OA10326A - Pesticides - Google Patents

Pesticides Download PDF

Info

Publication number
OA10326A
OA10326A OA60857A OA60857A OA10326A OA 10326 A OA10326 A OA 10326A OA 60857 A OA60857 A OA 60857A OA 60857 A OA60857 A OA 60857A OA 10326 A OA10326 A OA 10326A
Authority
OA
OAPI
Prior art keywords
formula
cyano
unsubstituted
methyl
phenyl
Prior art date
Application number
OA60857A
Inventor
Hugo Ziegler
Stephan Trah
Saleem Farooq
Rene Zurflueh
Original Assignee
Ciba Geigy Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Ag filed Critical Ciba Geigy Ag
Publication of OA10326A publication Critical patent/OA10326A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C07D213/77—Hydrazine radicals
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/76—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/78—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/80—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/61—Carboxylic acid nitriles containing cyano groups and nitrogen atoms being part of imino groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/28—Nitrogen atoms
    • C07D295/30—Nitrogen atoms non-acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/58—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Landscapes

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

Abstract

The invention relates to imino-alkyl-imino-oxy-tolyl derivatives having the formula (I): and to the isomers thereof, as well as to mixtures of said isomers, to the processes for their preparation, to the composition and method for pest control and prevention.

Description

01 03 26
Pesticides
The invention relates to novcl pesticidally active compounds of lhe formula 1
5 and to the isomers, and isomer mixtures, thereof which are possible, in which cithcr a) X is an N atom and Y isOR„ orN(RI2)R,3.or " b) X is CH and 10 YisORjj, and in which funbennore.· R, ! is Cj-Chatkyl; R12 and Rj3. independently, arc hydrogen or C^C^alkyl; A is an O atom or the group NR4; 15 R( hydrogen, Cj-C^aLkyl. halo-C)-C4alkyl, cyclopropyl, cyano or methylthio; R2 :s hydrogen, Cj-C^alkyl, Cj-Cûcycloalkyl, a group _// \\ ^-=^( D) 11
/-V Z' B a group # Λ , or thicnyl; \=^<(D) n D racdcals are identical or different and arc halogcn, C1-C4alkyl, C,-C,,alkoxy, 20 Cj-C^haloalkyl, Ci-C2haloaikoxy, Cj-C^alkenyloxy, Cj-C^alkynyloxy,
Ci-Ci-alkylenedioxy, cyano or nitro;n is 0„ 1,2, 3 or 4; 2 is -Ό-. -C-(C1-C4alkyl)-. -(C,-C4alkyi)-O-. -S(O)m-, -(C1-C4utkyl)-S(O),„-. -S(0)OT-(CrC4alkyl)·, 25 m is ü„ l or 2. B is C:;-C6«itkyl, halo-Ci-C6alkyl, C3-C6cycloalkyl, or is C2-C6alkenyl or C2-C4arlkynyl-C1-C2a!kyl, cach of which is unstibstituted or substituted by 1 to 3 halogcn
Jll—»! HgggiSSTt»»1—1 W 10 10 15 15 -0 -Ο .0 010326 moins, or is aryI or heteroeyclyl. cach of thèse two, indepeudeutIy. being unsubsthuicd or mono- to peniasubstiluied by C|-C6alkyl, halo-Cj-Cf,alkyl, halogen, C(-C6alkoxy or
R5, R6, R7, R8 and R9, indepcndently, arc hydrogeu, C,-C4alkyl or halogen andp is 0, 1,2 or 3; R3 is hydrogen, C|-C6alkyl, C|-C6haloalkyl having 1 10 5 halogen aïoms, C,-C43lkoxy-C1-C2alkyl, C2-C4aikenyl-C1-C2alkyl, which is unsubstituted or substitutedby 1 co 3 halogen acoms, C2-C4alkynyl-Cl-C2-alkyl, C3-C6cycloalkyl which isunsubstituted or substituted by 1 to4 halogen acoms, C3-C,5-cycloalkyl-Ci-C4alkyl whichis unsubstituted or substituted by 1 to 4 halogen atoms, cyano-C|-C4alkyl;C1-C4aIkoxycarbonyl-C1-C2alkyl.,C1-C4alkoxycarbamoyl-C1-C2alkyl. phenyl-C^-Cjalkylwhich is unsubstituted or substituted by halogen, CyGjalkyl, C,-C4alkoxy.C,-C4haloalkyl, cyano, nitro or Cj-C^alkylcnedioxy, it being possible for the phenyl groupto be monosubstituted to trisubstituted by idcntical or different substituents; phenyl whichis unsubstituted or mono- to disubstituted, indepcndently, by C|-C4alkyl, CyC^alkoxy.hs.iogen, C]-C2haloalkyl having 1 to 3 halogen atoms, nitro or cyano, or pyridyl which isunsubstituted or mono- to disubstituted, indepcndently, by C t-C-alkyl. Ci-C4alkoxy,hoiogen. C|-C2haloalkyl having l to 3 halogen atoms, nitro or cyano; is CL-C4alkyl, phenyl, or R3 and ?_4 together with the nitrogen atom to which they arc bondcd form a saturated orur.-saturated 5- to 7-membered ring which is unsubstituted or substituted by C|-C4alky 1 andwr.ich can hâve 1 to 3 additional hetero atoms selcctcd from amongst N, O and S.
The compounds according to the invention hâve fungicidai, acaricidal and insccticidalproscrites and are suitable as active ingrédients for use in agriculture, horticulture and thehygiène ftcld.
The invention furthermore also relates to a process for the préparation of the compoundsaccording to the invention, and to fungicidai. acaricidal and insccticidal compositionswhrck comprise such compounds as active ingrédients, and to the use of such cotnpoundsand compositions for controlling phytopathogcnic fungi, Acarina and insccts and forprewer.-ing such an atttick.
If asymmetric carbon atoms exist in the compounds of the formula 1. the compounds exist 010326 in opticaliy active l'onn. The compounds exist in any case in | ΙΞ| and/or |Z| forms, merelybecause of die presence of die aliphaiic, the oximino and die hydrazono double bonds.Ftirtsiennore, atropisonierism may exist. The formula l is intended to enibrace ail dieseisomeric forms which are possible and their mixtures, for example racemic mixtures, andany [E/Z] mixtures.
Uniess ot’nerwisc defined, the general tenns used hereinabovc and hereinbelow areintended to mcan the following:
Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine orbromine, especially fluorine or chlorine.
Alkyl is either straight-chain, for cxample methyl, cthyl, n-propyl, n-butyl, n-he.xyl,n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, or branched. for examplebsopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl is straight-chain or branched alkenyl, for example vinyl, 1-mcthylvinyl, allyl,I-butcnyl, isopropenyl, in particular allyl.
Alkynyl is. for example, ethynyl, 1-propynyl or 1-butynyl, in particular propargyl,
Cycloa.kyl is to bc understood as mcaning cyclopropyl, cyclobutyl, cyclopcntyl orcycîohexyl.
Kaloger.-substituted groups such as haloalkyl and haloalkoxy can bc partially or fullyhadogertated by identical or different substituents. Examples of haloalkyl are methyl whichis mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHE2. CF3 orCH2C1; cthyl which is mono- to pcntasubstituted by fluorine, chlorine and/or bromine,
Aryl is, for example, phenyl or napluhyl, in particular phcnyl. 010326
Heterocyclyl is a 5- to 7-membered arcnnaiic or non-aromatic ring hnving one to tluce iietero atoms selecicd from the group consisting of N. O and S. Prct'ened arc aronintic 5and ό-menibered rings which bave a nitrogcn atom as lictcro atom and, if appropriait;, afurtker hetcro atom, preferably niirogcn or sulfur, in particular nitrogcn.
The 'emi of die 5- to 7-menibered ring which is formcd by R3 and R4 togedicr with dienirrogen atom to which they are bonded encompasses, in particular, pyrrolidinc,piperidine, morpholine, thiomorpholine, hexamethylencimine, imidazolc, pyrazole,pvrroîe. 1,2,4-triazole, 1,2,3-triazole, tetrazole, isoxazolc, oxazole, isoxazolidine,oxazolidinc, thiazole, isothiazole, thiazoline and isothiazolidine,
Preferred within the scope of the invention are (I) Compounds of the formula I in which either a) X is an N atom and Y is OCH3 or NHCH3, or b) X is CH andY is OCHj, amc in which furthermorc: A is an O 2:0m or the group NRd; R; is hycrogen, Ct-C4alkyl, halo-C1-C4alkyl, cyclopropyl, cyano or mcthylthio;
2- B or thienyl; n D radierais are identical or different and are halogen, C1-C4alkyl, CrC4alkoxy.
B iis C:-Cs2tkyl, halo-Cj-Qalkyl. C3-C6cycloalkyl, or iis Cj-Cf.alkenyl or C2-C4aIkynyl-CI-C3alkyl, eacii of which is unsubsiilutcd or 010326 substiiuied by I to 3 halogen atoms, or is aiyI or licterocyclyl, or ai yl or licterocyclyl, eachot thèse. indcpendently, being monosubstituted lo pentasubstituted by C|-C<-,alkyl.halt>-C|-C6alkyl, halogen, C, -C^alkoxy or iialo-C| -C^alkoxy, or a group
R6. IÎ.7, Rs and R.9, indcpendently, are hydrogen, Cj-C,(alky 1 or halogcn andp is 0, 1,2 or 3; R3 is hydrogen, C1-C6alkyl, CfC^haloalkyl having I to 5 halogcn atoms,
Ci-C422koxy-CI-C2alkyl, C2-C4alkenyl-Cj-C2alkyl which is unsubstituted or substitutedby 1 to 3 halogcn atoms, C2-C4alkynyl-Ci-C2alkyl, C3-C6cycloalkyl which isunsubstituted or substituted by 1 to 4 halogcn atoms, Cj-C^cycloalkyl-CpCdalkyl which isunsubstituted or substituted by 1 to.4 halogen atoms, cyano-Ct-C4alkyl;C:-C4aikoxycarbonyl-Ci-C2alkyl, phcnyl-Cj-Cjalkyl which is unsubstituted or substitutedby halogen, Cl-C3alkyl, C1-C4alkoxy, Ci-C4haloalkyl, cyano. nicro, Ci-C4alkylenedioxy,ic being possible for the phcnyl group to be monosubsbtuted to crisubsrituted by identicalor different substituents; phenyl which is unsubstituted or mono- to disubstituted,indepencently, by CpC^alkyl, Ci-C4alkoxy, halogcn, Cj-C2haloatkyl having 1 to 3halogcn atoms, nicro or cyano, or pyridyl which is unsubstituted or mono- to disubstituted,indepencently, by CpC^alkyl, Cj-C4alkoxy, halogcn, Ct-C2haloalkyl having 1 to 3halogen atoms, nicro or cyano; R4 is Cl-24alkyl or phenyl, or R3 and together with the nirrogen atom to which they are bonded form a saturated orunsaturated 5- to 7-membered ring which is unsubstituted or substituted by Ci-C4alkyl andwhich car. hâve 1 to 3 additional hetero atoms selcctcd from amongst N, O and S; (2) compounds of the formula I in which X is N and Y is OCH3; (3) compounds of the formula I in which X is CK; (4) compounds of the formula 1 in which X is N, Y is NHCKj and Γ<5 is K. CHj. cycbopropyl or CN; (5) compounds of the formula ! in which Λ is oxygen, NCH3 or n-Cf.blj. in panicularoxygen or NCH3, very panicularly oxygen; 010326 (6) compounds of the (orinula I in which R, is hydrogen, methyl. cyclopropyl or cyano. inparticular incthyl; Ç7) compounds of the formula I in which R2 's C,-C4alkyl or cyclopropyl. in particularmethyl or cyclopropyl; (3) compounds of the formula 1 in which R2 *s 3 SrouP _(/ \\ and n D is naiogen. Cj-C4alkyl, CpC^alkoxy. Ci-C2alkyl which is substituted by 1 to 5 halogenaroms, Cj-C^haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Cj-C^alkylenedioxy,cyano, or nicro, or thienyl, D is, in particular, fluorine, chlorine; bromine, CpC^alkyl or -CF3; (9) compounds of the formula I in which R2 is a group // Λ
Z- B and n Z is -O-. -O-(C,-C4alkyl)-. -(C,-C4alkyl)-O-, -S(O)2-, -(C,-C4alkyl)-S(O)2-, -S;O)2'CCrC4alkyl)-, in particular -O-, -CH2-O- or -O-CH2-, very parcicularly -O-CH2; ( IC ) compounds of the formula I in which R2 is a group // Λ
Z- B and B is CyC.alkvl, halogcn-C|-C4alkyl. or is C2-C4alkcnyl or C2-C4alkynyl-C1-C2alkyl. cachof which is unsubstituted or substituted by 1 to 3 halogen atoms, or is aryl or aryl which ismonosubstituted or disubstituted, independcntly. by C,-C2alkyl, halo-C|-C2alkyl, halogen. C,- Z2alkoxy or halo-C|-C2alkoxy, or is a group ~ (CH) R.-.
Rs Vnz
Ra
Rs. ί?.ύ, R.-. R8 and Rg, independcntly, are hydrogen, Ct-C2alkyl or halogen. andp is D. 1.2 or 3; B is.. in particular. Ct-C2alkyl, halo-CrC3alkyl, or is allyl or propargyl, each of which isunsubstiturted or in each case substituted by 1 or 2 halogen atoms or 1 or two methyl . 7 · 010326 consjsttng groups. or phcnyl, phcnyl which is substitutcd by a substituent sclcctcd from (lie group
Cl
Cl (11) compounds of thc formula I in which R2 *s a phcnyl group winch is substitutcd in thc 4-position by -2-B; (12) compounds of thc formula I in which R3 is hydrogen, C^C^alkyl or Q-C^haloalkyl having 1 to 3 halogcn aiorns,C!-C2alkoxy-C1-C2alkyi, Cl-C4alkoxycarbonyl-CI-C2alkyl, propcnyl which isunsubstitutcd or substituted by 1 to 3 halogcn atoms, propargyl, C3-Cgcycloalkyl, 10 cyclopropylmethyl which is unsubstitutcd or substitutcd by 1 to 2 halogcn atoms,cy2no-Cj-C2alkyl, phenyl-C1-C2alkyl which is unsubstitutcd or substitutcd by halogcn,methyl, mcthoxy or halomcthyl having 1 to 3 halogcn atoms, it being possible for thcphcnyl group to bc monosubstituted to disubstituted by idcntical or different substituents;phcnyl which is unsubstitutcd or monosubstituted to disubstituted. indcpcndcntly, by 15 halogcn, methyj, mcthoxy, halomcthyl having 1 to 3 halogcn atoms, cyano or nitro; orpyridyl which is unsubsrituted or monosubstituted to disubstituted, indcpcndcntly, byhalogcn, methyl, mcthoxy, halomcthyl having 1 to 3 halogcn atoms, cyano or ηίσο; or R3and R4 cogcther with the nirrogen atom to which they arc bondcd form a saturated orunsaturated 5- to 7-mcmbcrcd ring which is unsubstitutcd or substitutcd by Cl-C4alkyl and 20 which C2n hâve 1 to 3 additional hetero atoms sclcctcd from amongst N, O and S; R3 is preierabîy hydrogen, Cj-C6alkyl, Cl-C4haloalkyl having 1 to 3 halogcn atoms, C· -C2alicoxycnethyl, prop-2-cn-1 -yl which is unsubstitutcd or substitutcd by l to 3 halogcnatoms, propargyl, Cj-Cgcycloalkyl, cyclopropylmethyl which is unsubstitutcd orsubstituted by 1 to 2 fluorine or chlorinc atoms, cyano-Cj-C^alkyl, phcnyl-Ct-C2alkyl 25 wrr.ich is unsubstitutcd or substituted by halogcn, methyl, mcthoxy or halomcthyl having ito 3 halogcn atoms, it being possible for thc phcnyl group to bc monosubstituted todisubstituted by idcntical or different substituents; phcnyl which is unsubstitutcd ormonosubstituted to disubstituted, indcpcndcntly, by halogcn, methyl. mcthoxy, halomcthylhaving l £□ 3 halogcn atoms. cyano or nitro; or pyridyl which is unsubstitutcd or 30 monosubstituted to disubstituted, indcpcndcntly, by halogcn, methyl. mcthoxy. halomcthylhaviing I to 3 halogcn atoms, cyano or nitro; or R3 and R4 together with thc nitrogen atomto w-hich chcy arc bondcd arc 1,2.4-triazolyl, 4-morpholtnyl, l-azcpinyl, l-pipcridinyl or1 -pyrrolitiSnyl, R3 is penicularüy prcfcrably methyl; • s - 010326 (13) compounds of the formula 1 in which R4 is methyl or phenyl, pariicularly methyl; (14) compounds of die formula I in wliich X is Cri; Y is OCH3; R( is CH3; A is oxygen; R2 is either 4-methylphenyl or 4-allyloxyphenyl or 4-(3-trifluoromethyl-bcnzyloxy)phenylor 4-(2.2-dichlorocyclopropylmethoxy)phcnyl andR3 is CH3; C15) ccmpounds of the formula I in which cither a) X is an N atom and Y is OCH3 or NHCH3. or t) X is CH. and Y is OCH3, a_nd in which funhermore A. is an O atom or the group NR4; RI is hydrogen; Cj-C4alkyl; cyclopropyl; cyano or mcthylthio; R 2 is hydrogen; CfCgalkyl; C3-C6cycloalkyl; phenyl which is unsubsntuted or rmor.ûsubsdtuted to disubstituted, independendy, by halogen, C^C^alkyl, C1-C4all:oxy,C—Crhaloalkyl, Ci-C^haloalkoxy, C3-C6alkenyloxy, C3-C6aLkynyloxy, C -C4al2:ylcnedioxy, cyano or nitro; thicnyl; R: io hydrogen; Cj-Cgalkyl; C^CghaloaLkyl having 1 to 5 halogen atoms; C -C^aikoxy-Cj-C^alkyl; C2-C4alkenyl-C1-C2alkyl which is unsubsütuted or substitutedby I :o 5 halogen atoms; C2-C4alkynyl-Ci-C2-alkyl; C3-C6cycloalkyl which isurrcucsdcutcd or substituted by 1 to 4 halogen atoms; C3-C6cycloalkyl-Cj-C4alkyl which isuncabsdcuicd or substituted by 1 to 4 halogen atoms; cyano-C(-C4alkyl;C1-C4alk:Dxycarbonyl-Ct-C2alkyl; phenyl-CrC3alkyl which is unsubsütuted or substitutedby .halogen, Cj-C3alkyl, C^Cdalkoxy, C|-C4haloalkyl, cyano. nitro. Cl-C4alkylencdioxy.il teir.g possible for the phenyl group to bc monosubsrituted to crisubsbtuted by idcnticalor ciiiercmt substituents; phenyl which is unsubstituted or monosubstitutcd todisuiosiiiurted. independendy, by Ci-C4alkyl, Ci-C4alkoxy, halogen, Ct-C2haloalkyl having1 10 3 nalogen atoms, nitro or cyano; pyridy! which is unsubstituted or monosubstitutcd todistubsbturted, independendy, by C1-C4alkyl. C^Ci-alkoxy, halogen, Cj^haloalkyl having1 te 3 zalcgcn atoms, nitro or cyano; R4 is Cj-Ckalkyl; phcnyl; or R3 tunb Ræ togciher with the nitrogen atom to which they arc bonded fotm a saturated orunsHttumtcd 5- to 7-membered ring which is unsubstituted or substituted by Cj-C4alkyl and 9 - 010326 whicit eau bave I to 3 udditional hetero moins selccted lïom nmixmst N O and S. O *
( 16) totupounds of die formula I in whichX is CH or N 5 Y is OCH3A isOorN-R4 R, is methyl, cyclopropyl or mcthylthio; R2 is methyl; cyclopropyl; phenyl which is unsubstituted or monosubstituted todisubsiituted, independently, by halogcn, C1-C4alkyl, C)-C4alkoxy, Ct-C2alkyi which is 10 substkuted by 1 to 5 haJogen atoms, Ct-C2haloalkoxy, C3-C6-alkcnyloxy, C3-C6alkynyloxy, C1-C4alkylenedioxy, cyano, or nitro; or thienyl; and in whichR-3 is as defined for formula I and R.4 is methyl or phenyl, or 5.3 and. R4 together with the nitrogen atom to which they are bondcd are either pyrrolidine, 15 piperidine, morpholinc, thiomorpholine, hexamethylcneimine, imidazole, pyrazolc,pyrrole. 1,2,4-triazole or 1,2,3-triazole. C"7) Compounds of the formula I in which: X is N, 20 Y is NHCH3. A. is O or N-R4, R is methyl, cyclopropyl or mcthylthio; R- is methyl; cyclopropyl; phenyl which is unsubstituted or monosubstituted todisubsticuted, independently, by halogen, CrC4aJkyl, Cj-C4alkoxy, Ci-C2aJkyl which is 25 suostituced by 1 to 5 halogen atoms, CrC2haloalko;\y, C3-C6alkenyloxy,C—Cgalkynyloxy, CI-C4alkylenedioxy. cyano or ηίσο; or thienyl; and in whichR3 is as defined for formula I and R4 is methyl or phenyl, or R3 2nd R^ together with the nitrogen atom to which they arc bondcd are either pyrrolidine. 30 piperidine, morpholine, thiomorpholine, hexamcthylencimine, imidazole, pyrazolc,pyrrole. L_2.4-triazole or 1,2,3-triazole. ( IS’j Compounds of the formula I in which: A is oxy-pen, 35 R| is methyl.
Ri is methyl; phenyl which is unsubstituted or monosubstituted to disubsiituted,indcpcndemtly. by halogcn, C(-C4alkyl, C|-C4alkoxy, C|-C2alkyl which is .substituted by 1 010326 • 10 - tu 5 iialogeu moins, C|-C2haloalko.\y, CyC^nlkcnyloxy, Cj C6alkvnyloxy, C|-C4alkylenetlioxy, cyano or nitro; or thicnyl; and R-3 is CpCf.alkyl; wliile X and Y are as defined for formula i. C19) Compounds of the formula I in which R.j is methyl, R-2 is methyl and R3 is as described and
Rjj is methyl or phenyl, or R3 and R4 together with the nitrogen atom to which they are bonded form a saturated orunsaturaied 5- to 7-membered ring which is unsubstituted or subscituted by Cj-C^alkyl andwriich can hâve 1 to 3 additional hetero atoms selected from amongst N, O and S;wnile A. X and Y are as defined for'formula I. (20) Compounds of the formula I in which: R3 is hydrogen; CpC^alkyl; Ci-C4haloalkyl having 1 to 3 halogen atoms; C^C^aHeoxy-Cj-Cjalkyl; propenyl which is unsubstituted or substituted by 1 to 3 halogenatcons; ptropargyl; C3-C6cycloalkyl; C3-C6cycloalkylmethyl which is unsubstituted orsubstituted by 1 to 2 halogen atoms; cyano-C|-C2-alkyl; C[-C2allcoxycarbonyl-C1-C2alkyl; phenyl-C^C^alkyl which is unsubstituted or substitutedby halogen, methyl, methoxy, halomcthyl having 1 to 3 halogen atoms, cyano, nitro orC^-C^alkylenedioxy, it being possible for the phenyl group to bc monosubsrituted todisübstitoicd by identical or different substituents; phenyl which is unsubstituted ormooosubstituted to disubstituted, independently, by halogen, methyl, methoxy, halomcthylhaving 1 ao 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormooosubsiituted to disubstituted, independently, by halogen, methyl, methoxy, halomcthylhaving 1 to 3 halogen atoms, cyano or nitro; R.,i 5s meahyl or phenyl; or
Rj amd RÆ together with the nitrogen atom to which thev are bonded form a saturated orunsaauratesd 5- to 7-membercd ring which is unsubstituted or substituted by C;-C,.alky 1 andwhtch care hâve 1 to 3 additional hetero atoms selected from amongst N. O and S;whilre A, X. Y, R, and R2 are as defined for formula 1. (21) Amotagst the compounds of the formula 1 mentioncd under (20). thosc in which R3and St4 together with the nitrogen atom to which they are bonded are triazolyl,ntorpholittyl, 2.6-diineihylinorpholinyl. azcpinyl. piperidyl or pyrrolidinyl.
0KI32S (22) Compounds of (lie formula I in wliiclt;is oxygen, 2;, is methyl, R2 's methyl; phenyl which is unsubstituted or monosubstituted to disubstituted. 5 iridepeodently, by halogen, C^Qalkyl, C|-C4alkoxy, C,-C2alkyl which is substituted by 1to 5 halogen atoms, Ct-C2haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy,C1-C4alkylenedioxy, cyano or nitro; or thienyl; and R3 is bvdrogen; Cv-C4alkyl; C1-C4haloalkyl having 1 to 3 halogen atoms;C;-C2alkoxy-C|-C2alkyl; propenyl which is unsubstituted or substituted by 1 to 3 halogen 10 atoms; propargyl; C3-C6cycloalkyl; C3-C6cycloalkylmethyl which is unsubstituted orsc bs:itu:ed by 1 to 2 halogen atoms; cyano-C1-C2-alkyl; C--C2aLkoxycarbonyl-Ci-C2alkyl; phenyl-C1-C2alkyl which is unsubstituted or substitutedby halogen, methyl, methoxy, halomethyl having 1 to 3 halogen atoms. cyano, nitro orC --CoaLtylenedioxy, it being possible for the phenyl group to bc monosubstituted to 15 disubsticuted by identical or different subsrituents; phenyl which is unsubstituted or monosubstituted to disubstituted, independcntly, by halogen, methyl, methoxy, halomethylhaving 2 to 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormonosubstituted to disubstituted, independcntly, by halogen, methyl, methoxy, halomethylhaving 1 to 3 halogen atoms, cyano or nitro; 20 wh.iie X and Y arc as defined for formula I.
Amongst the compounds of the formula I mentioned under (22), thosc in which: ts oxygen.is methyl, me is methyl; phenyl which is unsubstituted or monosubstituted to disubstituted,per.dently, by halogen, methyl, methoxy, trifluoromethyl or trifluoromcthoxy; andIs methyl. 1,24 Ccmoour.bs of the formula I in which: 50 hv!, 35 indt cya is metthyl; phenyl which is unsubstituted or monosubstituted to disubstituted. C'he.ntty, oy halogen, methyl, methoxy, trifluoromethyl or trifluoromcthoxy; ;S metthyl; phenyl which is unsubstituted or monosubstituted to disubstituted. aerdemtiy, by halogen, methyl, methoxy, halomethyl having l to 3 halogen atoms. o cr n.uro; or pyridyl which is unsubstituted or monosubstituted to disub:::nuted. 12 - 01 0 3 2 6 independently, by halogen, methyl, mcthoxy. Iialomethyl liavmg | k> 3 halogen atoms,cyano or nitro; while X and Y are as defined for formula I. 5 (25) Compounds of the formula I in which: X is an N atom; Y isOR,,; R,, is C^Qalkyl; and in which A, Rb R2 and R3 are as defined for formula I. 10 (26) Amongst the compounds menrioned undcr (25), thosc in which: A is an O atom;
Rj and R2 are methyl; R.3 is taydrogen; Ci-C4alkyl; Cj-Qhaloalky! having 1 10 3 halogen atoms;C1-C2aLkoxy-Ci-C2aikyl; propenyl which is unsubstituted or substituted by 1 10 3 halogen 15 atoms; propargyl; C3-C6cycloalkyl; C3-C6cycloalkylmethyl which is unsubstituted orsobstituced by 1 10 2 halogen atoms; cyano-C]-C2-a!kyl·, C:-C2a[lk:oxycarbonyl-C1-C2alkyl; phenyl-CrC2alkyl which is unsubstituted or substitutedby halogen. methyl, mcthoxy, halomethyl having 1 to 3 halogen atoms, cyano, ηΐσο orCr-C2ailûylenedioxy, it being possible for the phcnyl group to be monosubstituted to 20 disubstituted by idencical or different substituents; phcnyl which is unsubstituted or monosubstituted to disubstituted, independcntly, by halogen, methyl, mcthoxy. halomethylha-’ing 1 10 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormonosubstituted to disubstituted, independently, by halogen, methyl, mcthoxy, halomethylhaving 1 ko 3 halogen atoms, cyano or ηΐσο. 25 (27.) Amcmgst the compounds menrioned undcr (26), thosc in which: R-j is hydrogcn; C^C^alkyl or Ci-Cdhaloalkyl having 1 to 3 halogen atoms. (2S)’: Compounds of the formula I in which: 30 X is an iX atom; Y is N(R,2)RJ3; R12 and R^. independently, are hydrogcn or C(-Cdalkyl; and in winchA, Rq, R2 and R3 are as defined for formula 1. 35 (29) Amomgst the compounds menrioned undcr (2S). thosc in winch: Y es NHtk, N(CHj)2 or NHC2H5; 010326 ϊ Λ · s an O a K h u ; R, at :1 R2 ;ne methyl; ► R3 ia hydrogen; Cj-C^alkyl; C,-C„haloalkyl having l to 3 halogen atoms;
Ci-C-alkoxy-C]-C2alkyl; propcnyl which is unsubstituted or substituted by I to 3 halogen 5 atome; propargyl; C3-C6cycloalkyl; C3-C6cycloalkylincihyl which is unsubsiituied orsubstituted by 1 to 2 halogen atoms; cyano-C|-C2-aikyl; C^C^alkoxycarbonyl-Ci-C^alkyl; phenyl-Cj-Cjalkyl which is unsubstituted or substitutedby halogen, methyl, methoxy, halomethyl having 1 to 3 halogen atoms. cyano, nitro or2i-C23!kylenedioxy, it being possible for the phenyl group to be monosubstituied to 10 cisubstituted by identical or different substituents; phenyl which is unsubstituted or monosubstituted to disubstituted, indepcndcntly. by halogen, methyl, methoxy, halomethylr.2vine 1 to 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormonoscbstituied to disubstituted, indepcndcntly, by halogen, methyl, methoxy, halomethylh aving 1 to 3 halogen atoms, cyanô-or nitro. 15 (30) Amongst the compounds mendoned under (29), thosc in which: P-3 is hydrogen; C^Caalkyl or C^-Cjialoalkyl having 1 to 3 halogen atoms. (3 1) Ccmpounds of the formula I in which the X=C double bond is in the E form. 20
The compounds of the formula 1 can bc prepared as follows: A. To octain a compound of the formula I in which Y is N(R1?)R13 , a compound of thefc —nula ( in which Y is ORU is rcactcd with HN(Rj2)Ri3. The réaction is carried ont 25 ad --amageously in an inert organic diluent, for cxample in an alcohol such as éthanol, in anether such as tetrahydrofuran or dioxanc, an ester such as ethyl acctatc, a sulfoxide such asdi~’.ethyL sulfoxide, an amide such as dimcthylformamide or a kctonc such as methylisccety'. itetone. Mcthylaminc can bc used in gascous form or elsc in dissolvcd form. forexemple .in the form of a solution in éthanol. The process température is convention.nll\- 30 bc: veer. ?3C and 40°C, prefcrably room température. 3) "To prépare a compound of the formula I in which X. 3’, A and RrR3 are as deimcd forfor—·.nia f (and in which R3 is not hydrogen): A com.poi_m.d cf the general formula 0 î (13 2 6
HON
R in which A and R1-R3 arc as defined abovc is reactcd with a compound of the generalformula
O
U
III ir which X and Y are as defined abovc and U is a lcaving group.
This reaction is a nucleophilic substitution réaction which can bc carried out under theréaction conditions conventionally used in such a case. The lcaving group U is prcferablychlorine. bromine, iodine, mesyloxy or tosyloxy. The réaction is advantagcously carricdoct in an inert organic diluent such as a cycltc ether, for cxamplc tcirahydrofuran ordioxane. a ketone such as acétone, an amidc such as dimcthylformamidc, a sulfoxidc suchas dimerhyl sulfoxide, in the présence of a base such as sodium hydride, sodiumcarbonate, potassium carbonate, sodium amide, a tertiary amine, for exampletrialkylamine, in particular diazabicyclononanc or diazabicycloundccanc, or silvcr oxide,at températures between -20°C and SO°C, prcferably in a température range of 0°C to5C“C.
Alrernatively, the reaction can bc carricd out with phase transfer catalysis in an organicsoL vent for example methylenc chloride, in the présence of an aqueous alkaline solution,for example sodium hydroxidc solution, and of a phase transfer catalyst, for exempletecrabutyiammonium hydrogen sulfate, at room température.
The resuEiing compounds of the formula I can bc isoiated and purifted by methods knownperse. Equally, tsomer mixtures obtained, for cxamplc E/2 isomer mixtures, can bescpmratedby methods known per se 10 givc the pure isomers, for cxamplc by means ofchromatography or fractional crystallization. 010326
The oximcs of tue general formula II which are tiscd as siartiug tnaterials aie eitlici knowucr can oc préparée! by known rnelhods (J. Cliein. Soc., Perkiu Trans U 537 (1990); Per.Deutsch. Chem. Ges. 62, S66 (1929); Gazz. Chim. liai. 37 11, 147 ( 1907); Liebigs Ann.Chem. 262, 305 (1891)). 5
Equally, the starting tnaterials of the formula III can be préparée! in a mauner knowu perse, for example as describcd in the Européen Patent Publication EP-A-203 606 (BASF)ar.d the iiterature cited therein, or as describcd in Angew. Chem. 7 1,349-365 (1959). 10 C, To préparé a compound of the formula I in which A is oxygen and X, Y and Rp-Rj arcas defïr.ed for formula I: A. compound of tne general formula”
ir. · .-hier. X. Y. R, and R2 are as defincd above is reacted with a compound of the generalformula ;.p v, R;, seing ss detmed under formula I and U being as defineci under formula III (and R320 bc." g r.ciaacr hydrogen rror phenyl nor pyridyl).
Tin; reacron is a nuclcophilic substitution réaction as describcd. under B) D) Te préparé a compound of the formula IV in which X, Y, R, and R2 are as dcFmcd tor25 forrr cia I, a nrceedure is followcd in which: A ccmpou-.d of the general formula ûî 0326 • -I 6 ·
in which X, Y, Ri and R^ are as defined above is reactcd with hydroxylaminc or a salithereof, for example the hydrochloride. The réaction is carried out advantageously inpyridine or methanol as the solvent at températures between -20°C and +S0°C or theboiling point of methanol, preferably in a température range of 0°C to 50°C, a base beingreqoired if methanol is used, for example an alkali métal carbonate, such as potassiumcarbonate, a tertiary amine such as triethylamine or diazabicyclononane, pyridine or silveroxide.
The ketonc of the general formula VI is prepared analogously to the method describedunder B). The ketones of the general formula VI and their préparation arc described, forexample, in EP-370 629, EP-506 149, EP-403 61 S, EP-414 153, EP-463 4SS, EP-472 300,EP-560 575. WO-92/1S494 and in other publications. E) To préparé a compound of the formula I in which A, X. Y and R|-R3 are as defined forformula I but in which R3 is not hydrogen, a procedure is followed in which, for cxamplc: A compound of the general formula
in whïich A... X. Y and Rj-R3 arc as defined above is rcacted witn a methylating agent, forcxamplc meihyi iodidc, dimcthyl sulfate or diazomcthanc. The reaction is advantageouslycarriesd ouc ân the présence of a base, for cxample potassium carbonate or sodium hydride.in a smhable solvent and at suitablc réaction températures (sec, for cxample. H.S. Ankcrund HLT. Qtarke; Organic Synthcsis, Coll. Vol. 3. 172). Ί'7 010326
Fj Το préparé a compound of the formula Vil in which Λ. X. Y and K,-I<3 are a.·, ddincdfor formula I. a procedure is advaniageously followed in which: A compound of die formula
vin in which A, Y and R,-R3 are as defîned above is reactcd with a formate in lhe présence ofa base ar.alogously to the method dèseribed in EP-A-17S S26. or is subjccted to nitrosationwith nitrous acid or a nitrite in the presence of a base analogously to the method describedin ΞΡ-Α-254 426. A further possibility of synthesizing a compound of die formula VH is foc followingréaction: A compound of the formula
in v.nich .A. Y and Rt to R3 are as defîned above is reactcd with metroxymethylcnctriphcnylphosphoranc analogously to foc method described inEP-.-.-17S 326 or with O-mcthylhydroxylaminc (or a sait thercof) analogously to themets od described in EP-A-254 426.
The novel compounds of the forniulae VII. VIII and IX arc also providcd by the invention.
Ithas now peen found thaï compounds of foc formula ! hâve a microbicidal spccinim lor IS - 010326 controlling phyiopathogenic tnicroocgiinisms, in particular fungi. which is pariicularlyfavourable for practical requirements. They hâve vcry avantageons curative, préventiveand, in particular, systemic properties and can be used for protecting a large number ofcrop plants. Using the active ingrédients of the formula 1. the pesis which are found onplants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of various crops ofusefuE plants can be contained or destroyed, and even pans of plants which arc formed at alater point in time remain free front phytopathogenic microorganisms.
The compounds of the formula I can funhermore be used as secd-dressing agents for therreatrncnt of seed (fruits, tubers, grains) and nursery plants for the protection againstfungal infections and against soil-borne phytopathogenic fungi.
Compounds of the formula I are active for examplc against phytopathogenic fungi whichbelong to the following classes: Fungi imperfecti (in particular Botrytis, furthermorcPyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Ccrcosporella andAhemaria); Basidiomycetes (for example Rhizoctonia, Hcmileia, Puccinia); AscomycètesÇfor example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula); Oomycctes (forexampEc Phytophthora, Peronospora, Brcmia, Pythium, Plasmopara).
Compounds of the formula I are furthermore valuable active ingrédients against inscctsand Acarina which are found on uscful plants and ornamentals in agriculture andhorticuLTure, in particular in crops of rice, cotton, vegctables and fruit, and in forests, andare welL tolerated by warm-blooded species, fish and plants. The compounds I areparticuLarly suitable for controlling insects in crops of rice, fruit and vegetables, inpariicutar plant-injurious insects. Other fields of application for the active ingrédients ofthe invention are the protection of stored products and matcrials and, in the hygiène sector,in particular the protection of domcstic animais and productive livestock. The compoundsof the formula I are active against ail or individual development stages of normallysensitive, but also résistant, pest species. Their activity can bccome apparent, for example,from the destruction of the pests, either immediately or only after sonie time lias claused,foc examplc during molting, or from reduced oviposition and/or hatching rates.
The abo'vementioned animal pests includc. for examplc: from the order Lcpidoptera, for example,
Ac3eris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabatna argillaccac, Amyloisspp., Amücarsta gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseolafusca. Cadra camélia. Carposina nipponensis, Chilo spp., Chotistoncura spp.. Clysia .-19- 0 î (»326 motgcella, Cnaplialocrocis spp.. Cnepliasia spp.. Cochylis spp., Coleophora spp..Crooicolomia binotalis, Crypiophlebia Iciicotrcia. Cydia spp.. Diatrnca spp., Diparopsiscastane?., Earias spp.. Ephcsiia spp., Eucosma spp., Eupoccilia ambiguella, Euprocns spp.,Suxoa spp., Grapholiia spp., Hcdya nubiferana, Hcliothis spp., Hellula undalis, I lyphantria 5 cor.ea, Keiferia lycopersicelln, Lcucoptcra scitclla, Lithocollcihis spp., Lobcsia botrana.Lymaniria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicac, Manduca sexta,Opcroçhtcra spp., Osrrinia nubilalis. Pammene spp., Pandemis spp., Panolis flammca,Pectincphora gossypiella, Phthorimaea operculella, Picris rapac, Picris spp., Plu tel laxylostcZla, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., 10 Synanthedon spp., Thaumetopoea spp,, Tortrix spp., Trichoplusia ni and Yponomeuiaspp.; frorr. the order Coleoptera, for cxample,
Agioter spp., Anthonomus spp., Atomaria lincaris. Chactocncma tibialis, Cosmopolitesspp.. Cerculio spp., Dermestes spp.’.'Diabrotica spp., Epiiachna spp., Eremnus spp., 15 Lcptinosarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp.,Ociorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,Soarabeidae, Sitophilus spp., Sitotroga spp., Tcncbrio spp., Tribolium spp. andTogcdcrma spp.; frem b.e order Orthoptcra, for examplc, 20 Blntca spp.. Blatiella spp., Gryllotalpa spp., Lcucophaca madcrac, Locusta spp.,
Pe—pianota spp. and Schistocerca spp.;frer-. :r.e order Isoptera, for example,
Rcniccbtermes spp.; fro~. ;-.e crder Psocoptera, for example, 25 Lipcsccli* spp.; frorr. me crder Anoplura, for example,
Haomctoplnus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxérason. ; frorr me crder Mallophaga. for examplc, 3 2 Darr.alm.se spp. and Trichodectes spp.;frorr me ecesr Thysar.optera. for cxample,
Frar.nimtsLa spp., Hcrcinothrips spp., Taeniothrips spp.. Thrips palmi. Thrips tabaci and
Scirr e:r ripe aerantii; frorr me orner rieteroptera, for cxample, 35 C’.mex spp... Disiantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp.
Lcpconcriss- spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbcrgella singniaris,
Scomnorhara spp. and Triatoma spp.; Ûî 0326 from the order Homoptera, l'or example.
Aleuroihrixus floccosus, Aleyrodes brassicac, Aouidiella spp., Apliididae. Aphis spp.,Aspidiotus spp., Beiuisia labaci, Ccroplasier spp., Chrysomphalus aonidimn,Chrysomphalus dictyospcrmi, Coccus hespcridum, Empoasca spp., Eriosoma larigennn,Erythroneura spp., Gascardia spp., Laodclphax spp., Lccanium corni, Lepidosaphcs spp.,Macrosiphus spp., Myzus spp., Ncphotettix spp., Nilaparvata spp., l’aratoria spp.,Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialcurodes vaporariorum, Triozaerymeae and Unaspis ci tri; from the order Hymenoptera, for example,
Acromyrmcx, Atta spp., Cephus spp., Diprion spp., Diprionidac, Gilpinia polytoma,Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.and Vespa spp.; from the order Diptera, for example,
Aedes spp., Aniherigona soccata, Bibio hortulanus, Callipbora crythroccphala, Ccratitisspp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila mclanogastcr,Fannia spp., Gascrophilus spp., Glossina spp., Hypodcrma spp., Hyppobosca spp.,Liriomyza spp., Lucilia spp., Mclanagromyza spp., Musca spp., Ocstrus spp., Orseoliaspp., Oscinella frit. Pegomyia hyoscyami, Phorbia spp., Rhagolcds pomonclla. Sciara spp.,Scomoxys spp,, Tabanus spp., Tannia spp. and Tipula spp.; from the order Siphonaptcra, for example,
Ccraiopfayllus spp. and Xenopsylla chcopis; from the order Th ysanura, for example,
Lerpisma saccharina and from the order Acarina, for example,
Acarus szro. Aceria sheldoni, Aculus schlcchtendali, Amblyomma spp., Argas spp.,Boophilus spp., Brcvipalpus spp., Bryobia praetiosa, Calipitrimcrus spp., Chorioptcs spp.,Decmanyssus gallinae, Eoterranychus carpini, Eriophycs spp., Hyalomrna spp., Ixodcsspffc-, Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocopcruta olcivora.Potyphagoiarsonemus laïus, Psoropics spp., Rhipiccphalus spp., Rhizoglyphus spp.,Sarcoptes spp.. Tarsonemus spp. and Tctranychus spp..
Target craps for crop-proteciing use arc, within the scope of the invention. for example thefottowing îypes of plants: cercals (wheat, barley, rye, oais, ricc, maize, sorghuin andrelaeed species); beet (sugar and foddcr bcci); pome fruit, stonc fruit and soft fruit (apples,pcacs. plunns. penches, nlmonds, chcrries, strawbcrries. raspberries and blackberrics); -71 ouïses (beans, lemils, peas, soya beans); oit crops (oilseed râpe, mustard, poppy, olives,sur.fto-vers, cocouut, castor, cocoa, groundnuis); cucurbiis (ptunpkiu. cuciimbers, melons);;":b:e pnuits (coiton, flax, hemp, jute); citrus fruit (oranges, leinons. grapefruit, tangcrines);•-egetaoles (spinach, lettuce, asparagus, cttbbagcs, carrots. onions, tomatocs, potatoes, bell 5 pepper;; trie laurel Family (avocado, cinammon, camphor), and plants such as tobacco,r.uts, coffec, egg plants, sugarcane, tea, pepper, vines, hops, the banana farnily. latex plantsand orr.amentals.
The acrion of the compounds of the formula I according to the invention and of die 10 compositions comprising them can be broadencd considcrably and adapted to prevailingcrrcumstances by adding other microbicides, insecticides and/or acaricides.Représentatives of the following active ingrédient classes arc examples of suitableauditives: organophosphorus compounds, nirrophenols and dérivatives, fomnamidines.créas. carbamaces, pyrethroids, chlô'rinated hydrocarbons and Bacillus thuringiensis 15 préparations.
Ac a raie, active ingrédients of the formula I are used in the fonn of compositions and canbe 2pplied to the area or plants to be treated simultancously or in succession with otheractive in gredtents. Thèse other active ingrédients can be fertilizers. trace élément 20 media tors or other préparations which hâve an effect on plant growth. Sélective herbicidesans a.jo .insecticides, fungicidcs, bactéricides, ncmaticides, tnolluscicidcs or mixtures of aplerarity of these préparations, with or without other carriers convcntionally used in the artof ; orme ..a don. surfactants or other application-cnhancing additives, can also be used. 25 Suirad.e carriers and additives can be solid or liquid and are those substances which arcexpiectenr :n. trie art of formulation, for example natural or rcgencratcd minerai substances,soi '-en.·.-. dispersants, wetting agents, tackificrs, thickencrs, binders or fertilizers.
The fc-.o-vmg are suitable solvents; aromatic hydrocarbons. prcferablv the fractions Cs to 30 ter e.eamp.e xylenc mixtures or substituted naphthalcnes, phtimlates such as dibutvlph;e.r..r;e or dicety 1 phthalatc, aliphatic hydrocarbons such as cyclohexaue or paraffuis.alcC'-.o.: a-.d giycols as well as their ethers and esters, such as éthanol. ethylene glycol,cthy :ere g yao'. monomethyl ether orethyl ether, ketones such as cyclohexanonc. stronglypôle - sa.v-rc'.ts. such as N-methyl-2-pyrrolidonc, ditncthyl sulfoxide or 35 dimedy-'.fermarnide. and unepoxidized or epoxidized vcgctable oils. such as epoxidized coccinu: oi ' or soya oil; or water. • ΊΊ · 010326
Solid carriers which are gencrally tised, for exuni pie for dusis and dispersible powders, aregrouttd natural rocks, such as calciic, talc, kaolin, monnuorilloniie or attapuigite.
Particularly advantageous application cnhancing additives which may resuit in a gieatlyreduced rats of application are, moreover, natural (animal or vcgetablc) or syntlieticphospholipids from the sériés of the ccphalins and lccithins, which can bc obtained front,îor example, soya beans.
Suitable surface-active compounds are, depending on the nature of the active ingrédient oftthe formula I to be formulated, non-ionic, cationic and/or anionic surfactants which hâvegood emuisifying, dispersing and wetting properties. Surfactants are also to bc understoodas meaming surfactant mixtures.
Suitable anionic surfactants can be'so-called water-solublc salts and also water-solublesynthecûc surface-active compounds. S-oaps are the alkali métal salts, alkalinc carth métal salts or substituted or unsubstitutedammonium salts of highcr fatty acids (C10-C22). for cxample the sodium salts or potassiumsalts of oieic or stearic acid, or of natural mixtures of fatty acids which can bc obtainedfrom, for cxample, coconut oil or tallow oil. The fatty acid methyltaurates must also bementioraed.
Suitable non-ionic surfactants arc polyglyco! ether dérivatives of aliphatic or cyoloalîphatic alcohols, saturated or unsaturated fatty acids and alkylphcnols which hâve 3to 30 glycol ether groups and S to 20 carbon atoms in the (aliphatic) hydrocarbon radicalarrd 6 to 28 carbon atoms in the alkyl radical of the alkylphcnols.
Examples of rton-ionic surfactans arc nonylphcnol polycthoxycthanols, castor oilpoLy glycol ethers, polypropylene/polyethylcnc oxide adducts, tributylphcnoxy-pobyethoxyethanol, polycthylcnc glycol and octylphcnoxypolyethoxyethanol.
Otber suicable substances arc fatty acid esters of polyoxycthylenc sorbitan, such aspobyoxyechylcnc sorbitan triolcatc.
The catioroïc surfactants are mainly quatemary ammonium salts which hâve, asN-SKjbstituicnts, ai least onc alkyl radical having S to 22 C atoms and, as furthersubstitueras. lower, halogcnated or free alkyl. bcnzyl or lower hydroxyalkyl radicals. 010326
As a raie, the agrochemical préparations comprise ü. 1 to 99 %. m particular 0.1 to ‘>5 %.of active ingrédient of the formula I, 99.9 to I %, in particular 99.9 to 5 %. of a soin! oriiquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant.
While concentrated compositions are more preferred as commercial products, the endconsumer will, as a rule, use di lu te compositions.
The compositions can also comprise other additives such as stabilizers, antifoams,viseosity regulators, binders, tackifiers, fertilizers or other active ingrédients for achievingspécifie effects.
The formulations, i.e. the compositions, préparations or combinations comprising theactive Ingrédient of the formula I together or without a solid or liquid additive, arcprocucc-d in a known manner, for example by intimately rnixing and/or grinding the activeingrédient with an extender, for example a solvent (mixture), a solid carrier and, ifapprepriate. surface-active compounds (surfactants). A preferred process for applying an active ingrédient of the formula 1 or an agrochemicalcomposition which comprises at least one of thèse active ingrédients, is application to theforage (toliar application). Frequcncy and rate of application dépend on the danger ofatcack by the pathogen in question. However, the active ingrédients of the formula 1 canalsoreacr. the plant via the soit through the root System (systemie action) by drcnching thelocus of me plant with a liquid préparation or by incorporating the substances in solidform ir.tc the soil, for cxample in the form of granules (soil application). In the case ofpaddy rice, such granules can be metered out into the flooded ricc ficld. Altcmatively, thecompounds of the formula I can be applied to secd kernels (coating). cithcr by soaking thekernels ir. a liquid préparation of the active ingrédient or by coating them with a solidprscarcticm. In principle, any type of plant propagation material can be protected using thecom.pcunds of the formula I. for cxample seed, roots or stalks.
The ccmçcunds of the formula 1 are used as pure compounds o:, preferably, together ^ iththe cuxiliamies conventionally used in the art of formulation. To this end. they areadva.ntt.gecus!y proccssed in the known manner, forexampte to give émulsionconcentrâtes, spreadablc pastes, dircctly sprayablc or dilutablc solutions, dilute émulsions,wctcr.bie powders, soluble powders, dusts, granules, and encapsulations, for cxample inpolymeric substances. The methodsof application, such as spraying, atomizit.g. dusting. • 24 - 010326
co suie the intended aims and the prevailing circumstanccs. Pavoutablc raies of application are, as a rule, 1 g to 2 kg of active ingrédient (a.i.) per ha, prelcrably 25 g to 800 g of a.i./ha, particularly preferably 50 g to 400 g of a.i./ha. When used as seed dressingproducis, dosage rates of 0.001 g to 1.0 g of active ingrédient arc advantagcously used perkg of seed.
The examples which follow are intended to illustrate the invention in greater detailwithou: imposing any restriction thercto.
Préparation Examples
Example. H-l:
Préparation of
OH 1.32 g of hydroxylaminc hydrochloridc are added to a solution of 5.2 g of mcthyl3-Methoxy-2-((((3-oxo-2-butyl)imino]oxy)o-tolyl]acrylatc (EP-A-370 629, No. 156) in20 ml of pyridine. After the mixture has been stirred for 6 hours at 30°C, ice-watcr isadded, the crystal cake which has formed after a fcw hours is filtered off, and the crystalsare washed with water. Recrystallization from cthanol/watcr gives 4.8 g of methyl3-methoxy-2-[(((3-hydroximino-2-butyl)imino]oxy)o-tolyl)acrylate (Comp. No. 1.73) asyeîtow crystals of melting point 104-l07°C.
Example H-2:
Préparation of
25 · 0 1 0326 : ;i a pressure pipe, 5 ιηI of dimethylfonnamitle are added to 0.2 g of au approximatcly65 % sodium hydride suspension washed witli liexane. Tlien, 1.6 g of metliyl 3-niethoxy- 2- [(((3-hydrox.imino-2-buiyl)imino]oxy)o-tolyl]acrylatc and hcreupon l.l g of2.2,2-trifluoroethyl iodide arc addcd. A fier die évolution of hydrogeu lias subsided. die 5 pressure pipe is sealcd, and die mixture is stirTcd for 5 liours at 50°C. Tlien, tlie réactionsolution is poured into ice-water and cxtracted using ctliyl acétate, and die product iscnromatographed on silica gel using ethyl acetate/hexane (1:3). This gives 1.2 g of metliyl 3- methoxy-2-((((3-(2,2,2-trifluoroethoxyimino)-2-butyl)imino]oxy)o-tolyl]acrylate(Comp. No. 1.74) as a colourless oil. 10 lH NMR in CDCI3: Chemical shift of the two imino-substituted metliyl groups: 1.99 and2.34 ppm. E.-tampie H-3:
Préparation of
A solution of 15.0 g of p-methylpropiophcnonc and 20 ml of isopcntyl nitrite in 30 ml ofmetthanol is slowly added dropwise to 20 ml of sodium mcdiylate (30 % in mcdianot).Af'.er the mixture lias been stirred for 5 liours, 30 ml of water arc added dropwise, and themixture is subsequently acidificd using acedc acid. The mixture is cxtracted using ethyl 20 acétate, and the extract is washed with water, dried (Na2SO4) and concentrated in vacuo.The residoe is rccrystallized from dicthyl cther/n-hcxanc. This givesa-h -'droxy:mino-4-methyIpropiophcnonc as colourless crystals of mclting point S. 1 g of the prcviously obtaincd compound and 4.6 g of o-mcthylhydroxylamine 25 hydrechioridc in 40 ml of pyridine are refluxed for 1 hour. Aftcr an addition of toluène,the mixture is concentrated in vacuo, treated with water and cxtracted using ethyl acctate.The organio phase is washed with water, dried over sodium sulfate and conccrmatcd invacuo. c.-Kydroxyimirio-4-mctliylpropiophcnonc O-mcihyl oxime arc crystnl hzed from 010326 26 - diethyl ether/n-hexaue in the l'onn of colourlcss crystals ot melting point 156- I5/°C. 1.87 gofthc previously obtained oxime and 2.58 g ol methyl 2-(a.-bromo-o-tolyl)-3-methoxyacrylaie arc added to a suspension of 0.4 l g of sodium5 hydrïdc in 25 ml of Ν,Ν-dtmethylformantidc, and the réaction mixture is stirred for 3 hours. It is lhen acidificd using acetic acid, treated with svaicr and extracied using ctltylacetane. The organic phase is washcd twice using saturated sodium hydrogen carbonatesolution and once using saturated sodium chloridc solution. Aftcr drying over anhydroussodium sulfate, the solvent is distilled off in vacuo. H-3 crystallizcs front diethyl 10 ether/m-hexane in the form of colorless crystals of mclting point 9S-l0l°C (Comp. No.1.117).
Exanwle H-4:
Préparation of
0.37 g of an approximately 65 % sodium hydridc suspension is washcd with hcxanc, and10 ml a>f dimethylformamide arc added. A mixture of 2.59 g of methyl2-(2-bromomethylphenyl)glyoxylate O-methyloxime and 2.42 g of 2-(diphenyl-hydrazamo)-3-hydroximinobutane is added to this suspension, and the mixture is 20 subseqœntly heated to 40-50°C using a hot-air blower unitl hydrogen is evolvcd vïgorotasly. The mixture is then stirred for onc hour with the exclusion of moisture, andpoured into ice-water. Extraction using cthyl acetate and chrontatography on silica gelusingedhyl acetate/hcxane (1:2) gives 3.7 g of methyl 2-[(((3-diphcnylhydrazono-2-butvl)-imino]aïKy)o-tolyl]glyoxylate O-mcthyloxime (Comp. No. 2.19) as a yellow oïl. 25 NMR in CDCI3: Chemical shift of tl te two imino-substituted methyl groups: 1.64 and2.12 pptm. J**? 0 î 0326 • '27 · IZxaripic 11-5:
Pi épuration of
2.9 g ci methyl 2-[(((3-diphenylhydrazono-2-butyl)-imino)o.xy)o-tolyl)glyoxylate5 O-meihyloxime are stirred for 2 hours at room température in 10 ml of a 33 % methyLamine solution in éthanol. Ethanol and the excess of methylamine are distillcd off.The residue is taken up in diethyl exher, the solution is filtered, the filcrate is evaporated todcyness, the product remaining as a crystalline solid. Washing with hexane gives l.S g ofN'-monomethyl 2-(({(3-diphenylhydrazono-2-butyl)imino)oxy)o-tolyl)glyoxylamide 10 C-methyloxime (Comp. No. 3.19) as pale beige crystals of mclting point 135-136°C. » t » /* exaetpie n-o:
Preoarasion of
1.7- g of Z-[~-(2,2-dichlorocyclopropylmethoxy)phcnyl)propane-1,2-dionc1-( C'-met.-’,yloxime)-2-oxime, of the formula (AA), arc added to 0.13 g of sodium hydride 22_ô ml cf N.N-dimethylformamide. 1.5 g of methyl 2-(2-bromomcthylphcnyl)-3-met.-.oxyacrylatc, of the formula (BB), arc subscqucntly added, and tire mixture is stirred 2 3 for 3 heurs a: rcom température. The mixture is acidified using acctic acid, and water ande::ty.. acétone are added. The aqueous phase is separated off, and the organic phase iswasnco or.-ioe using saturated sodium hydrogen carbonate solution and dried overanhyOrctiS sodium sulfate. The solvent is evaporated in vacuo, and the residue obtaincd ispuritfod on silice gel using hcxane/cthyl acétate (3: l). The title compound is obtaincd as an 23 oll. Stp.-.racio:: by column chromatography on silica gel (hexanetethyl acétate solution 3:1) 010326 • ?s - givcs duce isomcis: isomer Λ. m.p. 86-S8°C. isomer I}. oil, isomer C. oil (Compound 5.V).
H-.C COOCHg (AA) /Λκ
Br (BB)
The following compounds can be prepared in this nianner or analogously to one of the5 methods described furiher above: (A.bbrevi2tions: Me=methyl, Et=ethyl, A=cyclopropyl, Ph=phcnyI, m.p.=melting point).N’MR: The Chemical shifts are given as δ (ppm) in CDCIj. • 79 0)0326
Table I
Ex. No. A R. r2 *3 or NR3R4 Physical data** 5 1.1 NMc Mc Mc 6-CF3-2-pyridyl 2.17/2.19 1.2 NMc H Mc 6-CF3-2-pyridyl 1.3 NMc Me Δ 6-CF3-2-pyridyl im NMc Mc H phenyl 1.5 NMt Me Me phenyl 2.09/2.1 S 10 1.6 NMc Δ Me phenyl 1." NMc Mc Mc 4-CF3-2-pyridyl m.p. 100°' 1.Ξ NMc H Mc 4-CF3-2-pyridyl l.ç NMc Δ Δ phenyl l.l J NMc Mc Mc 5-CF3-2-pyridyl 2.17/2.1S 15 î.i : NMc PI Mc 5-CF3-2-pyridyl 1.12 - H Mc 4-(l,2,4-triazolyl) 1.12 - Mc Mc 4-(1,2,4- triazolyl) 161-163°C 1.1- - Mc Δ 4-(1,2,4-triazolyl) 2C 1.15 - Mc Δ 4-morpholinyl 1.15 - Mc Me 4-morpholinyl 113°C i.r - H Mc 4-morpholinyl 1.12 N?h‘ H Mc phenyl 1.1Ç Mc Mc phenyl 1.74/2.22 25 ! .22 N?h- Mc Δ phenyl 1.21 1’?b* ώ Mc phenyl 1.22 NMc Mc Mc 2-nitrophenyl 1.93/2.06 1.23 N Mc H Mc 2-nitropheny! 1.24 C' Me Mc Mc 76-7S°C 30 1.25 c H Mc Mc 1.97/7.68 -30 - 01 0326
Ex. A Ro '<3 or NRjR., Physical data* * No. 1.26 O Δ Me Me 1.96/2.00 1.27 0 Mc Δ Me 60-62°C 5 î.28 0 Mc H Me 1.29 NMc H Mc 3-CF3-2-pyridyl 1.30 NMc Me Me 3-CF3-2-pyridyl 2.06/2.1 S 1.31 N Mc Δ Me 3-CF3-2-pyridyl 1.32 Nivic Δ Me 3-nicro-2-pyridyl 10 1.33 NMc H Me 3-nitro-2-pyridyl 1.34 NMc Me Mc 3-nicro- 1.94/2.26 2-pyridyl 1.35 NMc Me Me 2-CF3-phcnyl 1.85/2.10 1.36 NMc Me Δ 2-CF3-phcnyl 15 1.37 NMc H Me 2-CF3-phcnyl 1.38 NMc Me Mc 3-CF3-phcnyl 1.39 NMc Mc Δ 3-CF3-phcnyl 1.410 NMc H Mc 4-CF3-phcnyl 1.411 NMc Mc Me 4-CF3-p!icnyl 20 1.412 NMc Mc Me 2-ch!orophcnyl 1.73/2.13 1.413 NMc Me Mc 3-chlorophcnyl 2.12/2.17 1.44 NMc H Me 4-chloroplienyl 1.4-5 NMc Me Me 4-ch lorophcn y 1 2.10/2.15 1.45 O Mc Me phcnyl 2.14/2.22 25 1.47 O Me Δ phcnyl 1.4S O Me Me bcnzyl l06-108°C 1.45 O Mc Me Et 1.92/1.95 1.50 O H Me Et 1.51 O Δ Mc Et 30 1.52 O Me Δ Et 1.53 G Me H Et 1.54 G H Me mcthoxynicthyl 1.55 G Mc Mc mcthoxynicthyl S3-S4°C 1.56 G Mc Δ mcthoxvmethvl • r>l - 0 1 0326
No. R, r2 l<3 or NR3R., Pli y s ic a 1 (.lata * * ; .57 0 Δ Mc mcthoxymethyl 1.5S 0 Me Me ctlioxy metliy 1 2.04/2.04 2.59 0 FI Me cyanomcthyl 1.60 0 Me Me cyanomcthyl 2.04/2.04 1,61 0 Δ Me cyanomcthyl 1.62 - Me Me azepino 2.02/2.04 1.63 - Me Me piperidino 1-64 - Me Me pyrrolidino 1.65 0 H Me tcrt-but y 1 1.56 0 Me Me tcrt-bu ty 1 1.96/2.04 1.57 O Me Me propargyl 114-115°- 1.5S 0 Δ Me propargyl 1.59 0 Me Δ propargyl l.~0 3 Mc Me 2,2-dich loro- cyclopropylmcthyl 2.02/2.02 I.~l "7 U Δ Me 2,2-dichloro- cyclopropylmcthyl 1.72 «*-v H Mc H 1.7? Me Me H 104-107°' 1.7~ Me Me cf3ch2 1.99/2.04 1.75 Q Δ Me cf3ch2 1.75 o Me H cf3ch2 1.7* Me H cf3ch2ch. 1.7? L. Me Mc cf3ch2ch2 1.77 Me Me cf3ch2ch2ch2 2.10/2.13 l.S? Λ Mc cf3ch2ch2ch? î.s i \ ?»*c M C Me Mc 94-9S°C 1.S2 \r .* * Δ Mc l.S? J Me Me CH2-CC1=CH2 80°C 1.S4 3 Δ Me ch2-cci=ch2 1.S5 3 Mc propyl I.S6 3 Me Me bu ty 1 ?>6-3S°C 010326
Ex. A R, 1½ 'b or NR3R(1 Physical data* * No. 1.87 0 Me Me licxyl . 1.99/2.01 1.88 0 Me Mc mcthoxycarbonÿl- 90-93°C 5 1.89 0 ' H Me mcthyl mcthoxycarbonyl- mcthyl 1.90 0 Me Me 3-Ouorobcnzyl 2.00/2.04 1.91 0 Me Me 4-chlorobenzyl 10 1.92 0 Me Mc 2-chlorobenzyl 1.93 0 Me Me 2-CF3-benzyl 1.94 0 Me Me 3-CF3-benzyl 56-5S°C 1.95 0 Me Me 4-CF-j-benzyl 1.96 0 Me Me 3,4-dichlorobenzyl 15 1.97 0 Me Me 2.4,6-trimcthylbcnzyl 1.98 0 Me Mc 4-chloro-2-nitrobcnzyl 1.99 0 Me Me 3-mcthoxybcnzyl 1.100 0 Me Mc 2-phencthyl 1.97/2.02 1.101 0 Mc Mc 3-phcnylpropyl 20 1.102 O Me Mc 2-(4-nitrophenyl)cthyl 1.103 O Me Mc 2-(2-CF3-phcnyl)ethyl 1.104 O Mc Me 2-(4-mcthoxyphcnyl)cthyl 1.105 O Me Me 2-chloro-6-fluorobcnzyl 1.106 O Me Me 3,4-methylcncdioxybenzyl 25 1.107 O Me Me 2-cyanobcnzyl 1.10S O Me Mc 2-(4-chlorophcnyl)cthyl 1.109 O Me Me cyclopropyl- mcthyl 2.01/2.01 i.i io O Mc Mc 2-(l .3-dioxolanyl)incthy 1 30 1.111 O Mc Mc 2,2,3.3-tctrafluorocyclo-bu ty 1 met h y 1 1.112 O Mc Mc a-fluorocthoxy carbonyltnethyl 1.113 O Mc 2-thienyl Mc 2.06/2.10/ 010326 - -
Ex. No. A K| l<3 or NR31<, Pltysical data' * 1.11^ 0 Mc 4-meihyl- Et 2.20 (E/Z) 2.12 1.115 N.Me Me phcnyl 4-methyl- Mc 2.10 (isomerl) 1.116 0 Me phenyl Me ch2fch2 2.08 (isomer2) 50-51°C 1.117 0 Me Me 2-(4-morpho- 1.99/2.01 1.118 Me Me lino)cthyl 1-pyrryl 89-91°C 1.119 0 Me Me 2-(l-pipcridino)- 1.120 0 Me Me echyl 2-fluorobcnzyl 93-96°C 1.121 0 Me Me 4-fluorobcnzyl 104-106’C ~.p . cr lH NMR of R|/R2 or ^3 010326
Ex. No. A r2 or NR3R4 Physic.il data** 2.1 NMc Mc Me 6-CF3-2-pyridyl 2.2 NMc H Me 6-CF3-2-pyridyl 2.3 N Me Me Δ 6-CF3-2-pyridyl 2.4 NMe Me H phenyl 2.5 NMc Me Me phcny! 87-SS°C 2.6 NMe Δ Me phenyl 2.7 NMe Me Me 4-CF3-2-pyridyl 2.S NMe H Me 4-CF3-2-pyridyl 2.9 NMc Δ Δ phenyl 2.10 NMc Me Mc 5-CF3-2-pyridyl 2.11 NMe H Mc 5-CF3-2-pyridyl 2.12 - H Me 4-( 1,2,4 - rriazol y 1) 2.13 - Me Me 4-( 1,2,4-iriazolyl) 2.14 - Mc Δ 4-(l,2,4-triazolyl) 2.15 - Me Δ 4-morphoIinyl 2.16 - Me Me 4-morpholinyl 2.17 - H Me 4-morpholinyl 2.1S NPh H Me phcny! 2.19 NPh Me Mc phenyl 1.64/2.12 2.20 NPh Mc Δ phenyl 2.21 NPh Δ Me phenyl 2.22 NMc Me Mc 2-nitrophenyl 2.23 NMc H Me 2-nitrophenyl 2.24 O Mc Mc Mc IO4-1O6°C 2.25 0 H Mc Me
LlUMWiia'lMlir' 010326 - '55 · Ελ. Νο. ? \ K. R2 *3 or NR3R„ Pli y s ic ;i 1 data" ' 2.26 0 Δ Me Me 1.92/1.97 2.21 0 Me Δ Mc 67-70"C 5 2.23 0 Mc K Me 2.29 NMe H Me 3-CF3-2-pyridyl 2.22 NMe Me Me 3-CF3-2-pyridyI 2.31 NMe Δ Me 3-CF3-2-pyridyI 2.22 NMe Δ Mc 3-nirro-2-pyridyl 10 2.22 NMe H Me 3-niOO-2-pyridyl Ό * NMe Me Me 3-nitro-2-pyridyl 2.35 NMe Me Me · 2-CF3-phcnyl 2.3c NMe Me Δ 2-CF3-phenyl 2.3~ NMe H Me 2-CF3-phenyl 15 2.35 NMe Me Me 3-CF3-phcnyl 2.39 NMe Me Δ 3-CF3-pbcnyl 2.4C NMe H Mc 4-CF3-phenyl ·* /* ' NMe Me Mc 4-CF3-phenyl — 4 NMe Mc Me 2-cbloropbcnyl Sl°C 20 -- X ” ». *“4 _ NMe Mc Mc 3-chIoropbcnyl 2.10/2.13 ~ X -^_. **** NMe H Me 4-chlorophcnyt ~ X Ç NMe Mc Mc 4-chlorophcnyl 2.OS/2.13 2.46 0 Me Me phcnyl S9-90°C 2.-47 O c Me Δ phcnyl 25 2.-4S .·-> l_· Me Mc bcnzyl 2.4? r-s U Mc Me El ~ι Γ> k» H Mc Et *1 — ζ Δ Mc Et ο Me Δ Et 30 2.53 Λ Mc H Et 2. “·- Λ i-l Mc mcthoxymcthy! 2.55 Mc Mc methoxymethyl S7-SS°C 2.55 ο Me Δ methoxymethyl 2.57 ο Δ Me methoxymethyl 010326 36 -
Ex. No. A R, r2 or NR3R„ Physical data* * 2.5 S 0 Me Mc cthoxymctliyl 2-59 O H Me cyanomcihyl 5 2.60 0 Me Mc cyanomcihyl 94-95°C 2-ôl 0 Δ Me cyanomcthyl 2.52 - Me Me azcpino 2.63 - Me Me ptperidino 2.64 - Me Me pyrrolidino 10 2.65 0 H Me tert-butyl 2.66 0 Me Me tert-butyl 1.93/2.02 2.67 0 Me Me propargyl 120-122° 2.68 O Δ Me propargyl 2.69 O Me Δ propargyl 15 2.70 O Me Me 2,2-dichloro- cyclo- propylmcthyl 1.99/1.99 2.71 O Δ Me 2,2-dichlorocyclo- propylmethyl 20 2.72 O H Me H 2.73 O Me Me H 1 14-116°' 2.7Æ O Me Me cf3ch2 52-53°C 2.75 O Δ Me cf3ch2 2.76 O Me H cf3ch2 25 2.77 O Me H cf3ch2ch2 2.78 O Me Me cf3ch2ch2 2.79 0 Me Me cf3ch2ch2ch2 S6°C 2.80· O Δ Mc cf3ch2ch2ch2 2.8 L HMc Me Mc Me SO-Sl°C 30 2.S2 NMe Me Δ Me 2.83 0 Me Mc CH2-CCl=CH2 66°C 2.S4 0 Δ Me ch2-cci=ch2 2.S5 0 Me Mc propyl 2.86 0 Me Mc but yl 5S-62°C 0 1 0326 - 37
Ex. Λ r2 1<3 or NR3k,t Pli y sic al data** No. 2.87 0 Me Me hcxyl 50-53°C 2.83 0 Me Me mctlioxycarbonyl- 1.96/2.04 5 2.85 0 H Me nicthyl mctlioxycarbonyl-methyl 2.90 0 Me Me 3-fluorobenzyI 2.9: 0 Me Me 4-chlorobcnzyl 10 2.92 0 Me Me 2-chlorobcnzyl 2.93 0 Me Me 2-CF3-bcnzyl 2-94 0 Me Me " 3-CF3-bcnzyl 87-8S°C 2.95 0 Me Me 4-CF3-benzyl 2-96 0 Mc Me 3,4-dichlorobenzyl 15 2.97 0 Mc Me 2,4,6-crimctliylbenzyl 298 0 Me Me 4-chloro-2-nicrobcnzyl 2.99 0 Me Me 3-mcthoxybcnzyl 2.10' 0 Me Mc 2-phencthyl 2. :o: *2 Me Me 3-phcnylpropyl 20 2. 102 Me Me 2-(4-nÎOOphcnyl)cihyl 2. 103 - Mc Mc 2-(2-CF3-phcnyl)cthyl 220- 2 Me Me 2-(4-mcthoxyphcnyl)cthyl 2.205 Me Mc 2-chloro-6-nuorobenzyl 2206 .2 Me Me 3,4-mcthylcncdioxybenzyl 25 22 0' "s O Mc Mc 2-cyanobcnzyl 22 03 2 Mc Me 2-(4-chlorophcnyl)ethyl 2.1 05 Mc Me cyclopropylmcthyl 1.9S/1.9S 2.1 10 Mc Mc 2-( 1,3-dioxolany l)mcthy I 2. : 2 Mc Mc 2,2,3,3-tctrafluorcyclo- 30 bmylmethyl 2.1 12 2 .Mc Mc a-fluoroethoxycnrbonylnicthyl 22 13 2 Me 2-ihienyl Mc S3-8ô°C 2.1 .2 c Mc 4-meiliy 1 - phcuy 1 Et 94-y6°C η 010326
Ex. No. A R. r2 1½ or NR3R4 l’h y ica 1 data* * 2.115 N Mc Me 4-methyl- Me 5 2.116 0 Me phcnyl Me ch2fch2 62-63°C 2.117 0 Me Me 2-(4-morpho- 1.97/1.99 2.11S Me Me lino)ethyl l-pyrryl 2.119 0 Me Me 2-(l-pipcridino)-1.95/2.00 10 2.120 0 Me Me ethyl 2-fluorobenzyl Sl-S3°C 2.121 0 Me Me 4-fluorobenzyl 116-11S°C ** m.p. or lH NMR of Rt/R2 or R3 01 0326 • 39 - ' ‘ Table 3 f -
Ex. A Rj R 2 R3
No. or NR3R4
Physical data** 5 3.1 NMc Mc Me 6-CF3-2-pyridyl 3.2 NMe H Me 6-CF3-2-pyridyl 3.3 NMe Me Δ 6-CF3-2-pyridyl 3.4 NMe Me H phenyl 3.5 NMe Me Me phenyl 10 3.6 NMc Δ Me phenyl 3.7 NMe Mc Me 4-CF3-2-pyridyl 3.S NMe H Mc 4-CF3-2-pyridyl 3.9 NMc Δ Δ phenyl 3.10 NMc Me Mc 5-CF3-2-pyridyl 15 3.11 NMc H Me 5-CF3-2-pyridyl 3.12 - H Me 4-(l ,2,4-criazoly!) 3.13 - Mc Mc 4-(l ,2.4-triazolyl) 3.14 - Mc Δ 4-(l,2,4-triazolyI) 3.15 - Me Δ 4-morpholinyl 20 3.16 - Mc Mc 4-morpholinyl 3.17 - H Me 4-morpholinyl 3.1S NPh H Me phenyl 3.19 NPh Me Me phenyl 3..20 NPh Me Δ phenyl 25 3..21 NPh Δ Mc phenyl 3_22 NMc Mc Mc 2-nitrophcnyl 3-23 NMe H Mc 2-nitrophcnyl 3.24 0 Me Me Mc 3325 0 1-1 Mc Mc 2.07/2.15
135-136°C
90-92°C
1.97/7.6S 010326 •40-
Ex. A K. orNR3R„ Physical data** No. 3.26 0 Δ Mc Mc 1.94/1.95 3.27 0 Me Δ Mc 88-90°C 5 3.28 0 Me H Mc 3.29 NMc H Mc 3-CF3-2-pyridyl 3.30 N Mc Me Mc 3-CF3-2-pyridyl 3.31 N Me Δ Mc 3-CF3-2-pyridyl 3.32 NMe Δ Mc 3-nicro-2-pyridyl 10 3.33 NMc H Me 3-nitro-2-pyridyl 3.34 NMc Me Mc 3-nicro-2-pyridyl 3.35 NMc Me Mc 2-CF3-phcnyl 3.36 NMc Mc Δ 2-CF3-phcnyl 3.37 NMe H Mc 2-CF3-phcnyl 15 3.3S NMe Me Me 3-CF3-phenyl 3.39 NMc Mc Δ 3-CF3-phcnyl 3.40 NMc H Mc 4-CF3-phcnyl 3.41 NMc Mc Me 4-CF3-phcnyl 3.42 NMc Mc Mc 2-chlorophenyl 1.72/2.11 20 3.43 NMc Me Mc 3-chlorophcnyl 2.09/2.14 3.44 NMc H Me 4-chlorophcnyl 3.45 NMc Me Mc 4-chlorophcnyl 2.08/2.13 3.46 O Mc Mc phenyl 3.47 O Mc Δ phenyl 25 3.43 O Mc Me bcnzyl 3.49 O Me Me Ec 3.50 O H Me El 3.5 S O Δ Mc Et 3.52 O Mc Δ Et 30 3.53 O Mc H Et 3.54 O H Me mcthoxymcthyl 3.55 O Mc Me mcthoxymcthyl 2.00/2.03 3.56 O Mc Δ mcthoxymcthyl 3.57 O Δ Mc mcthoxymcthyl .à 01 0326 - 41 £x. A R i R-2 r3 or NR3R(1 Physical data* * No. 3.5S 0 Me Me ethoxymcthyl 3.59 0 H Mc cyanomcthyl 5 3.60 0 Me Me cyanomcthyl 2.00/2.01 3.61 0 Δ Me cyanomcthyl 3.62 - Me Me azcpino 3.63 - Me Me piperidino 3.64 - Me Me pyrTolidino 10 3,65 0 H Me tert-bu ty 1 3.66 0 Me Me tert-butyl 1.95/2.01 3.67 0 Me Me propargyl 114-1 15°i 3.6S 0 Δ Me propargyl 3.69 0 Me Δ propargyl 15 3.70 0 Mc Me 2,2-dichloro- cyclopropyl- methyl 3.71 0 Δ Me 2,2-dichIoro- cyclopropyl- 20 3.72 0 H Mc mcthyl H 3.73 O Mc Me H 3.74 O Me Me CF3CH2 94-96°C 3.75 O Δ Me cf3ch2 25 3.76 O Me H cf3ch2 3.77 O Me H cf3ch2ch2 3.72 O Me Mc cf3ch2ci-i2 3.79 O Me Mc cf3ch2ch2ch2 3.SO O Δ Me cf3ch2ch2ch2 30 3.83 NMe Me Me Mc 90-9 l°C 3.S2 NM: Me Δ Me 3.83 □ Me Me CH2-CC1=CH2 1.97/2.02 3.8-4 O Δ Me ch2-cci=cii2 3.85 C3> Me Mc propyl U 1 Ο 326 ·1'.'
Ex. No. A R. R2 1-3 or NRjR,, l’Iiysicat data * * 3.86 0 Me Me butyl 9l-92‘’C 3.S7 O Me Me hcxyl S4-86°C 3.88 0 Me Me mcthylcarbamoyl- meihyl 127-1?O°C 3.89 0 H Me mcthoxycarbonyl- metbyl 3.9Û 0 Me Me 3-fluorobenzyl 3.91 0 Me Me 4-chlorobenzyl 3.92 0 Me Me 2-chlorobenzyl 3.93 0 Me Me 2-CFj-bcnzyl 3.94 0 Me Me 3-CF3-bcnzyl 1.96/2.00 3.95 0 Me Me 4-CFybcnzyl 3.96 0 Me Me 3,4-dichlorobcnzyi 3.97 0 Me Me 2,4,6-trimethylbenzyl 3.9S 0 Me Me 4-chIoro-2-nirrobenzyl 3.99 0 Mc Mc 3-mcthoxybcnzyl 3.100 0 Mc Me 2-phenctli y 1 3.101 0 Mc Mc 3-pheny1propy 1 3.102 0 Me Me 2-(4-nitrophenyl)ethyI 3.103 0 Me Me 2-(2-CF-j-phenyl)etbyl 3.104 0 Me Me 2-(4-rncthoxyphcnyl)eihyl 3-105 0 Mc Me 2-chloro-6- fluorobenzy 1 3-106 0 Me Me 3,4-mcthylcnedioxybenzyl 3.107 0 Mc Me 2-cyanobcnzyl 3. 10S 0 Nie Mc 2-(4-chlorophcnyl)cthyl 3.109 0 Mc Mc cyclopropylmethyl 2.00/2.00 3. 1 10 D Me Mc 2-( 1,3-dioxolanyl)mcihyl n « · .).,11 0 Me Me 2,2,3,3-tetrafluorocyclo- bu t y 1 ni et i t y 1 3.1 12 D Mc Me a-nuorocihoxy- carbonylmeihyl 3.1 13 O Me 2-lhienyl Me î»iws«nnnn5»’”’ra'rt-'*''r 010326 - '13 -
Ex. No. A K, ^2 *3 or NR3R4 Physical data** 3.114 0 Mc 4-metÎiylphenyl Et 1O3-1O4°C 3.115 N Me Mc 4-methylphcnyl Mc 5 3.116 0 Mc Me CH2FCH2 95-97°C 3.117 0 Me Me 2-(4-morpho- lino)c[hyl 1.98/2.06 3.118 - Me Me l-pyrryl 3.119 0 0 Me Me 2-(l-pipcridino)- ethyl 1.96/1.98 3.120 0 Me Me 2-fluorobenzyl- 90-91°C 3.121 0 Me Me 4-fluorobcnzyl 13O-131°C ** τη.ρ. car !Η NMR of R^/R^ or R3 0 1 0326
Table 4:
ix. X Y Ri 2* n B or D Physical dam** .1 CH OMe Me - 1 3-CFj 133-135°C ,2 CH OMe Me - l 4-chloro 140-142°C •n -J CH OMe Me - 1 3-chloro 175-177°C .4 CH OMe Me - 1 2-fluoro 136-137°C .5 CH OMe Me - 1 4-mcthyl isom.l: 9S-l0l°C isom.2: oit isom.3: oit . 5 pu OMe Mc 0 0 mcihyl- 1O4-1O6°C *— «. OMe Me - 1 4-bromo 126-128°C T1 <** OMe Mc - 1 4-fluoro 141-144°C .9 ^u OMe Me - 2 3-F-5-CF3 164-t66°C .10 •~*u OMe Me - 0 - 141-143°C î -~*u OMe Me - 1 2-mcihyl 113-115°C • ? —u OMe Me - 1 3-bromo 176-17S°C . ί 7» — OMe Me - 2 3,4-mcthy- 143-145°C lenedioxy .14 •-^U OMe Me O 0 allyl- 77-S0°C (isomcrl ) 2.0S(isomer2) 1 < .‘“'‘U OMe S Me - 1 4-methyl 2.OS (isomcrl) 2.11 (isomcr2) .15 OMe E: - 1 4-methyl 3.90 (isomer 1 ) 3.97 (isomer2) .Γ Cr OMe Me - 1 4-isobutyl- 2.11 (isomcrl) 2.OS (isome:2) .18 Cr ΐ OMe Mc O 0 propargyl- 2.06/2. ! 1 (E/Z) 01 0326 - 45 ·
Ex. X Y R. Z* n Il or D Physicnl (.hua* ’ 4.19 CH OMc Me O 0 2,2.2-tn- fluorocthyl 2.11 (isomer 1) 2.07 (isomcr2) 4.20 CH OMc Me O 0 cthyl 93-95°C (isonicrl)2.06 (isonicr2) 4.21 CH OMc CN - 1 4-methyt 98-133°C(E/Z) 4.22 CH OMe CN - l 4-chloro 106-10S°C 4.23 CH OMe CN 2 3,4-dichloro 128-13O°C 109-111°C(E/Z) 4.24 CH OMc CN O 0 -cf3 oil (E/Z) 4.25 CH OMc CN - 1 3-CF3 4.26 CH OMe CN - 1 2-chloro 4.27 CH OMc CN 1 4-fluoro 4.28 CH OMe Me O 0 phenyl 112-114°C(iso. 1) oil (iso.2) 4.29 CH OMc Me O 0 -CH2CH=CC12 4.30 CH OMc Me O 0 cfi2-ch=cf2 4.31 CH OMc Mc O 0 -CH2CH=CBr2 4.32 CH OMc Mc O 0 4-Cl-phcnyI 4.33 CH OMc Mc O 0 4-F-phenyl 4.34 CH OMe Me s 0 phenyl 4.35 CH OMc Mc -CH2O- 0 phenyl isomer 1: rcsin isomer 2: rcsin 4.3ό CH OMc Mc -och2- 0 phenyl *** oil 4.37 N OMe Mc - 1 3-CF3 4.3S N OMe Me - 1 4-chloro 4.39 N? OMc Mc - 1 3-chloro 4.40 N? OMc Mc - 1 2-fluoro 111 -112°C 4.41 N? OMe Me - 1 4-meihyt 10l-103°C 4.42 Ni OMc Me O 0 4-meihyl- 104-106°C 4.43 NF OMe Mc - l 4-bromo 134-136°C 4.44 Ni OMc Mc - 1 4-fluoro 4.45 N? OMc Mc - 2 3-F-5-CF3 4.46 Ni OMc Mc - 0 - 4.47 Ni OMc Mc - 1 2-methyl 1O5-1O7°C 01 0326 - -te - χΞχ. X Y Ri' Z* fl B oc ü Physical il; 4.4 S N O Mc Mc - l 3-bromo 4.49 N OMc Mc - 2 3,4 - nie i li y le ncd i o.\ y 4.50 N OMc Me O 0 allyl 74-76°C 5 4.5; N OMc S Me - 1 4 - tncihy 1 S8-9l°C 4.52 N OMc Et - 1 4-mcthyl 4.53 N OMc Mc - 1 4-isobutyl- 4.54 N OMc Me O 0 propargyl oil 4.55 N OMe Me O 0 2,2,2-trifluoroethyl 10 4.56 N OMe Me O 0 ethyl oil 4.57 N OMc CN - 1 4-mcthyl 4.5S N OMc CM - 1 4-chloro 4.59 N OMc CN 2 3.4-dichloro 4.60 N OMe CN O 0 -cf3 15 4.61 N OMe CN - 1 3-CF3 4.62 N OMc CN - 1 2-chloro 4.63 N OMe CN - 1 4-Huoro 4.64 N OMe Me O 0 phcnyl 4.65 24 OMe Me O 0 -CK2CH=CC12 20 4.66 34 OMe Me O 0 -ch2ch=cf2 4.67 24 OMe Mc O 0 -CH2CH=CBr2 4.63 24 O.Me Me O 0 . 4-Cl-phcnyl 4.6? 24 O.Me Me O 0 4-F-phenyl 4.73 24 O;Me Me s 0 phcnyl 25 4.7: 2·4 OMe Me -CH2O- 0 phenyl *** 4.72 ^4 OMe Me -och2- 0 phenyl *** 4.72 24' nkch3 Me - 1 3-CF-j 4.74 X nhch3 Me - 1 4-chloro 4.75 N" nhch3 Mc - 1 3-chloro 50 4.76 X xkch3 Mc - 1 2-fl ’.ioro 2.1 1 4.77 X NKCHj Mc - 1 4-mcthyl 2.10 4.7S X nhch3 Mc O 0 mcthyl- 4.79 \r NKOH-s Me - 1 4-bromo 2.09 4.80 X nkch3 Mc - 1 4-fli.ioro 35 4.81 X nhci-i3 Mc - 2 3-fliioro-5-CF3 01 0326 - 47 ·
Ex. X Y K. 2* II β οι 0 Physical data* * 4.S2 N NHCH3 Mc - 0 - 4.83 N NHCH3 Me - 1 2-metliy l 2.05 4.84 N NHCH3 Me - 1 3-bromo 4.85 N NHCH3 Mc - 2 3,4-tncihylcnedioxy 4.86 N NHCH3 Mc 0 0 allyl 118-120°C 4.87 N NHCH3 S Mc - 1 4-mcthyl 2.06 4.88 N NHCH3 Et - 1 4-mcthyl 4.89 N NHCH3 Me - 1 4-isobutyl- 4.90 N NHCH3 Me 0 0 propargyl oil 4.91 N NHCH3 Me 0 0 2,2,2-trifluorocthyl 4.92 N NHCH3 Me 0 0 cthyl oit 4.93 N NHCH3 CN - 1 4-methyl 4.94 N NHCH3 CN - 1 4-chloro 4.95 N NHCH3 CN - 2 3,4-dichloro 4.96 N NHCH3 CN 0 0 -cf3 4.97 N NHCH3 CN - 1 3-CF3 4.98 N NHCH3 CN - 1 2-chloro 4.99 N NHCH3 CN - 1 4-fluoro 4.100 N NHCH3 Mc 0 0 phcnyl 4.101 N NHCH3 Mc 0 0 -CH2CH=CC12 4.102 N NHCH3 Me 0 0 -ch2ch=cf2 4.103 N NHCH3 Me 0 0 -CH2CH=CBr2 4.104 N NHCH3 Me 0 0 4-CI-phenyl 4.105 N NHCH3 Mc 0 0 4-F-phenyl 4.106 N NHCH3 Me s 0 phcnyl 4.107 N NHCH3 Me -CH2O- 0 phenyl * M * 4.1 OS N NHCH3 Mc -och2- 0 phcnyl * * *' 4.109 CH OCH3 Me 0 0 n-propyl isomer 1 : oil isorucr 2: oil 4.110 CH OCH3 Mc 0 0 3.3-dimethyl allyl 107-1 l0°C(iso 1) oil (iso 2) 4. il 11 CH OCHj Me 0 0 2-mcthy 1 -allyl isomerl: 97-99°C isottier 2: oil 010326 - 48
Ex. X Y R. Z* n ΰ or D Physieal tlaia*" 4.112 CH OCH3 Mc 0 0 3-mcihy 1 - isomer l : oil allyl isomer 2: oil 4.1 13 CH OCH3 Me 0 0 allyl isomer l : 74-76°C 5 4.114 CH OCH3 Me 0 0 propargyl oi! 4.115 CH NHCH3 Me 0 0 allyl 4.116 CH NHCH3 Me O 0 propargyl 4.117 CH OCH3 Me -och2- 0 3-CF3-phenyl isomer 1: 83-85°C isomer 2: resin 10 4.118 CH OCH3 Me 0 0 3-CF3-phenyl isomer 1: 127-128 isomer 2: oil 4.119 CH OCH3 Me -OCH2- 0 6nl l isomer 1 : oil isomer 2: oil 4.120 CH OCH3 Me -och2- 0 phenyl*** isomer l: oil 15 isomer 2: oil 4.121 CH OCH3 Me -och2- 0 4-F-phenyl isomer 1: oil $ * * isomer 2: oil 4.122 CH OCH3 Mc s 0 ch3 isomer 1: 119-121°C isomer 2: resin 20 4123 CH OCH3 Mc -so2- 0 ch3 isomer 1: foam isomer 2: resin 4. 124 CH OCH3 Mc -ch2o- 0 phenyl*** isomer 1 : oil isomer 2: resin 4.125 CH OCH3 Me -och2- 0 4-CF3-phenyl*** 25 4.126 CH OCH3 Me -och2- 0 4-Br-phcnyl*** 4.127 CH QCHj Me -och2- 0 4-CH3-phcnyl*** 4.12S CH OCH3 Me -och2- 0 4-OCH3-phcnyl“* ai( 4.129 CH OCH3 Mc -och2- 0 2-CF3-phenyl‘'** 4.130 CH OCH3 Me -och2- 0 2-F-phcnyl*'1* isomer 1 : oil 30 isomer 2: oil 4.131 CH OCH3 Me -och2- 0 2-Cl-phenyH ’ * 4.132 CH OCH3 Me -och2- 0 2-Br-phcnyl**' 4.133 CH OCHj Me -och2- 0 3-F-phcnyl*’ - isomer 1: 111 -112°C isomer 2: oil 35 4.134 CH OCHj Me •och2- 0 3-Cl-phenyl“** isomer 1 : oil 010326
Ex. X Y R, Z* (1 U or D Physical (.lata" isomer 2: oil 4.135 CH och3 Me -OCHr 0 3-Br-phcayt*** isomer 1 : re.sii) v isomer 2: Hnrz 4.136 N och3 Me -och2- 0 allyl*** 4.137 N och3 Me -och2- 0 3-CF3-plicnyl*** 4.138 N nhch3 Me -OCH2- 0 3-CF-j-phcnyl*** 4.139 N OCH3 Me 1 2-CF3 oil 4.140 N OCH3 Me - 1 2-CH3 isomer 1: 105- IO7°C isomer 2: resta 4.141 N NHCH3 Me - 1 2-CF3 resirt -.142 N NHCH3 Me ··. 1 2-CH3 isomer 1 : oil isomer 2: oil 4,143 CH OCH3 CH - - H oil 4J44 CH OCH3 CN O 0 ch3 isomer 1: 136-13S°C isomer 2: rcsia 4.145 CH OCH3 CN - l 4-t-buiy 1 oil 4,145 CH OCH3 CN O 0 phcnyl oil 4.. 147 CH OCH3 Me O 0 CF2CHF2 isomer 1: 80-S2°C 4..14S CK och3 Mc O 0 cf2chci2 4. 149 CH OCH3 Me O 0 CF2CHBr2 4.150 N OCH3 Mc O 0 cf2chfcf3 4.151 N OCH3 Me O 0 cf2chf2 4.,52 N OCH3 Me O 0 cf2chfcf3 4. 253 N NHCH3 Me O 0 cf2chf2 4. 25- N NHCH3 Mc O 0 cf2chfcf3 4.2 55 CH OCH3 Mc - l 4-eihyl isomer 1 : oil isomer 2: oil
4.156 CH OCH3 Mc 1 4-t-buty! tsomer isomer 1 : resta 2: oil 4,15” CH CCH3 Me - 1 4-CF3 isomer 1 : resta isomer 2: 101- 1O2°C 4.15S CH OCH34.159 CH OMe Mc CN -OCH2- 0 1 0 4-Cl-pli pltcayl 4.150 M OCH3 Me -so2- 0 El foata 010326 50 -
Ex. X Y R, Z* . n B or υ Physical data** 4.161 N NHCH3 Me _SO2 0 Et 141-I43°C 4.162 CH OCH3 Me -OCH2- 0 SiMc3 isomer 1 : rcsin isomer 2: oil 4.163 CH OCH3 Me O 0 CF2CHFC1 isomer 1: 75-76°C 4.164 CH OCH3 Me O 0 CF2CHFBr isomer 1 : resin 4.165 CH OCH3 Me O 0 cf2chfcf3 isomer l: 82-S4°C 4.166 CH OCH3 Me S 0 Et isomer 1: oil isomer 2: oil 4.167 CH OCH3 Me S 0 n-C3H7 isomer 1: oil isomer 2: oil 4.16S CH OCH3 Me -SCH2- 0 3-CF3-phenyl 4.169 CH OCH3 Me -SO2CH2- 0 3-CF3-phenyl B_ D_ 4.170' CH OCH3 Mc -SO2CH2- 1 3-CF3-phcnyl 3-F ft
Kisom. 1:112-114°ftisomcr 2: rcsin * The character in column 2 mcans thc compound does not havc a substituent -2-B. ** Pny-sical data: m.p. or Ή NMR of R, or R3, R3 always being CH3 in accordance withcrie structura! formula in thc heading of thc table.
Trre radicals Z are to be read in such a manner that the skcleton of thc structure is ontihc lefcof the srructural élément in question, while thc substituent B is on thc right. Foreatampke, the substituent Z-B in compound 4.107 is -CH2O-phcnyt. 51 010326
Ex. No. X Y A R. r3 r6 R.7 P 5.: CH OCH3 N Me Me.. Me Cl Cl 1 5.2 CH och3 NMe H Me Cl Cl 1 5.3 CH och3 NMe Me Me F F 1 5.4 CH och3 NMe Me Et F F 1 5.5 CH och3 NMe Me Me Br Br 1 5.6 CH och3 NPh Mc Mc Cl Cl 1 5.7 CH och3 NPh H Me Cl Cl 1 5.S CH och3 NPh Mc Et Cl Cl 1 5.9 CH och3 0 Mc Mc Cl Cl 1
Physical data isom.l: 86-SS°eisom.2: resinisom.3: resta 5.10 CH och3 0 H Me Cl Cl 1 5.1’ CH och3 0 Me Mc F F 1 5.12 CH och3 0 H Me F F 1 5.13 CH och3 0 Me H F F 1 5.14 CH och3 0 Me C3H? Cl Cl 1 5.15 CH och3 0 Me Δ Cl Cl l 5.16 CH och3 0 Δ Me Cl ci 1 5.17 CH och3 0 Me Δ Cl Cl ! 5.1S CK och3 0 Me Me Br Br 1 5.19 CH och3 0 H Me Br Br 1 5.20 CH och3 0 Mc Mc Cl Cl 2 5.21 CH och3 0 H Mc Cl Cl 2 foam 01 0326 - 52 ε.χ. No. z\ Y A n U-, P Phyical dat; 5.22 CH och3 0 Me Mc F F 2 5.23 N och3 N Mc Me Me Cl Cl 1 5 5.24 N ocfi3 NMc H Mc Cl Cl' 1 5.25 N ocfi3 NMe Me Me F F 1 5.26 N och3 NMe Me Et F F 1 5.27 N och3 NMc Me Br Br 1 5,28 N och3 NPh Me Me Cl Cl 1 10 5.29 N och3 NPh H Me Cl Cl 1 5-30 N och3 NPh Me Et Cl Cl 1 5-31 N och3 0 Me Me Cl Cl 1 5.32 N och3 0 H Me Cl Cl 1 5.33 N och3 0 Me Me F F 1 15 5.34 N och3 0 H Me F F 1 5.35 Ni och3 0 Me H F F 1 5.36 N" och3 0 Mc C3H7 Cl Cl 1 5.32 N och3 0 Mc Δ ci Cl 1 5.3S N och3 0 Δ Mc Cl Cl 1 20 5.39 N' och3 0 Mc Δ Cl Cl 1 5.40 N och3 0 Me Mc Br Br l 5.41 N och3 0 H Mc Br Br 1 5.42 N och3 0 Me Me Cl Cl 2 5.43 N och3 0 H Me Cl Cl 2 25 5.44 N och3 0 Mc Me F F 2 5.45 N nhch3 NMe Me Mc Cl Cl 1 5.4S N nhch3 NMc H Mc Cl Cl 1 5.47 N nhch3 NMe Mc Mc F F 1 5.4S N nhch3 NMe Mc Et F F 1 30 5.49 N NHCHj NMe Me Br Br 1 5.50» CH och3 0 Me Mc E-l H 1 isoni. 1 : oi 1 isoni.2: oil 5.51 N och3 0 Mc Mc Cl Cl 1 isom. 1: oil 5.52 N nhch3 0 Mc Mc Cl Cl 1 137-139°C 35 5.53 N nhch3 0 Mc Mc ci Cl 1 «10326 - 5? - ISx. No. zY Y A K. ‘<3 l<6 K 7 1’ 5.54 N nhcî-i3 O H Mc Cl Cl 1 5.55 N nhch3 0 Me Me F F 1 5.56 N nfich3 0 H Mc F F 1 5.57 N nhch3 O Me H F F 1 5.5S N nhch3 0 Mc Mc Cl Cl 2 5.59 N nhch3 0 H Me Cl Cl 2 5.60 N nhch3 0 Me Mc F F 2 and the compounds :.62 o.oj 15 5.61
H3C
isomer 1 : oil / isomer 2: oil H3C,
H Cl
ch3 ch3
Cl resin ίίΚ—ΙΜ. MWHaaw·»»·· — 01 0326 - $Λ 5.64
155-16O°C 5.65
5.66
* Physical data: m.p. or 'H NMR of R,/R2 or R3 010326 - 55 ·
Table 6
Z
Ξχ. X Y Z*' n B or D ό.Ι CH OCH3 Me 0 0 allyl 5 6.2 CH OCH3 Me - 1 4-Br 6.3 N OCH3 Me 0 0 allyl 6.4 N OCH3 Me - 1 4-Br 6.5 N NHCH3 Me 0 - allyl 10 6.6 N NHCH3 Me - 1 4-Br 6-7 CH OCH3 Mc - 1 4-metti y 1- 15 6. z- N OCH3 Mc - 1 4-mcthyl- 65 N XHCH3 Me - 1 4-mcthyl-
Physical data** oil isom. 1 : oilisom.2: oiloil
131-132°C oil
isom.l: 117-119°C isom.2: oil
isomer 1: 2.10isomer 2: 2.OS - 56 - 010326
Table 7: Ο
Ex. No. Y A Rt r2 r3 or NR3R„ 5 7.1 OEt N Me Me Me Me 7.2 OEt NMe H Me 6-CF3-2-pyridyl 7.3 OEt NMe Mc Δ 6-CF3-2-pyridyl 7.4 OEt NMe Me H phenyl 7.5 OEt NMe Me Mc phcnyl 10 7.6 OEt NMe Δ Mc phenyl 7.7 OEt NMe H Me 4-morpholinyl 7.8 OEt NPh FI Mc phenyl 7.9 OEt NPh Mc Mc phcnyl 7.10 OEt NPh Me Δ phenyl 15 7.11 OEt NPh Δ Mc phenyl 7.12 OEt 0 Me Me Me 7.13 OEt 0 H Me Me 7.14 OEt 0 Δ Mc Me 7.15 OEt 0 Mc Δ Me 20 7.16 OEt 0 Mc Fl Me 7.17 OEt 0 Mc Me phcnyl 7.1S OEt 0 Mc Mc bcnzyl 7.19 OEt 0 Mc Mc 3-CF3-2-pyridyI 7.20 OEt 0 Mc Mc 3-CF2-phcnyI 25 7.21 nh2 NMe Mc Δ 3-CF3-phcnyl 7.22 nh2 NMe 1-1 Mc 4-CF3-phcnyl
Physical d.**
75°C 010326 • 5·7 -
Ex. λ' A li2 K3 No. oi' NR31\,|
Physical cl. * * 7.23 nh2 N Me Me Me 4-CF3-phcnyl 7.24 nh2 NMc Me Mc 2-chlorophcnyl 7.25 nh2 NMc Me Me 3-clilorophcnyl 7.26 nh2 NMe Me Me 4-chlorophenyl 7.27 nh2 O Me Me phenyl 7.28 nh2 0 Me Me Mc 7.29 nh2 O Me Mc benzyl 7.30 nh2 0 Me Me Et 7.31 nh2 0 H Me Et 7.32 nh2 0 Δ "Me Et 7.33 NH2 0 Mc Δ Et 7.34 nh2 0 Mc H Et "35 nh2 0 Mc Me methoxymethyl 7.36 nh2 0 Me Δ methoxymethyl 7.37 νή2 0 Δ Mc methoxymethyl 7.3S νή2 0 Mc Mc cthoxymcthyl 7.39 nh2 0 H Me propargyl 7.40 nh2 0 Me Mc cyanomcthy! 7.41 νή2 0 Me Mc H 7.42 nh2 0 Me Me cf3ch2 7.43 nh2 0 Δ Me cf3ch2 7.44 nh2 0 Me H cf3ch2 7.45 nh2 0 Me H cf3ch2ch2 7.46 nh2 0 Mc Mc cf3ch2ch2 7.47 NH, 0 Mc Mc cf3ch2ch2ch 7.43 N H, 0 Δ Mc cf3ch2ch2ch 7.49 NHEt NMe Me Δ 3-CF3-phcnyl 7.70 ’xHEt NMc H Mc 4-CF3-phcnyl 7.51 NHEt NMe Mc Mc 4-CF3-phenyl 7.52 N'HEt NMc Mc Mc 2-chlorophenyl 7.52 NHEt NMc Mc Me 3-chlorophenyl 7.54 NHEt NMe Me Me 4-chlorophcnyl - 5S -
Ex. Y Λ R, K2 No. or NR3R 010326
Pliysical d* 7.55 NHEt 0 Mc Me phcnyl 7.56 NHEt 0 Me Me Mc 7.57 NHEt 0 Mc Mc bcnzyl 7.58 NHEt O Mc Me Et 7.59 NHEt 0 H Me Et 7.60 NHEt O Δ Mc Et 7.61 NHEt 0 Me. Δ Et 7.62 NHEt 0 Me H Et 7.63 NHEt 0 Mc Me methoxymethyl 7.64 NHEt 0 Mc "Δ methoxymethyl 7.65 NHEt O Δ Mc methoxymethyl 7.66 NHEt O Me Me ethoxymethyl 7.67 NHEt O H Mc propargyl 7.68 NHEt O Me Mc cyanomcthyl 7.69 NHEt O Mc Me H 7.70 NHEt O Mc Mc CF3CH2 7.71 NHEt O Δ Mc . cf3ch2 7.72 NHEt O Me H cf3ch2 7.73 NHEt O Me H cf3ch2ch2 7.74 NHEt O Me Mc cf3ch2ch2 7.75 NHEt O Me Me cf3ch2ch2ch 7.76 NHEt O Δ Me cf3ch2ch2ch 7-77 N(Mc)2 N Mc Me Δ 3-CF3-phenyl 7-7S N(Mc)2 NMc H Me 4-CF3-phenyl 7.79 N(Mc)2 NMc Me Mc 4-CF3-phcnyl 7-SO N(Mc)2 NMc Mc Mc 2-chlorophcnyl 7.S1 N(Mc)2 NMc Mc Mc 3-chlorophcnyl 7.S2 N(Mc)2 NMc Mc Me 4-chlorophenyl 7.S3 N(Mc)2 O Mc Mc phcnyl 7.S4 N(Mc)2 O Me Mc Mc 7.S5 îN(Mc)2 O Mc Me bcnzyl 7.S6 N(Me); O Mc Me Et
77°C 0 1 »*32 6
No. Y A R2 or NR3R„ ~ S7 N(Me)2 0 H Me Et 7.SS N(Me)2 0 Δ Me Et 5 7.89 N(Mc)2 0 Mc Δ Et 7.90 N(Me)2 0 Me H Et 7.91 N(Me)2 0 Me Me methoxymethyl 7.92 N(Me)2 0 Me Δ methoxymcthyl 7.93 N(Mc)2 0 Δ Me methoxymethyl 10 7.94 N(Mc)2 0 Me Me ethoxymethyl 7.95 N(Me)2 0 H Me propargyl 7.96 N(Me)2 0 Me Me cyanomethyl 7.97 N(Me)2 0 Me Me H 7.9S N(Me)2 0 Me Me CF3CH2 15 7.99 N(Me)2 0 Δ Me cf3ch2 7.Σ 00 N(Mc)2 0 Me H cf3ch2 7.:01 N(Me)2 0 Mc H cf3ch2ch2 7.:02 N(Mc)2 0 Me Me cf3ch2ch2 7.:03 N(Me)2 0 Mc Mc cf3ch2ch2ch· 20 7.:04 N(Mc)2 0 Δ Mc cf3ch2ch2ch- 2. -omeiation ExamDles of active ingrédients of the formula 1 f% - percent by weight) 2. L. V.’-rcable Dowdcrs a) b) c) Acrive ingrédient of Table 1-7 25 % 50 % 75 % Socium ifgnosulfonate 5 % 5 % - Socium. Iceryl sulfate 3 % - 5 % Socium d-iisobutylnaphthalcncsulfonatc - 6 % 10 % Ocryipncrio: polyethylenc glycolet hcr 2 % (7-c mol of ethvlene oxide) Highly disperse silica 5 % io % 10 % Kaolin 62 % 27 % 01 0326 - 60 ·
The active ingiediciu is mixed thoroughly with the addiiives, and the mixture is gtouudthoroughly in a suitable mill. Tliis gives weltable powdcrs whicli can bc dilutcd widi wntcrto givc suspensions of any desired concentration. 2.2. Emulsion concentrate
Active ingrédient of Table 1-7 10 %
Octylphenol polyethylcne glycol ether 3 % (4-5 mol of ethylene oxide)
Calcium dodecylbcnzcnesulfonate 3 %
Cyclohcxanone 34 %
Xylenc mixture 50 %
Emulsions of any desired dilution can be prepared from tins concentrate by diluting it withwater. 2.3. Dusxs
Active ingrédient of Table 1-7
Talc
Kaolin a) b) 5 % S % 95 % 92 %
Ready-touse dusts are obtaincd by mixing the active ingrédient with the carrier andgrinding ihe mixture in a suitable mill. 2.4. Extrader granules
Active ingrédient of Table 1-7 10%
Sodium lïgnosulfonate 2 %
Carboxyrnethyicellulose 1 %
Kaolin S7 %
The active ingrédient is mixed with the addiiives, and the mixture is ground and moistenedwitfc water. Tliis mixture is extruded and sttbscquently dried in a sircam of air. 2.5. Coated granules
Active ingrédient of Table 1-7 3 %
Polyethylcne glycol (MW 200) 3 %
KaoUîn 94 % - 61 010326 (jVlW = molecular wcigln) in a mixer. Oie fincly ground active ingrédient is applied unifomily to the kaolin winch basbeen moistencd with polycthylcnc glycol. This givcs dust-frec coated granules. 2.6. Suspension concentratc
Active ingrédient of Table 1-7Hthyleme glycol
Nonylphenol polyethylene glycol cthcr(15 mol of cthylene oxid)
Sodium îignosulfonate
Carboxymethylcellulose 37% aqneous formaldéhyde solution
Silicone oil in the form of a75 % aqucous émulsionWatcr 40%10%6 % 10% 1 % 0.2 % 0.8 %32 %
The fincly ground active ingrédient is mixed incimatcly with the additivcs. This givcs asuspension concentratc from which suspensions of any desired dilution can bc prepared bydiluting in with watcr. 3. Sloiogricai Examplcs A) Microoicid?.! action
Example B-l: Action against Phytophthora infestans on tomatocs a) Curative action
Tomato plants cv. "Roter Gnom" are grown for three weeks and then sprayed with azoosoc rc suspension of the fungus and incubated in a cabinet at 18 to 20° and saturatedatmosphères humidity. The humidification is interrupted after 24 bouts After the plantshâve dried. they are sprayed with a mixture which comprises the active ingrédient,formulatcd as a wcttablc powdcr. at a concentration of 200 ppm. After the spray coatinghas cried, che plants arc rcturned to the humid chambcr for 4 days. Numbcr and size of thetypical leaf spots which hâve dcvelopcd after this period arc used to assess the activity ofthe test substances. ·61· 010326 b) Prevcntive-systemic action
The active ingrédient, fonnulated as a wcttable powder, is applied at a concentration of 60ppm (relative to the soil volume) to the soi 1 surface of threc-wcck old tomato plants cv."Roter Gnom" in pots. After the plants hâve been left to stand for threc days, the undcrside 5 of the leaves is sprayed with a zoospore suspension of Phytophthora infcstans. The plantsare then kept for 5 days in a spray cabinet at 18 to 20°C and saturatcd atmospherichumidity. After this period, typical leaf spots develop, whosc number and sizc are used forassessing the activity of the test substances.
While untreated, but infected, control plants show an infestation of 100 %, the active 10 ingrédients of the formula I in accordance with one of the tables, in particular the compounds No. 1.5, 1.24, 1.117, 2.24, 2.74 and 3.24, allow the infestation in both tests tobe reduced to 20 % or less.
Example B-2: Action against Plasmopara viticola (Bcrt, et Cun.) (Berl, et De Toni) on 15 vincs a) Residual-preventive action
Vine cutcings cv. "Chasselas" are grown in the grecnhousc. Whcn they have rcachcd the 10-leaf stage, 3 plants are sprayed with a mixture (200 ppm of active ingrédient). After thespray coating on the plants has dried, the leaf undersidc is inoculatcd uniformly with a 20 spore suspension of the fungus. The plants are subscqucntly kept in a humid chambcr for 8days. After this period, the discase symptoms of the conuol plants arc clearly dcvelopcd.Number and size of the lésions on the treated plants arc used to assess the activity of thetest substances. 25 b) Curative action
Grapc cuttings cv. "Chasselas" are grown in the grecnhousc and, when they have rcachcdthe 10-leaf stage, are inoculated on the undersidc of the leaves with a spore suspension ofPlasmopara viticola. After the plants have remained for 24 hours in a humid cabinet, theyarc sprayed with a mixture of active ingrédient (200 ppm of active ingrédient). The plants 30arc subsequently kept for 7 more days in the humid cabinet. After this period, the diseasesymptoms have developed on the control plants. Number and sizc of the lésions on thetreated plants are used to assess the activity of the test substances.
In comparison with the control plants, the infestation of plants which have been mcatedwith active ingrédients of the formula I is 20 % or less. 010326 - 63 -
Example 13-3: Action against Pythimn debaryanmn on sugar bect (Betn vulgaris) a) Aciion after soit application
The fungus is grown on stérile oat grains and added to a mixture ol· soi 1 and sand. Thisinocuiated soil is fillcd into flower pots and sugar bect seeds arc sown. Imnicdiatcly aftersowing, the test préparations, formulated as wcttablc powders, arc poured over the soil inthe fonrt of an aqueous suspension (20 ppm of active ingrédient relative to the soilvolume). Thereupon, the pots are placed in a greenhouse for 2-3 weeks at 20-24°C. AU the:ime, the soil is kept uniformly moist by spraying it gently with water. Whcn the test isevaluaied, the emergence of the sugar beet plants and the proportion of hcalthy anddiseascd plants is determined. b) Action after seed-dressing
The fungus is grown on stérile oat grains and added to a mixture of soil and sand. Thisinoculaied soil is fillcd into flowei'pots and sugar beet seeds which hâve been dresscdwith the test préparations, formulated as seed-dressing powdcrs (1000 ppm of activeingrédient relative to the weight of the seeds), arc sown. The pots together with the seedsare placed in a greenhouse at 20-24°C for 2-3 weeks. The soil is kept uniformly moist bygently spraying it with water. When the test is evaluated, the émergence of the sugar bectplants and the proportion of hcalthy and diseascd plants is determined.
After treatment with active ingrédients of the formula I, in particular with the compoundsNo. 1.5, 1.24, 1.117, 2.24, 2.74 and 3.24, over S0 % of the plants émergé and hâve ahcalthy appearance. In the control pots, only few plants of unhcalthy appcarancc hâveemerged-
Examplc B-4: Residual-protective action against Cercospora arachidicola on groundnuts
Groundncn plants 10 to 15 cm high are sprayed to drip point with an aqueous spraymixture (Ό.02 % of active ingrédient) and, 48 hours later, inoculatcd with a conidiasuspension of the fungus. The plants are incubated for 72 hours at 21 ° and highatmospheric humidity and subsequently placed in a greenhouse until the typical leaf spotshâve devcloped. The aciion of the active ingrédient is assessed 12 days after theinoculation on the basis of the number and size of the leaf spots.
Active ingrédients of the formula I cause a réduction in leaf spots to less than approximaiely 10 % of the leaf surface area. In somc cases, the discase is redueedcomnletcly (0-5 % infestation).
Example B-5: Action against Puccinia sramïnis on wheat 010326 - 64-· a) Residual-protcctivc action 6 days after sowing, wheat plains are sprayed to drip point wiili an aqueous spray mixture(0.02 % of active ingrédient) and. 24 hours later, inoculated with a ureidosporc suspensionof the fungus. After an incubation time of 48 hours (conditions: relative humidity of 95 to100 % at 20°), the plants are placed in a greenhouse at 22°. 12 days after the inoculation,the development of rust pustules is assessed. b) Sysnemic action 5 days after sowing, an aqueous spray mixture (0.006 % of active ingrédient relative to thesoil volume) is poured next to wheat plants. Any contact of the spray mixture with acrialparts of the plants is carcfully avoided. 48 hours later, the plants arc inoculated with aureidosporc suspension of the fungus. After an incubation rime of 48 hours (conditions:relative humidity of 95 to 100 % at 20°), the plants are placed in a greenhouse at 22°. 12days after the inoculation, the development of rust pustules is assessed.
Compotunds of the formula I, in particular those of Table 1, in particular No. 1.5, 1.24,1.117,2L74, cause a marked réduction in fungus infestation, in somc cases down to10-0 %.
Example B-6: Action against Pyricularia oryzae on ricc a) Rcsichaal-protective action
Rice plants are grown for two weeks and lhen sprayed to drip point with an aqueous spraymixture ([0.02 % of active ingrédient), and, 4S hours later, inoculated with a conidiasuspension of the fungus. The fungus infestation is assessed 5 days after the inoculation,during wihich period the relative atmosphcric humidity was kept at 95 to 100 % and thetempcracnrc at 22°. b) Systenaic action
An aqueatus spray mixture (0.006 % of active ingrédient relative to the soil volume) ispoured next to 2-week old rice plants. Contact of the spray mixture with the acrial parts ofthe plants as carcfully avoided. The pots arc then filled with such an amount of water thatthe lowest parts of the stems of the rice plants are submerged. After 96 hours, the plantsare imoculaued with a conidia suspension of the fungus and kept for 5 days at a relativeatmosphcric humidity of 95 to 100 % and a température of 24°C.
In ntany cases, compounds of the formula 1 prevent the development of disease on theinfected pliants. 010326 - 65 ·
Exanulc 13-7: Residual-protectivc action a.^ainst Venturin inaequalix ou applesApple cuttings having fresh shoots 10 to 20 cm iti length arc sprayed to chip point with aspray mixture (0.02 % of active ingrédient) and, 24 hours later, inoculatcd with a conidiasuspension of the fungus. The plants arc incubated for 5 days at a relative atmospheric 5 humiôity of 90 to 100 % and kept in a greenhouse for a further 10 days at 20 to 24°. Theinfestation witlt scab was assessed 15 days after the inoculation.
Most of the compounds of the formula I of one of Tables 1,2 or 3 have a sustainablcaction against scab diseases. ^0 Example B-S: Action against Erysiphe graminis on barley a) Resâdual-protective action
Barley plants approximately 8 cm high are sprayed to drip point with an aqucous spraymixture (0.02 % of active ingrédient) and, 3 to 4 hours later, dusted with conidia of thefungus. The inoculated plants are prlaced in a greenhouse at 22°, The fungus infestation îs 15 assessed 10 days after the inoculation. b’’! Systemic action
Am aqucous spray mixture (0.002 % of active ingrédient relative to the soil volume) ispoured next to barley plants approximately S cm high. Contact of the spray mixture with 20 aedaî parts of the plants is carefully avoided. 48 hours later, the plants are dusted withconidia of the fungus. The inoculated plants arc placcd in a greenhouse at 22°. The fungusinfestation is assessed 10 days after the inoculation.
Compounds of the formula I, in particular compounds No. 1.117, 2.24 and 3.24, arcgenerally capable of reducing the disease to less than 20 %, in some cases also completely. 25 Exemple B-9: Action against Podosphaera leucotricha on apple shoots
Residual-nrotective action
Apple cuaings having fresh shoots approximately 15 cm long are sprayed with a spraymixtrure (0.05 % of active ingrédient). After 24 hours, the treated plants arc inoculatcdwith a conidia suspension of the fungus and placed in a controllcd-cnvironment cabinet at 30 a relative atmospheric humidity of 70 % and at 20°C. The fungus infestation is assessed12 cays arâer the inoculation.
Acti ve ingrédients of the formula 1 allow the disease to bc reduced to less than 20 %.Cortcroi plrar.es show a disease level of 100 %. 35 Exarmp-e S^-10: Action against Botrytis cinerea on apple fruits. Residual- protective action 010326 66
AriiCicially wtnmdcd apples are treaied by npplying iliopwisc a spiay tnixtuic (0.02 % ol'active ingrédient) to the wounds. The treaied fruits are subsequently inoculated with aspore suspension of lhe fungus and incubatcd for one week at high atmospheric humidityand at approximately 20°C. The ftingicidal action of lhe test substance is deduced front lhe 5 number of wounds showing signs of rot.
Active ingrédients of the formula I arc capable of reducing the spread of rot, in sonie casescompleiely.
ExampSe B-l 1: Action against Helminthosporinm gramineum 10 Wheat grains are contaminated with a spore suspension of the fungus and allowed to dry.The coraiaminated grains are dressed with a suspension of the test substance (600 ppm ofactive ingrédient relative to the weight of the seeds). After two days, the grains arearrangée! in suitable dishes containing agar, and, after a funher four days, the developmentof fungal colonies around the grainS’is assessed. The test substance is assesscd on the basis 15 of the number and size of the fungal colonies. A good action, i.e. inhibition of fungal colonies, is shown, in some cases, by compoundsof the formula I.
Examplc B-12: Action against Colletotrichum lagcnarium on cucumbcrs 20 Cccumber plants are grown for two weeks and then sprayed with a spray mixture (concentration 0.002 %). After 2 days, the plants arc inoculated with a spore suspension(1-5 x l0s sporcs/ml) of the fungus and incubatcd for 36 hours at 23° and high atmospherichumidity. The incubation is then continucd at normal atmospheric humidity atapproximately 22-23°C. The fungus infestation which has dcvelopcd is assesscd 8 days 25 after the inoculation. Untreated, but infccted, control plants show a fungus infestation of100) %. A vïnualty complété inhibition of the infestation with diseasc is shown, in some cases, bycompounds of the formula I, in particular by No. 1.5 and 3.24. 30Examplc B-13: Action against Fusarium nivale on rve
Rye cv. Taraheîl, naturally infccted with Fusarium nivale, is dressed with the testfungicide Esing a mixing roller, the following concentrations being used: 20 or 6 ppm ofa.i. (relative, to the weight of the seed). 35Usireg a secd driU, the infccted and treaied ryc is drilled in Octobcr in a ficld in 3 m plots of 6 seed farrows. 3 replicatcs per concentration. 010326 - 67 -
Until the infestation is evaluated, the test plants aie grown untler normal field conditions(preferably in a région with a complète covcring of snow during die winter montlis).
To assess the phytotoxicity, seed émergence is scored in autumn and number of plants perunit area/number of tillers per plant in spring.
To deccrmine the activity of the active ingrédient, the percentage of Fusarium-infcstedplants is counted immediately after the snow has mclted. In the présent case, the numberof infested plants was lower than 5 %. The plants which emerged had a healthy2ppearance.
Example B-14: Action against Septoria nodorum on wheat
Whcat plants in the 3-leaf stage are sprayed with a spray mixture (60 ppm of a.i.) preparedwiih a wettable powder of the active ingrédients (2.8:1).
After 24 hours the treated plants are inoculated with a conidia suspension of the fungus.Trie plants are subsequently incubated for 2 days at a relative atmosphcric humidity of90-100 °ïo and placed in a greenhouse at 20-24°C for a further 10 days. 13 days after theinoculation, the fungus infestation is assessed. Lcss than 1 % of the whcat plants wcrcir.fcstecL
Example B-15: Action against Rhizoctonia solani on ricc
Protective-local soil application
The soil around 10-day old rice plants was watered with a suspension (spray mixture)prepared with a formulated test substance without aerial parts of the plants coming intocontact with the suspension. Three days later, the plants wcrc inoculated by placing a stemof barlcy straw infected with Rhizoctonia solani between the ricc plants of cach pot. Afterincubation for 6 days in a controlled-environment cabinet at 29°C day-time and 26°Cnight-time température and a relative atmosphcric humidity of 95 %, the fungusinfestation is assessed. Fewcr than 5 % of the rice plants are infested. The plants had ahccitny appearance.
Proccctive-local foliar application 12-tday old ricc plants are sprayed with a suspension prepared with formulated testsubsiances. One day later, inoculation is carried oui by placing a stem of barlcy straw. 010326 - ¢,8 ïnl'ecied with Rhizoctonia solani, between llic lice plains ol cacli pot. The plants wc.rcscorcd aftcr incubation for 6 days in a controlled-enviionment cabinet ai 29°C day-timeand 26°C night-time température and a relative atmosplicric humidity of 95 %. Untreated,but inoculated, control plants showed a fungal infestation of 100 %. Compounds of the 5 formula I cause in some cases complété inhibition of the infestation with disease. B. Insccticidal action
ExampSe B-16: Action against Aphis craccivora 10 Pea seedlings are populated with Aphis craccivora, subsequently sprayed with a spraymixture comprising 400 ppm of active ingrédient and then incubated at 20°. Thepercentage réduction in population (% action) is determined after 3 and 6 days bycomparing the number of dead aphids on the peated and the untrcated plants,la this test, compounds of Tables l-"7 hâve a good action. Compound No. 4.5, isonier 1, in 15 particular, has an action of over 80 %.
Example B-17: Action against Diabrotica balteata
Maize seedlings are sprayed with an aqucous émulsion spray mixture comprising 400 ppmof active ingrédient, then, after the spray coating has dried on, populated with 10 second 20 instar larwae of Diabrotica balteata and subsequently placed in a plastic container. Thepercentage réduction in population (% action) is determined after 6 days by comparing thenumber af dead larvae of the treated and untreated plants.
In Ehis tesx, compounds of Tables 1-7 hâve a good action. In particular, compounds No.1.5„ 1.24.2.24, 3.24, 4.5, isomer 1,4.14, isomer 1,4.14, isomer 1, 4.117, both isomers, 25 4.121,4.170,5.9, isomer 1 and 5.51, isomer 1, hâve an action of over 80 %.
Example B-18: Action against Heliothis virescens
Yotung soja beau plants are sprayed with an aqueous émulsion spray mixture comprising400 ppm of active ingrédient, then. after the spray coating has dried on, populated with 10 30ftrsc instarcatcrpillars of Heliothis virescens and subsequently placed in a plastic container. The percentage réduction in population and the feeding damage (% action) aredctannunedl after 6 days by comparing the number of dead catcrpillars and the feedingdamage of tthe treated and untrcated plants.
In this tesucompounds of Tables 1-7 show a good action. In particular, compounds No. 354.5. csotner 1.4.14. isomer I, 4.18. 4.117. both isomers. 4.121, 5.9, isomer I. and 5.52, îsotner 1. have an action of over S0 %. - 69 - 010326
Exantpic B -19: Action against Spodoptera littoralis
Young soya bcan plants arc spraycd with an aqueous cmulsion spray mixture comprising400 ppm of active ingrédient, then, after the spray coating bas dried on, popttlated with 10third instar caterpillars of Spodoptera littoralis and subscqucntly placed in a plasticcontainer. The percentagc réduction in population and the perccntage réduction in feedingdamage (% action) are determined after 3 days by comparing the number of dcadcaterpillars and the feeding damage of the treated and untreated plants. în this test, compounds of Tables 1-7 show a good action. In particular. compounds No.L.5, 1.24. 2.24, 3.24, 4.18, 4.5, isomer 1, 5.9, isomer 1, and 5.52. isomer l, hâve an actionof over S0 %. C. Acaricidal activity
ExampEe B-20: Action against Tetranychus urticae
Young bcan plants are populated with a mixed population of Tenanychus urticae, then, 1dsy latear. sprayed with an aqueous émulsion spray mixture comprising 400 ppm of activeingredieatt, incubatcd for 6 days at 25° and subsequently evaluatcd. The percentagcréduction in population (% action) is determined by comparing the number of dead cggs,larvae and adults on the treated and untreated plants.
In this lest, compounds of Tables 1-6 show a good action. In particular, compounds No. 1.5, 1.24t„ 2.24 und 3.24, 4.5, isomer 1,4.14, isomer 1, 4.117, both isomers, 5.9, isomer 1.and 5.52, isomer 1, hâve an action of over 80 %.
Example B-21: Action against Boophilus microplus
Achslt female ticks which hâve sucked themselves full are attached to a PVC board andcovered with a cottonwool bail, and 10 ml of aqueous test solution comprising 125 ppm ofactive ingrédient are poured over the ticks. The cottonwool bail is removed, and the ticksare incubaied for 4 weeks for oviposition. The action bccomcs apparent cither, in the caseof the fcnaalc, in the form of mortality or sterility or, in the case of the cggs, in the fonn ofan ovicidad action.

Claims (41)

  1. -70- 010326 What is claimcd ix: L A compound of the formula 1
    5 and the isomers, and isomer mixtures, thereof which are possible, in which either a) X îs an N atom and Y is ORn or N(Ri2)R13, or b) X is CH andYisORn, 10 and in which funhermorc: Rju is Ci-C4alkyl; Rl2 and Rl3, independcntly, are hydrogen or Ci-C4alkyl; A is an O atom or the group NR4; Rt is hydrogen, CrC4alkyl, halo-CI-C4alkyl, cyclopropyl, cyano or mcthylthio; 15 R2 is hydrogen. Ci*C6alkyl, Çj-Cgcycloalkyl, a group ^-(D) n
    , or thienyl; 20 25 n D radicals are idcntical or different and are halogcn, C1-C4alkyl, Cl-C4alkoxy,CpÇjhaloalkyl, Cl-C2haloalkoxy, C3-C$alkcnyloxy. C3-C6alkynyloxy,Ci-C^alkylenedioxy, cyano or nicro; n is Ο. 1.2.3 or 4; Z is -O-, -O-(CrC4alkyI)-. -(C,-C4alkyl)-O-, -S(O)m-, -(C,-C4alkyl)-S(O)m-,-S(OV(CrC4aîkyl)-.m is O, l or 2, B is Cj-C^alkyl, halo-C,-C6alkyl. CyC^cycloalkyl, or is C2-C6nlkenyl or C2-C8alkynyl-C1-C2alkyl. each of which is unsubstituted or substituted by 1 to 3 halogcn 010326 - 71 - moins, or is aryi or hcterocyclyt. eacti of thèse iwo, indepentlently. being tmsubsiitutetl or mono- to pentasubstituted by C(-Qalkyl, halo-C^C^alkyl, halogen, C|-C6alkoxy or
    R5, R6, R7, Rs and R9, independently, hydrogen, C[-Crtalkyl or halogen and 5 p is O, 1,2 or 3; R3 is hydrogcn, C[-C6alkyt, Cj-Cghaloalkyl having 1 ιο 5 halogen atoms,C1-C4alkoxy-C1-C2alkyl, C2-C4alkenyl-C;-C2alkyl, which is unsubstituted or substitutedby 1 to 3 halogen atoms, Cj-^alkynyl-Ci-C^-alkyl, C3-C6cycloalkyl which isunsubstituted or subsrituted by 1 to 4 halogen atoms, C3-C6-cycloalkyl-C1-C4alkyl which 10 is unsubstituted or substituted by 1 to 4 halogen atoms, cyano-C|-C4alkyl; C1-C4alkoxycarbonyl-C1-C2alkyl, Ç^CLjalkoxycarbamoyl-Cj-C^alkyl, phcnyl-C^C^tlkylwhich is unsubstituted or substituted by halogen, Cj-C3alkyl, C1-C4alkoxy, Ct'C4haloalkyI, cyano, nimo or C1-C4alkylenedioxy, it being possible for thc phcnyl groupto be monosubstituted to rrisubstituted by identical or different substitucnts; phcnyl which 15 is unsubstituted or mono- to disubstituted, indepcndendy, by Ct-C4alkyl, C]-C4alkoxy.halogen, C]-C2haloalkyl having 1 to 3 halogen atoms, nitro or cyano, or pyridyl which isunsubstituted or mono- to disubstituted, indcpendently, by CI-C4alkyl, C|-C4alkoxy,halogen, C1-C2haloalkyl having 1 to 3 halogen atoms, nitro or cyano; R4 is Cj-C4alkyl, phenyl, or 20 ?,3 and R4 togcther with the nicrogcn atom to which thcy are bondcd form a saturatcd orunsaturatcd 5- to 7-membered ring which is unsubstituted or substituted by C[-C4alkyl andwhich can hâve l to 3 additional hetero atoms selccted front amongst N, O and S.
  2. 2. A com.pound of the formula I according to daim 1, in which cithera; X is an N atom and 25 Y is OCH3 or NHCH3, orb\ X is CH and Y is OCH3. and in which funhcrmorc, A is an O atom or the group NR4; 30 R· is hycrogen. C(-C4alkyl, halo-Cj-C4alky 1, cyclopropyl, cyano or methylthio; 010326 - 72 · R2 is hydrogen. Cj-C6alkyl, C3-C6cycloalkyl, a group
    . a group '(D) 11
    2- B or thienyl; (D) 11 D radicals arc idcntical or different and are halogen, C,-C4alkyl, C[-C4alkoxy,CrC2haloalkyl, C^C^haloalkoxy, C3-C<;alkenyloxy, C3-C6alkynyloxy,Cl-C4alkylenedioxy, cyano or nicro; π is 0, 1, 2. 3 or 4; Z is -O-, -O-(CrC4alkyl)-, -(CrC4alkyl)-O-, -S(O)m-, -(C,-C4alkyl)-S(OV. -S(O)m-(CrC4aIkyl)-. m is 0, 1 or 2, B is Cj-C5alkyl, halo-Cj-Cgalkyl, CyC^cycloalkyl, oc is C2*Cgalkenyl or C2-C4alkynyl-Ci-C2alkyl, each of which is unsubstituted orsabstituied by 1 to 3 halogen atoms, or is aryl or heterocyclyl, or aryl or hctcrocycly!, eachof thèse» indcpendenüy, being monosubstituted to pentasubstituted by C|-C6alkyl,ha3o-C[-CÊalk;yl, halogen, C(-C6alkoxy or halo-Ci-C6alkoxy, or a grotip
    R5„ R6, R-j, Rs and R9, indcpendently, arc hydrogen, C1-C4alkyl or halogen andp is 0, 1,2 cr 3; R3 is hydrogen. Cj-C6alkyl, Cj-Cghaloalkyl having 1 to 5 halogen atoms, Cj-iC4aUGOxy-Cl-C2alkyl, C2-C4alkenyl-Cj-C2alkyl which is unsubstituted or substitutedby 2 to 3 'halogen atoms, C^-Cdalkynyl-CpC^alkyl, C3-C6cycloalkyl which isunsnbstimied or substituted by 1 to4 halogen atoms, C3-C6c.ycloalkyl-C1-C4alkyl which isunsubstiusted or substituted by 1 to 4 halogen atoms, cyano-C1-C4alkyl;C1~C4alkaxycarbonyl-C1-C2alkyl, phenyl-C1-C3alkyl which is unsubstituted or substitutedby tealogea, C,-C3alkyl, C[-C4alkoxy, CrC4haloalkyl, cyano, nitro. C|-C4alkylenedioxy.it being possible for the phenyl group to be monosubstituted to trisubstituted by idcnticalor (fiiffereait substituents; phenyl which is unsubstituted or mono- to disubstituted,indepcndemtly, by CrC4alkyl, CrC4alkoxy, halogen, CpCjhaloalkyl having l to 3halogen atoms, nitro or cyano, or pyridyl which is unsubstituted or mono- to disubstituted,independenuly. by C(-C4alkyl, C[-C,talkoxy, halogen, C)-C2haloalkyl having t to 3 01 0326 - 7? - liaiogen atoms, niiro or cyano; R4 i_- C;-C4alkyI or plienyl, or R3 ar.d Fd together with the nitrogen atom to which thcy arc bonded l'onn a samraicd orur.sazurated 5- to 7-membered ring which is unsubstitutcd or substituted by C|-C„alkyl andwhich can bave 1 to 3 addilional hetero atours selcctcd from amongst N, O and S.
  3. 3. A compound of the formula I according to daim 2, in which X is and Y is OCH3. A. A coæpound of the formula I according to claim 2, in whichX is CH. A ccmpoond of the formula I according to claim 2, in whichis N, Y is NHCHj and F., is H, Cri3, cyclopropyl or CN. C. A cocnpoimd of the formula I according to any onc of daims 2 to 5. in whichA is oxy gen, NCH3 or n-C6H3.
  4. 7. A corr.poucd of the formula I according to any onc of daims 2 to 6, in whichR is hycrogtr., methyl, cyclopropyl orcyano. S. .A compourtd of the formula I according to any onc of daims 2 to 7, in whichR? is C--C4aikyl or cyclopropyl. ?. A. ccmpound of the formula I according to any onc of daims 2 to ô, in which and (D) 2? is na.og’er.. C;-C,.alkyi, Ci-Cdalkoxy, Cj-Cîalkyl which is substituted by 1 to 5 halogcn2-.or-.s. C:-2Y.a'ioalkoxy, C3-Cgalkenyloxy, ^-Cgalkynyloxy, C|-Cdalkylcncdioxy,cyano, cr mire, cr thienyl, and
    0 1 0326
    - 7-1 - K). Λ compound of the formula 1 according ιο any one ol daims 2 to 7, in which2- B and (D) n 2 is -O-, -O-(C,-C4alkyl)-. -(C,-C4alkyl)-O-, -S(O)2-, -(C,-C4alkyl)-S(O)2-,-S(O)2-(C,-C„alkyl)-.; and wherein B. D and n are as defined in claim 2.
  5. 11. A compound of the formula I according to any onc of daims 2 to 7, in winch/-v/ Z’ B R2 >s a group _// and B is Cj-C-alkyl, halogen-Cj-C4alkyl, or is C2-C4alkcnyl or C2-C4alkynyl-Ci-C2alkyl, cachof which is unsubstituted or substituted by 1 to 3 halogcn atoms, or is aryl or aryl which ismonosubstituted or disubstituted, independently, by CpC^alkyl, halo-CrC2alkyl, halogcn. 10 C]-C2alkoxy or halo-Ci-C2alkoxy, or is a group — (CH)
    R5, R^, R7, Rs and Rç, indepcndcntly, arc hydrogen, CrC2alkyl or halogcn, andp is 0. 1,2 or 3 ; and wherein Z is as defined in claim 2.
  6. 12. A compound of the formula I according to any onc of daims 2 to 7, in which 15 R2 is a phcnyl group which is subsdtutcd in the 4-position by -Z-B; and wherein 2 and B are as defined in claim 2.
  7. 13. A compound of the formula I according to any one of daims 2 to 12, in whichR-3 is hydrogen, Cj-Cgalkyl or C]-C4haloalkyl having 1 to 3 halogen atoms, 20 Cj-C^alkoxy-C^Çjalkyl, Ct-C4alkoxycarbonyl-CrC2aLkyl, propcnyl which iscnsubsdtuicd or substituted by 1 to 3 halogcn atoms, propargyl, C3-C6cycloalkyl,cyclopropylmcthyl which is unsubstituted or substituted by 1 to 2 halogcn atoms,cyano-C;-C2alkyl, phcnyl-CrC2alkyl which is unsubstituted or substituted by halogcn,methyl. methoxy or hnlomcthyl having 1 to 3 halogcn atoms, it being possible for the 25 phcnyl group to bc monosubstituted to disubstituted by idcntical or different substituents;phcnyl which is unsubstituted or monosubstituted to disubstituted, indcpcndently, byhalogène, methvl, methoxy, halomethyl having 1 to 3 halogen atoms, cyano or nitro; orpyridyl which is unsubstituted or monosubstituted to disubstituted, indcpendcntly. byhalogen» mcthyl, methoxy, halomethyl having 1 to 3 halogen atoms, cyano or nitro; or 010326 - 75 - R3 and R4 togetlier with the nitrogen aiom to which they arc. bonded fonn a saltiraied orunsaturaied 5- to 7-membered ring which is unsubstituted or substituted by C,-C4alkyl andwhich can hâve l to 3 additional hctcro moins selected from amongst N, O and S.
  8. 14. A compound of the formula I according to any onc of daims 2 to 13, in whichR4 is methyl or phenyl.
  9. 15. A compound of the formula I according to any one of daims 1 to 4, in whichX is CH; Y is OCH3; Rt is CH3; A is oxygen; R2 is 4-methylphenyl or 4-allyioxyphenyl or 4-(3-trifluororncthyI-bcnzyloxy)phenyl or4-(2,2-dichlorocyclopropylmethoxÿ)phenyl andR3 is CH3.
  10. 16. A compound of the formula I according to daim 1, in which cithcr a) X is an N atom and Y is OCH3 or NHCH3, or b) X is CH and Y is OCH3, and in which furthermore A is an O atom or the group NR4; R! is hydrogen; Cx-C^alkyl; cyclopropyl; cyano or mcthylthio; R2 is hydrogen; C1-C6alkyl; C3-C6cycloalkyl; phenyl which is unsubstituted ormonosubstituted to disubstituted, independently, by halogen, C,-C4alkyl, C1-C4alkoxy.CfC^haloalkyl, C]-C2haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Cj-Czjalkylenedioxy, cyano or nitro; thienyl; R3 is hydrogen; CpCgalkyl; C(-C6haioalkyl having 1 to 5 halogen atoms; C1-C4aîkoxy-Cl-C2alkyl; C2-C4alkenyl-C[-C2alkyl which is unsubstituted or substitutedby 1 to 3 halogen atoms; C2-C4alkynyl-C1-C2-alkyl; C3-Câcycloalkyl which isunsubstituted or substituted by 1 to4 halogen atoms; C3-C6cycloalkyl-C(-C4alkyl which isunsubstituted or substituted by 1 to 4 halogen atoms; cyanO’Cj-C4alkyl;C]-C4alkoxycarbonyl-C|-C2alkyl; phenyl-Ct-C3alkyl which is unsubstituted or substitutedby halogen, CI-C3alkyl, C|-C4alkoxy, C|-C4hnloalkyl, cyano. nitro, C,-C4aîkylcncdioxy,it being possible for the phenyl group to bc monosubstituted to trisubstituted by idcntical 010326 - 76 · or different substitnents; phenyl which is unsubstituted or nionosubstituicd to disubsiituted. independently, by C^C^alkyl, C|-C4alkoxy. halogcn, C|-C2haloalkyl having1 to 3 halogcn atoms, nitro orcyano; pyridyl which is unsubstituted or monosubstituted todisubsiituted, independently, by C|-C4alkyl, C|-C4alkoxy, halogen, C|-C2haloalkyl having1 to 3 halogen atoms, nitro orcyano; R4 is Cj-C4alkyl; phenyl; or R3 and R4 together with the nitrogen atom to which they are bonded form a saturated orunsaturated 5- to 7-membered ring which is unsubstituted or substituted by CrC4alkyl andwhich can hâve l to 3 additional hetero atoms selectcd from amongst N, O and S.
  11. 17. A compound of the formula I according to claim 16, in which X is CH or N Y is OCH3 A is O or N-R4 Rt is methyl, cyclopropyl or methylthio; R2 is methyl; cyclopropyl; phenyl which is unsubstituted or monosubstituted todisubsiituted, independently, by halogcn, C]-C4alkyl, C|-C4alkoxy, C^-C^alkyi which issubstituted by 1 to 5 halogcn atoms, Ct-C2haloalkoxy, C3-C6-alkenvloxy, Cj-Cgalkynyloxy, C1-C4alkylcnedioxy, cyano, or nitro; or thicnyl; and in whichR3 is as described in formula I andR4 is methyl or phenyl, or R3 and R4 together with the nitrogen atom to which they arc bonded arc cithcr pyrrolidinc,piperidine, morpholinc, thiomorpholine, hexamethylenciminc, imidazolc. pyrazolc,pyrrole, 1.2,4-triazole or 1,2,3-triazolc.
  12. 18. A compound of the formula I according to claim 16. in which X is N. Y is NHCH3, A is O or N-R4, Rj is methyl, cyclopropyl or methylthio; R2 is methyl; cyclopropyl; phenyl which is unsubstituted or monosubstituted todisubstituted, independently, by halogen, C|-C4alkyl, Ct-C4alkoxy. CrC2alkyl which issubstituted by 1 to 5 halogcn atoms. Cj-C2haloalkoxy, C3-C<;alkenyloxy. C3-C$alkynytoxy, C|-C4alkylenedioxy, cyano or nitro; or thicnyl; and in whichR3 ts as described in formula I andR4 is methyl or phenyl, or 010326 - 77 - R3 and R,, logether with the nitrogcn «nom to which they arc bonded arc eithcr pynolidine,pipcridine, morpholinc, thiomorpholinc, hcxamcihyleneiminc, ituidazolc, pyrazolc,pyrrolc, 1,2,4-triazolc or 1,2,3-triazolc.
  13. 19. A compound of the formula I according to daim 16, in which: A is an O atom, R( is methyl, R2 is methyl; phenyl which is unsubstitutcd or monosubstitutcd to disubstituicd,independently, by halogcn, Cj-C^alkyl, Ct-C4alkoxy, Cj-C2alkyl which is substituted by 1to5 halogen atoms, Ci-C2haloalkoxy, CyCgalkenyloxy, C3-C6alkynyloxy, CyC^alkylenedioxy, cyano or nitro; or thienyl; and R3 is CyC^alkyl.
  14. 20. A compound of the formula faccording to claim 16, in which; Rj is methyl, R2 is methyl and R3 is as described in claim 1 and R4 is methyl or phenyl. or R3 artd R4 together with the nitrogcn atom to which they arc bonded form a saturated orunsaturated 5- to 7-mcmbercd ring which is unsubstitutcd or substituted by C,-C4alkyi andwhich can hâve 1 to 3 additional hetero atoms sclected from amongst N, O and S.
  15. 21. A compound of the formula I according to daim 16, in which: R3 is nydrogen; Ci-C4alkyl; C1-Cdhaloalky 1 having 1 to 3 halogen atoms; CyC^alkoxy-Ci-C^alkyl; propenyl which is unsubstitutcd or substituted by 1 to 3 halogenatoms; propargyl; C3-C6cycloalkyl; C3-C6cycloalkylmcthyl which is unsubstitutcd orsubstituted by 1 to 2 halogen atoms; cyano-C|-C2-alkyl; CyC^aLroxycarbonyl-CyC^alkyl; phenyl-C|-C2alkyI which is unsubstitutcd or substitutedby halogen. methyl, methoxy. halomethyl having 1 to 3 halogcn atoms. cyano. nitro orC'-Coalkylenedioxy, it being possible for the phenyl group to bc monosubstituted todisubsticuted by identical or different substituents; phenyl which is unsubstitutcd ormonosubstituted to disubstituted, indcpendcntly, by halogcn, methyl, methoxy, halomethylhaving L to 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormonosubstituted to disubstituted, indepcndcntly, by halogcn, methyl, methoxy, halomethylhaving 1 to 3 halogcn atoms, cyano Or nitro; R4 is methyl or phenyl; or 010326 •78 R3 Jiiid R4 togethcr with (lie nitrogen atom to whieh thcy arc bontletl l'onu a sauu aicd orunsaturated 5- to 7-membcred ring winch is unsubstituted or substituted by Cj-C,(aIkyi andwhich can bave 1 to 3 additional lictcro atoms selected from amongst N, O and S.
  16. 22. A compoundof the formula I according to claim 21. in which R3 and R4 together with thc nitrogen atom to which thcy arc bondcd arc triazoly 1.morpholinyl, 2,6-dimethylmorpholinyl, azepinyl, piperidy 1 or pyrrolidiny 1.
  17. 23. A compound of thc formula I according to claim 16, in which: A is an O atom, Rj is methyl, R2 is methyl; phcnyl which is unsubstitutcd or monosubstituted to disubstituted,indcpcndently, by halogen, CrC4alkyl, CrC4alkoxy, C,-C2alkyI which is substituted by 1to 5 halogen atoms. CrC2haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, Cj-C4alkylenedioxy, cyano or nitro; or thienyi; and R3 is hydrogen; C^Qalkyl; Ci-C4haloalkyl having 1 to 3 halogen atoms; Cj-Czalkoxy-Ci-Çjalkyl; propenyl which is unsubstituted or substituted by 1 to 3 halogenatoms; propargyl; C3-C6cycloalkyl; C3-C6cycloalkylmethyl which is unsubstituted orsubstituted by 1 to 2 halogen atoms; cyano-Cj-C-^-alkyl; Ci-C2alkoxycarbonyl-Ct-C2aJkyl; phenyl-C^C^alkyl which is unsubstituted or substitutedby halogen, methyl, methoxy, halomethyl having 1 to 3 halogen atoms, cyano, nitro orC^-C^alkyienedioxy, it being possible for thc phenyl gïoup to be monosubstituted todisubstituted by identical or different substituents; phenyl which is unsubstituted ormonosubstituted to disubstituted, indcpcndently, by halogen, methyl, methoxy, halomethylhaving 1 to 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormonosubstituted to disubstituted, independently, by halogen, methyl, methoxy, halomethylhaving 1 to 3 halogen atoms, cyano or nitro.
  18. 24. A compound of the formula 1 according to claim 23, in which A is an O atom, R! is methyl, R2 is methyl; phenyl which is unsubstituted or monosubstituted to disubstituted, indcpcndently, by halogen, methyl, methoxy, trifluoromethyl or trifluoromethoxy; and R3 is methyl.
  19. 25. A compound of thc formula I according to claitn 16, in which: 010326 - 79 - A is NCt-i-j, R, is methyl, R2 is methyl; phenyl which is unsubstituted or monosubstituted to disubstituted,independently, by halogcn, methyl, mcihoxy, trifluoromcihyI or iriFluoromcthoxy; R3 is methyl; phenyl which is unsubstituted or monosubstituted to disubstituted.independently, by halogen, methyl, mcihoxy. halomethyl having l to 3 halogcn atoms,cyano or nitro; or pyridyl which is unsubstituted or monosubstituted to disubstituted,independently, by halogen, methyl, methoxy, halomethyl having 1 to 3 halogen atoms,cyano or nitro. 2ô. A compound of the formula I according to claim 1, in which: X is an N atom; Y isOR„; R-i is C^-C^alkyl; and in which A. R;, R2 and R3 are as defïned in claim 1.
  20. 27. A compound of the formula I according to claim 26, in which: A is an O atom; Rt and R2 arc methyl; R3 is hydrogen; C[-C4alkyl; C]-C4haloalkyl having 1 to 3 halogcn atoms; Ct-C22lkoxy-Cj-C2alkyl; propenyl which is unsubstituted or substituted by 1 to 3 halogcnatoms; propargyl; Qj-Cgcycloalkyl; CyC^cycloalkylmcthyl which is unsubstituted orsubstituted by I to 2 halogen atoms; cyano-Cj-Cj-alkyl; Cj-C2alkcxycarbonyl-Ci-C2alkyl; phenyl-Ct-C2alkyl which is unsubstituted or substitutedby halogcn, methyl, methoxy, halomethyl having 1 to 3 halogen atoms, cyano, nitro orCi-C2alkylenedioxy, it being possible for the phenyl group to bc monosubstituted todisuostituccd by identical or different substituents; phenyl which is unsubstituted ormon osubsdtutcd to disubstituted, independently, by halogcn, mcthyl, methoxy, halomethylhaving to 3 halogen atoms, cyano or nitro; or pyridyl which is unsubstituted ormonosubsoiiutcd to disubstituted, independently, by halogcn, mcthyl, methoxy, halomethylhaving ; te 3 halogen atoms, cyano or nitro. 2S. A compound of the formula I according to claim 27, in which R3 is hydrogen; C1-Caalkyl or C|-C4haloalkyl having 1 to 3 halogen atoms.
  21. 29. A ccmpound of the formula 1 according to claim 1, in which: 010326 , · su - ij ? - X is an N atom; Y isN(RI2)Rl3; R12 and Rl3, independently, arc hydrogen atom or C|-C..,alkyl; and in whichA, Rp R2 and R3 arc as dcfincd in daim 1. 5
  22. 30. A compound of the formula I according to daim 29, in which; Y is NH2. N(CH3)2 or NHC2H5; A is an O atom; Rt and R2 are methyl; 10 R3 is hydrogen; Ci-C4alkyl; C|-C4haloalkyl having 1 to 3 halogen atoms; Ci-C2aïkoxy-C1-C2alkyl; propenyl which is unsubstitutcd or substituied by 1 to 3 halogenatoms; propargyi; Çj-Qcycloalkyl; C3-C6cycloalkylmethyl which is unsubstitutcd orsubstituied by 1 to 2 halogen atoms; cyano-CpC^alkyl; CrC2alkoxycarbonyl-Ci-C2alkyl;phcnyl-Cj-C2alkyl which is unsub’itituted or substituied by halogen, methyl, methoxy, 15 halomethyl having 1 to 3 halogen atoms, cyano, nirro or CcC^alkylenedioxy. ic beingpossible· for the phenyl group to bc monosubstituted to disubstituted by identtcal ordifferent substituents; phenyl which is unsubsrituted or monosubstituted to disubstituted,independently, by halogen, methyl, methoxy, halomethyl having 1 to 3 halogen atoms,cyano or nirro; or pyridyl which is unsubstitutcd or monosubstituted to disubstituted, 20 independently. by halogen, methyl, methoxy, halomethyl having l to 3 halogen atoms. cyano or nirro.
  23. 31. A compound of the formula I according to daim 30, in which R3 is hydrogen; C|-C4alkyl or Cj-C4haloalkyl having 1 to 3 halogen atoms. 25
  24. 32. A compound of the formula I according to claims 1-31, in which the X=C double bondis in the E form.
  25. 33. A process for the préparation of a compound of the formula I according to claini 1. 3Q which comprises. A) to prépare a compound of the formula I in which Y is N(R)2)R13: rcacting a compoundof the formula I in which Y is ORt, with HN(Rl2)Rl3 in a solvent at 0°C to 40°; 35 B) io préparé a compound of the formula 1 in which X, Y, A and R(-R3 are as dcfincd for fonnala l (and wherc R3 is not hydrogen): 010326 II reacting an oxime of the general formula 11 R, HQN χΑ^
    ï R, N R-, in which A and RrR3 are as defined above, with a benzyl dérivative of the generalformula
    ir. whiefa X ar.d Y are as defined above and U is a lcaving group, in an inert organicdiluent, in thc présence of a base and in thc présence or absence of a phase transfercctaiyst 2:0°C 10 50°; 10 C;- to prcparc a compound of thc formula I in which A is oxygen and X, Y and RrR3 arcas defined for formula I: rcacting an oxime of the general formula IV
    IV in v*'h:ch X, Y, Rt and R2 are as defined above, with a compound of thc general formula V u-r3 V, 010326 in which R.-) is as defined undcr formula l and U as dcfined under fonuula (Il (and whercR-j is ncither hydrogcn nor phenyl nor pyridyl); D) to prépare a compound of the formula IV in which X, Y, R, and R2 are as dcfined forformula I: rcacting a ketone of the general formula VI
    in which X, Y, Rt and R2 arc as dcfined abovc, with hydroxylaminc or a sait thercof in asolvent ai 0°C to 50°C: E) to préparé a compound of the formula I in which A, X, Y and R,-R3 are as defincd forformula 2 (and wherc R3 is not hydrogen): reatcting an enol or oxime of the general formula VII
    in which A. X, Y and Rt-R3 are ns dcfined abovc, with a mcihylating agent, for example mcchyl iodHdc, dimethyl sulfate or diazomethanc in the présence of a base in a suitablc solvent.
  26. 34. A process for the préparation of a compound of the fonuula VU 010326 - Sa ·
    in which A. X, Y and RrR3 are as defincd for formula I. which comprises, A) co préparé a compound of the formula VII in which X is CH: rcacting a phenylacelic5 acid dérivative of the formula Vin
    in which A, Y and Rt-R3 are as defined abovc with a formate in the présence of a base; B) co préparé a compound of lhe formula VII in which X is N: O reaccing a phenylacelic acid dérivative of the formula VUI in which A. Y and RrR3 are as defined above, with nitrous acid or a nitrite in the présence of a base; C) co préparé a compound of the formula VII in which X is CH; rcacting a keto ester ofthe formula IX
    in which A, Y and R( - R3 are defincd as abovc withmcthoxymcthylenctriphcnylphosphoranc; 15 010326 D) to préparé a compound of the formula VII in which X is N: rcaciing a kcto ester of theformula IX in which A, Y and Rj-Rj are as defincd above, with O-inethylliydiOxylamineor a sali thereof. 5 35. A composition for controlling pests, comprising, as active ingrédient, a compoimdaccording to claim 1 together with a suitable carrier.
  27. 36. A composition according to claim 35 comprising, as active ingrédient, a compoimdaccording to any one of daims 2-15. 10
  28. 37. A composition according to claim 35 comprising, as active ingrédient, a compoundaccording to any one of daims 16-25. 3S. A composition according to claim 35 comprising, as active ingrédient, a compound15 according to any one of daims 26-32.
  29. 39. A composition according to any one of daims 35-3S, the pests being phytopathogenicmicroorganisms. 20 40. A composition according to claim 39, the microorganisms being fungi.
  30. 41. A composition according to any one of daims 35-3S, the pests being insects orAccrina.
  31. 42. The use of a compound of the formula I according to daim 1 for conrrolling pests.
  32. 43. A mernod of controlling and preventing pests, which comprises applying a compoundaccording lo daim 1 to the pests or their environment. 30 44. A process according to claim 43. whercin a compound according to any one of daims 2-15 îs applicd.
  33. 45. A process according to claim 43. whercin a compound according to any one of daims16-25 is aptpiied. 010326 - 85 -
  34. 46. Λ process according ιο daim 43. whcrein a compound according to any one of daims26-32 is applicd.
  35. 47. A process according lo any onc of daims 43-46. the pcsts bcing phytopaihogcnic5 microorganisms.
  36. 48. A process according to daim 47. lhe microorganisms bcing fungi.
  37. 49. A process according to any one of daims 43-46, the pcsts bcing insccts or Acarina. 10
  38. 50. A process according to any one of daims 43-46, whercin secd is treated.
  39. 51. Seed which has been treated according to daim 50. 15 52. A compound of the formula VII
    in which A. X. Y and are as defincd for formula I in daim l.
  40. 53. A compound of the formula VIH
    in which A, Y and RrR3 arc as defincd for formula I in daim 1.
  41. 54. A compound of lhe formula EX 010326 - S6
    in whtrh A, Y and RrR3 arc as defincd for formula I in claim 1.
OA60857A 1994-01-05 1996-07-05 Pesticides OA10326A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1294 1994-01-05
CH211794 1994-07-01

Publications (1)

Publication Number Publication Date
OA10326A true OA10326A (en) 1997-10-07

Family

ID=25683255

Family Applications (1)

Application Number Title Priority Date Filing Date
OA60857A OA10326A (en) 1994-01-05 1996-07-05 Pesticides

Country Status (16)

Country Link
JP (2) JP3058692B2 (en)
KR (1) KR100347836B1 (en)
AT (1) ATE204853T1 (en)
BG (1) BG62650B1 (en)
DE (1) DE69428127T3 (en)
DK (1) DK0738260T3 (en)
EE (1) EE03284B1 (en)
EG (1) EG20734A (en)
ES (1) ES2162633T5 (en)
NZ (1) NZ278385A (en)
OA (1) OA10326A (en)
PL (1) PL177309B1 (en)
PT (1) PT738260E (en)
RO (1) RO117374B1 (en)
RU (1) RU2142938C1 (en)
UY (1) UY23885A1 (en)

Also Published As

Publication number Publication date
JPH09511484A (en) 1997-11-18
DE69428127T2 (en) 2002-01-31
DE69428127D1 (en) 2001-10-04
KR100347836B1 (en) 2003-03-10
BG100760A (en) 1997-03-31
RO117374B1 (en) 2002-02-28
EG20734A (en) 1999-12-29
JP2000119236A (en) 2000-04-25
BG62650B1 (en) 2000-04-28
DE69428127T3 (en) 2007-06-14
UY23885A1 (en) 1995-06-30
JP3058692B2 (en) 2000-07-04
ATE204853T1 (en) 2001-09-15
JP4015788B2 (en) 2007-11-28
PT738260E (en) 2002-02-28
DK0738260T3 (en) 2001-12-10
EE03284B1 (en) 2000-08-15
RU2142938C1 (en) 1999-12-20
ES2162633T3 (en) 2002-01-01
NZ278385A (en) 1998-03-25
PL177309B1 (en) 1999-10-29
ES2162633T5 (en) 2007-07-01

Similar Documents

Publication Publication Date Title
CA2179418C (en) Pesticides
TWI376372B (en) 4-cyclopropyl-1,2,3-thiadiazole derivatives, agro-horticultural phytopesticides and the use methods thereof
DE69623806T2 (en) PESTICIDES
JPH05213868A (en) Cyanophenylpyrrole
HRP931151A2 (en) Indazole derivatives
JPH07224015A (en) Vinylcarboxylic acid derivative
IE902990A1 (en) Butyric acid derivatives
CA2019653A1 (en) Thioxotetrazolines
OA10326A (en) Pesticides
JPH04117380A (en) Composition for controlling harmful life
WO1997007103A2 (en) Pesticidal indazole derivatives
JPH06184084A (en) Carbamic acid derivative
DE69325083T2 (en) Imidazole derivatives and their use as agrochemicals
US5663379A (en) Substituted phenyl ethers
JP2001515888A (en) Heterocyclic compounds as pesticides
WO2023040736A1 (en) Substituted sulfite compound, and preparation method therefor and use thereof
EP0757671A1 (en) Perhaloalkoxybenzenophenone hydrazones and their use as pesticides