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 and plant growth regulating properties; to herbicidal compositions and processes utilising such compounds and to plant growth regulating compositions and processes utilising such compositions.
• R is substituted phenyl
• R 1 is H, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylsulfonyl, alkoxy, allcylthio, acyl, (un)substituted phenylalkyl or PhSO 2 ;
• R 2 is alkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl,
• R 3 is alkyl, fluoroalkyl, alkenyl, alkynyl, or phenyl.
• Watson et al teach that tetrahydropyran-2,4-dione derivatives which are substituted in 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
• R 9 is lower alkyl.
• R 1 is H
• R 2 is substituted alkyl wherein the alkyl group is substituted by optionally substituted 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 or 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.
• substituted groups R 1 to R 5 are similar to those described in WO
• 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
• 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 1 -C 4 alkyl, C 1 -C, 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl,
• C 1 -C 4 haloalkyl C 1 -C 4 haloalkoxy, nitro, cyano, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylaminocarbonyl, C 2 -C 6 dialkylaminocarbonyl, aminocarbonyl, phenyl, amino, C 1 -C 4 alkylamino, or C 1 -C 4 dialkylamino.
• 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 1 -C 3 alkylene or C 1 -C 3 alkenylene group optionally substituted with 1-4
• X is O, S, SO, SO 2 , NR 10 or a single bond
• R 1 is H, C 1 -C 4 alkyl, C 1 -C 4 alkenyl, C 2 -C 4 alkynyl, C 5 -C 6 cycloalkyl, C 5 -C 6
• R 2 is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylthio, C 6 cycloalkyl, C 1 -C 4 cycloalkenyl, phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, C 1 -
• R 5 and R 6 are independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 6 alkylthioalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyi or C 3 -C 6 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(O)(C 1 -C 4 alkyl), NR 18 SO 2 C 1 -C 4 alkyl), NR 21 C(O)(C 1 -C 4 alkyl), C(OR 16 )(OR 17 )R 22 ,
• C(SR 19 )(SR 20 )R 23 C 1 -C 4 alkoxycarbonyl and phenyl which may be substituted with a substituent selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, nitro, cyano, C 1 -C 4 haloalkyl and C 1 -C 4 haloalkoxy;
• R 7 , R 8 and R 9 are independentiy H, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4
• alkylthio C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, nitro, cyano, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylaminocarbonyl,
• C 2 -C 6 dialkylaminocarbonyl aminocarbonyl; amino; C 1 -C 4 alkylamino, C 2 -C 6 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, C 1 -C 4 alkyl,
• R 5 and R 6 are independentiy C 1 -C 4 alkyl, C 2 -C 4 alkenyl,
• R 7 , R 8 , or R 9 is an optionally substituted benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio or phenylamino gro or at least one of R 7 , R 8 or R 9 is phenyl substituted with 1-3 substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and CF 3 , R 10 is H, C 1 -C 4 alkyl or phenyl optionally substituted with 1-3 substituents select from the group consisting of halogen, C 1 -C 4 alkyl, C
• M is Li + , Na + , K + , NH 4 + or N(R 11 ) 4 + where R 11 is C 1 -C 4 alkyl;
• R 12 is H, C 1 -C 4 alkyl, C(O)(C 1 -C 4 alkyl)or CO 2 (C C -C 4 alkyl);
• R 13 , R 15 , R 18 , R 21 , R 22 and R 23 are independentiy H or C 1 -C 3 alkyl;
• R 14 , R 16 , R 17 , R 19 and R 20 are independentiy C 1 -C 3 alkyl
• R 16 and R 17 taken together may be -(CH 2 ) 2 - or -(CH 2 ) 2 -;
• 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
• 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”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “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 CHFCl.
• Alkylcarbonyl denotes acetyl, propionyl, and the different butyryl isomers.
• Alkoxycarbonyl denotes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and the different butoxycarbonyl isomers.
• C i -C j prefix where i and j are numbers from 1 to 10.
• C 1 -C 4 alkylthioalkyl would designate -CH 2 SCH 3 -CH 2 SC 2 H 5 -CH 2 CH 2 SCH 3 or -CH(CH 3 )SCH 3
• C 2 -C 5 alkoxyalkyl would represent -CH 2 OCH 3 through to -(CH 2 ) 4 OCH 3 or -CH 2 O(CH 2 ) 3 CH 3 and the various structural isomers embraced therein.
• Preferred groups of compounds of general Formula (1) for reasons including ease synthesis and greater herbicidal efficacy, include the following:
• R 1 is H or M
• R 2 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl .
• A is C 1 -C 4 alkylene or C 1 -C 4 alkenylene optionally substituted with CH 3 or QH 5 ;
• R 7 , R 8 and R 9 are independently H, CI, Br, F, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, nitro, cyano or C 1 -C 3
• alkoxycarbonyl or benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenyl, phenylthio or phenylamino optionally substituted with 1-3 substituent selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 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 3
• R 1 is H, Li+, Na+, or K+;
• R 2 is CH 3 , QH 5 , n-C 3 H 7 or n-QH 9 ;
• R 3 and R 4 are independentiy H, CH 3 or QH 5 ;
• R 7 , R 8 and R 9 are independentiy H, CI, Br, F, CH 3 , QH 5 , OCH 3 , OC 2 H 5 , SCH 3 , SC 2 H 5 , CF 3 , CHF 2 , CF 2 CF 3 , OCHF 2 , OCF 3 , OCH 2 CF 3 , NO 2 , CN CO 2 CH 3 , Ph, SO 2 Ph, COPh, CH 2 Ph, OCH 2 Ph, OPh, SPh,
• 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 C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 alkylthio or C 2 -C 6
• alkylthioalkyl alkylthioalkyl
• R 1 is H, Li + , Na+ or K+;
• R 2 is CH 3 , C 2 H 5 , n-QH 7 or n-C 4 H 9 ;
• R 3 and R 4 are independentiy H or CH 3 ;
• R 7 , R 8 and R 9 are independentiy H, CI, Br, F, CH 3 , QH 5 , OCH 3 , OC 2 H 5 , SCH 3 , SC 2 H 5 , CF 3 , CHF Z CF 2 CF 3 , OCHF 2, 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.
• 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
• R 1 is H, Li+, Na+ or K+;
• R 2 is CH 3 C 2 H 5 , n-QH 7 or n-QH 9 ;
• R 3 and R 4 are independently H, CH 3 or QH 5 ;
• R 7 , R 8 and R 9 are independentiy H, CI, Br, F, CH 3 , QH 5 , OCH 3 , OQH 5 , SCH 3 , SC 2 H 5 , CF 3 , CHF 2, CF 2 CF 3 , OCHF 2, OCF 3 , OCH 2 CF 3 , NO 2, CN, CO 2 CH 3 , Ph, SO 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 or 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 may in turn be generated in situ from appropriate precursors, to afford derivatives of the general Formula(1) 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. For example, compounds of the invention of Formula(l) wherein R 1 is is an organic or inorganic cation may be prepared fro compounds of the invention of Formula(1) wherein R 1 is hydrogen by reacting these latter compounds with an appropriate inorganic or organic base.
• the 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/benzene and then with benzene. The residue was either chromatographed (SiO 2 , dichloromethane) or, in some instances, crystallization of the pyrandione was achieved by diluting a concentrated benzene solution (ca.
• pre-emergent and/or post-emergent herbicides or plant growth regulants are particularly useful for controlling certain grass and broadleaf weeds dryland and paddy rice ( Oryza sativa), examples of which include, but are not limited to, Indica and Japonica varieties of the crop.
• grass weeds such as barnyardgrass (Echinochloa crusgalli), in paddy rice.
• Rates of application for compounds of this invention are determined by a number of factors. These factors include formulation selection, method of application, amount of vegetation present, growing conditions, etc. In general, the subject compounds should 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 desired level of weed control.
• the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of Formula (1) as hereinbefore defined with at least one other herbicide.
• the invention provides a met-hod for regulatihe the 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) as hereinbefore defined.
• Rates of application of these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Weed grasses in graminaceous crops can normally be killed when treated at a rate of from less than 0.1 to about 20 kg active ingredient/ha.
• the compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides, or other biologically active compounds in order 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.
• 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 these may be applied directly. Sprayable formulations can be extended in suitable media 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 contain 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, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth, and China clay.
• the compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also solid diluents, fillers and suspending agents.
• compositions for dressing seed may contain an agent (for example a mineral oil) for assisting the adhesion 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 e prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.

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

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• 1992
  • 1992-02-14 EP EP19920904717 patent/EP0573460A4/de not_active Withdrawn
  • 1992-02-14 TW TW81101064A patent/TW221430B/zh active
  • 1992-02-14 BR BR9205641A patent/BR9205641A/pt not_active Application Discontinuation
  • 1992-02-14 WO PCT/AU1992/000053 patent/WO1992014736A1/en not_active Application Discontinuation
  • 1992-02-14 JP JP4504784A patent/JPH06505240A/ja active Pending
  • 1992-02-14 PT PT10012992A patent/PT100129A/pt not_active Application Discontinuation
  • 1992-02-15 CN CN 92101624 patent/CN1065660A/zh active Pending

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