EP0659186A1 - Indolizines as herbicides - Google Patents

Indolizines as herbicides

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Publication number
EP0659186A1
EP0659186A1 EP94908879A EP94908879A EP0659186A1 EP 0659186 A1 EP0659186 A1 EP 0659186A1 EP 94908879 A EP94908879 A EP 94908879A EP 94908879 A EP94908879 A EP 94908879A EP 0659186 A1 EP0659186 A1 EP 0659186A1
Authority
EP
European Patent Office
Prior art keywords
compound
optionally substituted
formula
preparation
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94908879A
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German (de)
English (en)
French (fr)
Inventor
Glynn Mitchell
Stephen Christopher Smith
Eric Daniel Clarke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Ltd
Original Assignee
Zeneca Ltd
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Filing date
Publication date
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Publication of EP0659186A1 publication Critical patent/EP0659186A1/en
Withdrawn legal-status Critical Current

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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.
  • a herbicidal composition comprising a compound of formula (I), or a tautomer or a
  • R 8 9 8 9 optionally substituted aryl; NR R where R and R are independently selected from hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl or optionally
  • R 9 8 9 substituted aryl and R may additionally be acyl, or R and R together with the nitrogen atom to which they are attached form a heterocyclic ring; or R and R and/or any adjacent two of R , R and R 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
  • R , R , R and R are independently selected from hydrogen; optionally substituted alkyl; optionally substituted alkenyl; optionally substituted alkynyl; optionally substituted aryl; optionally substituted aromatic heterocyclic; halo; nitro; cyano; a group OR where R 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(0) R where n is 0, 1 or 2 and R is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl or
  • R selected from hydrogen, alkyl, alkenyl or alkynyl and R may additionally
  • 1 2 3 4 5 be acyl; or R and R and/or any adjacent two of R , R and R 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(0)R where R 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.
  • Suitable optional substituents for alkyl, alkenyl or alkynyl groups R , R , R , R , R , R or R 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
  • P 1 13 14 15 13 14 15 independently selected from OR or NR R and R , R and R are independently selected from hydrogen or alkyl; or P(0)R R where R and
  • R 17 are alkyl.
  • R , R or R and for aryl substituents on said groups include halo, haloalkyl and nitro W Whheenn oonnee oorr mmoore of R , R , R , R , R or R 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(0) R 20R21R21 where q is 0 or 1, or ammonium or quaternary
  • Suitable agriculturally acceptable esters include optionally substituted alkyl, alkenyl, alkynyl or aryl esters wherein the optional substiittuueennttss aarree tthhoossee aass ddeeffiinneedd aabboovvee ffoorr RR eettcc.
  • P Paarrttiiccuullaarr aaggrriiccuullttuurraal]ly acceptable amides are those of formula
  • Suitable quaternising groups include optionally substituted alkyl such as methyl, ethyl or benzyl.
  • R and R include hydrogen, optionally substituted alkyl, halo, OR where R is as hereinbefore defined, S(O) R where n and R are
  • a sub-group of compounds of formula (IA) or (IB) are those where R
  • 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 is alkyl such as methyl.
  • ⁇ 0 - ⁇ V fi not more than two of Y , Y and Y are N or N R
  • R and R 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 and/or R are independently selected from hydrogen, methyl, methoxy, isopropoxy, chloro or phenylthio.
  • R , R and R include hydrogen and alkyl such as methyl, halogen such as chlorine or bromine, and nitro.
  • R , R and R are hydrogen.
  • R , R and R form an optionally subtituted fused aromatic carbocylic or heterocylic ring;
  • R fused tetrachloro-benzo ring or R is not NH(C6H5) or Rl and R2 are not both n-butyl;
  • R , R and R are all hydrogen and R is methoxy, R is not methoxy, n-butyl,phenyl, n-butylacetyleno or phenylacetyleno;
  • R when R and R form a fused benzo ring, R is not carboethoxy.
  • novel compounds of formula (I) are 3-nitropyrrolo[l,2-b]- isoquinoline-5,10-dione, 2-bromopyrrolo[1,2-b]isoquinoline-5,10-dione, 2,3-dibromopyrrolo[1,2-b]isoquinoline-5,10-dione, 2,3-dichloropyrrolo- [l,2-b]isoquinoline-5,10-dione and 2-chloropyrrolo[l,2-b]-isoquinoline- -5,10-dione.
  • compounds of formula (IA) can be prepared by deprotecting and oxidising a compound of formula (III) ; where R 25 is a protecting group such as trimethylsilyl and R , R , R , R and R 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
  • 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.
  • 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 , R , R , R and R are as defined in relation to formula (I), with a dehydrating agent.
  • Suitable dehydrating agents include phosphorus oxychloride (P0C1 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
  • 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.
  • compounds of formula (IA) where R and R 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 tri ethoxyphenyl.
  • compounds of formula (IA) can be prepared by dehydrating a compound of formula (IX); where R 1, R2, R3, R4 and R5 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.
  • 26 27 defined with a compound of formula (XI) ; where R and R are independently alkyl groups such as ethyl, in the presence of a base.
  • 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, R2, R3, R4 and/or R5 can be converted from hydrogen to bromine or chlorine by halogenation using 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 80 C, conveniently at ambient temperature.
  • R 3, R4 and/or R5 can be converted from hydrogen to nitro by nitration using nitrating agents such as sodium nitrate in concentrated sulphuric acid.
  • Groups R and/or R 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.
  • 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 Preferably 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 water-immiscible organic solvent which is dispersed as droplets in water.
  • Surface-active agents may be of the cationic, anionic, or non-ionic type or mixtures thereof.
  • the cationic agents are, for example, quaternary ammonium compounds (e.g. cetyltri ethylammonium bromide).
  • Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium,calcium, and ammonium lignosulphonate, 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.
  • 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, meth lnaphthalene, the xylenes and trichloroethylene.
  • compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use.
  • the concentrates are usually required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Concentrates conveniently contain 20-902, preferably 20-702, by weight of the active ingredient(s) .
  • Dilute preparations ready for use may contain varying amounts of the active ingredient(s) depending upon the intended purpose; amounts of 0.012 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 saucorite. Bentonite is especially preferred.
  • Other 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);
  • D Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, dinoseb and its ester, dinoseb acetate;
  • dinitroaniline herbicides such as dinitramine, trifluraiin, ethalflurolin, pendimethalin, oryzalin;
  • arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, methabenzthiazuron;
  • phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
  • H 2-phenylpyridazin-3-ones such as chloridazon and norflurazon;
  • I uracil herbicides such as lenacil, bromacil and terbacil;
  • J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
  • K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
  • L. thiolcarbamate herbicides such as cycloate, vernolate, molinate,
  • 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 i azaquin, ii ⁇ azame habenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
  • arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
  • X. amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulphosate and bialaphos;
  • 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;
  • BB useful contact herbicides
  • useful contact herbicides include: bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat; * These compounds are preferably employed in combination with a safener such as dichlormid.
  • a safener such as dichlormid.
  • Triethylamine (8.32ml) was added to a solution of 3, -dichlorocyclobut-3-
  • the title compound was prepared by a method similar to that described in
  • the title compounds were prepared by a method similar to that described in Preparation 5, but using 3,4,5-trimethoxyphthalic anhydride (7.0g), pyrrole (2.03ml), toluene (60ml) and sodium hydride (l.l ⁇ g of a 602 oil dispersion) .
  • the mixture of title compounds was obtained as a dark red oil, yield 8.8g, containing 1.5 moles of ethyl acetate.
  • Compound 14 was prepared following the method of Yerxa and Moore (Tetrahedron Letters, Vol. 33, No. 51 pp 7811-7814, 1992).
  • a solution of dimethyldioxirane (5.82ml of a 0.095 molar solution in acetone, prepared according to the method of Adam, Chan, Cremer, Gauss, Scheutzow and Schindler, J. Org. Chem, 52, 2800, 1987) was added in one portion to a solution of Compound 35(0.078g) in dry acetone (5ml) at 0°C.
  • the reaction mixture was allowed to warm to room temperature overnight. After evaporation of the solvent, nmr of the crude material showed a mixture of the sulphoxide and sulphone. This material was re-submitted to the reaction conditions, using a further quantity of dimethyldioxirane (1.2ml of a 0.095 molar solution).
  • Compound 2 was prepared following the method of Comforth and Ming-hui (J. Chem. Soc. Perkin Trans I, 1463, 1990).
  • Phosphorous oxychloride (2ml) was added to a solution of 2-(pyrrol-l-ylcarbonyl)cyclohexene-l-carboxylic acid (prepared as described in Preparation 5 ) (2.00g) in dry pyridine (20ml) at room temperature under an atmosphere of nitrogen. The solution became hot and the colour darkened. After 2 hours the reaction was poured into water and extracted with ether (x3). The combined organic layers were washed with water, brine and dried over sodium sulphate. Evaporation gave a dark red oil which was purified by flash chromatography on silica, eluting with ethyl acetate/hexane (3:17) to give a yellow solid.
  • Compound 3 was prepared following the method of Comforth and Ming-hui (J. CHem. Soc. Perkin Trans I, 1463, 1990).
  • 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
  • H NMR also shows the presence of 1/3 mole of ethyl acetate of crystallisation.
  • the aqueous mixture was extracted with ethyl acetate (x5) and the combined organic layers dried over sodium sulphate and evaporated to a brown solid.
  • the components were separated by flash chromatography on silica, eluting with ethyl acetate/hexane (1:4).
  • the first component to be eluted was Compound 36 as a yellow solid, yield 0.048, m.p. 106-109°C.
  • Example Compound 43 Compound 2 (0.202g, prepared as described in Example 11 above) and N-bromosuccinimide (0.462g) were dissolved in dimethylformamide (5ml) and stirred at room temperature under a nitrogen atmosphere for 24 hours. The mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over sodium sulphate and then evaporated in vacuo. the crude product was purified by flash chromatography on silica, eluting with ethyl acetate to give a yellow solid. Crystallisation from ethyl acetate gave the title compound as a yellow solid, yield 0.181g, m.p. 195°C. ⁇ E NMR (CDC1 3 ): ⁇ 8.39(lH,m), 8.26(lH,m), 7.84(2H,m), 7.38(lH,s).
  • M.S. shows moleculor ions for both components.
  • EXAMPLE 38 Preparation of Compound 56 By a method and quantities similar to that described in Example 37, but using dimethylamine (0.5ml) in place of morpholine. Compound 56 was prepared. After addition of dimethylamine at 0°C, the reaction mixture was allowed to warm to room temperature, poured into cold water and extracted with ether (x3). The combined extracts were washed with water, brine and dried over magnesium sulphate. Evaporation of the solvent in vacuo followed by purification by preparative silica chromatography, eluting with ether gave the title compound as an orange solid, yield 0.14g, m.p. 1 13388--113399°°CC.. 11 HH NNMMRR ((CCDD(C1,): ⁇ 7.53(lH,t); 7.11(lH,dd); 6.30(lH,t); 5.37(lH,s); 3.24(6H,s)
  • 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 dichloromethane (50ml) before washing with water (20ml) and drying over sodium sulphate.
  • 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. If the chemical did
  • 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.

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  • 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)
EP94908879A 1992-09-10 1993-08-12 Indolizines as herbicides Withdrawn EP0659186A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9219141 1992-09-10
GB929219141A GB9219141D0 (en) 1992-09-10 1992-09-10 Novel composition
PCT/EP1993/002132 WO1994005662A1 (en) 1992-09-10 1993-08-12 Indolizines as herbicides

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EP0659186A1 true EP0659186A1 (en) 1995-06-28

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Application Number Title Priority Date Filing Date
EP94908879A Withdrawn EP0659186A1 (en) 1992-09-10 1993-08-12 Indolizines as herbicides

Country Status (7)

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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)

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Publication number Priority date Publication date Assignee Title
ES2934361T3 (es) * 2017-05-09 2023-02-21 Kind Pharmaceutical Derivados de indolizina y aplicación de los mismos en medicina

Family Cites Families (1)

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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 (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9405662A1 *

Also Published As

Publication number Publication date
WO1994005662A1 (en) 1994-03-17
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

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