EP0573460A4 - Herbicidal pyrones. - Google Patents

Herbicidal pyrones.

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Publication number
EP0573460A4
EP0573460A4 EP19920904717 EP92904717A EP0573460A4 EP 0573460 A4 EP0573460 A4 EP 0573460A4 EP 19920904717 EP19920904717 EP 19920904717 EP 92904717 A EP92904717 A EP 92904717A EP 0573460 A4 EP0573460 A4 EP 0573460A4
Authority
EP
European Patent Office
Prior art keywords
alkyl
optionally substituted
phenyl
compounds
group
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Withdrawn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
EP19920904717
Other languages
German (de)
French (fr)
Other versions
EP0573460A1 (en
Inventor
Andris Juris Liepa
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.)
Dunlena Pty Ltd
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Dunlena Pty Ltd
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Filing date
Publication date
Application filed by Dunlena Pty Ltd filed Critical Dunlena Pty Ltd
Publication of EP0573460A1 publication Critical patent/EP0573460A1/en
Publication of EP0573460A4 publication Critical patent/EP0573460A4/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • 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
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems

Definitions

  • the present invention relates to organic compounds having herbicidal properties a plant growth regulating properties; to herbicidal compositions and processes utilisin such compounds and to plant growth regulating compositions and processes utilisin such compositions.
  • R is substituted phenyl
  • R 1 is H, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylsulfonyl, alkoxy, all ylthio, acyl, (un)substituted phenylalkyl or PhS0 2
  • R 2 is alkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, haloalkyl, alkoxyalkyl, alkylthioalkyl or (un)substituted phenylalkyl
  • R 3 is alkyl, fluoroalkyl, alkenyl, alkynyl, or phenyl.
  • Watson et al teach that tetrahydropyran-2,4-dione derivatives which are substituted the 6-position with a substituted phenyl group exhibit particularly useful herbicidal activity.
  • R 1 is lower alkyl
  • R 2 is lower alkyl, lower alkenyl or lower alkynyl
  • R 3 is H or lower alkyl
  • R 4 is lower alkyl or phenyl
  • R 3 forms cycloalkylene of 4 to 5 carbon atoms by combining with R 4 ;
  • R 5 and R 7 are selected from the group consisting of H and lower alkyl; R 6 is lower alkyl;
  • R 8 is H or lower alkyl; and R 9 is lower alkyl.
  • the above compounds are substituted in the 5 and/ or 6- positions of the pyran rin by one or two alkyl groups
  • R ! is H
  • R 2 is substituted alkyl wherein the alkyl group is substituted by optionally substitute phenyl and optionally substituted heterocycle;
  • R 3 is alkyl
  • R 4 and R 5 together with the carbon to which they are attached form a substituted o unsubstituted saturated or partially saturated heterocyclic or carbocyclic ring containing 3 or more ring atoms; etc.
  • the last mentioned spirocyclic analogues are stated as being a preferred subgenus.
  • Further preferred are compounds in which R 1 is H, R 2 is alkyl, alkenyl or haloalke (specifically ethyl, allyl, 2-chloroallyl and 3-chloroallyI) and R 3 is ethyl or n-propyi.
  • WO 8800945 at Tables 1-4 lists 91 individual spirocyclic compounds, all with R 2 as ethyl, allyl or chloroallyl only.
  • the compounds of the invention are substantially more effective against monocotyledonous plants or grass species than against dicotyledonous plants or broad-leaved species.
  • certain of the compounds show selective herbicidal activity against wild grasses in monocotyledonous crop species and hence may be used for selective control of wild grass in graminaceous crops
  • the application emphasises th use of the disclosed compounds for control of grass weeds in broadleaf crops witho damage to the broadleaf crop.
  • PCT/AU89/00191 also in the name of the present applicants, describes herbicidal pyrones that are similar to those described in WO8800945, but which have an additional substituent, R 6 , on the pyrone ring.
  • the compounds described in PCT7AU89/00191 are of the general formula:
  • substituted groups R 1 to R 5 are similar to those described in WO 8800945, and, R 6 is selected from alkyl, alkoxy, alkylthio, halogen or substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio or halogen.
  • Preferred values for the oxime capping group R 2 are alkyl, alkenyl, alkynyl and haloalkenyi; specifically preferred are ethyl, propargyl, allyl, 2-chloroallyl and 3-chloroallyl.
  • PCT/AU89/00191 includes 15 examples relating to spirocyclic derivatives, but the oxime capping groups shown are restricted to ethyl, allyl or chloro allyl.
  • R 7 , R 8 and R 9 are independentiy H, halogen, C C 4 alkyl, C , alkoxy, C alkylthio, C : -C 4 alkylsulfinyl, C -C 4 alkylsulfonyl,
  • C j -Q haloalkyl, C C 4 haloalkoxy, nitro, cyano, C j -C 4 alkoxycarbonyl, C C ⁇ alkylaminocarbonyl, C-,-C 6 dialkylaminocarbonyl, aminocarbonyl, phenyl, amino, - alkylamino, or C ⁇ -Cg dialkylamino.
  • R 2 includes a phenyl group itself substituted with an optionally substituted phenyl group which is linked either directly or via a small group, for example by a methylene, oxy or thio bridge, are highly active and more selective pre-emergent and/or post-emergent herbicides or plant growth regulators which are particularly useful for controlling certain grass weeds in dryland and paddy rice. Accordingly, the invention provides a compound of Formula (1):
  • A is a C alkylene or C Q alkenylene group optionally substituted with 1-4 CfQ alkyl substituents;
  • X is O, S, SO, S0 2 , NR 10 or a single bond
  • R 1 is H, Q-Q alkyl, Q-C 4 alkenyl, Q-Q alkynyl, Q-Q cycloalkyl, Q-Q cycloalkenyl, Q-Q alkylcarbonyl, phenylcarbonyl, phenyl optionally substitut with 1-3 substituents selected from the group consisting of halogen, Q-C 4 alk
  • R 2 is Q-Q alkyl, Q-Q alkenyl, Q-Q alkynyl, Q-Q haloalkyl, Q- Q alkylthio, Q cycloalkyl, Q-Q cycloalkenyl, phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Q- alkylthio, nitro, cyano, Q-Q haloalkyl, amino, and Cf Q haloalkoxy, Q-Q alkoxyalkyl, Q-Q alkylthioalkyl, or Q-Q alkyl substituted with a substituent selected from the group consisting of phenyl, phenoxy and thiophenoxy where the aromatic ring of said substituents may be substituted with 1-3 substituents selected from halogen, Q-Q alkyl, Q-Q alkoxy, Q-Q alkylthio, nitro, cyano, amino, Cf Q
  • R 3 and R 4 are independently H or Q-Q alkyl
  • R 5 and R 6 are independently H, Cf Q alkyl, Q-Q alkenyl, Q-Q alkylthioalkyl, Q-Q haloalkyl, Q-Q haloalkenyi or Q-Q cycloalkyl wherein the alkyl, alkenyl and cycloalkyl groups are optionally substituted with 1-3 substituents selected from the group consisting of OR 12 , NR 13 R 14 , NR 15 C(0)(Q-Q alkyl), NR 18 S0 2 Q-Q alkyl), NR 21 C(0)(Q- Q alkyl), C(OR 16 )(OR 17 )R 22 , C(SR 19 )(SR 20 )R 23 , Cf Q alkoxycarbonyl and phenyl which may be substituted with a substituent selected from halogen, Cf Q alkyl, Q-Q alkoxy, Cf Q alkylthio, nitro, cyano, Q- Q haloalkyl and Q
  • R 7 , R* and R 9 are independentiy H, halogen, Q-Q alkyl, Q-Q alkoxy, Q-Q alkylthio, Cf Q alkylsulfinyl, Cf Q alkylsulfonyl, Cf Q haloalkyl, Cf Q haloalkoxy, nitro, cyano, Cf Q alkoxycarbonyl, Q- Q alkylaminocarbonyl, Q"Q dialkylaminocarbonyl, aminocarbonyl; amino; Cf Q alkylamino, Q-Q alkylamino; or benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio, phenylamino or phenyl group said group optionally substituted wit 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Cf C 4 alkoxy, and CF
  • ⁇ o is H, Cf C 4 alkyl or phenyl optionally substituted with 1-3 substituents select from the group consisting of halogen, Q-Q alkyl, Q- Q alkoxy, Cf Q alkylt Q-Q haloalkyl and Cf Q haloalkoxy;
  • M is Li + , Na + , K + , NH 4 ⁇ or N(R ⁇ ) 4 + where R 11 is Q-Q alkyl;
  • R is H, Q-Q alkyl, C(0)(Q- Q alkyl)or C0 2 (Q- Q alkyl);
  • R 13 , R 15 , R 18 , R 21 , R 22 and R 23 are independentiy H or CfQ alkyl
  • R 14 , R 16 , R 17 , R 19 and R 20 are independentiy CfQ alkyl
  • R 16 and R 17 taken together may be -(CH** ⁇ - or -(CH ⁇ -; and R 19 and R 20 taken together may be -(CH 2 ) 2 - or -(CH 2 ) 3 -.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl”, denotes straight chain or branched alkyl, e.g. meth ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers;
  • Alkoxy denotes methoxy, ethoxy, n-propoxy, isopropyloxy, and the different butyloxy isomers.
  • Alkenyl denotes straight chain or branched alkenes, e.g. vinyl, 1-propenyl, 2-propenyl, 3-propenyl, etc.
  • Alkynyl denotes straight chain or branched alkynes, e.g., ethynyl, 1-propynyl, 2-propynyl, and the different butynyl isomers.
  • Alkylsulfonyl denotes methylsulfonyl, ethylsulfonyl, propylsulfonyl, and the different butylsulfonyl isomers.
  • Alkylthio, alkylsulfinyl, alkylamino, etc. are defined in an analogous manner.
  • Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • halogen either alone or in compound words such as “haloalkyl”, denote fluorine, chlorine, bromine or iodine. Further, when used in compound words such "haloalkyl” said alkyl may be partially halogenated or fully substituted with halogen atoms which may be the same or different. Examples of haloalkyl include CH 2 CH 2 CF 2 CF 3 and CH 2 CHFC1.
  • Alkylcarbonyl denotes acetyl, propionyl, and the different butyryl isomers.
  • Alkoxycarbonyl denotes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and the different butoxycarbonyl isomers.
  • the total number of carbon atoms in a substituent group is indicated by the Ci-Cj prefix where i and j are numbers from 1 to 10.
  • Q-Q alkylthioalkyl would designate -CH j SCH ⁇ -CH- j SQH., - ⁇ CH- j S ⁇ or -CH(CH 3 )SCH 3
  • Q- alkoxyalkyl would represent -CH 2 OCH 3 through to -(CH 2 ) 4 ⁇ CH 3 or -CH 2 0(CH 2 ) 3 C and the various structural isomers embraced therein.
  • R 1 is hydrogen the compounds of the invention may undergo tautomerisation. All tautomeric forms are included in the scope of thi invention.
  • Preferred groups of compounds of general Formula (1) for reasons including ease synthesis and greater herbicidal efficacy, include the following:
  • R 2 is Q-Q alkyl, Q-Q haloalkyl, Q-Q alkenyl or Q-Q alkynyl .
  • A is CfQ alkylene or Q-Q alkenylene optionally substituted with CH 3 or QH 5 ;
  • R 7 , R 8 and R 9 are independently H, CI, Br, F, CfQ alkyl, CfQ alkoxy, Cf alkylthio, Cf Q haloalkyl, CfQ haloalkoxy, nitro, cyano or CfQ alkoxycarbonyl; or benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino optionally substituted with 1-3 substituent selected from the group consisting of halogen, Q- Q alkyl, Q- Q alkoxy, or
  • R 7 , R 8 , or R 9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group;
  • R 10 is H or CH
  • NHPh or N(Me)Ph provided that at least one of R 7 , R 8 , or R 9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
  • R 5 and R 6 are independently Q- Q alkyl, Q-Q alkenyl, Q-Q alkynyl, Cf Q alkylthio or Q-Q alkylthioalkyl.
  • R 1 is H, Li + , Na+ or K+;
  • R 2 is CH 3 , QH 5 , n-QH 7 or n-QH 9 ;
  • R 3 and R 4 are independentiy H or CH 3 ; and
  • R 7 , R 8 and R 9 are independentiy H, CI, Br, F, CH 3 , QH 5 , OCH 3 , OQH 5 , SCH 3 , SQH 5 , CF 3 , CHF Z CF 2 CF 3 , OCHF OCF 3 , OCH 2 CF 3 ,
  • R 7 , R 8 , or R 9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
  • R 3 and R 4 are independently H, CH 3 or QH 5 ; and R 7 , R 8 and R 9 are independentiy H, CI, Br, F, CH 3 , QH 5 , OCH 3 , OQH 5 , SCH 3 , SQH 5 , CF 3 , CHF CF 2 CF 3 , OCHF OCF 3 , OCH 2 CF 3 , NO CN, CO,CH 3 , Ph, S0 2 Ph, COPh, CH 2 Ph, OCH 2 Ph, OPh, SPh, NHPh or N(Me)Ph provided that at least one of R 7 , R 8 , or R 9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
  • the compounds of the invention may be prepared by a method similar to that disclosed in WO8800945, with appropriate alteration of starting reagents.
  • the compounds of the invention may be prepared from the dianion of an acetoacetate ester by condensation with an appropriate ketone(cf. Hukin,S.N., and Weller, L. Can J Chem, 1974, 52, 2157) followed by cyclization with or without intermediate hydrolysis to novel tetrahydro-2H.-pyran-2,4-diones.
  • the pyrandiones their tautomeric 4-hydroxy-5,6-dihydro-2H.-pyran-2-one equivalents can also be obtained by customary methods described in the literature.
  • the 6,6-disubstituted pyran-2,4-diones thus obtained may be acylated on oxygen and the enol esters isomerized (Fries rearrangement) to give novel C-substituted products.
  • C-acylated derivatives may be reacted with O-substituted hydroxylamines which ma in turn be generated in situ from appropriate precursors, to afford derivatives of th general Formula(l) wherein R 1 is hydrogen.
  • Compounds of the invention of Formula(l) wherein R 1 is not hydrogen may be prepared by standard synthetic procedures.
  • compounds of the inventi of Formula(l) wherein R 1 is is an organic or inorganic cation may be prepared fro compounds of the invention of Formula(l) wherein R 1 is hydrogen by reacting these latter compounds with an appropriate inorganic or organic base.
  • T ether extracts were washed with water (50 ml); and the combined aqueous phases were acidified to pH 1-2 with cone, hydrochloric acid and extracted with ether (100 ml). (At this stage of some reactions a first crop of the pyrandione crystallized from the ether solution and was recovered by filtration.) The ether solution was then evaporated and the residual water removed from the product mixture by azeotropic distillation with ethanol/be zene and then with benzene. The residue was either chromatographed (Si0 2 , dichloromethane) or, in some instances, crystallization of t pyrandione was achieved by diluting a concentrated benzene solution (ca.
  • these compounds also have utility for broad-spectrum pre- and/or post-emergence weed control in areas where control of all vegetation is required. Alternatively, these compounds are useful to regulate pla growth.
  • Rates of application for compounds of this invention are determined by a number o factors. These factors include formulation selection, method of application, amount vegetation present, growing conditions, etc. In general, the subject compounds shoul be applied at rates of 0.05 to 10 kg/ha with a preferred rate range of 0.1 to 2 kg/h One skilled in the art can easily determine application rates necessary for the desir level of weed control.
  • the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound Formula (1) as hereinbefore defined with at least one other herbicide.
  • the invention provides a met-hod for regulating t 5 growth of a plant comprising applying to the plant, to the seed of the plant, or to growth medium of the plant an effective amount of a compound of Formula (1) a hereinbefore defined.
  • Rates of application of these compounds can be influenced by many factors of the 10 environment and should be determined under actual use conditions.
  • Weed grasse graminaceous crops can normally be killed when treated at a rate of from less tha 0.1 to about 20 kg active ingredient/ha.
  • the compounds of this invention can be mixed with fungicides, bactericides, 15 acaricides, nematicides, insecticides, or other biologically active compounds in orde to achieve desired results with a minimum expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well-known to those skilled in the art. ft, 0
  • Useful formulation of the compounds within the scope of this invention can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of thes may be applied directly. Sprayable formulations can be extended in suitable medi and used at spray volumes of from one litre to several hundred litres per hectare. High strength compositions are primarily used as intermediates for further formulations.
  • the formulations broadly, contain about 1% to 99% by weight of active ingredients(s) and at least one of (a) about 0.1% to 20% surfactants(s) and about 5% to 99% solid or liquid inert diluent(s). More specifically, they will conta these ingredients in the following approximate proportions:
  • compositions may be in the form of dusting powders or granules comprisi the active ingredient and a solid diluent or carrier therefor, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fulle earth, gypsum, Hewitt's earth, diatomaceous earth, and China clay.
  • the compositi may also be in the form of dispersible powders or grains comprising a wetting age to facilitate the dispersion in liquids of the powder or grains which may contain al solid diluents, fillers and suspending agents.
  • compositions for dressing seed may contain an agent (for example a mineral oil) for assisting the adhesi of the composition to the seed.
  • aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s).
  • Suitable solvents are acetone, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene amongst others. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0 °C.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions ar prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granul and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.

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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)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pyrane Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

Compounds of formula (1) and/or tautomeric forms thereof, wherein A is a C1-C3 alkylene or C1-C3 alkenylene group optionally substituted with 1-4 C1-C3 alkyl substituents; X is O, S, SO, SO2, NR10 or a single bond; R1 is H, or one of a number of specified groups, or M; R2 is C1-C6 alkyl or one of a number of other specified groups; R?3 and R4¿ are independently H or C¿1?-C4 alkyl; R?5 and R6¿ are independently H, C¿1?-C4 alkyl or one of a number of other specified groups optionally substituted as specified, or optionally substituted with substituents that include R?12 to R23¿ as specified; or R?5 and R6¿ together with the carbon to which they are attached form one of a number of specified carbocyclic or heterocyclic rings optionally substituted as specified, where one of the carbon atoms of the ring may be a carbonyl group or its corresponding dimethyl, diethyl or ethylene or propylene ketal; R?7, R8 and R9¿ are independently H, or one of a number of specified groups; provided that when both R?5 and R6¿ are independently C¿1?-C4 alkyl, C2-C4 alkenyl, C2-C6 alkylthioalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl or C3-C6 cycloalkyl optionally substituted with specified substituents or when R?5 and R6¿ together form an optionally substituted saturated or unsaturated carbocyclic or heterocyclic ring, then at least one of R?7, R8, or R9¿ is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio or phenylamino group or phenyl substituted with 1-3 substituents selected from the group consisting of halogen, C¿1?-C4 alkyl, C1-C4 alkoxy and CF3; R?10¿ is H, C¿1?-C4 alkyl or phenyl optionally substituted as specified; M is Li?+, Na+, K+, NH¿4+, or N(R11)4+ where R11 is C1-C4 alkyl; herbicidal and plant growth compounds containing them, methods for regulating the growth of a plant and selectively inhibiting, damaging or killing weed grasses in a broad-leaf crop involving them.

Description

HERBICIDAL PYRONES
The present invention relates to organic compounds having herbicidal properties a plant growth regulating properties; to herbicidal compositions and processes utilisin such compounds and to plant growth regulating compositions and processes utilisin such compositions.
The use of certain cyclohexane-l,3-dione derivatives as grass herbicides is known in the art. Thus, for example, the compendium "Agricultural Chemicals - Book II Herbicides 1983-84 Revision" (W.T. Thomson Editor, Thomson Publications, California U.S.A.) describes the cyclohexane-l,3-dione derivatives known commercially as Alloxydim sodium
(methyl-3-[l-(aJlyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-ene carboxylate), Cycloproxydim ((E^)-2[l[l-[(3-chloro-2-propenyl)oxy]imino]butyl]-5- [2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-l-one), and Sethoxydim (2-[l -(ethoxyimino)butyl]-5-[2-ethylthio]propyl-3-hydroxy- 2-cyclohexen-l -one) as selective post-emergent herbicides. Alloxydim and Sethoxydim have been disclosed Australian Patent No. 464,655 and Australian Patent Application No. 35314/78 respectively.
Australian Patent No 560,716 (Watson et al, Application No 27196/84) in the name of ICI Australia Limited, published 22 November 1984, discloses herbicidal compounds of the formula:
wherein
*
R is substituted phenyl; R1 is H, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylsulfonyl, alkoxy, all ylthio, acyl, (un)substituted phenylalkyl or PhS02 ; R2 is alkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, haloalkyl, alkoxyalkyl, alkylthioalkyl or (un)substituted phenylalkyl; and R3 is alkyl, fluoroalkyl, alkenyl, alkynyl, or phenyl.
Watson et al teach that tetrahydropyran-2,4-dione derivatives which are substituted the 6-position with a substituted phenyl group exhibit particularly useful herbicidal activity.
United States patent No 4,008,067 (issued February 15, 1977) in the name of Hiro et al discloses herbicidal oxacyclohexane derivatives of the formula:
NHOR2 A
NRi wherein:
R1 is lower alkyl;
R2 is lower alkyl, lower alkenyl or lower alkynyl;
wherein
R3 is H or lower alkyl; R4 is lower alkyl or phenyl; or
R3 forms cycloalkylene of 4 to 5 carbon atoms by combining with R4 ; OR
wherein
R5 and R7 are selected from the group consisting of H and lower alkyl; R6 is lower alkyl;
wherein
R8 is H or lower alkyl; and R9 is lower alkyl. The above compounds are substituted in the 5 and/ or 6- positions of the pyran rin by one or two alkyl groups
International patent application PCT/AU87/ 00236, filed July 27, 1987 (Internation Patent Publication WO 8800945) in the name of the present applicants and corresponding to Australian patent application No 77583/87, European patent application No 87904820, Japanese patent application No 504 646 and United State Patent No. 4,939,278, describes herbicidal pyrones of the formula:
wherein, in part,
R! is H;
R2 is substituted alkyl wherein the alkyl group is substituted by optionally substitute phenyl and optionally substituted heterocycle;
R3 is alkyl;
R4 and R5 together with the carbon to which they are attached form a substituted o unsubstituted saturated or partially saturated heterocyclic or carbocyclic ring containing 3 or more ring atoms; etc. This is only a brief listing of the relevant groups. The last mentioned spirocyclic analogues are stated as being a preferred subgenus. Further preferred are compounds in which R1 is H, R2 is alkyl, alkenyl or haloalke (specifically ethyl, allyl, 2-chloroallyl and 3-chloroallyI) and R3 is ethyl or n-propyi.
WO 8800945 at Tables 1-4 lists 91 individual spirocyclic compounds, all with R2 as ethyl, allyl or chloroallyl only. At page 23A the specification teaches that "The compounds of the invention are substantially more effective against monocotyledonous plants or grass species than against dicotyledonous plants or broad-leaved species.". Although it is also stated on pages 23A and 25 of this specification that "certain of the compounds show selective herbicidal activity against wild grasses in monocotyledonous crop species and hence may be used for selective control of wild grass in graminaceous crops", the application emphasises th use of the disclosed compounds for control of grass weeds in broadleaf crops witho damage to the broadleaf crop.
International patent application PCT/AU89/00191 also in the name of the present applicants, describes herbicidal pyrones that are similar to those described in WO8800945, but which have an additional substituent, R6, on the pyrone ring. The compounds described in PCT7AU89/00191 are of the general formula:
wherein the substituted groups R1 to R5 are similar to those described in WO 8800945, and, R6 is selected from alkyl, alkoxy, alkylthio, halogen or substituted alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of alkoxy, alkylthio or halogen. Preferred values for the oxime capping group R2 are alkyl, alkenyl, alkynyl and haloalkenyi; specifically preferred are ethyl, propargyl, allyl, 2-chloroallyl and 3-chloroallyl.
This specification states "certain of the compounds of Formula 2 may be used for selective control of wild grass in graminaceous crops." However there is no specifi mention of which compounds or of usefulness on rice crops.
The specification of PCT/AU89/00191 includes 15 examples relating to spirocyclic derivatives, but the oxime capping groups shown are restricted to ethyl, allyl or chloro allyl.
International Patent Application PCT/AU91/00019 also by the present applicants claims a series of compounds with selectivity for weed grasses in rice wherein the capping group R2 is :
wherein R7, R8 and R9 are independentiy H, halogen, C C4 alkyl, C , alkoxy, C alkylthio, C:-C4 alkylsulfinyl, C -C4 alkylsulfonyl,
Cj-Q, haloalkyl, C C4 haloalkoxy, nitro, cyano, Cj-C4 alkoxycarbonyl, C C^ alkylaminocarbonyl, C-,-C6 dialkylaminocarbonyl, aminocarbonyl, phenyl, amino, - alkylamino, or C^-Cg dialkylamino.
We have discovered that compounds similar to those described in International Patent Application WO 8800945, PCT/AU89/00191 and PCT/AU91/00019 in whic R2 includes a phenyl group itself substituted with an optionally substituted phenyl group which is linked either directly or via a small group, for example by a methylene, oxy or thio bridge, are highly active and more selective pre-emergent and/or post-emergent herbicides or plant growth regulators which are particularly useful for controlling certain grass weeds in dryland and paddy rice. Accordingly, the invention provides a compound of Formula (1):
wherein A is a C alkylene or C Q alkenylene group optionally substituted with 1-4 CfQ alkyl substituents;
X is O, S, SO, S02, NR10 or a single bond;
R1 is H, Q-Q alkyl, Q-C4 alkenyl, Q-Q alkynyl, Q-Q cycloalkyl, Q-Q cycloalkenyl, Q-Q alkylcarbonyl, phenylcarbonyl, phenyl optionally substitut with 1-3 substituents selected from the group consisting of halogen, Q-C4 alk
Cf C4 alkoxy, Q-C4 alkylthio, nitro, cyano, -Q haloalkyl, amino, and Q-Q haloalkoxy, Q-Q alkylsulfonyl, benzenesulfonyl, Q-Q alkylcarbonyl, Q-C8 alkoxyalkyl, Q-Q alkylthioalkyl, Q-Q0 phenylalkyl or M;
R2 is Q-Q alkyl, Q-Q alkenyl, Q-Q alkynyl, Q-Q haloalkyl, Q- Q alkylthio, Q cycloalkyl, Q-Q cycloalkenyl, phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Q- alkylthio, nitro, cyano, Q-Q haloalkyl, amino, and Cf Q haloalkoxy, Q-Q alkoxyalkyl, Q-Q alkylthioalkyl, or Q-Q alkyl substituted with a substituent selected from the group consisting of phenyl, phenoxy and thiophenoxy where the aromatic ring of said substituents may be substituted with 1-3 substituents selected from halogen, Q-Q alkyl, Q-Q alkoxy, Q-Q alkylthio, nitro, cyano, amino, Cf Q haloalkyl and Cf Q haloalkoxy;
R3 and R4 are independently H or Q-Q alkyl;
R5 and R6 are independently H, Cf Q alkyl, Q-Q alkenyl, Q-Q alkylthioalkyl, Q-Q haloalkyl, Q-Q haloalkenyi or Q-Q cycloalkyl wherein the alkyl, alkenyl and cycloalkyl groups are optionally substituted with 1-3 substituents selected from the group consisting of OR12, NR13R14, NR15C(0)(Q-Q alkyl), NR18S02Q-Q alkyl), NR21C(0)(Q- Q alkyl), C(OR16)(OR17)R22, C(SR19)(SR20)R23, Cf Q alkoxycarbonyl and phenyl which may be substituted with a substituent selected from halogen, Cf Q alkyl, Q-Q alkoxy, Cf Q alkylthio, nitro, cyano, Q- Q haloalkyl and Q-Q haloalkoxy; OR R5 and R6 together with the carbon to which they are attached form a fully saturated or an unsaturated 3- to 7-membered carbocyclic ring, or a fully saturated or an unsaturated 5- to 7-membered heterocyclic ring containing 1- heteroatoms selected from the group consisting of 0-3 nitrogen, 0-2 oxygen a 0-2 sulfur atoms; said ring may be substituted with 1-4 substituents selected from the group consisting of halogen, Q-Q alkyl, Cf Q haloalkyl, Q-Q alkenyl, Q-Q alkynyl, Cf Q alkylcarbonyl, Q-Q alkoxy, Q-Q alkylthio, Cf alkoxycarbonyl, -COOH, Q-Q alkoxyalkyl, Q-Q alkylthioalkyl, and phenyl which is optionally substituted with a substituent selected from halogen, Cf Q alkoxy, Q-Q alkylthio, Q-Q haloalkyl, nitro, cyano and Cf Q haloalkoxy; one of the carbon atoms of said ring may be in the form of a carbonyl group or its corresponding dimethyl, diethyl or ethylene or propylene ketal;
R7, R* and R9 are independentiy H, halogen, Q-Q alkyl, Q-Q alkoxy, Q-Q alkylthio, Cf Q alkylsulfinyl, Cf Q alkylsulfonyl, Cf Q haloalkyl, Cf Q haloalkoxy, nitro, cyano, Cf Q alkoxycarbonyl, Q- Q alkylaminocarbonyl, Q"Q dialkylaminocarbonyl, aminocarbonyl; amino; Cf Q alkylamino, Q-Q alkylamino; or benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio, phenylamino or phenyl group said group optionally substituted wit 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Cf C4 alkoxy, and CF3; provided that when both R5 and R6 are independentiy Cf Q alkyl, Q-Q alkenyl, Q-Q alkylthioalkyl, Q-Q haloalkyl, Q-Q haloalkenyi or Q-Q cycloalkyl optionally substituted with a substituent selected from the group consisting of Q-Q alkoxycarbonyl and phenyl which may be substituted with a substitue selected from halogen, Cf Q alkyl, Cf Q alkoxy, Cf Q alkylthio, nitro, cyan Cf Q haloalkyl and Q-Q haloalkoxy, or when R5 and R6 together form an optionally substituted saturated or unsaturated carbocyclic or heterocyclic ri then at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio or phenylamino gro or at least one of R7, R8 or R9 is phenyl substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Cf Q alkyl, Q- alkoxy and CF3,\
►ιo is H, Cf C4 alkyl or phenyl optionally substituted with 1-3 substituents select from the group consisting of halogen, Q-Q alkyl, Q- Q alkoxy, Cf Q alkylt Q-Q haloalkyl and Cf Q haloalkoxy;
M is Li+, Na+, K+, NH4\ or N(Rπ)4 + where R11 is Q-Q alkyl;
R is H, Q-Q alkyl, C(0)(Q- Q alkyl)or C02(Q- Q alkyl);
R13, R15, R18, R21, R22 and R23 are independentiy H or CfQ alkyl;
R14, R16, R17, R19 and R20 are independentiy CfQ alkyl;
R16 and R17 taken together may be -(CH**^- or -(CH^-; and R19 and R20 taken together may be -(CH2)2- or -(CH2)3-.
In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", denotes straight chain or branched alkyl, e.g. meth ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers;
Alkoxy denotes methoxy, ethoxy, n-propoxy, isopropyloxy, and the different butyloxy isomers.
Alkenyl denotes straight chain or branched alkenes, e.g. vinyl, 1-propenyl, 2-propenyl, 3-propenyl, etc.
Alkynyl denotes straight chain or branched alkynes, e.g., ethynyl, 1-propynyl, 2-propynyl, and the different butynyl isomers.
Alkylsulfonyl denotes methylsulfonyl, ethylsulfonyl, propylsulfonyl, and the different butylsulfonyl isomers.
Alkylthio, alkylsulfinyl, alkylamino, etc. are defined in an analogous manner.
Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
The term "halogen", either alone or in compound words such as "haloalkyl", denote fluorine, chlorine, bromine or iodine. Further, when used in compound words such "haloalkyl" said alkyl may be partially halogenated or fully substituted with halogen atoms which may be the same or different. Examples of haloalkyl include CH2CH2 CF2CF3 and CH2CHFC1.
Alkylcarbonyl denotes acetyl, propionyl, and the different butyryl isomers.
Alkoxycarbonyl denotes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and the different butoxycarbonyl isomers.
The total number of carbon atoms in a substituent group is indicated by the Ci-Cj prefix where i and j are numbers from 1 to 10. For example, Q-Q alkylthioalkyl would designate -CHjSCH^ -CH-jSQH., -α^CH-jSα^ or -CH(CH3)SCH3, and Q- alkoxyalkyl would represent -CH2OCH3 through to -(CH2)4θCH3 or -CH20(CH2)3C and the various structural isomers embraced therein.
Alkylene denotes methyene (-CH2-), ethylene (-CH2CH2-), propylene and butylene; alkenylene denotes -CH = CHCH2-, -CH = CHCH2CH2-, and -CH2CH = CHCH2-.
It should be recognized that when R1 is hydrogen the compounds of the invention may undergo tautomerisation. All tautomeric forms are included in the scope of thi invention. Preferred groups of compounds of general Formula (1), for reasons including ease synthesis and greater herbicidal efficacy, include the following:
(1) Compounds of Formula (1) wherein R1 is H or M and
R2 is Q-Q alkyl, Q-Q haloalkyl, Q-Q alkenyl or Q-Q alkynyl .
(2) Compounds of 1 above wherein
A is CfQ alkylene or Q-Q alkenylene optionally substituted with CH3 or QH5;
R7, R8 and R9 are independently H, CI, Br, F, CfQ alkyl, CfQ alkoxy, Cf alkylthio, Cf Q haloalkyl, CfQ haloalkoxy, nitro, cyano or CfQ alkoxycarbonyl; or benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino optionally substituted with 1-3 substituent selected from the group consisting of halogen, Q- Q alkyl, Q- Q alkoxy, or
CF3; provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group; and
R10 is H or CH,
(3) Compounds of 2 above wherein X is O
(4) Compounds of 2 above wherein X is S, SO or S02.
(5) Compounds of 2 above wherein X is NR10.
(6) Compounds of 2 above wherein X is a single bond.
(7) Compounds of 6 above wherein:
A is -CH,-, -CH2CH2- or -CH2CH = CH- ; R^ H, Li+, Na+, or K+; R2 is CH3, QH5, n-C3H7 or n-QH9 ; R3 and R4 are independentiy H, CH3 or QH5 ; and R7, R8 and R9 are independentiy H, CI, Br, F, CH3, QH5, OCH3, OQH5, SCH3, SQH5, CF3, CHF2, CF2CF3, OCHF2, OCF3, OCH2CF3, N02, CN C02CH3, Ph, S02Ph, COPh, CH2Ph, OCH2Ph, OPh, SPh,
NHPh or N(Me)Ph provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
(8) Compounds of 6 above wherein R5 and R6 are independently Q- Q alkyl, Q-Q alkenyl, Q-Q alkynyl, Cf Q alkylthio or Q-Q alkylthioalkyl.
(9) Compoimds of 6 above wherein R5 and R6 together with the carbon to which they are attached form a saturated or unsaturated 5-, 6- or
7-membered carbocyclic ring which is optionally substituted with 1-4 CH3 groups.
(10) Compounds of 9 above wherein A is -CH2-, -CH2CH2- or CH2CH = CH- ;
R1 is H, Li + , Na+ or K+; R2 is CH3, QH5, n-QH7 or n-QH9; R3 and R4 are independentiy H or CH3; and R7, R8 and R9 are independentiy H, CI, Br, F, CH3, QH5, OCH3, OQH5, SCH3, SQH5, CF3, CHFZ CF2CF3, OCHF OCF3, OCH2CF3,
N02, CN, C02CH3, Ph, S02Ph, COPh, CH2Ph, OCH2Ph, OPh, SPh, NHPh or N(Me)Ph provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
(11) Compounds of 6 above wherein R5 and R6 together with the carbon to which they are attached form a saturated or unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1-2 heteroatoms selected from the group consisting of 0-2 nitrogen, 0-1 oxygen and 0-2 sulfur atoms; said ring is optionally substituted with 1-4 CH3 groups.
(12) Compounds of 11 above wherein A is -CH2-, -CH2CH2- or -CH2CH = CH- ; R1 is H, Li+, Na+ or K+; R2 is CH3 QH5, n-QH7 or n-QH9;
R3 and R4 are independently H, CH3 or QH5 ; and R7, R8 and R9 are independentiy H, CI, Br, F, CH3, QH5, OCH3, OQH5, SCH3, SQH5, CF3, CHF CF2CF3, OCHF OCF3, OCH2CF3, NO CN, CO,CH3, Ph, S02Ph, COPh, CH2Ph, OCH2Ph, OPh, SPh, NHPh or N(Me)Ph provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
Specifically preferred, for reasons of greatest herbicidal efficacy, greatest selectivity rice and/or most favorable ease of synthesis are:
9-hydroxy-8-[ 1 -((3-(phenoxy)phenyl)methoxyimino)butyl]-6- oxaspiro[4.5]dec-8-en-7-one, which has the formula;
- _Λ
8-[ l-((4-(4-fluorophenyl)phenyl)methoxyimino)butyl]-9-hydroxy-6- oxaspiro[4.5]dec-8-en-7-one, which has the formula;
9-hydroxy-8-[ 1 -((4-(phenyl)phenyl)methoxyimino)butyl]-6- oxaspiro[4.5]dec-8-en-7-one, which has the formula;
6,6-dimethyl-4-hydroxy-3-(l-((4-(phenyl)phenyl)methoxyimino)butyl)pyr any¬ one, which has the formula;
and 6,6-dimethyl3-(l -((4-(4-fluorophenyl)phenyl)methoxyimino)butyl)-4- hydroxypyran-2-one, which has the formula;
Specific examples of compounds of the invention of Formula (1) include those compounds detailed in Tables 1-4 below. Unless otherwise specified in the Tables is taken to be a single bond.
Table 1
R - H, X = single bond
Compd. R R3 R7 Rβ
CH2 H Pr CH2 H Pr CH2 H Pr CH, H Pr CH, H Et
1.13 CH, H Pr Me H 3-CH2Ph 4-F
1.15 CH, Me Pr H H 3-CH,Ph 4-C1
H
H -16
1.31 Et 132 Pr 1.33 Pr 1.34 Pr 1.35 Pr 1.36 Pr
Pr Pr Pr
Pr Pr Pr Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr
Me
Et
Pr Pr
1.62 CH, H Pr H H 4-F 3-Ph 1.63 CH, 1.64 CH, 1.65 CH,
Me H 3-(4-F)PhO H
Me H 3-(4-CN)PhO H
Me H 3-(4-CF3)PhO H
Me Me 3-Ph H
Me Me 3-F 4-Ph
Me Me 4-(4-F)Ph H
Me Me 4-(4-CN)Ph H
Me Me 3-(4-F)PhO H
Me Me 3-(4-CN)PhO H
H H 4-Ph H
H H 4-(4-F)Ph H
H H 4-(4-F)Ph H
H H 4-Ph H H H 4-Ph H 1.100 2 CH2 H Pr
Pr
Pr Pr Pr Pr Pr Pr
Pr Pr Pr Pr Pr
1.116 CH, H Pr H H 3-(4-F)PhO H
Table 2
R = H, X= single bond
3.4 CH, Pr H H Me H
3.6 CH, Pr H H Me H
3.8 CH, Pr H H Me H
24 -
Table 4
R9 = H, X=
R2 R3 R4 R7 R8
3-Ph H
4-Ph H
3-Ph H
4-Ph H
3-Ph H
4-Ph H
3-Ph H
4-Ph H
4-Ph H
4-Ph H
4-(4-F)Ph H
2-F 4-Ph
3-F 4-Ph
4-F 3-Ph
4-(4-CN)Ph H
4.18 CH2 4-(4-SO2Me)Ph H
4-(4-F)Ph H 4.19 CH, 4.20 CH2 3-PhO H O H 4.21 CH, 3-(4-CN)Ph 4.22 CH2 4-Ph H 4.23 CH2 4-(4-F)Ph H 4_24 CH, 4-Ph H 425 CH, 4-(4-F)Ph H
4.32 2 CH2 4-(4-CN)Ph H
The compounds of the invention may be prepared by a method similar to that disclosed in WO8800945, with appropriate alteration of starting reagents. For example, the compounds of the invention may be prepared from the dianion of an acetoacetate ester by condensation with an appropriate ketone(cf. Hukin,S.N., and Weller, L. Can J Chem, 1974, 52, 2157) followed by cyclization with or without intermediate hydrolysis to novel tetrahydro-2H.-pyran-2,4-diones. The pyrandiones their tautomeric 4-hydroxy-5,6-dihydro-2H.-pyran-2-one equivalents can also be obtained by customary methods described in the literature. The 6,6-disubstituted pyran-2,4-diones thus obtained may be acylated on oxygen and the enol esters isomerized (Fries rearrangement) to give novel C-substituted products. The
C-acylated derivatives may be reacted with O-substituted hydroxylamines which ma in turn be generated in situ from appropriate precursors, to afford derivatives of th general Formula(l) wherein R1 is hydrogen.
Compounds of the invention of Formula(l) wherein R1 is not hydrogen may be prepared by standard synthetic procedures. For example, compounds of the inventi of Formula(l) wherein R1 is is an organic or inorganic cation may be prepared fro compounds of the invention of Formula(l) wherein R1 is hydrogen by reacting these latter compounds with an appropriate inorganic or organic base.
Esterification of the vinylogous acid in compounds of the invention of Formula(l) wherein R1 is hydrogen provides further herbicidal and growth regulating derivatives
The general procedure for preparation of Compounds of the Invention is described i detail in the following section.
Geπeral Procedure for Preparation of Compounds of the Invention
(a) Synthesis of the Pyran-2,4-diones
To a stirred solution of the sodium salt of an (alkyl) acetoacetate ester [ca. 55 mm either preformed or made in situ from the (alkyl) acetoacetate ester ( 55 mmol) an sodium hydride (55 mmol) according to the method of Huckin, S.N., and Weiler, L Can. J. Chem., 1974, 52, 2157] in dry tetrahydrofuran (50 ml) under nitrogen and cooled to 0 °C, was added dropwise a solution of n-butyllithium (21.2 ml, 2.6M in hexane, 55 mmol). After 1 h the mixture was treated with an appropriate ketone ( mmol) (solid ketones were dissolved in tetrahydrofuran prior to addition ) and left stirring at 0 °C for 120 min before being quenched with methanol (2.4 ml, 60 mmol After addition of further methanol (20 ml) and water (10 ml) [and in certain instances acid] the mixture was boiled for ca.30 min then diluted further with wate (40ml) and concentrated (to ca. 40 ml) at reduced pressure. Upon cooling and addition of water (ca. 150 ml) the mixture was extracted with ether (2 x 100 ml). T ether extracts were washed with water (50 ml); and the combined aqueous phases were acidified to pH 1-2 with cone, hydrochloric acid and extracted with ether (100 ml). (At this stage of some reactions a first crop of the pyrandione crystallized from the ether solution and was recovered by filtration.) The ether solution was then evaporated and the residual water removed from the product mixture by azeotropic distillation with ethanol/be zene and then with benzene. The residue was either chromatographed (Si02, dichloromethane) or, in some instances, crystallization of t pyrandione was achieved by diluting a concentrated benzene solution (ca. 20 ml) of the residue cautiously with cyclohexane to a faint turbidity, and then stirring vigorously. When crystallization ensued, the mixture was cautiously diluted with mor cyclohexane (ca. 20 ml) and stirred for a further 4 h, after which the precipitate was collected and washed with cyclohexane /benzene (4:1) to afford the pyrandione . Method B
A solution of n-butyllithium (45 ml, 2.45M in hexane, 110 mmol) was added to a stirred solution of diisopropylamine (15.6 ml, 111 mmol) in tetrahydrofuran (50 ml maintained at 0 °C under argon. The stirring was continued for 15 min at room temperature; the mixture was then chilled in ice. The (alkyl) acetoacetate ester(52 mmol) was then added and the resultant mixture stirred at 0 °C for 30 min whereupon an appropriate ketone (50 mmol dissolved in the minimum quantity of tetrahydrofuran to form a homogeneous solution) was added and stirring continued for an additional 90 min (or until the reaction mixture paled to light orange or yellow) before quenching with methanol (4.8 ml, 120 mmol). The reaction mixture was then worked up as in Method A to give the pyrandione.
(b) Acylation of Pyrandiones
To a stirred solution of the pyrandione (6.10 mmol) and DBU [l,8-diazabicyclo(5.4.0)-7-undecene](0.99g, 6.5 mmol) in toluene (20ml) at 0 °C was added an appropriate acyl chloride (6.6 mmol) and the mixture stirred at 0 °C for 2 then at room temperature for 24 h. Dilution with water <_50 ml) and toluene (30 ml and shaking the mixture gave an organic phase which was quickly washed with 5% hydrochloric acid, dried (sodium sulf ate) and evaporated in vacua The residue and 4-dimethylaminopyridine (40 mg, 0.3 mmol) were heated under reflux in toluene (10 ml) for 3 h (or until thin layer chromatography showed that the reaction was complete) and then the toluene was removed in vacua and the residue chromatographed [Si02, dichloromethane:light petroleum (b.p. 40-60C): ethyl acetat (4:4:1)] to give the C-acylated compound.
(c) Qximation of Acylated Compounds.
A mixture of the C-acylated compound (3.75 mmol), the appropriate O-substitued hydroxylamine hydrochloride (4.00 mmol), triethylamine (0.41 g, 4.0 mmol) and methanol (5 ml) was stirred at room temperature for 48 h, then poured into water (50 ml). Acidification of the mixture to pH 4 with 5M hydrochloric acid, extractio with diethyl ether or ethyl acetate (2 x 50 ml), evaporation of the organic phase an chromatography [SiOj, dichloromethane or dichloromethanerlight petroleum (b.p. 40-60C):ethyl acetate (4:4:1)] of the residue then afforded examples of compounds the invention (1).
Activity of Compounds of the invention
Test results indicate that the compounds of this invention are highly active pre-emergent and/or post-emergent herbicides or plant growth regulants. These compounds are particularly useful for controlling certain grass and broadleaf weeds dryland and paddy rice ( Oryza sativa), examples of which include, but are not limite to, Indica and Japonica varieties of the crop. Many of the compounds of this invention are especially useful for the control of selected grass weeds, such as barnyardgrass (Echinochloa crusgalli), in paddy rice.
At the appropriate application rates, these compounds also have utility for broad-spectrum pre- and/or post-emergence weed control in areas where control of all vegetation is required. Alternatively, these compounds are useful to regulate pla growth.
Rates of application for compounds of this invention are determined by a number o factors. These factors include formulation selection, method of application, amount vegetation present, growing conditions, etc. In general, the subject compounds shoul be applied at rates of 0.05 to 10 kg/ha with a preferred rate range of 0.1 to 2 kg/h One skilled in the art can easily determine application rates necessary for the desir level of weed control.
Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides or fungicides. A list of such commercial compounds is given in Appendix A of PCT/AU91/00019 which is incorporated here by reference. Accordingly, in yet a further embodiment, the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound Formula (1) as hereinbefore defined with at least one other herbicide.
In yet a still further embodiment, the invention provides a met-hod for regulating t 5 growth of a plant comprising applying to the plant, to the seed of the plant, or to growth medium of the plant an effective amount of a compound of Formula (1) a hereinbefore defined.
Rates of application of these compounds can be influenced by many factors of the 10 environment and should be determined under actual use conditions. Weed grasse graminaceous crops can normally be killed when treated at a rate of from less tha 0.1 to about 20 kg active ingredient/ha.
The compounds of this invention can be mixed with fungicides, bactericides, 15 acaricides, nematicides, insecticides, or other biologically active compounds in orde to achieve desired results with a minimum expenditure of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well-known to those skilled in the art. ft, 0
Formulation
Useful formulation of the compounds within the scope of this invention can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of thes may be applied directly. Sprayable formulations can be extended in suitable medi and used at spray volumes of from one litre to several hundred litres per hectare. High strength compositions are primarily used as intermediates for further formulations. The formulations, broadly, contain about 1% to 99% by weight of active ingredients(s) and at least one of (a) about 0.1% to 20% surfactants(s) and about 5% to 99% solid or liquid inert diluent(s). More specifically, they will conta these ingredients in the following approximate proportions:
Percent by Weight Active Ingredient Diluents(s) Surfactant(s)
Lower or higher levels of active ingredients can, of course, be present depending o the intended use and d e physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation of by tank mixing. The compositions may be in the form of dusting powders or granules comprisi the active ingredient and a solid diluent or carrier therefor, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fulle earth, gypsum, Hewitt's earth, diatomaceous earth, and China clay. The compositi may also be in the form of dispersible powders or grains comprising a wetting age to facilitate the dispersion in liquids of the powder or grains which may contain al solid diluents, fillers and suspending agents.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, NJ. The more absorptive diluents are preferred for the wettable powders and the denser ones for dusts. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Compositions for dressing seed, for example, may contain an agent (for example a mineral oil) for assisting the adhesi of the composition to the seed.
The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable solvents are acetone, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene amongst others. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0 °C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions ar prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granul and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.
The synthesis of the compounds of the invention is further illustrated by the descriptions in the following examples.
Example 1 (Compound 1.32)
Preparation of 9-hydrc x -8-[l-(3-(phenrxy)phenyl)methox ^ oxaspiro[45]dec-8-en-7-one.
To a mixture of 0-(3-(phenoxy)phenyl)methyl hydroxylamine hydrochloride (0.63g) and triethylamine (0.25g) in ethanol (10.0 ml) stirred at 20'C was added 8-butyryl-6-oxaspiro[4.5]dec-7,9-dione (0.48 g). After 24 hours at 20'C the mixture diluted with water (100 ml), acidified to pH 3 with 5 N hydrochloric acid and extracted with diethyl ether. Evaporation of the organic phase and chromatography the residue over silica gel gave the product (0.41 g) as a pale yellow oil, 1H n.m.r. δ (CDC13) 0.97, broad t, J 7 Hz, CH3; 1.2-2.4, m, 10 H, cyclopentyl and CH2CH3; 2.65, s, COCH, 2.94, broad t, J 8Hz, CH2CH2CH3; 4.98, s, OCH2 and 7.0-7.5, s, aromatic H.
Other compounds of the invention were prepared by the general method given abo they were characterised by their proton nmr spectra and by melting point (if solid). Physical data for selected compounds is given below.
compound 131 pale yellow oil, **H n.m.r. δ (CDC13) 1.12, t, J7Hz. CH3; 1.4-22, m, cyclopent H; 2.65, s, COCH*,; 2.9, q, J7Hz, CH-jCH3; 4.98, s, OCHj and 6.9-7.4, m, ArH compound 1.33 colourless oil, H n.m.r. δ (CDC13) 0.92, t, J7Hz. CH2CH3; 1.15, d, J6Hz,
CHCH3; 1.3-2.1, m, cyclopent H and CH2CH2CH3; 2.42, q, J6Hz; CHCH3; 2.85-3.2, m, CH2CH2CH3; 4.98, s, OCH2 and 6.8-7.4, m, ArH compound 1.34 pale yellow oil, lH n.m.r. δ (CDC13) 0.95, t, J7Hz. CH3; 1.4-2.2, m, cyclopent H and CH2CH2CH3; 2.64, s, COCH2; 2.96, q, J7Hz, CH2CH3; 4.98, s, OCH2 and 7.0-7.5, m, ArH compound 152 yellow oil, lH n_m.r. δ (CDCI3) 0.92, t, J7Hz. d^CH3; 1.15, d, J6Hz,
CHCH3; 1.2-2.0, m, cyclohex H and Cf-y^CH^ 2.40, q, J6Hz; CHCH3; 2.87, t, J7Hz, CH^CH^C^ 4.88, s, OCH-, and 6.8-7.3, m, ArH compound 156 pale yellow oil, l nsa.r. δ (CDα3) 0.92, t, J7Hz. CH2CH3; 1.1-2.1, m, cyclohept H and CH,CH2CH3; 231, s, OCH2; 2.91, t, J7Hz, CH2CH2CH3; 4.88, s, OCH2 and 6.8-7.4 ArH compound 159 m. p. 70, XH n_m.r. δ (CDC13) 0.93, t, J7Hz. CH3; 12-2.0, m, cyclopent and CH2CH2CH3; 2.65, s, COCH2; 2.93, q, J7Hz, CH2CH2CH3; 5.06, s, OCH2 and 72-7.7, m, ArH compound 1.63 pale yellow oil, -Η n_m.r. δ (CDC13) 0.88, t, J7Hz. CH3; 13-2.1, m, cyclopent H and CH2CH3; 2.62, s, COCH2; 2.92, q, J7Hz, CHjCH-jCH^ 5.02, s, OCH2 and 6.9-7.7, m, ArH compound 1.66 pale yellow oil 1H n.m.r. δ (CDC13) 0.94, t, J7Hz. CH3; 1.5-2.1, m, cyclopent H and CHjCH^ 2.62, s, COCB^; 2.94, q, J7Hz, CH2CH*,CH3; 5.08, s, OCϊ*^ and 7.1-7.7, m, ArH compound 1.70 m.p. 100, 1H n.m.r. δ (CDQ3) 0.83, t, J7Hz. CH3; 13-2.1, m, cyclopent and CH2CH3; 2.62, s, COCH2; 2.94, q, J7Hz, CH2CH2CH3; 5.14, s, OCH2 and 6.7-7.6, m, ArH compound 1.77 colourless oil, lH njm.r. δ (CDCI3) 0.80-1.1, m, 2xCH3; 12-2.2, m, cyclopent H and CH2CH2CH3; 2.61, s, COCH-,; 2.94, q, J7Hz, CH2CH2CH3; 5.06, s, OCH2 and 6.9-7.4 m, ArH compound 1.79 pale yellow oil, lH n.m.r. δ (CDQ3) 0.92, t, J7Hz. CH2CH3; 1.14, d, J6H
CHCH3; 13-2.1, m, cyclopent H and CH2CH2CH3; 236, q, J6Hz; CHCH3; 2.80-3.15, m, CH2CH2CH3; 5.06, s, OCH, and 7.2-7.7, m, ArH compound 1.80 m. p. 69, XH n_m.r. δ (CDCl3) 0.97, t, J7Hz. CH2CH3; 125, d, JδHz,
CHCH3; 1.4-2.1, m, cyclopent H and C^CHjCH^ 2.42, q, J6Hz; CHCH3; 2.85-3.1, m, ^OAfil^ 5.05, s, OCH, and 7.1-7.65, m, ArH compound 1.89 m. p. 109, lH njn.r. δ (CDQ3) 0.92, t, J7Hz. CH2CH3; 1.2, s, 2xCH3;
13-2.0, m, cyclopent H and CH2CH2CH3; 3.0, t, J7Hz, CH2CH2CH3; 5.08, s, OCH2 and 7.0-7.7, m, Ar compound 1.95 pale yellow oil, lK n n.r. v(CDCl3) 0.8-1.1, m, CH2CH3 and CHCH3;
1.4-23, m, cyclopent H, CH2CH2CH3 and CHCH3; 2.85-3.2, m, CH2 CH2CH3; 5.07, s, OCH2 and 72-7.8, m, ArH compound 1.97 m. p. 57, --H njn.r. δ (CDQ3) 0.8-1.1, m, CH2CH3 and CHCH3; 13-2.1, cyclohex H, CH2CH2CH3 and CHCH3; 2.68, s, COCH2; 3.0, t, J7Hz, CH2CH2CH3; 5.08, s, OC^ and 6.9-7.7, m, ArH compound 1.98 m. p. 61, XH n_m.r. δ (CDα3) 0.%, t, J7Hz. CH3; 1.1-2.0, m, cydcΛex H and CH*,CH2 CH 3; 2-52» s- COCHj; 3.0, q, J7Hz, CH^CHjCH-^; 5.03, s, OCBj and 72-7.7, m, ArH compound 1.99 m. p.107, lH n.m.r. δ (CDC13) 0.8-1.1, m, CH2CH3 and CHCH3; 12-2 cyclohex H, C^CI^C^ and CHCH3; 2.50, s, COCH^ 2.97, t, J7Hz, CHjCl^C^; 5.05, s, OCH*,
72-7.7, m, ArH compound 1.100 m. p. 78, -*H njn.r. δ (CDC13) 0.95, t, J7Hz. CH3; 1.1-2.0, m, cyclohex and CH2CH2 CH3. 2.53, s, COCH2; 3.04, q, J7Hz, CH2CH2CH3; 5.06, s, OCH2 and 6.9-7.7, m, ArH compound 1.111 pale yellow oil, *H njn.r. δ (CDα3) 0.96, t, J7Hz. CH3; 12-2.0, m, cyclohept H and CH2CH2CH3; 2.51, broad s, COCH^ 2.98, t, J7Hz, CH2 CH2CH 3^ 5-03> s- OCH2 and
6.9-7.7, m, ArH compound 1.112 colorless oil, 1H n.m.r. δ (CDC13) 0.98, t, J7Hz. CH2CH2CH3; 1.16, d, J6Hz, CHCH3;13-2.1, m, cyclohept H and C^CHjCR,; 2.41, q, J6Hz, CHCH3; 2.98, t, J7Hz, CH2CH2CH3; 5.09, s, OCH2 and 7.3-7.8, m, ArH compound 1.113 pale yellow oil, 1H n_m.r. δ (CDC13) 0.96, t, J7Hz. CH3; 1.2-2.1, m, cyclohept H and CHjCH^CH,; 2.51, broad s, COCBj; 2.98, q, J7Hz, CHsCl^C ^ 5.03, s, OCI^ an 6.9-7.7, m, ArH compound 3.16 colourless oil, lH n.m.r. δ (CDα3) 0.92, t, J7Hz. CH3; 1.46s, 2xCH3; 23 s, COCH2; 2.95, q, J7Hz, CH2CH2CH3; 5.02, s, OCI^ and 6.9-7.4, m, ArH compound 3.25 m. p. 61, 1H n.m.r. δ (CDQ3) 0.95, t, J7Hz. CH3; 1.44, s, 2xCH3; 1.6-2. m, cyclopent H and CH2CH3; 2.56, s, COCH2; 3.0, q, J7Hz, CH2CH2CH3; 4.8, broad s, OCH; 5.02, s, OCH2 and 6.8-7.4, m, ArH compound 3.64 pale yellow oil, !H n_m.r. δ (CDQ3) 0.94, t, J7Hz. CH3; 0.97, s, 3xCH3;
1.4-3.1, m, CH2CH2CH3 and COCH2; 5.06, s, OCH2 and 7.2-7.7, m, ArH compound 3.66 m.p. 96, l n.m.r. δ (CDQ3) 0.91, t, J7Hz. CH3; 1.42, s, 2xCH3; 1.4-1.8,
CH2CH3; 2.51, s, COCI^; 3.02, q, J7Hz, CH^C^C^; 5.04, s, OCHj and 7.3-7.7, m, ArH compound 3.67 pale yellow oil^H n_m.r. δ (CDQ3) 0.98, t, J7Hz. CH3; 1.42, s, 2xCH3; 1.4-1.8, m, CH2CH3; 232, s, COCH2; 3.02, q, J7Hz, CH2CH2CH3; 5.08, s, OCH2 and 7.3-7.7, m, ArH compound 3.74 m.p. 82, l njn.r. δ (CDα3) 0.94, t, J7Hz,. CH3; 1.44, s, 2xCH3
1.4-1.7, m, CH2CH3; 235, s, COCH2; 2.98, q, J7Hz, CH2CH2CH3; 5.06, s, OCH2 and 7.0-7.6, m, ArH compound 3.77 pale yellow oil^H n_m.r. δ (CDQ3) 0.97, t, J7Hz. CH3; 1.42, s, 2xCH3;
1.4-1.8, m, CH2CH3; 233, s, COCH2; 2.98, q, J7Hz, CH2CH2CH3; 5.08, s, OCH2 and 7.4-83, m, ArH compound 3.80 m.p. 97, lH n.m.r. δ (CDQ3) 0.86, t, J7Hz. CH3; 1.45, s, 2xCH3; 1.4-1.8,
CH2CH3; 2.58, s, COC^; 2.95, q, J7Hz, CH2CH2CH3; 5.12, s, OCI*^ and 6.8-7.7, m, ArH. and compound 3.82 m.p. 82, l n.m.r. δ (CDQ3) 0.98, t, J7Hz,. CH3; 131, s, CH3; 134, m,
CH2CH3; 2.3-3.1, m, COCH2 and CH2CH2CH3; 5.02, s, OCH2 and 7.3-7.7, m, ArH compound 3.84 colourless oil, lH n.m.r. δ (CDC13) 0.8-1.0, 2t, J7Hz, J7Hz,. 2xCH3; 1
CH3; 1.4-1.8, m, CH2CH3 and CHjCILjC^; 22-2.7, m, COCRjj 2.97, q, J7Hz, CK-jCHjCH^ 5.06, OCH-, and 7.2-7.7, m, ArH compound 3.94 pale yellow d&. K n_m.r. δ (CDC13) 0.8-1.1, m,. CH2CH2CH3 and CH(CH3)2; 13, s, CH3; 1.53, q, J7Hz, CH2CH2CH3; 1.93, q, J7Hz, CH(CH3)2; 22-3.2, m, COO^ a COsZli^CΑ^ 5.07, s, OCH2 and 73-7.7, m, ArH compound 3.103 pale yellow oil., lH n_m.r. δ (CDα3) 0.98, t, J7Hz. CH3; 1.07, d, J6Hz,
CHCH3; 13, 1.42, s, s, , s, 2xCH3; 13-1.8, m, CH-jCHjO-iy, 23, q, J8Hz, CHCH3; 3.03, t, J7Hz, CH2 CH2CH3; 5.05, s, OCH2 and 7.0-7.7, m, ArH compound 3.104 m. p. 57, 1H n_m.r. δ (CDC13) 0.97, t, J7Hz. CH3; 1.13, 137, s, s, 4xCH
13-1.8, m, CH2CH2CH3. 3.02, t, J7Hz, CH2CH2CH3; 5.06, s, OCH2 and 6.9-7.7, m, ArH compound 3.122 pale yellow oil, 1H n_m.r. δ (CDC13) 0.9, t,. J7Hz, CH2CH2CH3; 135, s,
CH3; 1.45-1.7, q, J7Hz, CK^Cf^CH^ 2.2-3.1, m, CBjC^C^ and COCB,; 333, s, 2xOCH3; 42, s, CH; 5.08, s, OCH, and 7.3-7.7, m, ArH compound 3.123 colourless oil, lH n.m.r. δ (CDCI3) 0.95, t,. J7Hz, CH2CH2CH3; 136, s,
CH3; 1.45-1.7, q, J7Hz, CH2CH2CH3; 2.2-3.1, m, CH2CH2CH3 and COCH2; 33, s, 2xOCH3; 4.18, s, CH; 5.03, s, OCH2 and 6.9-7.7, m, ArH compound 3.124 pale yellow oil, lH n_m.r. δ (CDC13) 0.91, t,. J7Hz, CH2CH2CH3; 1.41, s
CH3; 1.4-1.7, q, J7Hz, CH2CH2CH3; 2.2-3.1, m, CH2CH2CH3 d COCH2; 332, s, 2xOCH3; 4.17, s, C 4.98, s, OCH2 and 6.9-7.5, m, ArH compound 4.10 pale yellow oil, lH njn.r. δ (CDCI3) 0.96, t, JTtiz. CH2CH3; 12-32, m,
CH2CH2CH3 and hetero H; 5.0, s, OCH2 and 7.2-7.7, m, ArH compound 4.11 pale yellow oil, lH n_m.r. δ (CDα3) 0.91, t, J7Hz. CH2CH3; 13-32, m,
CHjCH-jC^ and hetero H; 5.04, s, OCH2 and 6.9-7.7, m, ArH compound 4.20 pale yellow oil, H n_m.r. δ (CDQ3) 0.93, t, J7Hz. CH2CH3; 12-32, m,
CH2CH2CH3 and hetero H ; 4.96, s, OCH2 and 6.7-7.5, m, ArH compound 424 m.p. 114, XH n_m.r. δ (CDQ3) 0.96, t, J7Hz. CH2CH3; 13-33, m,
CHjCI^C^ and hetero H; 5.08, s, OCH2 and 7.2-7.7, m, ArH compound 4.30 m. p. 85, XH n.m.r. δ (CDC13) 0.92, t, J7Hz. C^^; 1.2-32, m, CH2CH2CH3 and hetero H; 5.02, s, OCH2 and 6.9-7.6, m, ArH
Barnyard grass is one of the most difficult grasses to eliminate from rice crops because of its similarity to rice, currentiy available herbicides do not have satisfacto selectively for barnyard grass in rice crops. To demonstrate the effectiveness of compounds of Formula (1) of the present invention as selective herbicidal agents fo the control of weeds in rice crops, compoimds of Formulae 1.32 and 1.59 of Table 1 were applied to barnyard grass and rice. Compounds according to US 4008067 (Hirono et. al.), and AU560716 (27196/84) (Watson et al ), were also applied to Barnyard grass and rice for comparative purposes. The herbicidal data are shown i Table 4. In this table 0 signifies no effect and 10 signifies plant dead.
As can be seen from Table 4 compounds according to the present invention are clearly superior to prior art compounds at providing selective weed control in rice crops.
Table 4 Comparison of Compounds of this Invention with known compounds
Herbicidal Rating at 0.4 Kg/ Ha Compound (scale of 0-10, where 10 indicates plant dead) post-emergent pre-emergent
Disclosure of Hirono et al ;
A: 8-(l-allyloxyaminobutylidine)-6,10-dioxaspiro[4.5]decene-7,9-dione B : 9-( 1 -allyloxyaminobutylidine)-7,l 1 -dioxaspiro[5.5]-4- methylundecene-8,10-dione
Disclosure of Watson et al; C: 3-( 1 -allyloxyiminobutyl)-6-(4-chlorophenyl)-4-hydroxypyran-2-one To further demonstrate the effectiveness of compounds of Formula (1) of the pr invention as herbicidal agents, compounds of Formula (1) listed in Tables 1-4 we applied to bamyardgrass and rice post-emergent at 0.1 kg/hectare and 0.4 kg/hec The herbicidal data are shown in Table 5 In the table 0 signifies no effect and 10 signifies plant dead. As can be seen the compounds of Formula (1) selectively control bamyardgrass in rice.
Table 5 Compound ice ice tables 1-4
1.32
1.33
1.34
1.52
1.56
1.58
1.59
1.63
1.77
1.95
1.99
1.111
1.113
3.16
3.66
3.67
3.74
3.82
3.94
3.122
3.124
3.127
4.10
4.11
4.24
4.30

Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:
1. Compounds of the formula (1) and isomeric and/or tautomeric forms thereof:
wherein
A is a C C3 alkylene or Cf C3 alkenylene group optionally substituted with 1-4 Cf alkyl substituents;
X is O, S, SO, S02, NR10 or a single bond; R1 is H, Q-Q, alkyl, -Q, alkenyl, C2-C4 alkynyl, C5-C6 cycloalkyl, C5-C6 cycloalkeny Cj-C,, alkylcarbonyl, phenylcarbonyl, phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q, alkyl, Cj-C4 alkoxy, Q-Q alkylthio, nitro, cyano, Q-Q haloalkyl, amino, and C , haloalko C Q alkylsulfonyl, benzenesulfonyl, CfQ alkylcarbonyl, Q-Q alkoxyalkyl, Q-Q alkylthioalkyl, Q-Q0 phenylalkyl or M;
R2 is Q-Q alkyl, Q-Q alkenyl, Q-Q alkynyl, CfQ, haloalkyl, Q-Q alkylthio, Q-Q cycloalkyl, Q-Q cycloalkenyl, phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Q-Q alkylthio, nitro, cyano, Q-Q haloalkyl, amino, and Q-Q haloalkoxy, Q-Q alkoxyalkyl, Q-Q alkylthioalkyl, or Q-Q alkyl substituted with a substituent selected from the grou consisting of phenyl, phenoxy and thiophenoxy wherein the aromatic ring of said substituents may be substituted with 1-3 substituents selected from halogen, Q-Q alkyl, CfC4 alkoxy, Q-Q alkylthio, nitro, cyano, amino, Q-Q haloalkyl and Q- haloalkoxy;
R3 and R4 are independently H or C , alkyl; R5 and R* are independently H, CfQ alkyl, Q-Q alkenyl, Q-Q alkylthioalkyl, Cf Q haloalkyl, Q-Q haloalkenyi or Q-Q cycloalkyl wherein the alkyl, alkeny and cycloalkyl groups are optionally substituted with 1-3 substituents selected the group consisting of OR12, NR13R14, NR15C(0)(Q- Q alkyl), NR18S02Cf Q alkyl), NR21C(0)(Q- alkyl), C(OR16)(OR17)R22, C(SR19)(SR20)R23, Q-Q alkoxycarbonyl and phenyl which may be substituted with a substituent selected from halogen, Q-Q alkyl, Cf Q alkoxy, Q-Q alkylthio, nitro, cyano, Q-Q haloalkyl and Q-Q haloalkoxy; OR R5 and R6 together with the carbon to which they are attached form a fully saturated or an unsaturated 3- to 7-membered carbocyclic ring, or a fully satura or an unsaturated 5- to 7-membered heterocyclic ring containing 1-3 heteroato selected from the group consisting of 0-3 nitrogen, 0-2 oxygen and 0-2 sulfur atoms; said ring may be substituted with 1-4 substituents selected from the grou consisting of halogen, Q-Q alkyl, Q-Q haloalkyl, Q-Q alkenyl, Q-Q alkynyl,
Cf Q alkylcarbonyl, Q-Q alkoxy, Q-Q alkylthio, Q- Q alkoxycarbonyl, -COOH Q-Q alkoxyalkyl, Q-Q alkylthioalkyl, and phenyl which is optionally substitute with a substituent selected from halogen, Cf Q alkoxy, Q-Q alkylthio, Q-Q haloalkyl, nitro, cyano and Q-Q haloalkoxy; one of the carbon atoms of said ri may be in the form of a carbonyl group or its corresponding dimethyl, diethyl or ethylene or propylene ketal;
R7, R* and R9 are independently H, halogen, Q- Q alkyl, Q-Q alkoxy, Q-Q alkylthio, Q- Q alkylsulfinyl, Cf Q alkylsulfonyl, Q-Q haloalkyl, Cf Q haloalkoxy, nitro, cyano, Q-Q alkoxycarbonyl, Q-Q alkylaminocarbonyl, Q-Q dialkylaminocarbonyl, aminocarbonyl; amino; Q-Q alkylamino, Q-Q alkylamin or benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio, phenylamino or phenyl group said group optionally substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Q-Q alkoxy, and CF3; provided that when both R5 and R6 are independentiy Cf Q alkyl, Q-Q alkenyl, Q-Q alkylthioalkyl, Cf Q haloalkyl, Q-Q haloalkenyi or Q-Q cycloalkyl optionally substituted with a substituent selected from the group consisting of Cf Q alkoxycarbonyl and phenyl which may be substituted with a substituent selected from halogen, Cf Q alkyl, Q-Q alkoxy, Cf Q alkylthio, nitro, cyano,
Cf Q haloalkyl and Q-Q haloalkoxy, or when R5 and R6 together form an optionally substituted saturated or unsaturated carbocyclic or heterocyclic ring then at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio or phenylamino group, or at least one of R7, R8 or R9 is phenyl substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Cf Q alkyl, Q-Q alkoxy and CF3;.
R10 is H, Q-Q alkyl or phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, Q-Q alkyl, Q-Q alkoxy,
Q-Q alkylthio, Cf Q haloalkyl and Q-Q haloalkoxy;
M is Li+, Na+, K+, NH4 +, or N(RU)4 + where R11 is Q-Q alkyl; R12 is H, Cf C4 alkyl, C(0)(Q- Q alkyl)or C02(Q-Q alkyl); R13, R15, R18, R21, R22 and R23 are independentiy H or Q-Q alkyl; R14, R16, R17, R19 and R20 are independentiy Q-Q alkyl; R16 and R17 taken together may be "(CH2)2- or -(CH2)3-; and R19 and R20 taken together may be -(CH2)2- or -(CH2)3-.
2. Compounds of formula (1) characterised in that R1 is H or M; and R2 is Cf Q alkyl, Cf Q haloalkyl, Q-Q alkenyl or Q-Q alkynyl .
3. Compounds as claimed in Claim 2, characterised in that A is CfQ alkylene or Q-Q alkenylene optionally substituted with CH3 or QH5
R7, R8 and R9 are independentiy H, CI, Br, F, Cf Q alkyl, Cf Q alkoxy, Q-Q alkylthio, CfQ haloalkyl, CfQ haloalkoxy, nitro, cyano or Q-Q alkoxycarbon or benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenylthio or phenylamino optionally substituted with 1-3 substituents selected from the gro consisting of halogen, Q-Q alkyl, Q-Q alkoxy, or CF3; provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group; and R10 is H or CH,.
4. Compounds as claimed in Claim 3, characterised in that X is O.
5. Compounds as claimed in Claim 3, characterised in that X is S, SO or S02.
6. Compounds as claimed in Claim 3, characterised in that X is NR10, as defined Claim 1.
7. Compounds as claimed in Claim 3, characterised in that X is a single bond.
8. Compounds as claimed in Claim 7, characterised in A is -CH2-, -CH2CH2- or -CH2CH = CH- ; R1 is H, Li+, Na+, or K+;
R2 is CH3, QH5, n-QH7 or n-QH9 ;
R3 and R4 are independentiy H, CH3 or QH5 ; and
R7, R8 and R9 are independentiy H, CI, Br, F, CH3, QH5, OCH3, OQH5,
SCH3, SQH5, CF3, CHF2, CF2CF3, OCHF2, OCF3, OCH2CF3, NOj, CN C02CH3, Ph, S02Ph, COPh, CH2Ph, OCH2Ph, OPh, SPh, NHPh or N(Me)Ph provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
9. Compounds as claimed in Claim 7, characterised in that R5 and R6 are independentiy Q-Q alkyl, Q-Q alkenyl, Q-Q alkynyl, Q-Q alkylthio or Q-Q alkylthioalkyl. 10. Compounds as claimed in Claim 7, characterised in that R5 and R6 toget with the carbon to which they are attached form a saturated or unsaturat 5-, 6- or 7-membered carbocyclic ring which is optionally substituted with 1-4 CH3 groups.
11. Compounds as claimed in Claim 10, characterised in that A is -CH2-, -CH2CH2- or CH2CH = CH- ;
R1 is H, Li + , Na+ or K+ ;
R2 is CH3, QH5, n-QH7 or n-QH9; R3 and R4 are independentiy H or CH3; and
R7, R8 and R9 are independentiy H, CI, Br, F, CH3, QH5, OCH3, OQH5, SCH3, SQH5, CF3, CHF^ CF2CF3, OCHF2, OCF3, OCH2CF3, N02, CN, C02CH3, Ph, S02Ph, COPh, CH2Ph, OCH2Ph, OPh, SPh, NHPh or N(Me)Ph provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
12. Compounds as claimed in Claim 7, characterised in that
R5 and R6 together with the carbon to which they are attached form a saturated or unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1-2 heteroatoms selected from the group consisting of 0-2 nitrogen, 0-1 oxygen and 0-2 sulfur atoms; said ring is optionally substituted with 1-4 CH3 groups.
13. Compounds as claimed in Claim 12, characterised in that A is -CH2-, -CH2CH2- or -CH2CH = CH- ;
R1 is H, Li + , Na+ or K+ ; R2 is CH3 QH5, n-QH7 or n-QH9; R3 and R4 are independently H, CH3 or QH5 ; and
R7, R8 and R9 are independently H, CI, Br, F, CH3, QH5, OCH3, OQH5, SCH3, SQH5, CF3, CHF2, CF2CF3, OCHF2, OCF3, OCH2CF3, NOj, CN, C02CH3, Ph,
SQ2Ph, COPh, CH2Ph, OCH2Ph, OPh, SPh, NHPh or N(Me)Ph provided that at least one of R7, R8, or R9 is an optionally substituted benzenesulfonyl, benzoyl benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino group.
14. 9-hydroxy-8-[ l-((3-(phenoxy)phenyl)methoxyimino)butyl]-6- oxaspiro[4.5]dec-8-en-7-one.
15. 8-[ l-((4-(4-fluorophenyl)phenyl)methoxyimino)butyl]-9-hydro3_y-6- oxaspiro[4.5]dec-8-en-7-one.
16. 9-hydroxy-8-[ l-((4-(phenyl)phenyl)methoxyimino)butyl]-6- oxaspiro[4.5]dec-8-en-7-one.
17. 6,6-dimethyl-4-hydroxy-3-(l-((4-(phenyl)phenyl)methoxyimino)butyl)pyra one.
18. 6,6-dimethyl3-(l-((4-(4-fluorophenyl)phenyl)methoxyimino)butyl)-4- hydroxypyran-2-one.
19. Any one of the compounds listed in the foregoing of Tables 1 to 4.
20. A plant growth inhibiting, plant damaging, or plant killing composition characterised in that it comprises a compound of formula (1), as defined in Claim 1 and an inert carrier therefor.
21. A method for regulating the growth of a plant, characterised in that there applied to the plant, to the seed of the plant, or to the growth medium of the plant, an effective amount of a compound of formula (1), as defined in Claim 1.
22. A method for selectively inhibiting, damaging or killing weed grasses in a broad-leaf crop, characterised in that there is applied to the crop or its locus an effective amount of a compound of formula (1), as defined in Claim 1. 23. A herbicidal composition characterised in that it comprises a compound formula (1), as defined in Claim 1, and at least one other herbicide.
24. A plant growth regulating composition characterised in that it comprises compound of formula (1), as defined in Claim 1, and an inert carrier therefor.
25. The use of a compound of formula (1) as herbicide or plant growth regulator.
EP19920904717 1991-02-15 1992-02-14 Herbicidal pyrones. Withdrawn EP0573460A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPK462091 1991-02-15
AU4620/91 1991-02-15
AUPK997391 1991-12-11
AU9973/91 1991-12-11

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EP0573460A1 EP0573460A1 (en) 1993-12-15
EP0573460A4 true EP0573460A4 (en) 1994-03-17

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EP (1) EP0573460A4 (en)
JP (1) JPH06505240A (en)
CN (1) CN1065660A (en)
BR (1) BR9205641A (en)
PT (1) PT100129A (en)
TW (1) TW221430B (en)
WO (1) WO1992014736A1 (en)

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Publication number Priority date Publication date Assignee Title
DE19716591A1 (en) * 1996-08-05 1998-03-05 Bayer Ag 2- and 2,5-substituted phenylketoenols

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3560789A (en) * 1988-05-04 1989-11-29 Dunlena Pty. Limited Selective pyrone herbicides
AU7161391A (en) * 1990-01-22 1991-08-05 Dunlena Pty. Limited Herbicidal pyrones

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9214736A1 *

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BR9205641A (en) 1994-06-07
WO1992014736A1 (en) 1992-09-03
JPH06505240A (en) 1994-06-16
EP0573460A1 (en) 1993-12-15
CN1065660A (en) 1992-10-28
PT100129A (en) 1993-08-31
TW221430B (en) 1994-03-01

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