WO1994005662A1 - Indolizines as herbicides - Google Patents

Indolizines as herbicides Download PDF

Info

Publication number
WO1994005662A1
WO1994005662A1 PCT/EP1993/002132 EP9302132W WO9405662A1 WO 1994005662 A1 WO1994005662 A1 WO 1994005662A1 EP 9302132 W EP9302132 W EP 9302132W WO 9405662 A1 WO9405662 A1 WO 9405662A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
optionally substituted
formula
preparation
hydrogen
Prior art date
Application number
PCT/EP1993/002132
Other languages
English (en)
French (fr)
Inventor
Glynn Mitchell
Stephen Christopher Smith
Eric Daniel Clarke
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
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to EP94908879A priority Critical patent/EP0659186A1/en
Priority to AU49471/93A priority patent/AU4947193A/en
Priority to JP6506787A priority patent/JPH08501290A/ja
Publication of WO1994005662A1 publication Critical patent/WO1994005662A1/en

Links

Classifications

    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems

Definitions

  • the present invention relates to herbicidal compositions containing bicyclic compounds to novel herbicidal bicyclic compounds and to processes for their preparation.
  • optionally substituted alkyl optionally substituted alkenyl; optionally substituted alkynyl; optionally substituted aryl; optionally substituted aromatic heterocyclic; halo; nitro; cyano; a group OR 6 where R 6 is hydrogen or a salt thereof, carboxy or an ester thereof, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl; carboxy or a salt, ester or amide derivative thereof; S(O) n R 7 where n is 0, 1 or 2 and R 7 is optionally alkyl, optionally substituted alkenyl, optionally substituted alkynyl or optionally substituted aryl; NR 8 R 9 where R 8 and R 9 are independently selected from hydrogen, optionally substituted alkyl, optionally
  • substituted alkenyl optionally substituted alkynyl or optionally
  • substituted aryl and R 9 may additionally be acyl, or R 8 and R 9 together with the nitrogen atom to which they are attached form a heterocyclic ring; or R 1 and R 2 and/or any adjacent two of R 3 , R 4 and R 5 together with the carbon atoms to which they are attached form an optionally substituted fused saturated or unsaturated carbocyclic or heterocyclic ring; in combination with a carrier or diluent.
  • compositions comprising a compound of formula (I), where R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen; optionally substituted alkyl; optionally
  • R 6 is hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl; carboxy or a salt, ester or amide derivative thereof; S(O) n R 1 where n is 0, 1 or 2 and R 7 is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl or
  • NR 8 R 9 where R 8 and R 9 are independently selected from hydrogen, alkyl, alkenyl or alkynyl and R 9 may additionally be acyl; or R 1 and R 2 and/or any adjacent two of R 3 , R 4 and R 5 together with the carbon atoms to which they are attached form a fused saturated or unsaturated carbocyclic or heterocyclic ring; in combination with a carrier or diluent.
  • alkyl includes straight or branched alkyl chains, suitably containing up to 10 carbon atoms, preferably from 1 to 6 carbon atoms.
  • alkoxy relates to such an alkyl group linked with an oxygen atom.
  • alkenyl and “alkynyl” includes unsaturated straight or branched chain containing up to 10 carbon atoms, preferably from 2 to 6 carbon atoms.
  • aryl includes phenyl and naphthyl.
  • acyl includes groups of formula C(O)R 10 where R 10 is optionally substituted alkyl; such as acetyl.
  • Carbocyclic includes rings of up to 10, preferably up to 7 carbon atoms.
  • heterocyclic includes rings containing up to 10, preferably up to 7 atoms, up to three of which are selected from oxygen, sulphur or nitrogen.
  • halo or “halogen” includes chlorine, fluorine, bromine and iodine.
  • Suitable optional substituents for alkyl, alkenyl or alkynyl groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 or R 9 or for carbocyclic or heterocyclic rings formed by two of such groups include one or more groups selected from halogen such as chloro; hydroxy; nitro; optionally substituted aryl; or
  • R 11 and R 12 are independently selected from OR or NR 14 R 15 and R 13 , R 14 and R 15 are independently selected from hydrogen or alkyl; or P(O)R 16 R 17 where R 16 and
  • R 17 are alkyl.
  • Suitable optional substituents for aryl groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 or R 9 and for aryl substituents on said groups include halo, haloalkyl and nitro
  • R 1 , R 2 , R 3 , R 4 , R 5 or R 6 is a salt, ester or amide of carboxy
  • it is suitably an agriculturally acceptable salt or ester or amide.
  • agriculturally acceptable salts include sodium, potassium or calcium salts, sulphonium or sulphoxonium salts such as those of formula S(O) q R 20 R 21 R 21 where q is 0 or 1, or ammonium or quaternary ammonium ions of formula N + R 21 R 22 R 23 R 24 where R 21 , R 22 , R 23 and R 24 are independently selected from optionally substituted alkyl, alkenyl, alkynyl or aryl groups.
  • Suitable agriculturally acceptable esters include optionally
  • Particular agriculturally acceptable amides are those of formula CONR 19 R 20 where R 19 and R 20 are independently selected from hydrogen or alkyl.
  • the expression 'quaternised derivatives' used in relation to formula (I) relates to those compounds of formula (I) where one or more of R 1 , R 2 , R 3 , R 4 or R 5 contain an optionally substituted amino group or where two of groups R 1 and R 2 or any adj acent two of R 3 , R 4 and R 5 form a nitrogen containing heterocyclic ring, and in which the nitrogen atoms have been quaternised.
  • Suitable quaternising groups include optionally substituted alkyl such as methyl, ethyl or benzyl.
  • R 1 and R 2 include hydrogen, optionally substituted alkyl, halo, OR 6 where R 6 is as hereinbefore defined, S(O) n R 7 where n and R 7 are as hereinbefore defined or NR 8 R 9 where R 8 and R 9 are as hereinbefore defined.
  • a sub-group of compounds of formula (IA) or (IB) are those where R 1 and R 2 together with the carbon atoms to which they are attached form an optionally substituted fused unsaturated carbocyclic or heterocyclic ring.
  • Such rings include fused cyclohexenyl, cyclopentenyl, benzo, pyridyl or pyrazinyl rings optionally substituted with for example one or more halo atoms or alkoxy groups and optionally quaternised where appropriate.
  • R 3 , R 4 and R 5 are as defined above and Y 1 , Y 2 and Y 3 are selected from CR 25 , N or N + R 26 where R 25 is selected from hydrogen or halogen in particular chlorine or fluorine and R 26 is alkyl such as methyl.
  • R 25 is selected from hydrogen or halogen in particular chlorine or fluorine and R 26 is alkyl such as methyl.
  • R 26 is alkyl such as methyl.
  • groups R 1 and R 2 are hydrogen, alkyl such as methyl or ethyl, hydroxy, alkoxy such as methoxy, ethoxy or iso-propoxy, substituted alkoxy such as ethoxycarbonylmethoxy, phenoxy, halo such as chloro or bromo, amino, substituted amino such as substituted piperazine or N,N,N'-trimethylethylene diamine or quaternised forms thereof, n-butylthio, phenylthio or phenylsulphoxy.
  • R 1 and/or R 2 are independently selected from hydrogen, methyl, methoxy, isopropoxy, chloro or phenylthio.
  • R 3 , R 4 and R 5 include hydrogen and alkyl such as methyl, halogen such as chlorine or bromine, and nitro.
  • R 3 , R 4 and R 5 are hydrogen.
  • R 3 , R 4 and R 5 are all hydrogen, R 1 and R 2 together do not form a fused tetrachloro-benzo ring or R 2 is not NH(C6H5) or R1 and R2 are not both n-butyl;
  • R 3 , R 4 and R 5 are all hydrogen and R 2 is methoxy, R 1 is not methoxy, n-butyl,phenyl, n-butylacetyleno or phenylacetyleno;
  • R 3 is not carboethoxy.
  • Examples of compounds of formula (IA) are set out in Table (I) and Examples of compounds (IB) are set out in Table II.
  • R 25 is a protecting group such as trimethylsilyl and R 1 , R 2 , R 3 , R 4 and R 5 are as defined in relation to formula (I).
  • deprotection is effected by reaction either with water or fluoride ion.
  • Suitable oxidising agents include ferric chloride or oxygen (air).
  • the reaction is suitably effected at moderate temperatures of from 5 to 60°C, conveniently at ambient temperature in the presence of an organic solvent such as xylene or toluene.
  • Compounds of formula (III) are suitably prepared by heating a compound of formula (IV); where R 1 , R 2 , R 3 , R 4 , R 5 and R 25 are as defined
  • Suitable temperatures are from 100 to 200°C, conveniently at the reflux temperature of the solvent.
  • the subsequent conversion to a compound of formula (I) is carried out in situ.
  • Compounds of formula (IV) can be prepared by reacting a compound of formula (V) where R 1 and R 2 are as hereinbefore defined; with a compound of formula (VI); in the presence of a base, and subsequently a protecting group R 25 introduced in to the molecule by conventional techniques.
  • Suitable bases are strong bases such as n-butyl-lithium, lithium diisopropylamide or sodium hydride.
  • the reaction is suitably effected in an inert organic solvent such as tetrahydrofuran, dioxan or diethyl ether at low temperatures of from -100 to 0°C under an inert atmosphere of, for example, nitrogen or argon.
  • an inert organic solvent such as tetrahydrofuran, dioxan or diethyl ether
  • Compounds of formula (IA) can be prepared by reacting a compound of formula (VII); where R 1 , R 2 , R 3 , R 4 and R 5 are as defined in relation to formula (I), with a dehydrating agent.
  • dehydrating agents examples include phosphorus oxychloride (POCl 3 ).
  • the reaction is suitably effected in a solvent such as pyridine, at temperatures of from 0 to 80°C, conveniently at room temperature.
  • a solvent such as pyridine
  • Compounds of formula (VII) can be prepared by reacting a compound of formula (VIII); where R 1 and R 2 are as defined in relation to formula (I), with a compound of formula (VI); as hereinbefore defined in the presence of a base.
  • Suitable bases include strong bases such as sodium hydride.
  • the reaction is suitably effected in a solvent such as tetrahydrofuran or toluene at elevated temperatures of from 25 to 110°C, conveniently at the reflux temperature of the solvent.
  • This route to compounds of formula (IA) is particularly suitable to produce compounds of formula (IA) where R 1 and R 2 together form an optionally substituted fused saturated or unsaturated carbocyclic or heterocyclic ring.
  • rings include cyclopentenyl, cyclohexenyl, phenyl and substituted phenyl such as dichlorophenyl, fluorophenyl or trimethoxyphenyl.
  • compounds of formula (IA) can be prepared by dehydrating a compound of formula (IX); where R 1 , R 2 , R 3 , R 4 and R 5 are as defined in relation to formula (I).
  • dehydration is effected by reacting with a dehydrating agent such as acetic anhydride at elevated temperatures of from 25 to 140°C, conveniently at 85°C.
  • Compounds of formula (IX) can be prepared by reacting a compound of formula (VIII) as hereinbefore defined with a compound of formula (VI) as hereinbefore defined with a Grignard reagent such as ethyl magnesium bromide.
  • a Grignard reagent such as ethyl magnesium bromide.
  • the reaction is effected at moderate temperatures of from 0 to 40°C conveniently at ambient temperature in the presence of a solvent such as tetrahydrofuran or diethyl ether.
  • Compounds of formula (IX) are either known compounds or they can be prepared from known compounds by conventional routes.
  • compounds of formula (I) can be prepared by reacting a compound of formula (X), where R 3 , R 4 and R 5 are as hereinbefore defined with a compound of formula (XI); where R 26 and R 27 are
  • Suitable bases include strong bases such as sodium hydride.
  • the reaction is suitably effected at elevated temperatures of from 25 to 80°C in a solvent such as tetrahydrofuran. Conveniently the reaction is effected at the reflux temperature of the solvent.
  • R 1 , R 2 , R 3 , R 4 and R 5 can be converted from hydrogen to bromine or chlorine by halogenation using halogenating agents such as n-bromosuccimide or n-chlorosuccimide.
  • halogenating agents such as n-bromosuccimide or n-chlorosuccimide.
  • the reaction is suitably effected in the presence of a solvent such as dimethylformamide at elevated temperatures of from 25 to 80oC, conveniently at ambient temperature.
  • R 3 , R 4 and/or R 5 can be converted from hydrogen to nitro by nitration using nitrating agents such as sodium nitrate in concentrated sulphuric acid.
  • Groups R 1 and/or R 2 may be converted from hydroxy to alkoxy groups by reaction with an alkyl halide such as methyl iodide in the presence of a base such as sodium hydride.
  • a suitable solvent for this reation may be dimethylformamide. This reaction will produce compounds of formula (IB) as well as (IA). These mixtures may be separated by conventional techniques.
  • R 1 and/or R 2 is OR 6 and R 6 is acyl, carboxy or an ester thereof.
  • Reaction with oxalyl chloride in a solvent such as chloroform and with a catalytic quantity of dimethylformamide will convert the hydroxy groups R 1 and/or R 2 to chlorine groups.
  • R 1 and/or R 2 are chloro can be converted to sulphides and amides by reaction with a thiol or amine respectively.
  • the reactions are suitably effected in an inert solvent such as tetrahydrofuran at temperatures of from -78 to 100oC, typically at -30oC to ambient
  • Quaternised derivatives of suitable compounds of formula (I) may be prepared by reaction with an alkyl halide such as methyl iodide in a solvent such as tetrahydrofuran, preferably at elevated temperatures such as the reflux temperature of the solvent.
  • an alkyl halide such as methyl iodide
  • a solvent such as tetrahydrofuran
  • 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 0.012 to 902 by weight of the active ingredient.
  • Dilute compositions ready for use preferably contain from 0.012 to 2Z of active ingredient, while concentrated compositions may contain from 202 to 902 of active ingredient, although from 202 to 702 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
  • sodium dodecylbenzenesulphonate sodium, calcium, and ammonium lignosulphonate, butyinaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid.
  • Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g. Agral 90) 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 L77).
  • a suitable mixture in mineral oil is Atplus 411F.
  • aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent(s).
  • organic solvents include, for example, ethylene di-chloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and
  • 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 0.012 to 10.02 and preferably 0.12 to 22, by weight of active ingredient(s) are normally used.
  • a preferred form of concentrated composition comprising 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 compounds of formula (I) are active as herbicides and therefore, in a further aspect the invention provides 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.
  • the compounds of formula (I) may be applied directly to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emergence application) . They are particularly useful when applied post-emergence.
  • 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 for example herbicides, fungicides, insecticides (optionally with an insecticide synergist) and plant growth regulators.
  • 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, trifluraiin,
  • arylurea 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 salts or ester thereof, nitrofen, bifenox. aciflurofen and salts and esters thereof, oxyfluorfen, fomesafen, chlornitrofen and chlomethoxyfen;
  • S. phenoxyphenoxypropionate herbicides such as diclofop 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, cycloxyidim, tralkoxydim, and clethodim;
  • U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as DPX-M6313, chlorimuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof, 2- [3-(4-methoxy-6-methyl-l,3,5- triazin-zyl)-3-methylureidosulphonyl) benzoic acid esters such as the methyl ester thereof (DPX-LS300) and pyrazosulfuron;
  • V. imidazolidinone herbicides such as imazaquin, ii ⁇ azamethabenz, imazapyr and isopropylammonium 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 (MSMA);
  • herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide and naptalam;
  • miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinclorac, dithiopyr and mefanacet;
  • 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;
  • Methyllithium (10.2ml of a 1.5 molar solution of 1:1 methyllithium/lithium bromide complex in ether) was added dropwise to a solution of
  • Triethylamine (5.05ml) was added to a solution of 3-chloro-4-methoxy-cyclobut-3-en-1,2-dione (2.65g) in dichloromethane (30ml) at 0°C under an atmosphere of nitrogen. Thiophenol (2.23ml) was then added dropwise and stirred for 1 hour. The resulting solid was filtered under suction, washing with a little dichloromethane and the filtrate was evaporated to give a solid. This was purified by flash chromatography on silica, eluting with ethyl acetate /hexane (1:4) to give the title compound as a yellow oil, yield 2.70g. 1 H. NMR (CDCl 3 ): ⁇ 7.58-7.35 (5H,m); 4.37(3H,s). Preparation 4
  • Triethylamine (8.32ml) was added to a solution of 3,4-dichlorocyclobut-3 ⁇
  • the title compound was prepared by a method similar to that described in
  • Compound 14 was prepared following the method of Yerxa and Moore (Tetrahedron Letters, Vol. 33, No. 51 pp 7811-7814, 1992).
  • 3,4-diphenoxycyclobut-3-en-l,2-dione (prepared as described in Preparation 4) (1.34g), pyrrole (0.35ml), n-butyllithium (2.01ml of a 2.5 molar solution in hexane) and trimethylsilylchloride (0.64ml),
  • Compound 2 was prepared following the method of Comforth and Ming-hui (J. Chem. Soc. Perkin Trans I, 1463, 1990).
  • Compound No. 21 was prepared by a method similar to that described in Example 12 but using a mixture of
  • Compound 3 was prepared following the method of Comforth and Ming-hui (J. CHem. Soc. Perkin Trans I, 1463, 1990).
  • Compound No. 23 was prepared by a method similar to that described in Example 21 above, but using Compound 51(0.031g, prepared as described in Example 36 below), tetrahydrofuran (15ml) and methyl iodide (5ml) heated under reflux for 120 hours. The title compound was obtained as a brick red solid, yield 0.041g, m.p. 183°C (dec). 1 H NMR (d 6 DMSO): ⁇ 9.34(1H,d);
  • the salt was dissolved in water, acidified to pH2, saturated with sodium chloride and extracted with ethyl acetate (x5). The solvent was evaporated and the residue recrystallised from ethyl acetate to give the title compound as fine yellow needles, yield 1.95g, m.p.
  • N-chlorosuccinimide (0.203g) was added in one portion to a solution of
  • the sodium salt of Compound 28 (3.60g, prepared as described in Example 25 or alternatively prepared by addition of 1 equivalent of sodium hydride, as an oil dispersion to Compound 28 in dimethylformamide) was suspended in dimethylformamide (40ml) and methyliodide (5ml) followed by 15-crown-5 (0.10ml) were added. The mixture was stirred at room temperature
  • the title compounds were prepared by a method similar to that described in Example 27, but using Compound 40 (0.710g, prepared as described in Example 29), methyl iodine (10ml), sodium hydride (0.16g of a 60% oil dispersion), dimethylformamide (10ml) and 15-crown-5 (3 drops), which were stirred at room temperature for 7 days. Separation of the components in the crude product by flash chromatography on silica, eluting with ethyl acetate/dichloromethane/hexeane (1:1:3), gave, after
  • Oxalyl chloride (0.173ml) was added to a suspension of example compound 28 (0.326g, prepared as described in Example 25) in chloroform (15ml) at room temperature under a nitrogen atmosphere. Dimethylformamide (2 drops) was added and immediate evolution of gas was observed. After 40 minutes, the solid had dissolved. The reaction was evaporated to % volume and the residue applied to a silica chromatography column. Elution with ethyl acetate /dichloromethane /hexane (1:1:3) gave the title compound as a yellow solid, yield 0.294g, m.p. 130°C (dec). 1 H NMR (CDCl 3 ): ⁇
  • M.S. shows molecular ions for both components.
  • M.S. shows moleculor ions for both components.
  • Example Compound 2 (0.202g, prepared as described in Example 11), potassium nitrate (0.114g) and 982 sulphuric acid (3ml).
  • the crude product was
  • N.N.N-trimethylethylenediamine (0.266ml) was added dropwise to a solution of Compound 48 (0.180g, prepared as described in Example 31 above) in dry tetrahydrofuran (20ml) at -20°C under a nitrogen atmosphere. After 1 hour at -20°C, the mixture was allowed to warm to room temperature. The solid present was filtered under suction and the filtrate diluted with
  • Example 40 The method of Example 40 was repeated, except that the reaction was carried out at -30°C and N-methylpiperazine (0.466ml), Compound 48 (0.364g) and tetrahydrofuran (35ml) were used.
  • the title compound was obtained after work up and silica chromatography as an orange solid, yield 0.402g, m.p. 127-128°C.
  • Example 42 The method of Example 42, was repeated but using Compound 58 (250mg, prepared as described in Example 41 above), methyl iodide (1ml) and tetrahydrofuran (15ml). The title compound was obtained as a yellow powder, yield 355g m.p. 315oC (dec).
  • Tween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan laurate.
  • Span 80 is a Trade Mark for a surface-active agent comprising sorbitan mono-laurate.
  • the volume was made up to 5cm 3 with water, glass beads were added and this mixture was then shaken to effect dissolution or suspension of the chemical, after which the beads were removed. In all cases, the mixture was then diluted with water to the required spray volume and 22 glycerol and 0.22 Silwett L77 added. If sprayed independently, volumes of 10cm 3 and 14cm 3 were required for pre-emergence and post-emergence tests respectively; if sprayed together, 20cm 3 was required. The sprayed aqueous emulsion contained 42 of the initial solvent/surfactant mix and the test chemical at an appropriate concentration.
  • the spray compositions so prepared were sprayed onto young pot plants at a spray volume equivalent to 1000 litres per hectare. Damage to plants was assessed 5 days after spraying by comparison with untreated plants, on a scale of 0 to 9 where 0 is 02 damage, 1 is 1-52 damage, 2 is 6-152 damage, 3 is 16-252 damage, 4 is 26-352 damage, 5 is 36-592 damage, 6 is 60-692 damage, 7 is 70-792 damage, 8 is 80-892 damage and 9 is 90-1002 damage.

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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
PCT/EP1993/002132 1992-09-10 1993-08-12 Indolizines as herbicides WO1994005662A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94908879A EP0659186A1 (en) 1992-09-10 1993-08-12 Indolizines as herbicides
AU49471/93A AU4947193A (en) 1992-09-10 1993-08-12 Indolizines as herbicides
JP6506787A JPH08501290A (ja) 1992-09-10 1993-08-12 除草剤としてのインドリジン類

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9219141.0 1992-09-10
GB929219141A GB9219141D0 (en) 1992-09-10 1992-09-10 Novel composition

Publications (1)

Publication Number Publication Date
WO1994005662A1 true WO1994005662A1 (en) 1994-03-17

Family

ID=10721686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002132 WO1994005662A1 (en) 1992-09-10 1993-08-12 Indolizines as herbicides

Country Status (7)

Country Link
EP (1) EP0659186A1 (en, 2012)
JP (1) JPH08501290A (en, 2012)
KR (1) KR940006467A (en, 2012)
AU (1) AU4947193A (en, 2012)
GB (2) GB9219141D0 (en, 2012)
TW (1) TW254940B (en, 2012)
WO (1) WO1994005662A1 (en, 2012)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11021478B2 (en) * 2017-05-09 2021-06-01 Kind Pharmaceutical Indolizine derivatives and their application in medicine

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2043649A1 (de) * 1970-09-03 1972-03-09 Farbenfabriken Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Imidazoisochinolindionen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2043649A1 (de) * 1970-09-03 1972-03-09 Farbenfabriken Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Imidazoisochinolindionen

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
B.R. YERXA ET AL.: "Synthesis of indolizine-5,8-diones and [3.2.2]cyclazines", TETRAHEDRON LETTERS, vol. 33, no. 51, 1992, OXFORD GB, pages 7811 - 7814 *
J. CORNFORTH ET AL.: "Pyrrolo[1,2-b]isoquinoline-5,10-diones and indolizine-5,8-diones", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, 1990, LETCHWORTH GB, pages 1463 - 1467 *
K. YAKUSHIJIN ET AL.: "Intramolecular ring formation of phenyl azide and furan moieties", CHEMICAL AND PHARMACEUTICAL BULLETIN, vol. 30, 1982, TOKYO JP, pages 140 - 151 *
L.A. MITSCHER ET AL.: "Antimicrobial agents from higher plants. Synthesis in the canthin-6-one series.", HETEROCYCLES, vol. 3, no. 1, 1975, TOKYO, JP, pages 7 - 14 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11021478B2 (en) * 2017-05-09 2021-06-01 Kind Pharmaceutical Indolizine derivatives and their application in medicine
US11655249B2 (en) 2017-05-09 2023-05-23 Kind Pharmaceutical Indolizine derivatives and their application in medicine
US11945817B2 (en) 2017-05-09 2024-04-02 Kind Pharmaceutical Indolizine derivatives and their application in medicine
US11970495B2 (en) 2017-05-09 2024-04-30 Kind Pharmaceutical Indolizine derivatives and their application in medicine

Also Published As

Publication number Publication date
EP0659186A1 (en) 1995-06-28
TW254940B (en, 2012) 1995-08-21
JPH08501290A (ja) 1996-02-13
AU4947193A (en) 1994-03-29
GB9316218D0 (en) 1993-09-22
GB9219141D0 (en) 1992-10-28
KR940006467A (ko) 1994-04-25

Similar Documents

Publication Publication Date Title
US5084083A (en) Herbicidal compositions
GB2253848A (en) Heterocyclic compounds
US5306692A (en) Herbicidal indazole and benzimidazole compounds
WO1994027969A1 (en) Isoquinolinetrione derivatives as herbicides
GB2237570A (en) Hydrazide and hydroxylamine herbicides
GB2276379A (en) Herbicidal compounds having a pentafluorosulphanyl group
JPS61148163A (ja) ２，６−置換ピリジンカルボン酸誘導体及び除草剤組成物
US5726129A (en) Pyrrolidine-2-thione derivatives as herbicides
EP0442655B1 (en) Benzisoxazole derivatives
EP0258182A1 (en) Semicarbazones and thiosemicarbazones
US5182402A (en) Herbicidal compositions
WO1994005662A1 (en) Indolizines as herbicides
US5190574A (en) Herbicidal pyrazolyloxy and pyrazolylamino-benzotriazoles
GB2253847A (en) Herbicidal benzofuran and benzothiophene compounds
US5167696A (en) Herbicidal aryloxy- and arylamino-indanes
WO1996001255A1 (en) 3-(cyanophenyl)-pyrazole derivatives as herbicides
US5133798A (en) Certain herbicidal 1,2,4-triazolo[4,5-b]pyridines
GB2253846A (en) Herbicidal substituted naphthalenes and azanaphthalenes
JPH04230253A (ja) 除草性化合物、その製造法及びそれを含有する除草剤組成物
CA2132746A1 (en) Herbicides
GB2257970A (en) 4 - oxo - quinazolines and benzotriazines as herbicides
GB2258233A (en) Herbicidal benzoisothiazoles
WO1996015116A1 (en) Herbicidal pyrazoles
GB2282539A (en) Normonylmethylethers and thioethers as herbicides
GB2293766A (en) Herbicidal compositions based on synergistic combination of glyphosate and 1,3,4,5-tetrasubstituted pyrazoles

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR BY CA CZ FI HU JP KP KR KZ LK MG MN MW NO NZ PL RO RU SD SK UA US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994908879

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1994908879

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1994908879

Country of ref document: EP