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WO1995033719A1 - Pyrrolidone, thiazolidones ou oxazolidones substitues utilises comme herbicides - Google Patents

Pyrrolidone, thiazolidones ou oxazolidones substitues utilises comme herbicides Download PDF

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Publication number
WO1995033719A1
WO1995033719A1 PCT/GB1995/001224 GB9501224W WO9533719A1 WO 1995033719 A1 WO1995033719 A1 WO 1995033719A1 GB 9501224 W GB9501224 W GB 9501224W WO 9533719 A1 WO9533719 A1 WO 9533719A1
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WO
WIPO (PCT)
Prior art keywords
compound
general formula
alkyl
phenyl
nmr
Prior art date
Application number
PCT/GB1995/001224
Other languages
English (en)
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
Original Assignee
Zeneca Limited
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 Limited filed Critical Zeneca Limited
Priority to BR9507838A priority Critical patent/BR9507838A/pt
Priority to JP8500502A priority patent/JPH10500985A/ja
Priority to AU25720/95A priority patent/AU696084B2/en
Priority to EP95920158A priority patent/EP0763020A1/fr
Publication of WO1995033719A1 publication Critical patent/WO1995033719A1/fr

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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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Definitions

  • This invention relates to chemical compounds useful as herbicides, to processes for preparing them, and to herbicidal compositions and processes utilising them.
  • heterocycles are known, for example from DE-A-2212558.
  • AU-A-8656417 also discloses compounds based upon nitrogen heterocycles and these are said to be useful as plant growth regulators. There is no mention of herbicidal activity.
  • X is 0, S or CR 4 R 5 ;
  • Z is 0, S or NR 4 ;
  • n 0 or 1
  • Y is 0, S, NR 6 or CR 4 R 5 ;
  • each R 4 and R 5 is, independently, hydrogen or C 1 -C 4 alkyl
  • R 6 is H, OH, CHO, NR 16 R 17 or C 1 -C 10 hydrocarbyl, 0-(C 1 -C 10 hydrocarbyl), either of which may be substituted with one or more substituents chosen from OR 16 , COR 16 , COOR 16 , OCOR 16 , CN, halogen, S(O) R 16 , NR 16 R 17 , NO 2 ,
  • R 16 , R 17 andR 18 are each, independently, hydrogen, C 1 -C 6 hydrocarbyl or C 1 -C 6 halohydrocarbyl;
  • p 0, 1 or 2;
  • Z is NR 4 ;
  • n 0;
  • R 14 represents hydrogen or C 1 -C 4 alkyl
  • W is 0 or S
  • R 1 is hydrogen or C 1 -C 10 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, SO 2 NR a R b (where R a and R b are independently H or C 1 -C 6 alkyl), SiR c 3 (where each R c is independently C 1 -C 4 alkyl or phenyl), cyano, nitro, amino, mono- and dialkylamino in which the alkyl groups have from 1 to 6 or more carbon atoms, acylamino, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulphinyl, C 1 -C 6 alkylsulphonyl, carboxy,
  • halogen i.e.
  • carboxyamide in which the groups attached to the N atom may be hydrogen or optionally substituted lower hydrocarbyl; alkoxy carbonyl wherein the alkoxy group may have from 1 to 6 or more carbon atoms, or aryl such as phenyl;
  • R 2 and R 3 are each independently hydrogen or C 1 -C 4 alkyl
  • A is an aromatic or heteroaromatic ring system optionally substituted with one or more substituents selected from: halogen or C 1 -C 10 hydrocarbyl, -O(C 1 -C 10 hydrocarbyl), -S(C 1 -C 10 hydrocarbyl), -SO(C 1 -C 10 hydrocarbyl) or -SO 2 (C 1 -C 10 hydrocarbyl), cyano, nitro, SCN, SiR c 3 , (where each R c is independently C 1 -C 4 alkyl or phenyl), COR 7 , CR 7 NOR 8 , NHOH, ONR 7 R 8 , SF 5 , COOR 7 , SO 2 NR 7 R 8 , OR 9 or NR 10 R 11 ; and in which 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 heterocycl
  • R 7 andR 8 are each independently hydrogen or C 1 -C 10 hydrocarbyl
  • R 9 is hydrogen, C 1 -C 10 hydrocarbyl, SO 2 (C 1 -C 10 hydrocarbyl), CHO,
  • R 10 and R 11 are each independently hydrogen, C 1 -C 10 hydrocarbyl,
  • any of the hydrocarbyl groups within the group A may optionally be substituted with halogen (i.e. chlorine, bromine, fluorine or iodine), hydroxy, SO 2 NR a R b (where R a and R b are independently H or C 1 -C 6 alkyl), cyano, nitro, amino, mono- and dialkylamino in which the alkyl groups have from 1 to 6 or more carbon atoms, acylamino, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulphinyl, C 1 -C 6 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 carbonyl wherein the alkoxy carbonyl wherein the alkoxy carbonyl wherein
  • R 1 is other than pyridyl, trimethoxyphenyl or
  • 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.
  • WO-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.
  • C 1 -C 10 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 1 -C 10 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.
  • alkyl, alkenyl, and alkynyl radicals cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, and cyclohexyl radicals, the adamantyl radical and the phenyl radical.
  • heterocyclyl in the foregoing definitions is intended to include both aromatic and non-aromatic radicals.
  • C 1 -C 6 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.
  • C 2- C 6 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- C 6 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,
  • Nitrogen atoms in the ring may be
  • 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,
  • benzoxazolyl benzisoxazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl.
  • fused saturated or partially saturated carbocyclic or heterocyclic ring refers to a ring system in which a 5- or 6- membered 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, n-propyl, iso-propyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, trichloromethyl, ethoxyvinyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, n-propoxy, iso-propoxy, difluoromethoxy,
  • each alkyl group may have from 1 to 6 or more carbon atoms, hydroxylamino, acyl (e.g. acetyl or trifluoroacetyl), methylthio, methylsulphinyl, methylsulphonyl, trifluoromethylthio, SCN, SF 5 ,
  • Preferred substituents of the group A include C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, O(C 1 -C 4 alkyl), O(C 1 -C 4 haloalkyl), S(C 1 -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 1 is hydrogen orC 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2- C 6 alkynyl, CO(C 1 -C 8 alkyl), CO(C 2- C 6 alkenyl), CO(C 2- C 6 alkynyl), C 3 -C 8 cycloalkyl, benzyl, phenyl or a 5 or 6 membered heterocyclic ring.
  • R 1 groups may be substituted with one or more substituents chosen from halo, SiR c 3 , CN, COOH, COO(C 1 -C 4 alkyl), COH N(C 1 -C 4 alkyl) 2 or CO(C 1 -C 4 alkyl) and cycloalkyl, benzyl, phenyl or heterocyclic R 1 groups may, additionally, be substituted with C 1 -C 6 alkyl, C 2- C 6 alkenyl or C 2- C 6 alkynyl.
  • preferred groups R 1 include optionally
  • substituted C 1 -C 6 alkyl for example methyl, -C(CH 3 ) 3 , -CH(CH 3 ) 2 ,
  • cycloalkyl for example cyclobutyl, 1-methylcyclobutyl,
  • 1-cyanocyclohexyl 1-acetylenylcyclopropyl, 1-acetylenylcyclobutyl, 1-acetylenylcyclopentyl, 1-acetylenylcyclohexyl; optionally substituted phenyl; optionally substituted heterocyclyl, for example pyrrolyl, methyl isoxazolyl or methylpyridyl; COC 1 -C 6 alkyl, for example COC(CH 3 ) 3 ; C 1 -C 6 alkylCOO(C 1 -C 4 alkyl), for example C(CH 3 ) 2 COOC 2 H 5 ; or SiR c 3 , for example trimethylsilyl.
  • 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 2 and R 3 are both hydrogen;
  • R is hydrogen, -CHO, C 1 -C 6 alkyl, C 2- C 6 alkenyl, C 2- C 6 alkynyl, C 3 -C 8 cycloalkyl, aryl, for example benzyl which is optionally substituted with C 1 -C 4 haloalkyl, or C 1 -C 4 haloalkoxy, (C 1 -C 6 alkyl)aryl, (C 1 -C 6 alkyl)heterocyclyl, -O(C 1 -C 6 alkyl), -O(C 1 -C 6 alkyl)aryl, -O(C 1 -C 6 alkyl)heterocyclyl, -C 1 -C 6 alkyl-OH, -(C 1 -C 6 alkyl)-O-(C 1 -C 6 alkyl), -(C 1 -C 6 alkyl)-S-(C 1 -C 6 alkyl
  • R 6 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-1-yl,
  • 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 diastereomeric 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
  • compounds of General formula I may be synthesised from compounds of general formula II, wherein A, R 2 , R 3 and X are as defined for
  • 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 50oC, preferably at room temperature.
  • the reaction generally proceeds most favourably in the presence of a base which may be an amine such as
  • DMAP 4-N,N dimethylaminopyridine
  • the base may be replaced with a catalytic amount of boron trifluoride etherate.
  • Compounds of general formula I where X is CR 4 R 5 , Z is NR 4 , W is 0, Y is NR 6 and n is 1 may be prepared by treatment of a compound of general formula II where R 15 is NHR 6 with a carbamoyl chloride of general formula R 1 R 4 NCOCl 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
  • Compounds of the formula R 1 R 4 NCOCl are known in the art or may be prepared by the treatment of an amine of formula NHR 1 R 4 with phosgene in a suitable solvent such as toluene.
  • Compounds of general formula II may be synthesised by various routes from compounds of general formula III, wherein A, R 2 , R 3 and X are as defined for general formula I and R 20 is a leaving group such as Cl , Br, I, methane sulphonyloxy or toluene sulphonyloxy.
  • 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).
  • 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 15 is NHR 6 and R 6 is other than hydrogen may be prepared from compounds of general formula III by reaction with a compound of formula NH 2 R 6 , wherein R 6 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
  • reaction 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) .
  • Compounds of general formula II in which R 15 is OH may be prepared from compounds of general formula III, in which R 20 is Cl, by reaction with an aqueous base, typically a weak base such as an alkali metal bicarbonate.
  • an aqueous base typically a weak base such as an alkali metal bicarbonate.
  • 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
  • Compounds of general formula II in which R 15 is OH may also be prepared from compounds of general formula IV, wherein A, R 2 , R 3 and X are as defined in general formula I, by reaction with a strong base such as LiN(Si(CH 3 ) 3 ) 2 or LiN(CH(CH 3 ) 2 ) 2 followed by reaction with a compound possessing an active oxygen, such as a compound of formula V in which, for example, Ar is a p-tolyl group and Ar' is a phenyl group.
  • the reaction is suitably effected in a solvent such as THF at a temperature of from about -100° to 30°C, preferably from -80° to 0°C.
  • a method for the preparation of compounds of general formula II in which R 15 is OH and X is CH 2 is by the reaction of a derivative of general formula VI in which A is as defined for general formula I with a compound of general formula VII wherein R 2 and R 3 are as defined for general formula
  • 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.
  • chlorination or bromination as appropriate.
  • the particular method of halogenation will depend upon the nature of the groups A and X but an appropriate route may be determined by the skilled chemist.
  • chlorination may be carried out using an agent such as sulphuryl chloride, N-chlorosuccinimide or chlorine.
  • the reaction may take place in a chlorinated solvent such as dichloromethane.
  • the chlorination reaction will preferably be carried out at a temperature of -15oto 5oC, preferably -5° to 0°C.
  • bromination is typically carried out by reaction with bromine in the presence of phosphorus tribromide or with
  • 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.
  • triphenylphosphine The solvent employed will preferably be an ether, particularly diethyl ether and the reaction may be initiated at a
  • R 20 is methane sulphonyloxy or toluene sulphonyloxy
  • R 15 is OH by reaction with methane sulphonyl chloride or toluene sulphonyl chloride as appropriate.
  • the reaction may be conducted at a temperature of from 0° to 30°C, usually at about 5°C in a solvent such as dichloromethane and in the presence of a base such as triethylamine.
  • Compounds of general formula III in which R 20 is I may be prepared from compounds of general formula III in which R 20 is Cl or Br by reaction with sodium iodide in a solvent such as acetone.
  • Compounds of formulae III and IV in which X is CR 4 R 5 may also be produced by cyclising a compound of formula XXIII in which A, R 2 , R 3 , R 4 and R 5 are as defined in relation to formula I, R 26 is H, Cl or Br and R 27 is halogen such as bromine or iodine in the presence of a base such as an alkali metal alkoxide or hydride in an appropriate solvent and at
  • temperatures of from 0°C to 70°C suitably at ambient temperature.
  • the base is an alkali metal alkoxide such as sodium methoxide
  • an alcohol will be a suitable solvent but when an alkali metal hydride, for example sodium hydride is chosen, it is more appropriate to choose an aprotic solvent such as THF.
  • R 2 , R 3 , R 4 and R 5 are as defined in relation to formula I and R 26 and R 27 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 IV in which X is S may be prepared from derivatives of general formula VI, in which A is as defined for general formula I, by reaction with thioglycolic acid and a compound of general formula R 2 R 3 CO with continuous removal of water from the reaction.
  • 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.
  • compounds of formula IV in which X is CR 4 R 5 may be produced from compounds of formula XXV, where A is as defined in relation to formula I and R 13 is halogen, by reaction with a compound of formula XXVI where R 2 , R 3 , R 4 and R 5 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.
  • 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.
  • Compounds of general formula II in which X is O and R 15 is OH may be prepared from compounds of general formula XIII, wherein A, R 2 and R 3 are as defined for general formula I and each R 19 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.
  • A is as defined for general formula I; by reaction with compounds of the formula R 19 OCR 2 R 3 X where X is halogen, particularly chlorine, and R 2 , R 3 and R 19 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 tetrabutyl ammonium 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 general formula XVI, wherein R 19 is as defined for general formula XIII; by known methods such as treatment with aqueous potassium carbonate in a solvent such as tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • Esters of general formula XVI may be prepared from dichloroacetic acid by reaction with a mixture of an alcohol of general formula R 19 OH, where R 19 is as defined above for general formula XIII, and its corresponding alkali metal alkoxide. The reaction will usually be conducted in the appropriate alcohol. All of the starting materials of this reaction are readily available.
  • Compounds of general formula XII may be synthesised from compounds of general formula XVII, wherein A, R 2 and R 3 are as defined for general formula I, R 21 is as defined above and R 23 is C 1 -C 6 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.
  • Compounds of general formula XVII may be obtained by the oxidation of compounds of general formula XVIII, wherein A, R 2 , R 3 , R 21 and R 23 are as defined above using, for example, an oxidising agent such as sodium periodate.
  • the 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.
  • R 2 and R 3 are as defined for general formula I
  • R 21 is as defined for general formula XII
  • 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.
  • Compounds of general formula XIX may be synthesised by reacting a compound of general formula VI with a compound of general formula XXXI, wherein R 23 is as defined above and R 22 is C 1 -C 6 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 15 is OH may prepared by solvolysis of compounds of formula XXI in which A, R 2 and R 3 are as defined in relation to formula I.
  • the reaction is conveniently carried out in the presence of an aqueous alcohol, such as methanol, in a solvent such as dichloromethane at temperatures of from 0 to 50°C, preferably ambient temperature.
  • aqueous alcohol such as methanol
  • a solvent such as dichloromethane
  • the reaction often proceeds more successfully if conducted in the presence of a weak base such as sodium or potassium bicarbonate.
  • trifluoroacetic acid at temperatures of -10°C to 70°C, suitably at ambient temperature.
  • 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 15 is SH
  • the second step is preferably carried out at a temperature of -10° to +10oC, usually about 0°C.
  • R 4 and R 5 are as defined for general formula I and R 25 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.
  • a compound of general formula I in which X is RR 4 R 5 , Y is 0, W is 0 and Z is NH may be prepared from a compound of general formula XXVIII using the same steps as described above but carried out in reverse order.
  • a compound of general formula I in which X is RR 4 R 5 , Y is 0, W is 0 and Z is NH may be prepared from a compound of general formula XXVIII using the same steps as described above but carried out in reverse order.
  • XXVIII may be cyclised to give a compound of general formula II in which R 15 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 2 , R 3 , R 4 and R 5 are as defined in general formula I, in the presence of a reagent such as boron tribromide, aluminium
  • the 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.
  • This reaction produces compounds of general formula I in which Y is CR 4 R 5 , Z is 0 and 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
  • An inert atmosphere such as nitrogen or argon may also be necessary for this reaction.
  • 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
  • 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
  • a suitable solvent such as toluene
  • a suitable base such as triethylamine
  • Compounds of general formula I in which Y is CR 4 R 5 and Z is NR 4 may be prepared from compounds of general formula X in which A, X, R 2 , R 3 , R 4 and R 5 are as defined in general formula I by reaction with amines of general formula NHR 1 R 4 . It is preferable that the 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.
  • Compounds of general formula X may be prepared from the parent acids, which are compounds of general formula I in which Y is CR 4 R 5 , Z is 0 and R 1 is H, by reaction with an agent such as oxalyl chloride or thionyl chloride. The reaction will generally take place under dry conditions.
  • 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
  • the parent acids of general formula I in which Y is CR 4 R 5 , Z is 0 and R 1 is H may be prepared from corresponding esters of general formula I in which Y is CR 4 R 5 , Z is 0 and R 1 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 1 is a group such as t-butyl
  • a strong acid such as
  • TFA trifluoroacetic acid
  • 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
  • An alternative method of preparation of parent acids of general formula I in which Y is CR 4 R 5 , Z is 0 and R1 is H is by hydrogenolysis of the corresponding esters of general formula I in which Y is CR 4 R 5 , Z is 0 and R1 is a benzyl group.
  • the reaction is carried out under an atmosphere of hydrogen in the presence of a catalyst such as 5% or 10% palladium on charcoal in an organic solvent such as ethyl acetate, tetrahydrofuran, dioxane or an alcohol such as methanol or ethanol.
  • a catalyst such as 5% or 10% palladium on charcoal
  • organic solvent such as ethyl acetate, tetrahydrofuran, dioxane or an alcohol such as methanol or ethanol.
  • the reaction will take place in the absence of an acid catalyst, but will often proceed more rapidly in the presence of a catalytic amount of an acid such as
  • reaction temperatures may range from 0° to 50°C with room temperature being preferred.
  • esters of general formula I in which Y is CR 4 R 5 , W is 0, Z is 0 and R 1 is an alkyl group may be converted directly to amides of general formula I in which Y is CR 4 R 5 and Z is NR 4 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. In some cases, halogen exchange may also occur to some extent during the reaction.
  • the catalyst is AlCl 3 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 CCl 3 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 4 R 5 , with at least one of R 4 and R 5 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 4 -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 -78oC.
  • 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
  • esters of general formula I may be prepared from compounds of general formula IV.
  • a further method for the synthesis of compounds of general formula I in which X is 0, Y is CH 2 or CHR 4 , W is 0, and Z is 0 is from compounds of general formula XI in which R 1 and A are as defined for general formula I.
  • Fumaric esters of general formula XI where A, R 1 and R 4 are as defined in relation to formula I are prepared from the corresponding fumaric monoalkyl esters of general formula XXXV where R 1 and R 4 are as defined in relation to formula I.
  • Fumaric monoalkyl esters of general formula XXXV are reacted with a compound of formula VI where A is defined in relation to formula I in the presence of a dehydrating agent such as dicyclohexylcarbodiimide.
  • the reaction is conducted in an aprotic organic solvent such as dichloromethane or chloroform, at temperatures of from 0 to 50°C with room temperature being preferred.
  • fumaric esters of general formula XI where A, R 1 and R 4 are as defined in relation to formula I may be prepared by converting fumaric monoalkyl esters of general formula XXXV where R 1 and R 4 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
  • fumaric esters of general formula XI where A and R 4 are as defined in relation to formula I and R 1 is benzyl may be prepared from the corresponding fumaric acids of general formula XI where A and R 4 are as defined in relation to formula I and R 1 is hydrogen.
  • Compounds of general formula XI in which R 1 is hydrogen may be reacted with benzyl alcohol in the presence of diethyl azodicarboxyl ate 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 4 are as defined in relation to formula I and R 1 is t-butyl may be prepared from the corresponding fumaric acids of general formula XI where A and R 4 are as defined in relation to formula I and R 1 is hydrogen.
  • Compounds of general formula XI in which R 1 is hydrogen may be reacted with dimethyl formamide
  • 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 4 are as defined in relation to formula I and R 1 is hydrogen may be prepared from fumaric acids of general formula XI where A and R 4 are as defined in relation to formula
  • I and R 1 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 1 and R 4 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 0o to 80oC, preferably room temperature.
  • R 20 is a leaving group such as I or Br by reaction with an imidazolinedione of general formula XXXVI where each of R 12 and R 13 independently represent hydrogen or C 1 -C 4 alkyl.
  • the reaction is carried out in an organic solvent such as N,N-dimethyl formamide or tetrahydrofuran, in the presence of a strong base such as sodium hydride.
  • 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 5o to 50°C but will, in most cases, be room temperature.
  • OR 28 wherein R 28 is C 1 -C 4 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 in 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.
  • Compounds of general formula I wherein X is CR 4 R 5 , Y and Z (if present) are other than S and the group A is a phenyl group with an S(C 1 -C 4 alkyl) or S(C 1 -C 4 haloalkyl) substituent may be oxidised to give compounds of general formula I with the corresponding sulfoxide substituent on the A group.
  • the oxidation may be carried out using, for example, one equivalent of an agent such as metachloroperbenzoic acid (MCPBA) in a halogenated solvent, for example chloroform.
  • MCPBA metachloroperbenzoic acid
  • the reaction is preferably conducted at a temperature of from 0°C to room temperature.
  • 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 CO(Z) m R 1 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
  • pre-emergence application but they are preferably applied to the soil before the unwanted plants emerge (pre-emergence 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 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
  • 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
  • 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. Agral 90TM) or
  • 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 L77TM).
  • a suitable mixture in mineral oil is Atplus 411FTM .
  • 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.
  • 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
  • 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
  • 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);
  • dinitroaniline herbicides such as dinitramine, trifluralin,
  • aryl urea herbicides such as diuron, flumeturon, metoxuron,
  • neburon isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, methabenzthiazuron;
  • 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, thiobencarb, butylate*, EPTC* , tri-allate, di-allate, esprocarb, tiocarbazil, pyridate, and dimepiperate;
  • N benzoic acid herbicides such as 2,3,6-TBA, dicamba and
  • O. anilide 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;
  • R. diphenylether herbicides such as lactofen, fluroglycofen or
  • 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 alloxydim 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-1,3,5- tri azin -zyl) -3-methy lu rei dosulphonyl) benzoi c acid esters such as the methyl ester thereof (DPX-LS300) and pyrazosulfuron;
  • V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropyl ammonium salts thereof, imazethapyr;
  • X. amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulphosate and bialaphos;
  • Y. organoarsenical herbicides such as monosodium methanearsonate
  • Z herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide and naptalam;
  • AA miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac, mefanacet, and triketone herbicides such as sulcotrione;
  • 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;
  • the invention is illustrated by the following Examples.
  • -NMR Nuclear Magnetic Resonance (performed at 270MHz and in CDCl3 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).
  • Steps 3 to 5 The procedures described in Steps 3 to 5 were also used to prepare Compounds 28 (m.p. 175-176°C), 53 (m.p. 175-176.5°C) and 55 (m.p.
  • Oxalyl chloride (0.127ml) was added via syringe to a suspension of
  • Step 1b Further alternative route for the preparation of
  • 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 in 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-1-(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
  • a 200ml 3 necked flask was equipped with stoppers, dropping funel, thermometer, nitrogen bubbler and magnetic stirrer.
  • the flask was charged with 15.0g of 1-(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. Tlc indicated incomplete reaction, so the mixture was heated to 105°C and a further quantity of bromine (0.73g) added. After 100 minutes, the reaction was cooled and washed with 75% Na 2 S 2 O 3 solution (3x25ml), dried over MgSO 4 and evaporated to give 17.7g of material which
  • 3-trifluoromethylaniline were prepared successively 2,4-dibromo- N(3-trifluoromethylphenyl)butanamide and 3-bromo-1(3-trifluoromethyl- phenylpyrrolidin-2-one).
  • the latter compound was identified by an NMR spectrum which was identical to that of the product of Step 1 above.
  • Methylamine gas was bubbled through a solution of 3-bromo-1-(3- trifluoromethyl)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
  • Oxalyl chloride (0.127ml) was added to a suspension of
  • Oxalyl chloride (0.190ml) was added to a stirred suspension of
  • Trifluoroacetic acid (1ml) was added to a solution of t-Butyl-[1- (3-trifluoromethyl)phenyl-2-pyrrolidinone-3-yl]acetate (prepared as described in Example 7) (0.70g) in dichloromethane (10ml) at room
  • 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 HyfloTM to remove catalyst.
  • the ester (Compound 7, 2.112g) was dissolved in THF (30ml) at -78°C. Lithium hexamethyldisilazide (6.79ml of a 1.0m THF solution) was added via syringe. After 30 minutes at -78°C, 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 4 . The solvent was evaporated and the residue purified by flash chromatography, eluting with 25% ethyl acetate in hexane to give a (1:1) mixture of the required product and the 3-methylpyrrol idone product (1.0g).
  • 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.
  • Step 1 Preparation of 3-(N-ethoxycarbonylmethyl)amino-1-(3-trifluoromethyl)phenyl -2-pyrrolidinone.
  • Ethyl bromoacetate (0.155ml) was added via syringe to a solution of 3-amino-1-(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 NaHCO 3 (aq) and extracted with ethyl acetate (x2). Combined extracts were dried (Na 2 SO 4 ), evaporated and the residue purified by flash chromatography (eluting with ethyl acetate) to give
  • 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-1-(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-1-(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 SO 4 ).
  • Step 2 Preparation of 3-(t-Butylcarbamoyl-N-methoxy)amino-1- -(3-trifluoromethyl)phenyl-2-pyrrolidinone.
  • Step 1 Preparation of 3-methylsulfonyloxy-1-(3-trifluoromethoxy)phenyl-2- pyrrolidinone.
  • Step 2 Preparation of 3-(N-formyl)amino-1-(3-trifluoromethoxy)phenyl-2- pyrrolidinone.
  • N-formyl compound prepared as in Step 2 (0.97g) was dissolved in CH 2 Cl 2 (20ml). triethylamine (0.51ml) was added, followed by
  • Step 1 Preparation of 3-(N-allyl)amino-1-(3-trifluoromethoxy)- phenyl-2-pyrrolidinone.
  • Step 2 Preparation of 3-(t-Butylcarbamoyl-N-allyl)amino-1-(3-trifluoromethoxy)phenyl -2-pyrrolidinone.
  • N-allyl derivative (0.23g) (prepared as described in Step 1) was dissolved in CH 2 Cl 2 (3ml) and treated with triethylamine (0.16ml) followed by t-butyl isocyanate (0.22ml). After 48 hours at room temperature, the reaction was diluted with CH 2 Cl 2 , washed with 2N HCl (aq) (x2), brine and dried over MgSO 4 . 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-1,3,4-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 extracts were washed, dried over magnesium sulphate, evaporated under reduced pressure and
  • thiazolidin-4-one (1.38g), prepared as described in Example 37, Steps 1-3, 1,1-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). NMR (CDCl 3 ): ⁇ 1.6(6H,s); 2.35(1H,s);
  • the title compound was prepared by a procedure similar to that described in Step 1 of Example 35, but using 2-amino-4,6-bis-trifluoromethylpyridine (5.0g), thioglycolic acid (2.0g), 37% aqueous formaldehyde solution
  • 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 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 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
  • Lithium bis(trimethylsilyl)amide (5.72ml, 1M solution in tetrahydrofuran) was added dropwise to a stirred suspension of 1(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),
  • 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
  • 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). NMR
  • 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 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.
  • thioglycolic acid (3.1g), 37% aqueous formaldehyde solution (2.7ml), p-toluenesulphonic acid (0.025g) and toluene (70ml), in a manner similar to that described in Example 51, gave a mixture (7.13g) of the title compound and ((5-trifluoromethylpyridin-2-yl)aminomethylthio)acetic acid in a ratio of 1:2.
  • the mixture was dissolved in dichloromethane (50ml), treated with triethylamine (1.44g), cooled to below 5°C, and the stirred solution treated with thionyl chloride (1.74g) then, after two hours, with
  • 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 extracted with ethyl acetate, the extracts dried and evaporated under reduced pressure and the residue chromatographed on silica, using dichloromethane-ethanol (49:1) as eluant, to give the title compound (0.21g, m.p. 150-151°C).
  • MS MH + 266.
  • 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
  • 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
  • 4-Amino-6(2,2,2-trifluoroethoxy)pyrimidine (0.61g, m.p. 113°C) was made by treating 4-amino-6-chloropyrimidine (1.0g) with sodium
  • 4-Amino-6-difluoromethoxypyrimidine (0.17g, m.p. 152-154°C) was made by passing chlorodifluoromethane into a solution of
  • 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.
  • Compound 193 (0.15g, m.p. 123°C).
  • Compound 192 had NMR (CDCl 3 ): ⁇ 1.35(9H,s); 2.3(1H,m); 2.6(1H,m); 2.9(3H,s); 3.9(1H,m);
  • Compound 194 had NMR (CDCl 3 ): ⁇ 1.37(9H,s); 2.13(1H,m); 2.47(1H,m); 2.84(3H,s); 3.75(2H,m); 4.44(1H,bs); 5.17(1H,dd); 7.04(1H,d); 7.12(1H,dd); 7.73(1H,d). MS: M + 369.
  • Compound 195 had NMR (CDCl 3 ): ⁇ 1.09(9H,s); 2.20(1H,d); 2.33(2H,d);

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

On décrit des composés de formule générale (I), où X représente O, S ou CR4R5; each R?4 and R5¿ représente indépendamment hydrogène ou alkyle C¿1-4?; Z représente O, S ou NR?4¿; n vaut 0 ou 1; Y représente O, S, NR?6 ou CR4R5; R6¿ représente H, OH, CHO, NR16R17 ou hydrocarbyle C¿1-10?, 0-(hydrocarbyle C1-10), l'un ou l'autre pouvant être substitué par un ou plusieurs substituants choisis parmi OR?16, COR16, COOR16, OCOR16¿, CN, halogène, S(O)¿p?R?16, NR16R17, NO¿2, NR?16COR17, NR16CONR17R18, CONR16R17¿ ou hétérocyclyle; R?16, R17 et R18¿ représentent chacun indépendamment hydrogène, hydrocarbyle C¿1-6? ou halohydrocarbyle C1-6; p vaut 0, 1 ou 2. Selon une autre possibilité, quand Y représente NR?6 ou CR4R5¿, et a) Z représente NR4 ou b) n vaut 0, les substituants d'Y et Z ou Y et R1 peuvent former ensemble un pont représenté par la formule -Q?1-Q2- ou -Q1-Q2-Q3-, où Q1, Q2 et Q3¿ représentent chacun indépendamment CR?12R13, =CR12¿, CO, NR14, =N, O ou S; R?12 et R13¿ représentent indépendamment hydrogène, alkyle C¿1-4?, OH ou halogène; R?14¿ représente hydrogène ou alkyle C¿1-4?; W représente 0 ou S; R?1¿ représente hydrogène ou hydrocarbyle C¿1-10? ou hétérocyclyle doté de 3 à 8 atomes d'un cycle; R?2 et R3¿ représentent chacun indépendamment hydrogène ou alkyle C¿1-4?; A représente un système cyclique aromatique ou hétéroaromatique éventuellement substitué, ou, selon une variante, au moins deux substituants du groupe A peuvent se combiner pour former un cycle carbocyclique ou hétérocyclique fusionné, saturé ou partiellement saturé, à 5 ou 6 éléments, où tout atome de carbone ou d'azote quaternarisé peut être substitué par tout groupe A susmentionné ou dans lequel un atome de carbone du cycle peut faire partie d'un groupe carbonyle ou un atome d'azote peut être oxydé.
PCT/GB1995/001224 1994-06-02 1995-05-26 Pyrrolidone, thiazolidones ou oxazolidones substitues utilises comme herbicides WO1995033719A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9507838A BR9507838A (pt) 1994-06-02 1995-05-26 Composto processo para preparar o mesmo composição herbicida e processo para danificar severamente ou exterminar plantas não-desejadas
JP8500502A JPH10500985A (ja) 1994-06-02 1995-05-26 除草剤としての置換ピロリドン、チアゾリドンまたはオキサゾリドン
AU25720/95A AU696084B2 (en) 1994-06-02 1995-05-26 Substituted pyrrolidone, thiazolidones or oxazolidones as herbicides
EP95920158A EP0763020A1 (fr) 1994-06-02 1995-05-26 Pyrrolidone, thiazolidones ou oxazolidones substitues utilises comme herbicides

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB9410998A GB9410998D0 (en) 1994-06-02 1994-06-02 Herbicides
GB9411004A GB9411004D0 (en) 1994-06-02 1994-06-02 Herbicides
GB9411004.6 1995-01-20
GB9410998.0 1995-01-20
GBGB9501158.1A GB9501158D0 (en) 1995-01-20 1995-01-20 Herbicides
GB9501158.1 1995-01-20

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CA (1) CA2190979A1 (fr)
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WO1996037466A1 (fr) * 1995-05-26 1996-11-28 Zeneca Limited Procede de preparation 2-pyrrolidonyl-3-esters, de thioesters et d'amides de l'acide (thio-)carbonique/carbamique
WO1996037483A1 (fr) * 1995-05-26 1996-11-28 Zeneca Limited Procede de preparation de 5-hydroxy-oxazolidin-4-one substituee
WO1997019920A1 (fr) * 1995-11-30 1997-06-05 Zeneca Limited Preparation de derives chiraux de 3-hydroxy-2-pyrrolidinone
WO1997028138A1 (fr) * 1996-02-02 1997-08-07 Zeneca Limited Procede de production de 5-hydroxy-oxazolidinones
WO1997045408A1 (fr) * 1996-05-24 1997-12-04 Zeneca Limited Indolines herbicides
US5705456A (en) * 1995-12-01 1998-01-06 Zeneca Limited Herbicides
EP0869123A2 (fr) * 1997-03-31 1998-10-07 Nihon Bayer Agrochem K.K. Dérivés de phénylacétylène
WO2000021928A1 (fr) * 1998-10-09 2000-04-20 Syngenta Limited Pyrrolidinone, thiazolidinone ou oxazolidinone substituee utilisee en tant qu'herbicides
WO2000034267A1 (fr) * 1998-12-04 2000-06-15 Takeda Chemical Industries, Ltd. Procede de production d'un compose d'amide cyclique
WO2000059285A2 (fr) * 1999-04-02 2000-10-12 Du Pont Pharmaceuticals Company Nouveaux inhibiteurs de lactame de metalloproteases matricielles, de tnf-alpha, et de l'aggrecanase
WO2002044173A2 (fr) * 2000-12-01 2002-06-06 E. I. Du Pont De Nemours And Company Heterocycles herbicides
WO2003005824A2 (fr) * 2001-07-11 2003-01-23 Bayer Cropscience Gmbh 3-heteroaryl(amino- ou oxy)-pyrrolidin-2-ones substituees, leur procede de production et leur utilisation comme herbicides ou comme regulateurs de la croissance vegetale
WO2004037787A1 (fr) * 2002-10-18 2004-05-06 Basf Aktiengesellschaft 1-phenylpyrrolidine-2-one-3-carboxamides
WO2005000824A1 (fr) * 2003-06-26 2005-01-06 Bayer Cropscience Aktiengesellschaft Derives d'azolidine en tant qu'agents herbicides
EP1827446A2 (fr) * 2004-12-06 2007-09-05 Siga Technologies, Inc. Semicarbazides de sulfonyle, semicarbazides et urees, leurs compositions pharmaceutiques et methodes pour traiter des virus a fievre hemorragique virale, y compris des infections associees a des adenavirus
EP1901752A2 (fr) * 2005-06-16 2008-03-26 Novartis AG Compositions et méthodes d'inhibition virale
WO2008036715A1 (fr) * 2006-09-22 2008-03-27 Novartis Ag Composés organiques
WO2009145286A1 (fr) 2008-05-30 2009-12-03 武田薬品工業株式会社 Composé hétérocyclique
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
US8063039B2 (en) 2003-11-21 2011-11-22 Newron Pharmaceuticals S.P.A. 3-aminopyrrolidone derivatives
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
WO2017002201A1 (fr) * 2015-06-30 2017-01-05 株式会社エス・ディー・エス バイオテック Composé d'amide d'acide cyclopropane carboxylique et herbicide le contenant
US10676431B2 (en) 2018-03-05 2020-06-09 Bristol-Myers Squibb Company Phenylpyrrolidinone formyl peptide 2 receptor agonists

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CN109761939B (zh) * 2019-01-08 2023-11-24 长江大学 取代芳基亚甲基型Rubrolide类化合物及其制备方法和应用

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US5670656A (en) * 1995-05-26 1997-09-23 Zeneca Limited Process for preparing pyrrolidinones
WO1996037483A1 (fr) * 1995-05-26 1996-11-28 Zeneca Limited Procede de preparation de 5-hydroxy-oxazolidin-4-one substituee
WO1996037466A1 (fr) * 1995-05-26 1996-11-28 Zeneca Limited Procede de preparation 2-pyrrolidonyl-3-esters, de thioesters et d'amides de l'acide (thio-)carbonique/carbamique
US5688962A (en) * 1995-05-26 1997-11-18 Zeneca Limited Cyclization process for making oxazolikinones
US5710283A (en) * 1995-11-30 1998-01-20 Zeneca Limited Preparation of chiral pyrrolidinone derivatives
WO1997019920A1 (fr) * 1995-11-30 1997-06-05 Zeneca Limited Preparation de derives chiraux de 3-hydroxy-2-pyrrolidinone
US5705456A (en) * 1995-12-01 1998-01-06 Zeneca Limited Herbicides
WO1997028138A1 (fr) * 1996-02-02 1997-08-07 Zeneca Limited Procede de production de 5-hydroxy-oxazolidinones
WO1997045408A1 (fr) * 1996-05-24 1997-12-04 Zeneca Limited Indolines herbicides
US6174839B1 (en) 1997-03-31 2001-01-16 Nihon Bayer Agrochem K.K. Phenylacetylene derivatives
EP0869123A2 (fr) * 1997-03-31 1998-10-07 Nihon Bayer Agrochem K.K. Dérivés de phénylacétylène
US5935907A (en) * 1997-03-31 1999-08-10 Nihon Bayer Agrochem K.K. Phenylacetylene derivatives
EP0869123A3 (fr) * 1997-03-31 2002-01-02 Nihon Bayer Agrochem K.K. Dérivés de phénylacétylène
WO2000021928A1 (fr) * 1998-10-09 2000-04-20 Syngenta Limited Pyrrolidinone, thiazolidinone ou oxazolidinone substituee utilisee en tant qu'herbicides
WO2000034267A1 (fr) * 1998-12-04 2000-06-15 Takeda Chemical Industries, Ltd. Procede de production d'un compose d'amide cyclique
WO2000059285A2 (fr) * 1999-04-02 2000-10-12 Du Pont Pharmaceuticals Company Nouveaux inhibiteurs de lactame de metalloproteases matricielles, de tnf-alpha, et de l'aggrecanase
WO2000059285A3 (fr) * 1999-04-02 2001-01-18 Du Pont Pharm Co Nouveaux inhibiteurs de lactame de metalloproteases matricielles, de tnf-alpha, et de l'aggrecanase
US6495548B1 (en) 1999-04-02 2002-12-17 Bristol-Myers Squibb Pharma Company Lactam inhibitors of matrix metalloproteinases, TNF-α and aggrecanase
US7138361B2 (en) 2000-12-01 2006-11-21 E. I. Du Pont De Nemours And Company Herbicidal heterocycles
WO2002044173A2 (fr) * 2000-12-01 2002-06-06 E. I. Du Pont De Nemours And Company Heterocycles herbicides
WO2002044173A3 (fr) * 2000-12-01 2002-10-10 Du Pont Heterocycles herbicides
WO2003005824A2 (fr) * 2001-07-11 2003-01-23 Bayer Cropscience Gmbh 3-heteroaryl(amino- ou oxy)-pyrrolidin-2-ones substituees, leur procede de production et leur utilisation comme herbicides ou comme regulateurs de la croissance vegetale
WO2003005824A3 (fr) * 2001-07-11 2003-05-01 Bayer Cropscience Gmbh 3-heteroaryl(amino- ou oxy)-pyrrolidin-2-ones substituees, leur procede de production et leur utilisation comme herbicides ou comme regulateurs de la croissance vegetale
US7355053B2 (en) 2002-10-18 2008-04-08 Basf Aktiengesellschaft 1-phenylpyrrolidine-2-one-3-carboxamides
WO2004037787A1 (fr) * 2002-10-18 2004-05-06 Basf Aktiengesellschaft 1-phenylpyrrolidine-2-one-3-carboxamides
WO2005000824A1 (fr) * 2003-06-26 2005-01-06 Bayer Cropscience Aktiengesellschaft Derives d'azolidine en tant qu'agents herbicides
US8063039B2 (en) 2003-11-21 2011-11-22 Newron Pharmaceuticals S.P.A. 3-aminopyrrolidone derivatives
US9115065B2 (en) 2004-12-06 2015-08-25 Kineta, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with Arenaviruses
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
US9067873B2 (en) 2004-12-06 2015-06-30 Kineta Four, LLC Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US8664274B2 (en) 2004-12-06 2014-03-04 Siga Technologies, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arena viruses
EP1827446A4 (fr) * 2004-12-06 2011-01-12 Siga Technologies Inc Semicarbazides de sulfonyle, semicarbazides et urees, leurs compositions pharmaceutiques et methodes pour traiter des virus a fievre hemorragique virale, y compris des infections associees a des adenavirus
US8658697B2 (en) 2004-12-06 2014-02-25 Siga Technologies, Inc. Sulfonyl 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
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
EP1827446A2 (fr) * 2004-12-06 2007-09-05 Siga Technologies, Inc. Semicarbazides de sulfonyle, semicarbazides et urees, leurs compositions pharmaceutiques et methodes pour traiter des virus a fievre hemorragique virale, y compris des infections associees a des adenavirus
EP1901752A2 (fr) * 2005-06-16 2008-03-26 Novartis AG Compositions et méthodes d'inhibition virale
EP1901752A4 (fr) * 2005-06-16 2009-07-08 Novartis Ag Compositions et méthodes d'inhibition virale
US8236835B2 (en) 2006-09-22 2012-08-07 Novartis Ag Heterocyclic inhibitors of stearoyl-CoA desaturase
WO2008036715A1 (fr) * 2006-09-22 2008-03-27 Novartis Ag Composés organiques
US8338622B2 (en) 2008-05-30 2012-12-25 Takeda Pharmaceutical Company Limited Heterocyclic compound
EP2295406A4 (fr) * 2008-05-30 2012-04-18 Takeda Pharmaceutical Composé hétérocyclique
CN102112440A (zh) * 2008-05-30 2011-06-29 武田药品工业株式会社 杂环化合物
EP2295406A1 (fr) * 2008-05-30 2011-03-16 Takeda Pharmaceutical Company Limited Composé hétérocyclique
WO2009145286A1 (fr) 2008-05-30 2009-12-03 武田薬品工業株式会社 Composé hétérocyclique
WO2017002201A1 (fr) * 2015-06-30 2017-01-05 株式会社エス・ディー・エス バイオテック Composé d'amide d'acide cyclopropane carboxylique et herbicide le contenant
US10676431B2 (en) 2018-03-05 2020-06-09 Bristol-Myers Squibb Company Phenylpyrrolidinone formyl peptide 2 receptor agonists
US11117861B2 (en) 2018-03-05 2021-09-14 Bristol-Myers Squibb Company Phenylpyrrolidinone formyl peptide 2 receptor agonists
US11708327B2 (en) 2018-03-05 2023-07-25 Bristol-Myers Squibb Company Phenylpyrrolidinone formyl peptide 2 receptor agonists

Also Published As

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HU9603248D0 (en) 1997-01-28
TW350756B (en) 1999-01-21
AU696084B2 (en) 1998-09-03
CA2190979A1 (fr) 1995-12-14
HUT75808A (en) 1997-05-28
CN1341594A (zh) 2002-03-27
BR9507838A (pt) 1997-09-16
IL113985A0 (en) 1995-10-31
EP0763020A1 (fr) 1997-03-19
AU2572095A (en) 1996-01-04
JPH10500985A (ja) 1998-01-27

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