EP0763020A1 - Substituierte pyrrolodone, thiazolidone oder oxazolidone als herbizide - Google Patents

Substituierte pyrrolodone, thiazolidone oder oxazolidone als herbizide

Info

Publication number
EP0763020A1
EP0763020A1 EP95920158A EP95920158A EP0763020A1 EP 0763020 A1 EP0763020 A1 EP 0763020A1 EP 95920158 A EP95920158 A EP 95920158A EP 95920158 A EP95920158 A EP 95920158A EP 0763020 A1 EP0763020 A1 EP 0763020A1
Authority
EP
European Patent Office
Prior art keywords
compound
general formula
alkyl
phenyl
nmr
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP95920158A
Other languages
English (en)
French (fr)
Inventor
John Michael Cox
John Martin Clough
Nigel John Barnes
David Philip John Pearson
Ian Richard Matthews
Shaheen Khatoon Vohra
Stephen Christopher Smith
Glynn Mitchell
Richard Anthony Barber
Russell Martin Ellis
David William Langton
Kevin James Gillen
Glenn Hatter
Anthony Marian Kozakiewicz
David Philip Bacon
Peter Bellini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Ltd
Original Assignee
Zeneca Ltd
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
Priority claimed from GB9410998A external-priority patent/GB9410998D0/en
Priority claimed from GB9411004A external-priority patent/GB9411004D0/en
Priority claimed from GBGB9501158.1A external-priority patent/GB9501158D0/en
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Publication of EP0763020A1 publication Critical patent/EP0763020A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N43/80—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic 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
    • 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
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/32—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/273—2-Pyrrolidones 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 other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D263/18—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/16—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/18—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to chemical compounds useful as herbicides, to processes for preparing them, and to herbicidal compositions and processes utilising them.
  • Z is 0, S or NR 4 ; n is 0 or 1;
  • Y is 0, S, NR 6 or CR 4 R 5 ;
  • each R and R is, independently, hydrogen or C,-C 4 alkyl
  • R 6 is H, OH, CHO, NR 16 R 17 or CJ-CJQ hydrocarbyl, 0-f.C j -C j g hydrocarbyl), either of which may be substituted with one or more substituents chosen from OR 16 , COR 16 , C00R 16 , 0C0R 16 , CN, halogen, S(0) R 16 , NR 16 R 17 , N0 2 ,
  • R , R and R are each, independently, hydrogen, C,-C ⁇ hydrocarbyl or
  • R represents hydrogen or C,-C» alkyl
  • W is 0 or S
  • R is hydrogen or C,-C,Q hydrocarbyl or heterocyclyl having 3 to 8 ring atoms, either of which may optionally be substituted with one or more substituents chosen from halogen (i.e. chlorine, bromine, fluorine or iodine), hydroxy, S0 2 NR a R (where R a and R are independently H or Cj_ 6 alkyl), SiR - (where each R c is independently C.-C, alkyl or phenyl), cyano, nitro, amino, mono- and dialkylamino in which the alkyl groups have from 1 to 6 or more carbon atoms, acyla ino, C, fi alkoxy, C, fi haloalkoxy,
  • R and R are each independently hydrogen or C,-C» alkyl
  • A is an aromatic or heteroaromatic ring system optionally substituted with one or more substituents selected from: halogen or C,-C,Q hydrocarbyl, -0(C,-C*-.Q hydrocarbyl), -S(C 1 -C 1Q hydrocarbyl), -S0(C 1 -C 10 hydrocarbyl) or hydrocarbyl), cyano, nitro, SCN, SiR c -, (where each R c is independ alkyl or phenyl), COR 7 , CR 7 N0R 8 ,NH0H, 0NR 7 R 8 , SF-*, COOR 7 , S0 9 NR 7 R 8 , OR 9 or
  • any ring nitrogen atom may be quatemised or oxidised; alternatively, two or more substituents of the group A may combine to form a fused 5- or 6-membered saturated or partially saturated carbocyclic or heterocyclic ring in which any carbon or quatemised nitrogen atom may be substituted with any of the groups mentioned above for A or in which a ring carbon atom may be part of a carbonyl group or a nitrogen atom may be oxidised;
  • R and R are each independently hydrogen or C,-C, n hydrocarbyl; g i iu
  • R is hydrogen, CJ-CIQ hydrocarbyl, S0 2 (C,-C, Q hydrocarbyl), CHO, C0(C 1 -C 10 hydrocarbyl), COO ⁇ -C ⁇ hydrocarbyl) or C0NR 7 R 8 ;
  • R and R are each independently hydrogen, C,-C, 0 hydrocarbyl, 0(C 1 -C 1Q hydrocarbyl), S0 2 (C 1 -C 1Q hydrocarbyl), CHO, C0(C 1 -C 1Q hydrocarbyl), COO ⁇ -C ⁇ hydrocarbyl) or C0NR 7 R 8 ; any of the hydrocarbyl groups within the group A may optionally be substituted with halogen (i.e.
  • R a and R b are independently H or C j _ 6 alkyl), cyano, nitro, amino, mono- and dialkylamino in which the alkyl groups have from 1 to 6 or more carbon atoms, acylamino, C, ⁇ alkoxy, C, g haloalkoxy, C j _ 6 alkylthio, C j _ 6 alkylsulphinyl , C, ⁇ alkylsulphonyl, carboxy, carboxyamide, in which the groups attached to the N atom may be hydrogen or lower hydrocarbyl optionally substituted with halogen; alkoxy carbonyl wherein the alkoxy group may have from 1 to 6 or more carbon atoms, or aryl such as phenyl; provided that: i) when A is a phenyl group or a substituted phenyl group in which no two adjacent substitu
  • GB 1345159 discloses compounds which are somewhat similar to those of the present invention. It is suggested in this document that the compounds may be active as herbicides but there are few examples and no data which eluidates the degree of activity of the compounds.
  • W0-A-9413652 published after the priority date of the present application discloses similar compounds which also have herbicidal activity. However, there are certain differences in the structure of these prior art compounds and, in particular, the equivalent atom to Z of the present invention is always nitrogen in the compounds of this prior art document.
  • Ci-Cin hydrocarbyl in the foregoing definitions, whether the expression is used on its own or as part of a larger radical such as, for example, C,-C, 0 hydrocarbyloxy, is intended to include hydrocarbyl radicals of up to ten carbon atoms. Subclasses of such hydrocarbyl radicals include- radicals with up to four or up to six carbon atoms.
  • hydrocarbyl is intended to include within its scope aliphatic, alicyclic, and aromatic hydrocarbyl groups and combinations thereof. It thus includes, for example, alkyl, alkenyl, and alkynyl radicals, cvclopropyl . cyclopropylmethyl . cvclobutvl . cvclopentvl . and cvclohexvl radicals, the adamantyl radical and the phenyl radical.
  • heterocyclyl in the foregoing definitions is intended to include both aromatic and non-aromatic radicals.
  • heteroaromatic radicals inclquiude pyridyl, pyrimidyl, triazinyl, thienyl, furyl , oxazolyl , isoxazolyl, and thiazolyl and examples of non-aromatic radicals include partially and fully saturated variants of the above.
  • C,-C,- alkyl refers to fully saturated straight or branched hydrocarbon chains having from one to six carbon atoms. Examples include methyl, ethyl, n-propyl , iso-propyl, n-butyl , t.-butyl and n-hexyl . Expressions such as “alkoxy”, “cycloalkyl” “alkylthio” “alkylsulphonyl”, “alkylsulphinyl” and “haloalkyl” should be construed accordingly.
  • 2 _Cg alkenyl refers to a straight or branched hydrocarbon chain having from two to six carbon atoms and at least one carbon-carbon double bond. Examples include ethenyl , 2-propenyl and 2-hexenyl . Expressions such as cycloalkenyl, alkenyloxy and haloalkenyl should be construed accordingly.
  • C 2 _Cg alkynyl refers to a straight or branched hydrocarbon chain having from two to six carbon atoms and at least one carbon-carbon triple bond. Examples include ethynyl , 2-propynyl and 2-hexynyl. Expressions such as cycloalkynyl , alkynyloxy and haloalkynyl should be construed accordingly.
  • aryl and aromatic ring system refer to ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl , anthracenyl or phenanthrenyl . Nitrogen atoms in the ring may be quatemised or oxidised.
  • heteroaryl refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to four and bicyclic systems up to five heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur.
  • groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl , tetrazolyl, oxazolyl , isoxazolyl, thiazolyl, isothiazolyl , 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl , 1,3,4-oxadiazolyl , 1,2,5-oxadiazolyl , 1,2,3-thiadiazolyl , 1,2,4-thiadiazolyl , 1,3,4-thiadiazolyl , 1,2,5-thiadiazolyl , 1,2,3,4-oxatriazolyl , 1,2,3,4-oxatriazolyl , 1,2,3,5-oxatriazolyl ,
  • fused saturated or partially saturated carbocyclic or heterocyclic ring refers to a ring system in which a 5- or 6- me bered carbocyclic or heterocyclic ring which is not of aromatic character is fused to an aromatic or heteroaromatic ring system.
  • examples of such systems include benzimidazolinyl , benzoxazolinyl and benzodioxolyl .
  • substituents of the group A include methyl, ethyl, ⁇ -propyl , iso-propyl, trifluoromethyl , difluoromethyl , pentafluoroethyl , trichloromethyl , ethoxyvinyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, n.-propoxy, iso-propoxy f difluoromethoxy, trifluoromethoxy, tetrafluoroethoxy, cyano, nitro, amino, mono- or dialkylamino in which each alkyl group may have from 1 to 6 or more carbon atoms, hydroxylamino, acyl (e.g.
  • acetyl or trifluoroacetyl ethylthio, methylsulphinyl, methylsulphonyl , trifluoro ethylthio, SCN, SF,-, trifluoromethylsulphinyl, trifluoromethylsulphony1 , sulphonamido, carboxy, alkoxycarbonyl in which the alkoxy group may have from 1 to 6 or more carbon atoms, carboxyamide in which the groups attached to the N atom may be hydrogen or optionally substituted lower hydrocarbyl; or acylamino (e.g. acetamido).
  • the substituents may be the same or different.
  • Preferred substituents of the group A include C,-C 4 alkyl, C,-C 4 haloalkyl, 0(C C 4 alkyl), 0(C C 4 haloalkyl), S(C C 4 alkyl), S(C 1 -C 4 haloalkyl) and halo.
  • substituents are trifluoromethyl , trichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, fluoromethoxy, chloromethoxy, trichloroethoxy, trifluoroethoxy, dichloroethoxy, difluoroethoxy, fluoroethoxy, trifluoromethylthio, ethoxy, methoxy, fluoro, chloro, bromo, iodo and methyl .
  • Preferred compounds include those in which R is hydrogen or C,-Cg alkyl, C 2 _Cg alkenyl, C 2 _Cg alkynyl, C0(C 1 -C 8 alkyl), C0(C 2 _Cg alkenyl), C0(C 2 _Cg alkynyl), C,-Cn cycloalkyl, benzyl, phenyl or a 5 or 6 me bered heterocyclic ring.
  • R groups may be substituted with one or more substituents chosen from halo, SiR c 3 , CN, COOH, C00(C,-C 4 alkyl), COH N(C,-C 4 alkyl) 2 or C0(C,-C 4 alkyl) and cycloalkyl, benzyl, phenyl or heterocyclic R groups may, additionally, be substituted with C,-Cg alkyl, C 2 _Cg alkenyl or C 2 _C ⁇ alkynyl.
  • R include optionally substituted Cj-Cg alkyl, for example methyl, -C(CH 3 ) 3 , -CH(CH 3 ) 2 , -CH 2 C(CH 3 ) 3 , -CH 2 CH 3 , C(CH 3 ) 2 CN, -CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 C(CH 3 ) 3 , -CH 2 CH 2 CH 3 , CH 2 C(CH 3 ) 2 or C(CH 3 ) 2 CH 2 C1;
  • Cj-Cg alkyl-OH for example C(CH 3 ) 2 CH 2 0H; optionally substituted C 3 -C 8 cycloalkyl, for example cyclobutyl , 1-
  • X is S, 0 or CH 2
  • Y is S, 0, CH 2 , CH(CH 3 ) or NR 6 ;
  • Z is NH or 0; or n is 0 and Z is not present;
  • R and R are both hydrogen
  • R is hydrogen, -CHO, C,-Cg alkyl, C 2 _C g alkenyl, 2 _C g alkynyl, C 3 -C ⁇ cycloalkyl, aryl, for example benzyl which is optionally substituted with C,-C 4 haloalkyl, or C j -C ⁇ haloalkoxy, (C j -Cg alkyl)aryl, (C,-Cg alkyl)heterocyclyl , -0(C j -Cg alkyl), -OCC j -Cg alkyl)aryl, -OfC j -Cg alkyl)heterocyclyl , -C j -Cg alkyl-OH, -(C j -Cg alkyl)-0-(C C 6 alkyl), -(C j -Cg alkyl)
  • R groups include hydrogen, CHO, methyl, ethyl, isopropyl, n-propyl , isobutyl, cyclopropyl, CH 2 -cyclopropyl , benzyl, substituted benzyl, for example p-trifluoromethoxybenzyl , phenyl, methoxy, 2-hydroxyethyl , 2-methoxyethyl , 2,2-dimethoxyethyl , 3-propen-l-yl , 3-propyn-l-yl, 2-(N,N-dimethylamino)ethyl , CH 2 C0 2 CH 3 , CH 2 C0 2 CH 2 CH 3 , CH 2 CH 2 0C0NHC(CH 3 ) 3 , CH 2 CH 2 C00CH 2 CH 3 , 2-acetoxyethyl and 2-thiomethylethyl .
  • the formula I given above is intended to include tautomeric forms of the structure drawn, as well as physically distinguishable modifications of the compounds which may arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or from the inability of parts of the molecule to rotate freely in relation to other parts, or from geometrical isomerism, or from intra-molelcular or inter-molecular hydrogen bonding, or otherwise.
  • Some of the compounds of the invention can exist in enantiomeric or diastereo eric forms.
  • the invention includes all individual forms and mixtures thereof in all proportions.
  • Me represents methyl
  • Et represents ethyl
  • Pr represents propyl
  • Ph represents phenyl
  • Bz represents benzyl
  • the conversion of a compound of general formula II to a compound of general formula I may be carried out in an organic solvent such as chloroform, dichloromethane or toluene at a temperature of from 0 to 50 C, preferably at room temperature.
  • the reaction generally proceeds most favourably in the presence of a base which may be an amine such as 4-N,N dimethylaminopyridine (DMAP) or triethylamine.
  • a base may be replaced with a catalytic amount of boron trifluoride etherate.
  • R R NC0C1 in a suitable solvent such as N,N-dimethyl formamide (DMF) in the presence of a suitable base such as DMAP at an appropriate temperature between 0°C and 100°C, usually at room temperature.
  • a suitable solvent such as N,N-dimethyl formamide (DMF)
  • DMF N,N-dimethyl formamide
  • DMAP a suitable base
  • R R NC0C1 Compounds of the formula R R NC0C1 are known in the art or may be prepared by the treatment
  • R is a leaving group such as Cl , Br, I, methane sulphonyloxy or toluene sulphonyloxy.
  • Compounds of general formula II in which R is NHR and R is H may be prepared from compounds of general formula III by reaction with an alkali metal azide such as sodium azide to give the equivalent azide compound followed by reduction of the azide by any known method, for example using 1,3-propane dithiol in a basic solvent, to give the appropriate compound of general formula II.
  • the first step of the reaction may be carried out at a temperature of from 0 to 30°C, but preferably at room temperature in a solvent such as dimethylformamide (DMF).
  • the conversion of the azide to a compound of general formula II is preferably carried out under an inert atmosphere such as nitrogen at 0 to 30°C, most suitably at room temperature.
  • the solvent may be an amine such as triethylamine.
  • Compounds of general formula II in which R is NHR and R is other than hydrogen may be prepared from compounds of general formula III by reaction with a compound of formula NH 2 R , wherein R is as defined in general formula I.
  • the reaction may be carried out at a temperature of from 0 to 80°C, preferably from 0°C to room temperature and it is particularly preferred for the reaction to be initiated at 0°C and subsequently allowed to warm to room temperature after most of the reactant has been converted to product.
  • the reaction is generally carried out in an organic solvent, particularly an ether such as tetrahydrofuran (THF) .
  • the group A is a heterocyclic group
  • mildly acidic conditions which may be provided by, for example, aqueous potassium hydrogen phosphate.
  • a solution of the compound of general formula III in a solvent such as an ether, for example THF is stirred with the aqueous reagent at a temperature of from 0° to 50 C, but preferably at room temperature.
  • reaction may be conducted in the absence of a solvent and at a temperature of from about 100° to 300°, preferably about 150°. This reaction is novel and forms a further aspect of the invention.
  • reaction works particularly well for compounds in which A is phenyl or substituted phenyl.
  • CH 2 by treatment with a chlorinating agent, particularly thionyl chloride.
  • a chlorinating agent particularly thionyl chloride.
  • the reaction may be initiated at room temperature and maintained at room temperature for about 2 to 14 hours before heating, preferably to the reflux temperature of the solvent.
  • 1 c ⁇ *- also be prepared from compounds of general formula II in which R is OH and X is CH 2 .
  • the compound of general formula II may be treated with agents such as 1,2-dibromotetrachloroethane and triphenylphosphine.
  • the solvent employed will preferably be an ether, particularly diethyl ether and the reaction may be initiated at a temperature from about -10° to 5°C, preferably about 0°C and subsequently allowed to warm to room temperature.
  • R , R , R and R are as defined in relation to formula I and R and R are as defined for general formula XXIII, in the presence of a base, such as triethylamine, in a solvent, such as diethyl ether, at 0°C to 100°C, suitably ambient temperature.
  • a base such as triethylamine
  • a solvent such as diethyl ether
  • Compounds of general formula XXX may be cyclised to give compounds of general formula IV by treatment with a weak base such as triethylamine in an organic solvent such as dichloromethane, followed by a halogenating agent such as thionyl chloride and further treatment with weak base.
  • a weak base such as triethylamine in an organic solvent such as dichloromethane
  • a halogenating agent such as thionyl chloride
  • the reaction is preferably conducted at a temperature of from about 15° to
  • the compound of general formula IX may be converted to the compound of general formula IV by decarboxylation which may be achieved simply by heating to the melting point and allowing decarboxylation to occur.
  • R , R , R and R are as defined in relation to formula I, in the presence of metals or metal oxides, suitably copper or copper I oxide, at temperatures of 30°C to 250°C, suitably 130°C to 180°C.
  • metals or metal oxides suitably copper or copper I oxide
  • Alternative procedures can include treatment of XXV with alkali metal salts of XXVI in solvents such as dimethyl sulphoxide and at temperatures of 0°C to 100°C, suitably ambient temperatures. This route is particularly useful for compounds in which A is a heterocyclic group.
  • each R is, independently, benzyl or substituted benzyl; by reduction, suitably hydrogenation over a palladium or platinum catalyst, in the presence of an acid such as trifluoroacetic acid.
  • reaction 19 and R are as defined above.
  • the reaction is carried out in a mixed aqueous/organic solvent such as water/dichloromethane and in the presence of a base, for example sodium hydroxide, and a phase transfer catalyst, for example tetrabutylammonium iodide.
  • a base for example sodium hydroxide
  • a phase transfer catalyst for example tetrabutylammonium iodide.
  • N,N-dimethylformamide (DMF) before reaction with the compound of general formula VI.
  • the reaction may take place in an organic solvent, preferably a chlorinated solvent such as dichloromethane.
  • Carboxylic acids of general formula XV may be prepared from esters of
  • Esters of general formula XVI may be prepared from dichloroacetic acid
  • R is C,-C ⁇ alkyl and A, R and R are as defined in general formula I; by reaction with an acid such as hydrochloric acid in an organic solvent such as 1,4-dioxan.
  • R is as defined above and R is C,-C ⁇ alkyl; by a two stage reaction in which the compound is firstly treated with a strong acid such as trifluoroacetic acid and then heated with a weak base such as sodium bicarbonate.
  • a strong acid such as trifluoroacetic acid
  • a weak base such as sodium bicarbonate
  • reaction is preferably carried out in a polar solvent such as a mixture of water and an alcohol, for example methanol or ethanol, at a temperature of between 0° and 100°C, preferably at room temperature.
  • a polar solvent such as a mixture of water and an alcohol, for example methanol or ethanol
  • R is as defined for general formula XII and X is a leaving group, particularly a halogen such as chlorine.
  • X is a leaving group, particularly a halogen such as chlorine.
  • the reaction requires basic conditions which may be provided by, for example, aqueous sodium hydroxide which may be mixed with an organic solvent such as dichloromethane. In this case, a phase transfer catalyst may also be present. Ethers of general formula XX are readily available or can easily be synthesised by a skilled chemist.
  • R is as defined above and R is C,-Cg alkyl.
  • R is C,-Cg alkyl.
  • Compounds such as these are readily available. It is greatly preferred that the reaction is carried out under basic conditions, for example in the presence of sodium hydride. A polar organic solvent such as DMSO may be used.
  • Compounds of formula II in which X is S and R is OH may prepared by
  • Compounds of formula XXII may be prepared from compounds of formula IV in which X is S, by reaction with, for example, a periodate salt.
  • a suitable solvent is an aqueous alcohol such as ethanol or methanol and a suitable temperature is ambient.
  • a peracid suitably m-chloroperbenzoic acid, in a solvent such as dichloromethane may be used.
  • R is SH
  • the second step is preferably carried out at a temperature of -10° to +10 C, usually about 0°C.
  • R 4 and R5 are as defined for general formula I and R25 is halogen such as chloro, bromo or iodo.
  • the reaction requires basic conditions which may be provided by, for example, an alkali metal hydride or alkoxide.
  • the solvent will, to a certain extent, depend on the base which is chosen with solvents such as THF being preferred for hydride bases and alcoholic solvents being more appropriate for alkoxide bases.
  • Compounds of general formula XXVII also show herbicidal activity and form a further aspect of the invention.
  • XXVIII may be cyclised to give a compound of general formula II in which
  • R is OH using the same reaction conditions as for the cyclisation of the compound of general formula XXVII.
  • Compounds of general formula XXVIII may be prepared by the reaction of an aniline derivative of general formula VI with a compound of general formula VII, wherein R , R , R and are as defined in general formula I, in the presence of a reagent such as boron tribromide, aluminium trichloride, tin tetrachloride or titanium tetrachloride in a solvent such as dichloromethane or dichloroethane.
  • a reagent such as boron tribromide, aluminium trichloride, tin tetrachloride or titanium tetrachloride in a solvent such as dichloromethane or dichloroethane.
  • reaction is preferably carried out under basic conditions, these being supplied by use of a weak base, especially an amine base such as triethylamine.
  • the reaction may be carried out under an inert atmosphere such as nitrogen or argon at a temperature of from -20° to 5°C, preferably about 0°C.
  • Y is CR R
  • Z is 0
  • W is 0.
  • the reaction may be carried out in an organic solvent, for example an ether such as THF and at a temperature of from -100° to 30°C, most suitably -80° to 0°C. It is greatly preferred that the compound of general formula IV is first reacted with a strong base and bases such as lithium hexamethyldisilazide have proved to be especially suitable for the purpose. Subsequently the compound of formula
  • Compounds of general formula XXXII can be prepared by a Curtius rearrangement reaction from an azide of general formula XXXIII in a suitable solvent such as toluene at an appropriate temperature between 20°C and 120°C, more typically between 90°C and 100°C.
  • Compounds of general formula XXXIII can be prepared from compounds of general formula IX by methods described in the literature (see March, "Advanced Organic Chemistry: Reactions, Mechanisms & Structure", 4th Edition, John Wiley & Sons, 1992, page 1092).
  • compounds of general formula IX can be converted to compounds of general formula XXXII in one step on treatment with a reagent such as diphenylphosphoryl azide in a suitable solvent such as toluene in the presence of a suitable base such as triethylamine at an appropriate temperature between 20°C and 120°C; more typically between 90°C and 100°C.
  • a reagent such as diphenylphosphoryl azide in a suitable solvent such as toluene
  • a suitable base such as triethylamine
  • reaction is carried out under dry conditions in an organic solvent such as dichloromethane and at a temperature of from -20° to 30°C. It is often preferred for the reagents to be added to one another at about 0°C, following which the reaction mixture may be allowed to warm to room temperature.
  • organic solvent such as dichloromethane
  • thionyl chloride When thionyl chloride is used, it may be added to the compound of general formula I and the mixture heated under reflux. When oxalyl chloride is used, on the other hand, much colder conditions will generally be used with the reaction temperature being from about -20° to 20°C, generally about
  • reaction solvent will also be employed in most cases with a typical solvent being a halogenated solvent such as chloroform. In many cases the reaction proceeds more rapidly in the presence of a catalytic amount of
  • R is H may be prepared from corresponding esters of general formula I in 4 5 1 which Y is CR R , Z is 0 and R is an alkyl group.
  • the ester may be reacted with an organic acid in an organic or aqueous solvent, or with an inorganic acid in a mixture of an organic solvent, such as an alcohol, and water.
  • R is a group such as t-butyl
  • a strong acid such as trifluoroacetic acid (TFA) is preferred and the reaction may be conducted in an organic solvent such as dichloromethane or chloroform, or carried out in the absence of a solvent.
  • the reaction temperature may be from 0° to
  • reaction may be carried out in a solvent such as toluene and at the reflux temperature of the solvent.
  • esters of general formula I in which Y is CR R , W is 0, Z is 0 and R is an alkyl group may be converted directly to amides of general
  • Y is CR R and Z is NR by reaction of an amine in the presence of a Lewis acid catalyst such as aluminium trichloride.
  • the reaction should be carried out under dry conditions in an aprotic solvent such as toluene, dichloromethane or chloroform.
  • halogen exchange may also occur to some extent during the reaction.
  • the catalyst is A1CU and one of the substituents on group A in the starting material contains a halogenated moiety such as CF 3
  • the product in which the substituent is CCU may be isolated as well as the CF 3 containing product.
  • Esters of general formula I in which W is 0, Z is 0 and Y is CR R , 4 5 with at least one of R and R being other than hydrogen may be prepared from the corresponding esters of general formula I in which Y is CH 2 by reaction with a strong base such as lithium hexamethyldisilazide followed by reaction with the appropriate compound R -Hal where Hal is a halo substituent, typically iodo.
  • the reaction should preferably be carried out under dry conditions at a reaction temperature of from -100° to 0°C, usually at about -78 C.
  • Suitable reaction solvents are aprotic organic solvents such as THF.
  • the reaction may generate both the required alkylated product and a product which has been alkylated at a different site. These products can be separated immediately if necessary but if the ester is being used as an intermediate to another compound of general formula I, the remaining reaction steps can be carried out before separation of the products if this is more convenient. If required, further alkylation can be carried out with a compound R -Hal to obtain a dialkylated product.
  • esters of general formula I may be prepared from compounds of general formula IV.
  • R R C 0 in a polar solvent such as DMF and in the presence of a strong base such as an alkali or alkaline earth metal hydroxide or sodium hydride.
  • the reaction may be carried out at a temperature of 10 to 50°C but preferably will be conducted at room temperature.
  • the method is particularly suitable for the the synthesis of esters of general formula I in which R is an alkyl group.
  • the esters may be converted to other compounds of general formula I if required by one of the methods given above.
  • fumaric esters of general formula XI where A, R and R are as defined in relation to formula I may be prepared by converting fumaric monoalkyl esters of general formula XXXV where R and R are as defined in relation to formula I to the corresponding acid chloride by treatment with thionyl chloride or oxalyl chloride by methods analogous to those described above for similar transformations, followed by reaction with the compound of general formula VI where A is defined in relation to formula I.
  • the reaction is carried out in an organic solvent such as dichloromethane or chloroform in the presence of a base such as triethylamine.
  • the reaction may be carried out at temperatures of from 0° to 70°C with room temperature being preferred.
  • fumaric esters of general formula XI where A and R are as defined in relation to formula I and R is benzyl may be prepared from the corresponding fumaric acids of general formula XI where A and R are as defined in relation to formula I and R is hydrogen.
  • Compounds of general formula XI in which R is hydrogen may be reacted with benzyl alcohol in the presence of diethyl azodicarboxylate and triphenyl phosphine.
  • the reaction is preferably conducted in an aprotic organic solvent such as dichloromethane or chloroform at temperatures of from -20 to 50°C.
  • fumaric esters of general formula XI where A and R are as defined in relation to formula I and R is t-butyl may be prepared from
  • reaction (bis) t-butyl dimethyl acetal in an organic solvent such as toluene.
  • organic solvent such as toluene.
  • Fumaric acids of general formula XI where A and R are as defined in relation to formula I and R is hydrogen may be prepared from fumaric acids of general formula XI where A and R are as defined in relation to formula
  • I and R is alkyl by reaction with an inorganic base such as sodium hydroxide or potassium hydroxide in an alcohol, preferably methanol or ethanol.
  • the reaction may be carried out at temperatures of from 0° to
  • Fumaric monoalkyl esters of general formula XXXV where R and R are as defined in relation to formula I are known compounds, or may be prepared from known compounds by standard methods.
  • the reaction is preferably carried out in the presence of a strong base such as sodium hydride, suitably in a solvent such as THF.
  • a strong base such as sodium hydride
  • the reaction temperature will be in the range of 0 to 80 C, preferably room temperature. They may alternatively
  • the reaction may be carried out in an organic solvent such as toluene at a temperature of from 30° to 120°C. Often, the reaction will be conducted at a temperature of about 80°C.
  • Y is NCH 2 CHL 2 , wherein L is a leaving group as defined above.
  • the reaction may be carried out in a solvent such as THF under acidic conditions which may be provided by the presence of an aqueous inorganic acid such as hydrochloric acid.
  • the reaction temperature may be from 5 to 50°C but will, in most cases, be room temperature.
  • OR wherein R is C,-C. alkyl or haloalkyl, may be converted into compounds of general formula I in which the phenyl ring is disubstituted and wherein the second substituent is a halo, particularly a chloro, group by treatment with a halogenating agent such as N-chlorosuccinimide in a solvent such as N,N-dimethylformamide (DMF).
  • a halogenating agent such as N-chlorosuccinimide
  • a solvent such as N,N-dimethylformamide (DMF).
  • the reaction may be carried out at a temperature of from 15° to 80°C, more usually at from 20° to 60°C.
  • the major product of the reaction is usually the 3,4-substituted compound with the 3,6-substituted compound being the minor product.
  • a similar process may be used to obtain the equivalent sulfone.
  • two equivalents of MCPBA may be used and the reaction mixture is preferably heated to a temperature of from 30° to 90°C, usually to the reflux temperature of the solvent employed.
  • the functional groups C0(Z) R may be inter-converted to different functional groups using techniques of esterification, transesterification, hydrolysis and amidation some of which are discussed above. Other such methods are standard procedures well known to the skilled chemist.
  • the compounds of formula I above are active as herbicides, and the invention therefore provides, in a further aspect, a process for severely damaging or killing unwanted plants, which process comprises applying to the plants, or to the growth medium of the plants, a herbicidally effective amount of a compound of formula I as hereinbefore defined.
  • the compounds of formula I are active against a broad range of weed species including monocotyledonous and dicotyledonous species. They show some selectivity towards certain species; they may be used, for example, as selective herbicides in soya, rice and maize crops.
  • the compounds of formula I are applied directly to unwanted plants (post-emergence application) but they are preferably applied to the soil before the unwanted plants emerge (pre-e ergence application).
  • the compounds of formula I may be used on their own to kill or severely damage plants, but are preferably used in the form of a composition comprising a compound of formula I in admixture with a carrier comprising a solid or liquid diluent.
  • compositions containing compounds of formula I include both dilute compositions, which are ready for immediate use, and concentrated compositions, which require to be diluted before use, usually with water.
  • the compositions Preferably contain from 0.01% to 90% by weight of the active ingredient.
  • Dilute compositions ready for use preferably contain from 0.01 to 2% of active ingredient, while concentrated compositions may contain from 20 to 90% of active ingredient, although from 20 to 70% is usually preferred.
  • the solid compositions may be in the form of granules, or dusting powders wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.
  • a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum.
  • a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite
  • Liquid compositions may comprise a solution or dispersion of an active ingredient in water optionally containing a surface-active agent, or may comprise a solution or dispersion of an active ingredient in a water-immiscible organic solvent which is dispersed as droplets in water.
  • Surface-active agents may be of the cationic, anionic, or non-ionic type or mixtures thereof.
  • the cationic agents are, for example, quaternary ammonium compounds (e.g. cetyltrimethylammonium bromide).
  • Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium, and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid.
  • Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g. Agra! 90 ) or octyl-cresol .
  • Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; the condensation products of the partial ester with ethylene oxide; the lecithins; and silicone surface active agents (water soluble surface active agents having a skeleton which comprises a siloxane chain e.g. Silwet L77 ) .
  • a suitable mixture in mineral oil is Atplus 411F .
  • aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent(s).
  • organic solvents include, for example, ethylene di-chloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.
  • compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use.
  • the concentrates are usually required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active ingredient(s) .
  • Dilute preparations ready for use may contain varying amounts of the active ingredient(s) depending upon the intended purpose; amounts of 0.01% to 10.0% and preferably 0.1% to 2%, by weight of active ingredient(s) are normally used.
  • a preferred form of concentrated composition comprises the active ingredient which has been finely divided and which has been dispersed in water in the presence of a surface-active agent and a suspending agent.
  • Suitable suspending agents are hydrophilic colloids and include, for example, polyvinylpyrrolidone and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth.
  • Preferred suspending agents are those which impart thixotropic properties to, and increase the viscosity of the concentrate. Examples of preferred suspending agents include hydrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorite, saponite, and saucorite. Bentonite is especially preferred.
  • Other suspending agents include cellulose derivatives and polyvinyl alcohol.
  • the rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an application rate of from 0.001 to 20 kilograms per hectare is suitable while from 0.025 to 10 kilograms per hectare may be preferred.
  • compositions of the invention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activity. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula I as hereinbefore defined with at least one other herbicide.
  • the other herbicide may be any herbicide not having the formula I. It will generally be a herbicide having a complementary action in the particular application.
  • Examples of useful complementary herbicides include:
  • B. hormone herbicides particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, clopyralid, and their derivatives (eg. salts, esters and amides);
  • D Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, dinoseb and its ester, dinoseb acetate;
  • dinitroaniline herbicides such as dinitramine, trifluralin, ethalflurolin, pendimethalin, oryzalin;
  • arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, onolinuron, chlorobromuron, dai uron, ethabenzthiazuron;
  • phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
  • H 2-phenylpyridazin-3-ones such as chloridazon and norflurazon;
  • I uracil herbicides such as lenacil, bromacil and terbacil;
  • J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
  • K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
  • L. thiolcarbamate herbicides such as cycloate, vernolate, molinate,
  • M. l,2,4-triazin-5-one herbicides such as metamitron and metribuzin
  • N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben
  • 0. am * 1ide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor
  • P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil
  • Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof
  • diphenylether herbicides such as lactofen, fluroglycofen or salts or ester thereof, nitrofen, bifenox, aciflurofen and salts and esters thereof, oxyfluorfen, fomesafen, chlor ⁇ itrofen and chlomethoxyfen;
  • S. phenoxyphenoxypropionate herbicides such as didofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester; T.
  • cyclohexanedione herbicides such as alloxydi and salts thereof, sethoxydim, cycloxydim, tralkoxydim, and clethodim;
  • U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as DPX-M6313, chlorimuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof, 2-[3-(4-methoxy-6-methyl-l,3,5- tri azirr-zyl ) -3 " -mett ⁇ yt ⁇ rei dosul phony 1 ) benzoi c acid " esters such as the methyl ester thereof (DPX-LS300) and pyrazosulfuron; V.
  • imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr
  • W arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl , diflufenican
  • X amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulphosate and bialaphos
  • Y organoarsenical herbicides such as monosodium ethanearsonate
  • Examples of useful contact herbicides include: bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat; * These compounds are preferably employed in combination with a safener such as dichlormid.
  • -NMR Nuclear Magnetic Resonance (performed at 270MHz and in CDC13 as solvent unless otherwise stated). The following abbreviations are used to indicate the multiplicity of the peaks in the NMR spectrum: s (singlet); d (doublet); t (triplet); q (quartet); quin (quintet); m (multiplet); br (broad) .
  • Step 1 Preparation of [3-(3-triflu ⁇ romethyl)phenyl-4-thiazolidinone-5- yljacetyl chloride.
  • Oxalyl chloride (0.127ml) was added via syringe to a suspension of 2-[1-(3-trif1uoromethyl)phen l-2-pyrrolidinone-3-y1]acetic acid (0.380g) (prepared as in Example 13 below) in chloroform (15ml) at room temperature. Dimethylformamide (1 drop) was added and stirring continued for 90 minutes during which time the effervescence stopped and the solid dissolved. t-Butyl amine (0.41ml) was added dropwise at 0°C causing an instant precipitate. The reaction mixture was diluted with chloroform (100ml) and washed with water (100ml), dried over N-a.-- . S0. and evaporated in vacuo.
  • Alpha-hydroxy-delta-butyrolactone (2.04g) and 3-trifluoromethyla ⁇ iline (2.74ml) were heated without solvent to 100°C with stirring. After 4 hours, the temperature was raised to 150°C (oil bath temperature) and stirring was continued for a further 20 hours. After cooling, the dark red liquid was taken up in dichloromethane (5ml) and applied to a silica flash column. Elution with ethyl acetate in hexane (a gradient of 40-60% ethyl acetate) gave the title compound as a pale orange crystalline solid (2.42g).
  • Oxalyl chloride (0.48ml) was added to a suspension of 2-pyrrole carboxylic acid (0.45g) in chloroform (10ml) at room temperature. After 2 hours, effervescence had ceased and the solvent was evaporated jjn vacuo to give a solid. Trituration with hexane left the crude crystalline acid chloride which was used directly.
  • 2-Pyrrole carboxylic acid chloride from Step 2 (0.25g) was dissolved in dichloromethane (10ml) along with 3-hydroxy-l-(3-trifluoro- methyl)phenyl-2-pyrrolidinone (0.38g) from Step 1. Triethylamine (0.26ml) was added. The solution turned reddish-orange and was left stirring overnight at room temperature. After diluting with dichloromethane (100ml), the solution was washed with sat. NaHCO**, (aq) (2x50ml), brine (50ml), dried (Na 2 S0.) and evaporated.
  • a 200ml 3 necked flask was equipped with stoppers, dropping funel , thermometer, nitrogen bubbler and magnetic stirrer.
  • the flask was charged with 15.Og of l-(3-trifluoromethyl)phenyl-2-pyrrolidinone (prepared as described in Steps 1 and 2 of Example 7), phosphorus tribromide (1.0ml) and chlorobenzene (65ml). This was heated to 105°C.
  • the dropping funnel was charged with bromine (10.6g) and this was added over a 70 minute period. After 165 minutes, the reaction was cooled and left at room temperature for 16 hours. Tic indicated incomplete reaction, so the mixture was heated to 105°C and a further quantity of bromine (0.73g) added.
  • Step 2 Preparation of 3-(t-Butylcarbamoyl-N-methyl)amino-l-(3- trif1uoromethyl)phen l-2-pyrrolidinone.
  • Methylamine gas was bubbled through a solution of 3-bromo-l-(3- trifluoromethy1)phenyl-2-pyrrolidinone (0.20g) from Step 1 in THF (25ml) at 0°C. After 15 minutes the reaction was allowed to warm to room temperature. After 1 hour, with methylamine still bubbling through the solution, tic showed no remaining bromide. The solvent was evaporated in vacuo and the residue re-dissolved in dichloromethane (10ml). t-Butylisocyanate (0.22ml) and triethylamine (0.27ml) were added and the yellow solution was stirred overnight at room temperature.
  • Oxalyl chloride (0.127ml) was added to a suspension of [l-(3-trifluoromethyl)phenyl-2-pyrrolidinone-3-yl]acetic acid (prepared as in Example 13 below) (0.38g) in chloroform (6ml) at room temperature. Dimethylformamide (1 drop) was added, causing effervescence. After 2 hours, the reaction was cooled to 0°C and 5-amino-3-methylisoxazole (0.14g) was added, followed by triethylamine (0.36ml). The reaction darkened and a brown solid appeared. After 6 hours, the mixture was poured into ethyl acetate (100ml) and washed with sat.
  • Oxalyl chloride (0.190ml) was added to a stirred suspension of [l-(3-trifluoromethyl)phenyl-2-pyrrolidinone-3-yl]acetic acid (prepared as in Example 13 below) (0.570g) in chloroform (10ml) at room temperature. Dimethylformamide (1 drop) was added and stirring continued for 2 hours. The solvent was evaporated in vacuo and the residue re-dissolved in dichloromethane (20ml) and cooled to 0°C. Triethylamine (0.55ml) was added, followed by 2-amino-2,2-dimethylethanol (0.55ml) and the mixture was stirred at 0°C for 1 hour before allowing to warm to room temperature.
  • Trifluoroacetic acid (1ml) was added to a solution of t-Butyl-[l- (3-trif1uoromethyl)phenyl-2-pyrrolidinone-3-yl]acetate (prepared as described in Example 7) (0.70g) in dichloromethane (10ml) at room temperature. The yellow solution was stirred for 24 hours and the solvent then evaporated in vacuo. Trituration of the residue with ether/hexane caused a pale yellow crystalline solid to separate out. This was filtered off to give the pure title compound (0.48g),m.p. 126-128°C.
  • the propargyl amide (Compound 16, prepared by a method similar to that described in Example 8) (0.407g) was dissolved in ethyl acetate (20ml). 5% Palladium on calcium carbonate, poisoned with lead (0.04g) in ethyl acetate (5ml) was added. With stirring, the flask was evacuated and flushed with hydrogen via a balloon. This procedure was repeated twice. After 2 hours hydrogenation at one atmosphere, the reaction was filtered through a pad of Hyflo to remove catalyst.
  • the ester (Compound 15, prepared as in Example 15) (0.8g) was dissolved in dry dichloromethane (20ml) and aluminium trichloride (0.84g) added. To this suspension was added dropwise 1,1-dimethylpropargylamine (l.l ⁇ g). When the effervescence had ceased and exotherm of 15°C died down, the mixture was stirred at room temperature for 1 hour. The mixture was then carefully quenched with 2M HCl(aq), the layers separated and the aqueous layer extracted with dichloromethane. The combined organics were washed with water, dried over MgSO, and evaporated.
  • the acid chloride (prepared as described in Example 8 from the corresponding acid, Compound 13, 0.5g) was dissolved in dichloromethane (18ml). Sodium carbonate (0.463g) was dissolved in water (18ml) and added to cyclobutylamine hydrochloride (0.207g). After the effervescence had subsided, this solution was added to the acid chloride. After vigorous stirring, the reaction was left to stand overnight. The reaction was diluted with dichloromethane (20ml) and washed with NaHC0 3 (aq) . The aqueous layer was re-extracted with dichloromethane and then with brine before drying over MgSO,.
  • the ester (Compound 7, 2.112g) was dissolved in THF (30ml) at -78°C.
  • Lithium hexa ethyldisilazide (6.79ml of a 1.0m THF solution) was added via syringe.
  • iodomethane (1.752g) was added. This was left to stir at -78°C for 20 minutes and then allowed to warm to room temperature. After 10 minutes at room temperature, the reaction was poured into water (30ml). The aqueous layer was re-extracted with ether (x2) and the combined organic layers were washed with sodium thiosulphate solution and dried over MgSO..
  • the thioacetate, prepared as in Step 1 (0.03g) was dissolved in methanol and cooled to 0°C. Ammonia gas was bubbled through the mixture for 15 minutes. The mixture was concentrated to dryness. Chromatography, eluting with ethyl acetate/hexane (25:75) gave the thiol compound.
  • the thiol compound obtained in Step 2 was reacted with t-Butylisocyanate according to Example 10 to give the thiocarbamate compound 41 as a colourless solid, m.p. 104-106°C.
  • a similar procedure was used to prepare Compounds 42 (m.p. 119-120°C), 75 (m.p. 111-112.5°C) , 76 (m.p. 83-86°C), 127, 309, 314, 319, 320, 323 and 327 of Table 1.
  • Step 1 Preparation of 3-(N-ethoxycarbonylmethyl)amino-1-(3-trifluoro ⁇ methyl)phenyl-2-pyrrolidinone.
  • Ethylbromoacetate (0.155ml) was added i_a syringe to a solution of 3-amino-l-(3-trifluoromethyl)phenyl-2-pyrrolidinone (prepared by a similar method to that described in Example 1, Step 4) (0.31g) and triethylamine (0.176ml) in THF (5ml) at room temperature. After 16 hours, the mixture was poured into saturated NaHC0 3 (aq) and extracted with ethyl acetate (x2) .
  • Step 2 Preparation of 3-(t-Butylcarbamoyl-N-ethoxycarbonyl-methyl)- amino-1-(3-trifluoromethyl)phenyl-2-pyrrolidinone.
  • Step 1 Preparation of 3-(N-methoxy)amino-l-(3-trifluoromethyl)phenyl-2- -pyrrolidinone.
  • Methoxylamine hydrochloride (3.39g) and sodium carbonate (4.29g) were stirred together in methanol (20ml) for 5 minutes. This mixture was then added to a solution of 3-bromo-l-(3-trifluoromethyl)phenyl-2-pyrrolidinone (2.5g) (prepared as described in Example 10, Step 1) in methanol (30 ml) at room temperature. The mixture was heated to reflux overnight. Further methoxylamine hydrochloride (3.39g) was added and heating continued for a further 24 hours. After cooling, the reaction was poured into water and extracted with dichloromethane (x3). The combined extracts were washed with brine and dried (Na 2 S0.) .
  • Step 2 Preparation of 3-(t-Butylcarbamoyl-N-methoxy)amino-l- -(3-trifluorometh 1)phenyl-2-pyrrolidinone.
  • Step 2 Preparation of 3-(N-formyl)amino-l-(3-trifluoromethoxy)phenyl-2- pyrrolidinone.
  • N-formyl compound (prepared as in Step 2) (0.97g) was dissolved in CH 2 C1 2 (20ml). triethylamine (0.51ml) was added, followed by 3,3-dimethylbutanoyl chloride (0.51ml) in CH 2 C1 2 (5ml) which was added dropwise over 5 min. The reaction was stirred at room temperature for 17 hours, whereupon further triethylamine (0.25ml) and 3,3-dimethylbutanoyl chloride (0.25ml) were added. After a further 3 hours, the reaction was diluted with CH 2 C1 2 and washed with water. After drying over MgSO., the solvent was evaporated to give the crude product as an orange oil. Chromatography, eluting with ether gave a pale yellow product which was triturated with ether/petrol to give the title compound as a white solid (0.57g).
  • Step 1 Preparation of 3-(N-allyl)amino-l-(3-trifluoromethoxy)- pheny1-2-pyrrolidinone.
  • Step 2 Preparation of 3-(t-Butylcarbamoyl-N-allyl)amino-l-(3-trifluoro- methoxy)phenyl-2-pyrrolidinone.
  • N-allyl derivative (0.23g) (prepared as described in Step 1) was dissolved in CH 2 C1 2 (3ml) and treated with triethylamine (0.16ml) followed by t-butylisocyanate (0.22ml). After 48 hours at room temperature, the reaction was diluted with CH 2 C1 2 , washed with 2N HCl (aq) (x2) , brine and dried over MgSO.. The mixture was filtered and concentrated and the residue purified by flash chromatography, eluting with 40% ethyl acetate in hexane. The urea title compound was obtained as colourless solid (0.293g), m.p. 107-108°C.
  • Compound 28 (prepared by a similar method so that described in Example 1) (0.115g) was dissolved in toluene (10ml). Paraformaldehyde (0.023g) and PTSA (catalytic amount) were added and the mixture heated under Dean and Stark conditions for 8 hours. Additional paraformaldehyde (0.023g) was added at 2 hour intervals over this time. The mixture was allowed to cool and the solvent evaporated. The residue was purified by chromatography (eluting with ethyl acetate/hexane 1:2) to give Compound 132 (0.018g).
  • N-chlorosuccinimide (2.84g) was added portionwise to a stirred solution of 3(5-methyl-l,3,4-thiadiazol-2-yl)thiazolidin-4-one (4.27g), prepared as described in Step 1 above, in dichloromethane (30ml). After twenty hours, the solvent was removed under reduced pressure. The residue was converted into the title compound by treatment with aqueous potassium dihydrogen phosphate solution in tetrahydrofuran by a procedure similar to that described in Example 35, Step 3. The reaction mixture was diluted with water and extracted with ethyl acetate.
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 5-hydroxy-3(6-trifluoromethylpyridin-2-yl) thiazolidin-4-one (l.Og), from Step 3, t-butyl isocyanate (0.41g), triethylamine (0.42g) and dichloromethane (30ml). Chromatography on silica, using hexane-ethyl acetate (3:1) as eluant, gave the title compound (1.02g, m.p. 118°C).
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 5-hydroxy-3(6-trifluoromethylpyridin-2-yl) thiazolidin-4-one (1.38g), prepared as described in Example 37, Steps 1-3, l,l-dimethylprop-2-ynyl isocyanate (14.38ml, solution in toluene), from Step 1, triethylamine (0.58g) and dichloromethane (30ml). Chromatography on silica gel, using hexane-ethyl acetate (3:1) as eluant, gave the title compound (1.39g, m.p. 85-86°C) .
  • the title compound was prepared by a procedure similar to that described in Example 37, Steps 2 and 3, but using 3(4,6-bis-trifluoromethylpyridin-2-yl) thiazolidin-4-one (3.53g), prepared as described in Step 1 above, sulphuryl chloride (0.46ml and 0.4ml) and dichloromethane (30ml). The reaction mixture was evaporated under reduced pressure to give a mixture (3.93g) of the desired 5-chloro derivative, the 5,5-dichloro analogue and hydrolysis products.
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 3(4,6-bis-trifluoromethylpyridin-2-yl)-5- hydroxythiazolidin-4-one (0.36g), from Step 2, t-butyl isocyanate (0.12g), triethylamine (0.12g) and dichloromethane (20ml). Chromatography on silica gel, using hexane-ethyl acetate (4:1) as eluant, gave the title compound (0.30g) as a pale yellow gum.
  • the title compound was prepared by a procedure similar to that described in Step 1 of Example 35, but using 3-amino-5-trifluoromethylpyridine (5.0g), thioglycolic acid (3.1g), 37% aqueous formaldehyde solution (2.7ml), p-toluenesulphonic acid (0.025g) and toluene (50ml).
  • the toluene layer was decanted, washed with sodium bicarbonate solution then brine, dried over magnesium sulphate and evaporated under reduced pressure to give the title compound (2.76g, m.p. 82-84°C) .
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 3(5-trifluoromethylpyridin-3-yl)thiazolidin-4-one (2.25g), prepared as described in Step 1 above, in dichloromethane (30ml) and adding sulphuryl chloride (0.73ml) dropwise at 0°C. Immediate precipitation occurred. The mixture was stirred at 5°C for thirty minutes and evaporated under reduced pressure. The residue was hydrolysed directly using aqueous potassium dihydrogen phosphate solution in tetrahydrofuran by a procedure similar to that described in Example 36, Step 2.
  • the title compound was prepared by a procedure similar to that described in Example 35, Step 1 but using 5-hydroxy-3(5-trifluoromethylpyridin-3-yl) thiazolidin-4-one (0.50g) from Step 2, t-butyl isocyanate (0.21g), triethylamine (0.21g) and dichloromethane (10ml). Chromatography on silica, using dichloromethane-ethanol (24:1) as eluant, gave the title compound (0.54g, m.p. 161-163°C).
  • Step 1 Preparation of ((2-trifluoromethylpyridin-4-yl)aminomethylthio)- acetic acid.
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 4-amino-2-trifluoromethylpyridine (2.35g), thioglycolic acid (1.33g), 37% aqueous formaldehyde solution (l.l ⁇ g), p-toluenesulphonic acid (0.025g) and toluene (90ml). After heating for ninety minutes, the mixture was cooled and the precipitate filtered off. This was washed with toluene, then hexane, and dried under reduced pressure to give the title compound as a white solid (3.22g), sufficiently pure for use in Step 2 below.
  • the title compound was prepared by a procedure similar to that described in Example 40, Step 2, but using 3(2-trifluoromethylpyridine-4-yl)thiazolidin- 4-one (1.67g), sulphuryl chloride (0.83g) and dichloromethane (30ml). The reaction was followed by hydrolysis with an aqueous solution of potassium dihydrogen phosphate in tetrahydrofuran. The crude product was chromatographed on silica, using ethyl acetate-hexane (1:1) as eluant, to give the title compound (0.635g) as a yellow oil.
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 2-amino-4-trifluoromethylpyridine (10.Og), thioglycolic acid (5.70g), 37% aqueous formaldehyde solution (4.80ml) and toluene (100ml). No p-toluenesulphonic acid catalyst was used.
  • the crude product was chromatographed on silica, using ethyl acetate-hexane mixtures as eluant, to give the title compound as a pale yellow oil (2.80g).
  • Lithium bis(trimethylsilyl)amide (5.72ml, 1M solution in tetrahydrofuran) was added dropwise to a stirred suspension of l(4-methoxypyridin-3-yl)- pyrrolidin-2-one (0.5g), prepared as described in Step 2 above, in tetrahydrofuran (20ml), under nitrogen at -78°C.
  • the reaction mixture was stirred for thirty minutes at -78°C, allowed to warm to 0°C, then treated with a stream of oxygen. After one hour, the mixture was poured into saturated aqueous sodium sulphite solution and shaken vigorously for five minutes.
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 2-amino-4,6-dimethylpyrimidine (5.0g), thioglycolic acid (3.74g), 37% aqueous formaldehyde solution (3.29ml), p-toluenesulphonic acid (0.025g) and toluene (70ml). After heating for three hours, the mixture was allowed to cool. The precipitate was filtered off and dried under reduced pressure. Soluble in aqueous sodium bicarbonate solution, it was shown to be the uncyclized title compound (4.0g, m.p. 164-165°C) . NMR (DMS0-d 6 /CDCl 3 ) : ⁇ 2.3(6H,s); 3.35(2H,s); 4.7(2H,d); 6.4(lH,s); 6.85(lH,t).
  • the title compound was prepared by a procedure similar to that described in Example 37 Step 2, but using 3(4,6-dimethylpyrimidin-2-yl)thiazolidin-4-one (0.5g),from Step 2 above, sulphuryl chloride (0.10ml and 0.09ml) and dichloromethane (10ml).
  • the crude chloro derivative was dissolved in tetrahydrofuran and treated with an aqueous solution of potassium dihydrogen phosphate in a procedure similar to that described in Example 36, Step 2.
  • the crude product was chromatographed on silica, using dichloromethane-ethanol (19:1) as eluant, to give the title compound (0.10g).
  • the title compound was prepared by a procedure similar to that described in Example 35, but using 3(4,6-dimethylpyrimidin-2-yl)-5-hydroxythiazolidin- 4-one (0.10g), from Step 3, t-butyl isocyanate (0.048g), triethylamine (0.05g) and dichloromethane (10ml). Chromatography on silica, using dichloromethane-ethanol (49:1) as eluant, gave the title compound (0.10g, m.p. 153-154°C).
  • the title compound was prepared by a procedure similar to that described in Example 47, Step 1, but using 2-amino-4-chlorobenzothiazole (9.20g), thioglycolic acid (4.60g), 37% aqueous formaldehyde solution (3.9ml) and toluene (75ml). No p-toluenesulphonic acid catalyst was used. The precipitate formed on cooling was filtered off, washed with ethyl acetate and dried to give the title compound as a white solid (8.00g).
  • the title compound was prepared by a procedure similar to that described in Example 48 Step 2, but using 3(4-chlorobenzothiazol-2-yl)thiazolidin-4-one (3.50g) from Step 2 above, sulphuryl chloride (1.05ml) and dichloromethane (50ml), followed by tetrahydrofuran (50ml) and saturated aqueous sodium bicarbonate solution (50ml). The crude product was recrystallised from toluene to give the title compound (0.45g, m.p. 220°C) .
  • the reaction was quenched with a mixture of 2M hydrochloric acid (11ml) and brine (50ml), and extracted with ethyl acetate (2x20ml). The extracts were washed with brine, dried over magnesium sulphate and evaporated under reduced pressure. The residue was chromatographed on silica, using ethyl acetate-hexane mixtures, then tetrahydrofuran-hexane mixtures, as eluants. The crude product was triturated with ether to give the title compound as a white crystalline solid (0.260g).
  • the compound was prepared by a procedure similar to that described in Example 36, Steps 1 and 2, but using 3-aminopyridine (5.0g), thioglycolic acid (4.9g), 37% aqueous formaldehyde solution (4.35ml), p-toluenesulphonic acid (0.025g) and toluene (70ml).
  • the toluene layer was decanted and evaporated under reduced pressure to give the title compound (2.79g) as a pale red solid sufficiently pure for use in Step 2.
  • the thiazolidinone (0.38g, prepared as described in Step 1 above) was chlorinated with sulphuryl chloride, then the total product hydrolysed with potassium dihydrogenphosphate buffer, both using a procedure similar to that described in Example 35, Steps 1-3.
  • the second reaction mixture was - Ill -
  • the title compound was prepared by a procedure similar to that described in Example 35, Step 4, but using the alcohol (O.lOg), prepared as described in Step 2 above, t-butylisocyanate (0.036g), triethylamine (0.037g) and dichloromethane (5ml). Chromatography on silica, using hexane-ethyl acetate (4:1) as eluant, gave Compound 159 (0.064g, m.p. 159-161°C).
  • the addition can also be catalysed using triethylamine or gaseous hydrogen chloride in place of boron trifluoride.
  • a rearrangement product can be formed in variable amounts which can necessitate purification of the desired material, for example by chromatography on silica using hexane-ethyl acetate (3:1) as eluant.
  • 4-Amino-6(2,2-difluoroethoxy)pyrimidine (0.86g, m.p. 127°C) was made by treating 4-amino-6-chloropyrimidine (2.50g) with sodium 2,2-difluoroethoxide in tetrahydrofuran. Reaction of it (0.91g), scaled to lactonecarbamate (l.Og) etc., gave the corresponding iodo-amide (1.28g, m.p. 42-44°C).
  • 4-Amino-6(2,2,2-trifluoroethoxy)pyrimidine (0.61g, m.p. 113°C) was made by treating 4-amino-6-chloropyrimidine (l.Og) with sodium 2,2,2-trifluoroethoxide in N,N-dimethylformamide. Reaction of it (0.59g), scaled to lactonecarbamate (0.58g) etc., gave the corresponding iodo-amide (0.55g, m.p. 46-47°C).
  • 4-Amino-6-difluoromethoxypyrimidine (0.17g, m.p. 152-154°C) was made by passing chlorodifluoromethane into a solution of 4-amino-6-hydroxypyrimidine (0.5g) in aqueous dioxan at 70°C, in the presence of sodium hydroxide. Reaction of it (0.94g), scaled to lactonecarbamate (1.06g) etc., gave the corresponding iodo-amide (l.Olg, pale yellow gum).
  • 4-Amino-6-difluoromethoxy-2-methoxypyrimidine (1.73g, m.p. 112-113°C) was made by passing chlorodifluoromethane into a solution of 4-amino-6-hydroxy-2-methoxypyrimidine (4.0g) in aqueous dioxan at 70°C, in the presence of sodium hydroxide. Reaction of it (0.84g), scaled to lactonecarbamate (O. ⁇ Og) etc., gave the corresponding iodo-amide (0.33g, m.p. 54-55°C).
  • 2-Amino-5-trifluoromethylthiazole (5.57g of hydrochloride salt after appropriate work-up) was made by treating 2-aminothiazole 5-carboxylic acid (8.20g) with sulphur tetrafluoride and hydrogen fluoride at 120°C.
  • the anhydrous free base (0.42g) liberated from the hydrochloride salt with aqueous sodium bicarbonate solution, scaled to lactonecarbamate (0.50g) etc, gave the corresponding iodo-amide (0.52g, m.p. 50-52°C) .
  • 3-Amino-l-(3-trifluoromethyl)phenyl-2-pyrrolidinone (0.305g), prepared in a similar manner to that described in Step 4 of Example 1, diisopropyl- carbamoylchloride (0.409g), and 4-N,N-dimethylaminopyridine (0.152g) were dissolved in DMF (2ml) and stirred at room temperature for 3 days. The reaction mixture was then poured into water and extracted into ethyl acetate (3 times). The combined ethyl acetate extracts were washed with water (twice) before drying (MgSO.) and concentrating to an oil.
  • Step 1 preparation of the ethyl ester of N-(3-trifluoromethyl-4- fluoro)phenyl fumaric acid amide
  • Diastereomer A eluted first, was a viscous, colourless gum (0.107g), IH NMR as in Table III; diastereomer B, eluted second, was a white powder (O.ll ⁇ g), IH NMR as in Table III.
  • Trifluoroacetic acid (1 drop) and 10% palladium on carbon (lOmg) were added successively to a stirred solution of diastereomer A of the propanoate from step 6 (0.105g) in ethyl acetate (15ml).
  • the resulting mixture was treated with hydrogen at atmospheric pressure for 6 hours at room temperature. The atmosphere of hydrogen was then replaced with nitrogen, and the reaction mixture was allowed to stand overnight and was
  • the sample then comprised the single diastereomer of N-t-butyl 2-[1-(3-[trifluoromethyl]phenyl)oxazolidin-2-on-3-yl]propanamide containing about 25% of the starting acid.
  • This material was a solid, with IH NMR for the amide as shown in Table III.
  • Bromine (4.3ml) was added over a period of 30 minutes, below the surface of the reaction mixture, to a stirred mixture of gamma-butyrolactone (8.60g) and phosphorus tribromide (0.2ml), heating the reaction mixture throughout to a temperature between 100 and 110 C. Following the addition, the mixture was heated with stirring at 100°C for 2 hours, then allowed to cool to 50 °C. Dry DMF (0.01ml) was added, the mixture was heated to 90 °C, thionyl chloride ( ⁇ . ⁇ ml) was added dropwise over 20 minutes (effervescence), and the resulting mixture was heated at 100°C for a further 3 hours.

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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP95920158A 1994-06-02 1995-05-26 Substituierte pyrrolodone, thiazolidone oder oxazolidone als herbizide Withdrawn EP0763020A1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
GB9410998 1994-06-02
GB9410998A GB9410998D0 (en) 1994-06-02 1994-06-02 Herbicides
GB9411004 1994-06-02
GB9411004A GB9411004D0 (en) 1994-06-02 1994-06-02 Herbicides
GB9501158 1995-01-20
GBGB9501158.1A GB9501158D0 (en) 1995-01-20 1995-01-20 Herbicides
PCT/GB1995/001224 WO1995033719A1 (en) 1994-06-02 1995-05-26 Substituted pyrrolidone, thiazolidones or oxazolidones as herbicides

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JP (1) JPH10500985A (de)
CN (1) CN1341594A (de)
AU (1) AU696084B2 (de)
BR (1) BR9507838A (de)
CA (1) CA2190979A1 (de)
HU (1) HUT75808A (de)
IL (1) IL113985A0 (de)
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GB9510750D0 (en) * 1995-05-26 1995-07-19 Zeneca Ltd Chemical process
GB9510744D0 (en) * 1995-05-26 1995-07-19 Zeneca Ltd Chemical process
GB9524526D0 (en) * 1995-11-30 1996-01-31 Zeneca Ltd Chemical process
GB9524667D0 (en) * 1995-12-01 1996-01-31 Zeneca Agrochemicals Herbicides
EP0880510A1 (de) * 1996-02-02 1998-12-02 Zeneca Limited Verfahren zur herstellung von 5-hydroxyoxazolidinonen
GB9610974D0 (en) * 1996-05-24 1996-07-31 Zeneca Ltd Herbicides
JPH10330359A (ja) 1997-03-31 1998-12-15 Nippon Bayeragrochem Kk フエニルアセチレン誘導体及び除草剤
GB9822116D0 (en) * 1998-10-09 1998-12-02 Zeneca Ltd Herbicides
AU1512600A (en) * 1998-12-04 2000-06-26 Takeda Chemical Industries Ltd. Process for producing cyclic amide compound
CA2361848A1 (en) * 1999-04-02 2000-10-12 Dupont Pharmaceuticals Company Novel lactam inhibitors of matrix metalloproteinases, tnf-.alpha., and aggrecanase
US7138361B2 (en) 2000-12-01 2006-11-21 E. I. Du Pont De Nemours And Company Herbicidal heterocycles
DE10135043A1 (de) * 2001-07-11 2003-01-30 Bayer Cropscience Gmbh Substituierte 3-Heteroaryl(amino- oder oxy)-pyrrolidin-2-one, Verfahren zu deren Herstellung und Verwendung als Herbizide oder als Pflanzenwachstumsregulatoren
WO2004037787A1 (de) * 2002-10-18 2004-05-06 Basf Aktiengesellschaft 1-phenylpyrrolidin-2-on-3-carboxamide
JP2005015390A (ja) * 2003-06-26 2005-01-20 Bayer Cropscience Ag アゾリジン誘導体及び除草剤
EP1533298A1 (de) 2003-11-21 2005-05-25 Newron Pharmaceuticals S.p.A. 3-aminopyrrolidonederivate
US8410149B2 (en) 2004-12-06 2013-04-02 Siga Technologies Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US7994221B2 (en) 2004-12-06 2011-08-09 Siga Technologies, Inc. Sulfonyl semicarbazides, carbonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US8642596B2 (en) 2004-12-06 2014-02-04 Siga Technologies, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arena viruses
US20090042858A1 (en) * 2005-06-16 2009-02-12 Paul Barsanti Lactam containing hcv inhibitors
CA2662574A1 (en) * 2006-09-22 2008-03-27 Novartis Ag Heterocyclic organic compounds
JP5566288B2 (ja) * 2008-05-30 2014-08-06 武田薬品工業株式会社 複素環化合物
CN103965138B (zh) * 2014-04-30 2016-01-20 西北农林科技大学 N-烷氧(硫)烷基苯并杂环衍生物及其作为除草剂的用途
WO2017002201A1 (ja) * 2015-06-30 2017-01-05 株式会社エス・ディー・エス バイオテック シクロプロパンカルボン酸アミド化合物及びそれらを含有する除草剤
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BR9507838A (pt) 1997-09-16
HU9603248D0 (en) 1997-01-28
CN1341594A (zh) 2002-03-27
JPH10500985A (ja) 1998-01-27
TW350756B (en) 1999-01-21
AU696084B2 (en) 1998-09-03
HUT75808A (en) 1997-05-28
CA2190979A1 (en) 1995-12-14
IL113985A0 (en) 1995-10-31
AU2572095A (en) 1996-01-04

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