3 cyclo-C3Hs s \ V H n^5 1.6160 /Hz- !■»! 4.8 3,4-(ch3)2-c6h} ch3 ch3 s \ \ / H V ro 04 CD cn CO ro » Table 4: (continuation) Comp.
Ri Rz R3 RI o R11 physical constant /CH2- 4.9 4-CF j-CfcHi, CH j CHJ s~\ \y CHj 4.10 3-F-C6H«. ch3 cyclo-C3Hs s n-C3H7 n-CsH? n^7 1.5510 4.11 c6h5 CH2OCH3 ch3 CH2C(CHj)j H 4.12 c6h5 CH2OCH3 ch3 H 4.13 c6h5 CH3 ch3 CH3 CH3 n™ 1 .5673 4.14 c6h5 ch3 ch3 C6HsCH2- H m.p. 56-57°C 4.15 c6h5 ch3 cyclo-CjHs H 4.16 4-F-C6H<, ch3 cyclo-CjHs V~- H H m.p. 83-84°C 4.17 c6h5 ch2och3 CH3 CH j nj^ 1 .5793 4.18 4.19 4.20 CsHs c6h5 c6h5 CH20CH3 CH20CH3 ch2och3 ch3 ch3 CHJ CH3CH=CHCH2-CF3CH2 n~C 3H7 H H H njj5 1 . 5635 ro 04 o cn CO ro \ v> ( /< ) Table 4: (continuation) Comp.
Ri Rz Rj Rio Ri 1 physical constant 4.21 c6h5 CH2OCH3 ch3 i i'i V\„ H 4.22 4-F-CeH.. ch3 cyclo-C3Hs C,Hs H .1^" 1 .5693 4.23 3-Br-CtHu CH 3 cyclo-C3Hs n~ C11H9 CH3 4.24 2-C1-4-CF3-C6H3 CH3 ch3 ch3 c2h5 4.25 c6h5 CzHs CHj h ch j 4.26 c6h5 n-CjHs ch3 H ch3 4.27 c6h5 CH(CH3)z ch(ch3)2 H ch3 4.28 c6h5 CH3 c(ch3)3 H ch3 4.29 c6h5 CzHs CzHs H ch3 • — • 4. 30 C6hs ch3 ch2och3 H A ^ 4.31 4-F-C6Hu ch3 ch3 c2h5 c2H5 nl? 1. 5533 m~p. 57-59°C 4.32 4-F-c6hu ch3 ch3 ch 1 H 4.33 c6h5 ch3 ch3 ch2cc13 H 4.34 c6h5 ch3 ch3 /*"\ \._y-?HCHJ H 4.35 c6h5 ch3 ch3 (ch3)2ch H 4.36 c6h5 cyclo-C3Hs ch3 (chj)2ch H r.^ 1 . 5772 4.37 C6hs cyclo-C3Hs ch3 c2h5(ch3)ch- H 4.38 C6hs CH3 ch3 brjCCH2- H 4.39 c6h5 ch3 CHj ch2ch2cn H 4.40 c6h5 CHj CHj ch2ch2cn ch2ch2cn 4.41 c6h5 ch3 cyclo-C3Hs ch2ch2cn ch2ch2cn ro Osl o (J1 CO ro •v ■ • ) I 9 Table 4; (continuation) Comp.
Ri Rz r} Ri o Rn physical constant 4.42 4.43 4.44 c6h5 c6h5 CSHS chi ch3 ch3 cyclo-C3Hs cyclo-C3Hs cyclo-CjHs CH2CH2CN cyclo-cshii CzHs H H H m.p. 75-77°C n^s 1 .5830 4.45 C6Hs ch3 cyclo-C3Hs CH3 H n£» 1 .5983 4.46 3-f-cshi, ch3 cyclo-C3Hs ch3 H n^& 1.5842 4.47 4.48 4.49 3-F-CsHi. 4-F-C6Hi, c6h5 ch3 ch3 ch3 cyclo-C3Hs cyclo-C3Hs CH3 c2h5 c2h5(ch3)ch H H H cyclo-CsHii n£3 1.57 78 4.50 CSH5 ch3 ch3 H /*~\ — • • \ / % — • 4.51 4.52 4.53 4.54 4.55 4.56 CSH5 CsHs CsHs 3-F-CsHu 3-F-CsHu 3-F-CsH!. ch3 ch2och3 CHzOCHj ch2och3 ch2och3 ch2och3 ch3 ch3 ch3 ch3 CHj ch3 H CH3OCH2(CH3)CH- (ch3)2nch2(ch3)ch- H H (CH3)2CH cyclo-CsH9 H (ch3)chch2 n-C3H7 H m.p. 84-86°C nj^ 1.5565 n^3 1.5450 4.57 4-I-CsHi, ch3 ch3 • s • nc—' y—ch2 H 4.58 CsHs ch3 cyclo-C3Hs H cyclo-CsHii m.p. 75-77°C 4.59 CsHs ch3 cyclo-C3Hs P-ar H ro Osf o cn CO ro (V I ) ) 1 Table 4: (continuation) comp.
Ri Rz Rj Ri o Rn physical constant 4.60 4.61 4.62 4.63 4.64 4.65 c6h5 c6h5 C&Hs 2-r-CsH!, 2-f-c6h^ 4-f-ceh., ch3 ch3 ch3 CHj c2h5 ch3 cyclo-c3H5 cyclo-c3Hs cyclo-c3Hs cyclo-C3H5 ch3 cyclo-C3Hs H H cf3ch2 Br 3cch2 ci2chch2 CHj f3/h n-c3H7 CsHs h h H H m.p.125-127°C 4.66 4.67 4.68 4.69 4-f-cthi, 4-f-cfihi. 4-f-Cshi. cshs ch3 ch3 ch3 ch3 cyclo-C3Hs cyclo-C3Hs cyclo-CjHs CH2OCH3 h h h ch3 i>-sr n-C3H7 (CH3)2CHCH2 ch3 n^ 1.5595 4.70 csh5 ch3 ch2och3 n—C 3H 7 n-CjH? n^3 1.5483 4.71 4.72 CsHs CsHs ch3 ch3 ch2och3 ch2och3 H BrCH2CH0 ch3(ch2)7 H 4.73 CsHs ch3 ch2och3 / \ V/ W H m.p. 67-68°c 4.74 CsHs ch3 ch3 ch3 H c2h5(ch3)ch- n^3 1.5638 4.75 CsHs ch3 ch3 c6h5(cf3)ch- H ro Cm O Cn 00 ro i; l) Table A: (continuation) Comp. ri r2 Rj Ri o Rn physical constant A.76 C6Hs ch3 ch j h j\'sc"! y w A.77 c6h5 ch3 chj (ch3)2chch2 h n^" 1.5623 A. 78 C6hs ch3 CHj h • —» • v- n^s 1.6175 A.79 c6h5 ch3 ch3 |)—ch2- H A.80 A.81 c6h5 C6Hs ch3 CHj CHj cyclo-CjHs CFjCH2-CHj H C2H5 njj" 1.5803 A.82 CsHs ch3 cyclo-CjHs H Br3CCH2- A.83 CsHs ch3 cyclo-CjHs Pp.- h A.8A c6h5 ch3 cyclo-CjHs chjs H /\ /HJ • • 1 ii V\H,- m.p. 62-63°C rv Cn 0 01 CO f>o Table 4; (continuation) Comp.
Ri Rz R3 RlO Ri 1 physical constant 4.85 4.86 cshs c6h3 CHj ch3 cyclo-CjHs cyclo-CjHs H <" J-™'- /\ /H2" • * l it ■y\i CI H m.p. 67-68°C 4.87 4.88 4.89 4.90 c6h5 C6Hs C6Hs 4-F-CsHu CHj CHj CHj CHj cyclo-CjHs cyclo-CjHs cyclo-C3Hs cyclo-CjHs H H CsHsCHz n-C3H7 (CHj)2CHCH2-CHjCH=CHCH2- h n-CjH7 n^ 1.5733 n^3 1.5483 4.91 4.92 4.93 4.94 4.95 4.96 4.97 4.98 3-F-C6H^ 3-F-C6Hu 3-F-C6Hu 4-CF jO-CsHi, 4-CF30-C6H<, 4-I-CsH!. 4-I-CbH,. CsHs CHjOCH2 CHjOCH2 CHjOCHz CHjOCH2 CHjOCH2 CHj CHj CHj CHj CHj CHj CHj CHj cyclo-CjHs cyclo-CjHs cyclo-CjHs H H H H CHj H H CHj CHj c2h5 n-Ci,H9 CzHs CHj n-CjH7 (CHj)2CHCH2 CHj n3,1 1.5813 u 4.99 CsH5 CHj cyclo-CjHs c2h5 c2h5 n^H 1 . 5762 4.100 4.101 4.102 C6Hs C6Hs CsHs CHj ch3 CHj cyclo-C 3H5 cyclo-CjHs cyclo-CjHs h CHjSCH2CH2CH2 CH j ch2»chch2-h ch2ch(ch3)2 n^° 1.5613 f 1 J ) Table 4: (continuation) Comp.
Ri Rz Rj Rio Rj i physical constant 4.103 CsHs CH 3 cyclo-CjHs /w • • l 1 h 4.104 CsHs C2Hs chzochj H chj 1.5753 u 4.105 4.106 4.107 4.108 4.109 c6h5 CsHs CsHs CsHs 3-f-cshu ch3 cyclo-CjHs cyclo-CjHs cyclo-CjHs n-CjH7 ch3 ch j ch3 ch j n-CjH7 CHj CH2=C-CH2-CHjOCH2(CH3)CH-CFj(CHj)CH-(CFj)2CH-H H chj ch j h n-CjH7 4.110 3-f-C6hu ch3 \l • CHj CHj n^3 1.5765 4.111 CsHs ch3 • — \ \l CH2C(CHj)3 H m.p. 69-70°c 2 30 5 9 2 2. Formulation Examples for liquid active ingredients of formula I (throughout, percentages are by weight) 2.1- F.mulsifiable concentrates a) b) c) a compound of Table 1 25 % AO % 50 % calcium dodecylbenzenesulfonate 5 % 8 % 6 % castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % A % cyclohexanone - 15 % 20 % xylene mixture 65 % 25 % 20 % Emulsions of any desired concentration can be produced from such concentrates by dilution with water. 2.2. Solutions a) b) c) d) a compound of Table 1 80 % 10 % 5 % 95 % ethylene glycol monomethyl ether 20 % - polyethylene glycol (mol. wt. 400) - 70 % - N-methyl-2-pyrrolidone - 20 % - epoxidised coconut oil - - 1 % 5 % petroleum fraction (boiling range 160-190°C) - - 9A % These solutions are suitable for application in the form of micro-drops. 2.3. Granulates a) b) a compound of Table 1 5 % 10 % kaolin 94 % highly dispersed silicic acid 1 % attapulgite - 90 % m 2 3 0 5 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. 2.4. Dusts a) b) a compound of Table 1 2 % 5 % highly dispersed silicic acid 1 % 5 % talcum 97 % - kaolin - 90 % Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.
Formulation Examples for solid active ingredients of formula I (throughout, percentages are by weight) 2.5. Wettable powders a) b) c) a compound of Table 1 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium laurylsulfate 3 % - 5 % sodium diisobutylnaphthalene- sulfonate - 6 % 10 % octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 % 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 the desired concentration. 2.6. Emulsifiable concentrate a compound of Table 1 10 % octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 230 5 9 2 calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 moles of ethylene oxide) 4 % cyclohexanone 34 X xylene mixture 50 % Emulsions of any required concentra trate by dilution with water. 2.7. Du s t s a compound of Table 1 talcum kaolin Ready-for-use dusts are obtained by carrier and grinding the mixture in 2.8. Extruder granulate a compound of Table 1 sodium lignosulfonate carboxymethyIcellulose kaolin ion can be obtained from this concen- a) b) % 8 % 95 % 92 % mixing the active ingredient with the a suitable mill. % 2 % 1 % 87 % The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air. 2.9. Coated granulate a compound of Table 1 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner. m 2 3 0 5 2.10. Suspension concentrate a compound of Table 1 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether (15 moles of ethylene oxiae) 6 % sodium lignosulfonate 10 % carboxymethylcellulose 1 % 37 % aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0.8 % water 32 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. 3. Biological Examples Example 3.1: Action against Venturia inaequalis on apple shoots Residual protective action Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006 % active ingredient) prepared from a wettable powder formulation of the test compound. 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 infestation is evaluated 15 days after infection.
Compounds of the Tables exhibit good activity against Venturia (infestation: less than 20 %). For example, compounds 1.79, 1.108, 1.122 and 4.45 reduce Venturia infestation to 0 to 10 %. On the other hand, Venturia infestation is 100 % on untreated and infected control plants. #* 2 30 5 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 % active ingredient) prepared from a wettable powder formulation or an emulsifiable concentrate of the test compound. The treated fruits are then inoculated with a spoc^ suspension of the fungus and incubated for one week at high humidity and about 20°C. Evaluation of the fungicidal action of the test compound is made by counting the number of damaged areas that have rotted.
Compounds of the Tables exhibit good activity against Botrytis (attack: less than 20 %). For example, compounds 1.4, 1.6, 1.7, 1.12, 1.17, 1.48, 1.55, 1.56, 1.65, 1.68, 1.79, 1.104, 1.108, 1.118, 1.119, 1.122, 1.124, 1.129, 1.137, 1.138, 3.5, 3.6, 3.7, 3.8, 3.10, 3.11, 3.25, 3.26, 3.35, 3.40, 3.41, 3.50, 3.52, 3.78, 3.79, 3.113, 3.115, 4.1, 4.4, 4.15, 4.17, 4.20, 4.45, 4.56, 4.73, 4.74, 4.87 and 4.98 reduce Botrytis attack to 0 to 10 %. On the other hand, Botrytis attack is 100 % on untreated and infected control plants.
Example 3.3: Action against Erysiphe graminis in barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. The treated plants are dusted with conidia of the fungus aftffer 3 to 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 Erysiphe (attack: less than 20 %). For example, compounds 1.32, 1.56, 1.104, 1.122, 1.124, 3.5, 3.8, 3.44 and 3.52 reduce the Erysiphe attack to 0 to 10 %. On the other hand, Erysiphe attack is 100 % on untreated and infected control plants. 2 30592 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 compound prepared from a wettable powder (600 ppm of active ingredient based on the weight of the seeds). Two diys later the grains are placed in suitable agar dishes and after a further 4 days the development of the fungus colonies around the grains is evaluated. Evaluation of the test compound 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 formulation of the test compound. 2 days later, the plants are infected with a spore suspension (1.5 x 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 and 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 graminis in wheat Wheat plants are sprayed 6 days after sowing with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. 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.

Claims (23)

  1. 2 30592 - 59 - 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 and infected control plants. Example 3.7: Action against Phytophthora on tomato plants a) Residual protective action After a cultivation period of 3 weeks, tomato plants are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. 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 3 weeks, tomato plants are watered with a spray mixture (0.002 % active ingredient based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken 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 and infected control plants. 2o0592 - 60 - WHAT *AVE CLAIM IS- 1- A compound of formula I R! /N=-n *>~v< Rj wherein: Ri is phenyl or phenyl mono- to tri-substituted by Ri,; Rz is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SRs, Cj-Cgcycloalkyl, Cj-Cscycloalkyl mono- to tri-substituted by Ci-Cualkyl or by halogen, C2-Csalkenyl, C2-Csalkynyl or a formyl radical; Rj is hydrogen, Ci-Cualkyl, Ci-Cualkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, Cj-C6cycloalkyl or Cj-Cscycloalkyi mono- to tri-substituted by Ci-Ci,alkyl or by halogen; Ru is halogen, Ci-Cjalkyl, Ci-C2haloalkyl, Ci-Cjalkoxy or Ci-Cjhaloalkoxy; Rj is hydrogen, Ci-Csalkyl, Cj-Csalkenyl, Cj-Csalkynyl or the radical (CH2)n-X-Ci-C3-alkyl; .Ra Jlio R7 is the group -NHz, —N=cf or —; Ki 1 Re is hydrogen, Ci-Cjalkyl or Ci-Cjhaloalkyl; R* is hydrogen, Ci-Cgalkyl, Ci-C3alkyl substituted by hydroxy, OR12, SRi2 or by N(Ri2)2, Cj-C6cyclo-alkyl, cyclopropyl substituted by SRi2, C3-C1oalkenyl, Ci-C3haloalkyl, phenyl, phenyl mono- to tri-substituted by halogen, Ci-C3alkyl, C1-C3-alkoxy, Ci-Cjhaloalkoxy, Ci-C2haloalkyl, hydroxy, nitro, cyano, amino or by dimethylamino, 1- or 2-naphthyl, 1-, 2- or 3-pyridyl, y~\ or y~\; Vs V 19 DEC 1991 Rs and R9, together with the carbon atom in the radical R7, a£e'» ^ / \ _ .<■ v' y 4-s.* C P t M v saturated or unsaturated ring comprising 4 to 7 carbon atoms; Rio^J-S.. .. CH(Ra)R9, phenyl, C3-Csalkenyl, Cs-Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms in the alkyl radical; R11 is hydrogen, -Csalkyl', ^ Cj-Csalkenyl, Cj-Csalkynyl or cyanoalkyl having 2 or 3 carbon atoms i 2 30 5 9 - 61 - in the alkyl radical; Ri2 is CHj or C2H$; X is oxygen or sulfur; Z is 0, S, NH or NCHj; and n is 1 to 3; including the acid addition salts and metal salt complexes thereof.
  2. 2. A compound of formula I according to cl«Jim 1, wherein: Ri is phenyl or phenyl mono- to tri-substituted by Ru; R2 is hydrogen, Ci-Jsalkyl, Ci-Csalkyl substituted by the radical OR5 or by the radical SR5, C3-C6-cycloalkyl, C3-C&cycloalkyl mono- to tri-substituted by Cj-Cualkyl or by halogen, C2-Csalkenyl, C2~Csalkynyl or the formyl radical; Rj is Cj-Ci.-alkyl, Ci-Ci,alkyl substituted by halogen, cyano or by the radical OR5 or by the radical SR5, Cj-C6cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by Ci-Ci.alkyl or by halogen; Rt, is halogen or Ci-C3alkyl; R5 is hydrogen, Ci-Csalkyl, Cj-Csalkenyl, Cj-Csalkynyl or the radical (CH2)n-X-Ci-C3alkyl; R9 is hydrogen, Ci-Csalkyl, Cs-Ctcycloalkyl, C3-C5-alkenyl, Ci-C3haloalkyl, phenyl or phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; Rg and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; R7, Rio, Ri1, Rij and Z are as defined under formula I; X is oxygen or sulfur; and n is 1 to 3.
  3. 3. A compound of formula I according to claim 1, wherein: Ri is phenyl or phenyl mono-substituted by halogen; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by ORs, C3-C6cycloalkyl, C3-C6cycloalkyl mono- to tri-substituted by Ci~Ci,alkyl or by halogen, C2-Csalkenyl, C2-C5alkynyl or the formyl radical; R3 is Ci-Cualkyl, Ci-Ci,alkyl substituted by halogen, cyano or by OR5, Cj-C6cycloalkyl or C3-C6cycloalkyl substituted by methyl; R5 is hydrogen or Cj-C2alkyl; R9 is hydrogen, Ci-Csalkyl, C3-C6-cycloalkyl, C3-Csalkenyl, Ci-Cshaloalkyl, phenyl or phenyl mono- to tri-substituted by halogen, methyl, methoxy, halomethoxy or by halomethyl; Re and R9, together with the carbon atom in the radical R7, are a saturated or unsaturated ring comprising 5 or 6 carbon atoms; and R7, Rio, Ri1 and R12 are as defined under formula I.
  4. 4. A compound of formula I according to claim 1, wherein: Ri is phenyl or phenyl mono- to tri-substituted by Ri,; R2 is hydrogen, Ci-Csalkyl, C1-C5-alkyl substituted by the radical ORs or by the radical SRs, C3-Ctcyclo- 2305 92 - 62 - alkyl, Cj-Cfccycloalkyl mono- to tri-substituted by Ci-Ci,alkyl or by halogen, Cj-Csalkenyl, Cz-Csalkynyl or the formyl radical; Rj is Ci-Ci,- alkyl, Ci-Ci,alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, Cj-C6cycloalkyl or Cj-C$cycloalkyl mono- to tri- substituted by Ci-Cualkyl or by halogen; R<, is halogen, Ci-Cjalkyl, Ci-Cjhaloalkyl, Ci-Cjalkoxy or Ci-Cjhaloalkoxy; Rs is hydrogen, Cj-Cs- alkyl, Cj-Csalkenyl, Cj-Csalkynyl or the radical (CH2) -X-C1-Cjalkyl; R7 n is -NHz; X is oxygen or sulfur; and n is 1 to 3; including the acid """ addition salts and metal salt complexes thereof.
  5. 5. A compound of formula I according to claim A, wherein; Ri is phenyl or phenyl mono- to tri-substituted by Rt,; R2 is hydrogen, Ci-Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SRs, C3-C6-cycloalkyl, C3-C&cycloalkyl mono- to tri-substituted by Ci-C<,alkyl or by halogen, Cj-Csalkenyl, Cj-Csalkynyl or the formyl radical; R3 is Ci-Cu-alkyl, Ci~Ci,alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, C3-C$cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by Ci-Ci,alkyl or by halogen; Ri, is halogen; Rs is hydrogen, Ci-Csalkyl, Cs-Csalkenyl, C3-Csalkynyl or the radical (CH2) -X-C1-C3- n alkyl; X is oxygen or sulfur; and n is 1 to 3.
  6. 6. A compound of formula I according to claim 1, wherein: Ri is phenyl or phenyl mono- to tri-substituted by halogen; R2 is hydrogen, Cj-Csalkyl, Ci-Csalkyl substituted by the radical ORs or by the radical SRs, C3-CU-cycloalkyl, Cs-Cjcycloalkyl mono- to tri-substituted by Ci-Cualkyl or by halogen, Cz-Csalkenyl, C2~Csalkynyl or the formyl radical; R3 is C1-C1,-alkyl, Ci-Ci,alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs, C3-C6cycloalkyl or C3-C6cycloalkyl mono- to tri-substituted by Ci-Cualkyl or by halogen; Rs is hydrogen, Ci-Csalkyl, C3-C5-alkenyl, C3-Csalkynyl or the radical (CH2)n-X-Ci-C3alkyl; X is oxygen or sulfur; and n is 1 to 3.
  7. 7. A compound of formula I according to claim 1, wherein: Ri is phenyl or phenyl mono-substituted by chlorine or by fluorine; R2 is Ci-Csalkyl, or is Ci~C2alkyl substituted by ORs, Cj-Cecycloalkyl, C3-C6cycloalkyl mono-to tri-substituted by Ci-Ci.alkyl or by halogen, C2-Csalkenyl, Cz-Cs- 230 5 92 - 63 - alkynyl or the formyl radical; R3 is Cj-Cualkyl, Cj-Cuhaloalkyl, Cj-C6-cycloalkyl or Cj-C6cycloalkyl substituted by methyl; and R5 is hydrogen or Ci~C2alkyl.
  8. 8. A compound of formula I .-according to claims 6 and 7, wherein R3 Is: methyl, fluoromethyl, chloromethyl, bromomethyl, C3-C6-cycloalkyl or methoxymethyl.
  9. 9. A compound of formula I according to claim 1 from the group: N-(4-fluoromethy1-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4-methy1-6-eyelopropylpyrimid-2-yl)-N-m-fluorophenylhydrazine; N-(4-methy1-6-cyclopropylpyrimid-2-yl)-N-£-fluorophenylhydrazine.
  10. 10. A compound of formula I according to claim 5 from the group: N-(4-methy1-6-cyclopropylpyrimid-2-yl)-N-phenylhydrazine; N-(4,6-dime thy lpy rimid-2-yl) -N-phenylhydr azine ; N-(4-methy1-6-methoxymethy1-pyrimid-2-yl)-N-phenylhydrazine.
  11. 11. A compound of formula I according to claim 1 from the group: N-(4,6-dimethylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4,6-dimethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methy1-6-methoxymethylpyrimid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methyl-6-methoxymethylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4-methyl-6-eyelopropylpyrimid-2-yl)-N-phenylpropionaldehyde hydrazone; N-(4-methy1-6-eyelopropylpyrimid-2-yl)-N-phenyl-n-butyraldehyde hydrazone; N-(4-methy1-6-cyclopropylpyritnid-2-yl)-N-phenylisobutyraldehyde hydrazone; N-(4-methy1-6-eyelopropylpyrimid-2-yl)-N-phenylt richloroacetaldehyde hydrazone; N-(4-methy1-6-cyclopropylpyrimid-2-yl)-N-2-fluorophenylacetaldehyde hydrazone; N-(4-methy1-6-cyclopropylpyrimid-2-y1)-N-£-fluorophenylisobutyraldehyde hydrazone; 2 30592 64 - N-( 4-n»ethy1-6-cyclopropy lpyrimid-2-yl)-N-m-fluorophenylisobutyraldehyde hydrazone; N-( 4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4, 6-dimethylpyrimid-2-y1)-N-phenyl-N'-dimethylhydrazine; N-( 4,6-dimethylpyrimid-2-yl)-N-phenyj-N'-n-propylhydrazine; N-(4,6-dimethylpyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; N-(4-methy1-6-roethoxyme thylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-(4-methyl-6-methoxyme thylpyrimid-2-yl)-N-phenyl-N'-n-propylhydrazine; N-(4-methy1-6-methoxyme thylpyrimid-2-yl)-N-phenyl-N1-dimethylhydrazine; N-( 4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-methylhydrazine; N-( 4-methyl-6-cyclopropylpyrimid-2-yl)-N-phenyl-N'-isobutylhydrazine; N-( 4-methy1-6-cyclopropy lpyrimid-2-yl)-N-phenyl-N'-dimethylhydrazine; N-(4-methy1-6-cyclopropy lpyrimid-2-yl)-N-phenyl-N'-diethylhydrazine; N-(4-methy1-6-cyclopropy lpyrimid-2-yl)-N-phenyl-N'-methyl-N'-ethylhydrazine ; N-(4-methy1-6-cyclopropy lpyrimid-2-yl)-N-£-fluorophenyl-N'-ethylhydrazine ; N-(4-methy1-6-methoxyme thylpyrimid-2-yl)-N-m-fluorophenyl-N'-isopropyl-hydrazine.
  12. 12. A process for the preparation of a compound of formula I according to claim 1, which comprises a) reacting a pyrimidine derivative of formula II (II) with a phenylhydrazine derivative of formula III Rx-NH-NH-R (III) »' o 2 30 5 65 - in the presence of a base, in an aprotic solvent and at temperatures of -50° to 150°C, wherein Y is halogen, the radical S02R6 or N^CCHs)}, Rj ij Cj-Ci,alkyl, phenyl or phenyl substituted by methyl or by chlorine and R is as defined for Rio and R11, and the latter and also Ri-Rj are as defined under formula I or b) reacting a pyrimidine hydrazine derivative of formula IV with an aldehyde or ketone of formula V to form a compound of formula VII with the removal of water )* + /C=° -H o" RK )* NH2\=-^ R, Hz \=l ^i=\ R3 R? R3 (IV) (V) (VII) in any desired solvent, in the presence of an acid and at temperatures o: -20° to 120°C, Ri~R3 and Re and R? being as defined under formula I or c) reducing a hydrazone derivative of formula VII RK f-\ /-< Rs. ^N— •. reduction s \=vr w=\ hn «=•' Rs *3 \ *3 CHRa(R9) (VII) (VIII) using a reducing agent, in an inert solvent and at temperatures of 0° to 50°C or by catalytic hydrogenation using catalysts, or 2 30 5 - 66 - d) subjecting a pyrimidine hydrazine derivative of formula IV /N— Q Ri-¥— ( )• (iv) NHZ N=\ Rj to reductive alkylation with an aldehyde or ketone of formula V Re-^-R* (V) in the presence of a reducing agent, in an inert solvent and at temperatures of 0° to 50°C, or e) alkylating a pyrimidine hydrazine of formula IV or VIII with an alkyl halide R Hal o *t£> * R°H*1 — R,rC> Rj R'\ \3 o o (IV) (IX) + R Hal Ri-H— f* ^ 2 "\ "*> A ^ CHR8(R9) R CHRe(R<») O (VIII) (X) in an inert solvent, in the presence of a base and at temperatures of 0°~60°C, R^ being Ci-Ci,alkyl and R1-R9 in processes (a-e) described above being as defined under formula I.
  13. 13. A composition for controlling or preventing attacks by insect pests or destructive microorganisms, which composition contains as active ingredient at least one compound of formula I according to claim 1 together with a suitable carrier. 2 3 0 5 - 67 -
  14. 14. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 4.
  15. 15. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 9.
  16. 16. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 10.
  17. 17. A composition according to claim 13, which contains as active ingredient at least one compound of formula I according to claim 11.
  18. 18. A method of controlling or preventing attacks on cultivated plants by insect pests or phytopathogenic microorganisms, which method 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.
  19. 19. A method according to claim 18, which comprises applying as active ingredient a compound according to any one of claims 2 to 11.
  20. 20. A method according to claim 18, which comprises controlling phytopathogenic fungi.
  21. 21. A process for the preparation of an agrochemical composition according to claim 13, which process comprises homogeneously mixing at least one compound of formula I according to claim 1 with suitable solid or liquid adjuvants and/or surfactants.
  22. 22. A compound of formula II JJ—' Y—( ;• (ii), wherein R2 is Ci-Csalkyl or Ci-Csalkyl substituted by the radical ORs or by the radical SRs? R3 is Ci~Ci,alkyl substituted by halogen, cyano or by the radical ORs or by the radical SRs; Rs is hydrogen, Ci-Csalkyl, 2 3 0 5 9 2 - 68 - Cj-Csalkenyl, Cj-Csalkynyl or the radical (CH2) -X-Ci-Cjalkyl; X is oxygen or sulfur; n is 1 to 3; Y is halogen or SO2RS: and Rs is Ci-Cu-alkyl or aryl, with the exception of the compounds 2-chloro-4-methyl-6-methoxymethylpyrimidine and 2-chloro-4-methy1-6-trichloromethy1-pyrimidine.
  23. 23. A compound of formula II according to claim 22, wherein R2 is hydrogen, Cj-Csalkyl or Ci-Csalkyl substituted by the radical OR5 or by the radical SRs; Rj is C2-Csalkenyl or C2-Csalkynyl; Rs is hydrogen, Ci-Csalkyl, Cj-Csalkenyl, Cj-Csalkynyl or the radical (CH2)n-X-Cx-C3alkyl; and Y is halogen. FO 7.5/HGT/sm* n CIBA-GEIGY AG -4- jaml/w) By their attorneys BALDWIN. SON & CAREY
NZ230592A 1988-09-09 1989-09-07 2-substituted-1,3-diazine derivatives, preparatory processes, intermediates and pesticidal compositions NZ230592A (en)

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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
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