EP0804423A1 - Insecticidal and acaricidal oxazolines and thiazolines - Google Patents

Insecticidal and acaricidal oxazolines and thiazolines

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Publication number
EP0804423A1
EP0804423A1 EP95940807A EP95940807A EP0804423A1 EP 0804423 A1 EP0804423 A1 EP 0804423A1 EP 95940807 A EP95940807 A EP 95940807A EP 95940807 A EP95940807 A EP 95940807A EP 0804423 A1 EP0804423 A1 EP 0804423A1
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Prior art keywords
group
compound
optionally substituted
formula
alkyl
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German (de)
English (en)
French (fr)
Inventor
Thomas Martin Stevenson
Jeffrey Keith Long
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms

Definitions

  • This invention relates to certain oxazolines and thiazolines, their N-oxides, agriculturally-suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
  • A is a direct bond or a lower alkylene group
  • R l and R 2 are independently H, lower alkyl, lower alkoxy, halogen, ⁇ O 2 , lower haloalkyl or lower haloalkoxy;
  • R3 is H, lower alkyl, lower alkoxy or halogen;
  • R 4 is broadly defined and includes a group of the formula
  • B is a direct bond, O or a variety of carbon chains;
  • Q is CH or N;
  • R5 is H, alkyl, alkoxy, halogen, haloalkyl, haloalkoxy or a tri(lower alkyl)silyl group; Z is O or S; and n is 0-5.
  • US 4,977,171 discloses insecticidal and acancidal oxa- or thia-zoline derivatives of the formula:
  • X 1 and X 2 are independently H, lower alkyl, lower alkoxy, halogen, CF3 or OCF3
  • Y 1 and Y 2 are independently H, lower alkyl, lower alkoxy, lower alkylthio, CN, NO 2 , halogen or CF 3
  • Z is O or S
  • n is 0 or 1.
  • This invention is directed to compounds of Formula I including all geometric an stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides in both agronomic and nonagronomic environments:
  • R 4 and R 5 are independently selected from the group H; halogen; CN; NO ;
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkylene” denotes a straight-chain or branched alkanediyl. Examples of “alkylene” include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH2, and CH 2 CH(CH 3 ).
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • alkylsulfonyl include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl and pentylsulfonyl isomers.
  • Alkyldithio denotes branched or straight-chain alkyldithio moieties.
  • alkyldithio examples include CH 3 SS, CH 3 CH 2 SS, CH 3 CH 2 CH 2 SS, (CH 3 ) 2 CHSS and the different butyldithio and pentyldithio isomers.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclohexylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected.
  • sai alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl examples include HC- ⁇ CCHCl, CF 3 G ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • C 1 -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • R 1 is selected from the group F and Cl in the 2-position
  • R 2 is selected from the group H, F and Cl in the 6-position
  • R 3 is selected from the group phenyl and pyridyl, each ring substituted with R 6 and optionally substituted with W. Preferred 2.
  • R 1 is selected from the group F and Cl in the 2-position
  • R 2 is selected from the group H, F and Cl in the 6-position
  • Preferred 3 Compounds of Preferred 1 wherein: R 3 is phenyl substituted with R 6 and optionally substituted with W;
  • R 5 is H;
  • X is O.
  • R 3 is phenyl substituted with R 6 and optionally substituted with W;
  • R 5 is H;
  • R 6 is selected from the group OR 15 ; S(O) m R 15 ; C r C 5 alkylsulfonyloxy; and C 2 -C5 alkenyl and C 2 -C alkynyl, each group optionally substituted with up to three R 9 ; and
  • R 15 is C 2 -C 4 cyanoalkyl optionally substituted with up to three R 9 .
  • Preferred 5 Compounds of Preferred 2 wherein:
  • R 8 is selected from the group phenyl optionally substituted with W and benzyl optionally substituted with W. Most preferred are compounds of Preferred 1 selected from the group:
  • This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of Formula I and at least one of a surfactant, a solid diluent or a Uquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of Formula I (e.g., as a composition described herein).
  • the preferred methods of use are those involving the above preferred compounds.
  • DETAILS OF THE INVENTION The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-21. The definitions of A, E, Z, R---R 15 , X, W, m, n and q in the compounds of Formulae I-XXXVI below are as defined above in the Summary of the Invention.
  • Compounds of Formula I can be made from amino alcohols (or thiols) of Formula II and benzoic acid derivatives as shown in Scheme 1.
  • the transformation generally consists of two steps.
  • a generally useful way to do this is to treat the compound of Formula II with an aroyl chloride in the presence of an acid acceptor (usually a tertiary amine base such as triethylamine) at room temperature or below.
  • an acid acceptor usually a tertiary amine base such as triethylamine
  • This reaction can be carried out in an inert solvent such as dichloromethane, tetrahydrofuran, toluene, and other solvents that will not react with acid chlorides or bases.
  • the second step carried out is the ring closure. This can be accomplished by treating the intermediate amide of Formula m with a dehydrating agent.
  • Some useful reagent systems for this transformation include but are not limited to triphenylphosphine carbon tetrachloride, diethyl azodicarboxylate/triphenylphosphine, and thionyl chloride.
  • An especially useful method for ring closure involves treatment of the amide with thionyl chloride in benzene or another inert solvent at reflux until the starting material is consumed (usually 30 min to 3 h).
  • compounds of Formula III can be prepared in two steps as shown in Scheme 2.
  • compounds of Formula IV are amidoalkylated with a compound of Formula V to form Formula VI compounds.
  • a typical reaction involves the combination of compounds of Formulae IV and V in an aci such as sulfuric acid, methanesulfonic acid, trifluoroacetic acid, polyphosphoric acid or perchloric acid.
  • the reaction can be run in a cosolvent such as acetic acid.
  • the reaction temperature can range from -10° to 200 °C with 0° -100 °C being preferred.
  • the reaction can be carried out in an inert solvent such as chloroform, methylene chloride, benzene, toluene or ether in the presence of a Lewis acid such as aluminum chloride or boron trifluoride.
  • a Lewis acid such as aluminum chloride or boron trifluoride.
  • the acid, temperature, and time of the reaction vary according to the relative reactivity of the Q group towards electrophilic substitution reactions. Amidoalkylation reactions have been extensively reviewed in the literature (see Zaugg, Synthesis (1984) 85-110).
  • the second step is the reduction of a Formula V compound to form a Formula m compound. Reductions of this type are well-known in the art (see Hudlicky, Reductions in Organic Chemistry (1984) 136-163).
  • Typical reducing agents include the alkali metal borohydrides and diborane.
  • V is a lower alkyl group
  • the use of lithium borohydride as reducing agent, tetrahydrofuran as solvent and performing the reactions at 65 °C for 1-6 h is preferred.
  • Formula V compounds can be accomplished by refluxing glyoxylic acid derivatives (Formula VII) and commercially available benzamides (Formula VIII) in an inert solvent such as acetone, benzene or chloroform (Scheme 3). This procedure is known in the art (see Ben-Ishai, Tetrahedron (1975) 31, 863-866 and Tetrahedron (1977) 33, 881-883). Scheme 3
  • V H, lower alkyl
  • amino alcohols of Formula II can be produced by the treatment of an amino acid derivative of Formula DC with a reducing agent.
  • aminoesters are preferred, but amino acids themselves can also be used.
  • treatment of a compound of Formula DC with lithium aluminum hydride at 0-50 °C in ethereal solvents such as tetrahydrofuran, ether, or dimethoxyethane gives an alcohol of Formula ⁇ .
  • amino alcohols of Formula ⁇ can be produced by the direct reduction of oximino acids and esters of Formula X with boranes or alkali metal hydrides.
  • the reaction conditions with lithium aluminum hydride are as described for Scheme 4.
  • V H, lower alkyl
  • Aryl-substituted amino acids and esters of Formula DC are known in the art as are methods for their preparation. Useful compendia of methods for their synthesis are contained in Kukolja (J. Med. Chem. (1985) 28, 1886-1896), Bohme (J. Med. Chem. (1980) 23, 405-412), and O'Donnell (Tetrahedron Lett. (1989) 30, 3909-3912) and references cited within.
  • Oxime esters of Formula X are especially suitable intermediates for the synthesis of compounds of Formula I. They can be made from aryl acetic esters of Formula XI by reaction, in the presence of base, with nitrosating agents such as inorganic and organic nitrites as shown in Scheme 6. Typically, the compound of Formula XI is treated with an alkyl nitrite such as butyl nitrite in an alcoholic solvent such as ethanol in the presence of a strong base such as sodium ethoxide at the reflux temperature of the solvent.
  • an alkyl nitrite such as butyl nitrite
  • an alcoholic solvent such as ethanol
  • a strong base such as sodium ethoxide at the reflux temperature of the solvent.
  • compounds of Formula X can be produced from aryl glyoxalates of Formula XII by treatment with a derivative of hydroxylamine.
  • Aryl glyoxalates can also be made by the reaction of an organometallic species with a derivative of oxalic acid.
  • diethyl oxalate can be treated with an aryl Grignard or lithium reagent at low temperature in ether/tetrahydrofuran mixtures (Rambaud, et al., Synthesis (1988) 564-567).
  • the Grignard or lithium reagent can be generated from an optionally substituted haloaromatic compound by conventional methods.
  • a compound of Formula XHI may be alkylated by a halide (or the corresponding alkyl or aryl sulfonate) of Formula XTV in the presence of an acid acceptor.
  • the reaction can be carried out in a variety of inert polar aprotic solvents such as acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or 2-butanone.
  • Suitable acid acceptors include both organic and inorganic bases such as alkali hydrides, carbonates, and hydroxides.
  • a preferred base and solvent combination is potassium carbonate in dimethylformamide.
  • the process can be carried out from 0-150 °C, preferably at 25 °C.
  • R m alkynyl, alkenyl, haloalkenyl, haloalkynyl, cyanoalkyl, cycloalkyl, cycloalkylalkyl, each substituted by R 9
  • Compounds of Formula XVII may be made from ketones of Formula XV by the known reaction of hydroxylamines of Formula XVI. This reactio is best carried out in alcoholic solvents between 20-100 °C.
  • the ketones of Formula XV can be made in several ways from halides and sulfonates of Formula XVm via transition metal catalyzed reactions as shown in Scheme 11.
  • Reaction of organometallic compounds of Formula XDC with carbon monoxide and the compounds of Formula XVHI leads to ketones in the presence of palladium catalysts.
  • the reactions are best carried out under an atmosphere of carbon monoxide in the presence of a palladium catalyst.
  • the optimal catalyst depends on the metal used. (For organoaluminum compounds see Wakita et al., J. Organometallic Chem., 288, 261-268 (1985); for organoboron compounds see Ishiyama et al., Bull. Chem. Soc.
  • Scheme 12 shows that the ketones of Formula XV can also be made by the reaction of vinyl ethers of Formula XX with compounds of Formula XVL .
  • Optimal reaction conditions for the arylation of vinyl ethers with aryl halides and sulfonates have been described by Cabri (J. Org. Chem., 57, 3558-3563 (1992)).
  • the reaction proceeds best in dipolar aprotic solvents such as dimethylformamide when tethered phosphine ligands are employed.
  • Bis(diphenylphosphino)propane is the preferred ligand.
  • W ile organic bases may be employed as acid acceptors in this process, inorganic bases such as silver or thallium salts are preferred.
  • Thallium acetate is most preferred. The reaction is best carried out at elevated temperature with temperatures from 60-150 °C being preferred. On conclusion of the reaction it must be worked up in the presence of protic acid to hydrolyze the vinyl ether intermediate. Dilute hydrochloric acid is preferred for this use.
  • R x alkyl
  • R v one carbon less than R 7
  • Lg halogen or (halo)alkylsulfonate
  • Compounds of Formula XXLLI can be made by the reaction of the appropriate known oxime of Formula XXII with a halide of Formula XXI as shown in Scheme 13.
  • the reaction is best carried out in dipolar aprotic solvents such as dimethylformamide using an inorganic base such as potassium carbonate, potassium hydroxide or sodium hydride as acid receptor.
  • the reaction can be carried out at temperatures between 0-100 °C with temperatures around 25 °C being preferred.
  • the halides of Formula XXI can be made by well known reactions of alcohols with halogenating agents as shown in Scheme 14.
  • One preferred method for this reaction uses triphenylphosphine and carbon tetrabromide in dichloromethane at 25 °C.
  • a compendium of methods for this process may be found in Larock, loc. cit. pp 353-363.
  • the requisite alcohols of Formula XXV can be made by the reduction of esters of Formula XXIV with hydride agents such as lithium aluminum hydride.
  • a useful compendium of reagents and conditions for this transformation can be found in Larock, loc. cit., pp 548-553.
  • Esters of Formula XXTV can be made by carbonylation of halides of Formula XVLTI in the presence of a palladium catalyst and a lower alcohol.
  • Tethered phosphines such as bis(diphenylphosphino)propane give optimal results in combination with palladium catalysis. The reaction is best carried out in dimethyl sulfoxide as solvent and the temperature is best maintained between 60-80 °C.
  • Organic bases such as tertiary amines are preferred as acid acceptor with triethylamine being especially preferred.
  • RX alkyl
  • compounds of Formula XX VII can be prepared by the palladium catalyzed reaction of compounds of Formula XVLTI with unsaturated alcohols of Formula XXVI.
  • Larock has studied the reaction of aryl halides with unsaturated alcohols and published a convement procedure for carrying out the process (Tetrahedron Lett., 30, 6629-6632 (1989)).
  • the reaction is best carried out in a dipolar aprotic solvent such as dimethylformamide or acetonitrile in the presence of a phase transfer agent such as tetrabutylammonium chloride or the like.
  • a phase transfer agent such as tetrabutylammonium chloride or the like.
  • an inorganic base such as sodium bicarbonate, potassium carbonate, lithium acetate, or sodium acetate is required.
  • the reaction may be carried out at 25 °C to 150 °C. In some cases the reaction is improved by the addition of a lithium salt such as lithium chloride.
  • Compounds of Formula XXDC can be made by reaction of substituted hydroxylamines of Formula XVI and an aldehyde or ketone of Formula XXVLLI in a lower alcoholic solvent as shown in Scheme 16. The reaction is best carried out at 25 to 100 °C.
  • Lg halogen, sulfonate
  • R x H, halogen, haloalkyl, alkyl, CN
  • R? H, halogen, haloalkyl, alkyl, CN
  • the compounds of Formula XXXi ⁇ can be made by the means of the Wittig or Horner-Emmons reaction as shown in Scheme 18. Reaction between phosphonium salts or phosphonates of Formula XXXV with strong base followed by reaction with compounds of Formula XXVHI give the alkenes. A compendium of conditions and references for these reactions can be found in Larock, loc. cit. pp 173-185 and 295-296. A convenient version of the reaction for making dichloroalkenes of Formula XXXm from compounds of Formula XXVIII is carried out by reaction of phosphines with carbon tetrahalides. Salmond (Tetrahedron Lett. 14, 1239-1240 (1977) has described conditions for carrying out this reaction. Typically the reaction is carried out in dichloromethane as solvent at 25 °C.
  • Compounds of Formula XXXVI can be made by reaction of compounds of Formula XXVIII with the anion of (trimethylsilyl)diazomethane as shown in Scheme 1 .
  • the anion is formed in an ether or tetrahydrofuran solvent system by reaction of the diazomethane with a strong base such as lithium diisopropylamide and then is treated with the compound of Formula XXVIII at low temperature (-20 to -70 °C). The mixture is then heated to 65 °C to effect the Colvin rearrangement.
  • the reaction has been described by Shioiri and coworkers in Syn. Lett. (1994), 107-108.
  • compounds of Formula XXXIV can be made from the compounds of Formula XXXI ⁇ substituted by 2 halogens.
  • the reaction is best carried out at low temperature (-30 to -80 °C) in ethereal solvents. Conditions for this transformation can be found in Villieras et al., Synthesis, 458-461, (1975).
  • Organometallic coupling reactions may be used to synthesize compounds of Formula Xi ⁇ , XXVIII and XXX as shown in Scheme 21.
  • Known or commercially available organometallic reagents may be coupled with aryl halides or sulfonates of Formula XVi ⁇ in the presence of palladium or nickel catalysts.
  • the wide range of catalysts and conditions for these transformations has been summarized by Tamao in Comprehensive Organic Synthesis, B. M. Trost, Ed., Pergamon, (1991), 3, 435-520.
  • arylboronic acids for the arylboronic acids
  • organometallic reagents can be made from commercially available or known aryl halides by methods disclosed in the references above.
  • Lithium borohydride (55 mL, 2 in tetrahydrofuran, 0.11 mol) was added slowly and, after completion of he addition, the mixture was heated at reflux for 1 h. The mixture was cooled and quenched by slow addition of aqueous hydrochloric acid (200 mL, IN). The mixture was extracted with dichloromethane (200 mL), dried over magnesium sulfate and evaporated under reduced pressure. The residue was then treated with toluene (100 mL) and thionyl chloride (23 mL, 0.3 mol). The mixture was heated to reflux for 45 min and then evaporated under reduced pressure.
  • Example 1 (0.30 g) were suspended in methanol (30 mL) and stirred for 4 h at 25 °C. The methanol was removed by evaporation at reduced pressure and the residue was partitioned between dichloromethane and water. The organic layer was dried and evaporated. The residue was subjected to silica gel chromatography with hexanes/ethyl acetate (4:1) to give the title compound of Example 1 (0.16 g), a compound of the invention, as a solid melting at 140-141 °C.
  • Hexamethylphosphorous triamide (1.2 mL in dichloromethane (50 mL)) was added and the mixture was allowed to stir at 25 °C for 72 h.
  • the reaction was charged with . bromotrichloromethane (0.8 g, 0.4 mL) and hexamethylphosphorous triamide (1.2 mL) and stirring was resumed for 18 h.
  • the reaction mixture was treated with water ( 100 mL) and the organic layer was washed with water (100 mL). The organic layer was dried and evaporated under reduced pressure.
  • Example 2 The residue was subjected to silica gel chromatography with hexanes ethyl acetate (6:1) as eluent to give the title compound of Example 2 (0.11 g), a compound of the invention, as a white solid melting at 156-157 °C. !H NMR (CDC1 3 ): ⁇ 7.6(m,6H), 7.4(m,3H), 7.0(m,2H), 6.9(m,lH), 5.5(m,lH), 4.9(m,lH), 4.3(m,lH).
  • Example 2 The title compound of Example 2 (0.25 g) was dissolved in tetrahydrofuran (8 mL) and treated with lithium diisopropylamide (0.6 mL, 1.5M in hexanes). The cooling bath was removed and the reaction was allowed to come to 25 °C. The reaction mixture was treated with saturated aqueous ammonium chloride solution (5 mL) and water (20 mL). The ether phase was dried over magnesium sulfate and evaporated to give 0.2 g of the tide compound of Example 4, a compound of the invention, as a solid melting at 120-123 °C.
  • Step B 1 - 4-[2-(2.6-Difluoropheny ⁇ -4.5-dihydro-4-oxazolynphenyllethanone O- fphenylmethvnoxime
  • the title compound of Step A 0.5 g
  • 0-benzylhydroxylamine hydrochloride (0.36 g) were suspended in methanol (15 mL) and treated with sodium acetate (0.23 g). The mixture was stirred at 25 °C for 2.5 h. More O-benzylhydroxylamine hydrochloride (0.1 g) was added and the mixture was heated to reflux for 10 min and allowed to stir at 25 °C for 1 h. The reaction mixture was partitioned between ether and water. The organic layer was dried over magnesium sulfate.
  • Step A Ethyl 4-r2-(2.6-difluorophenyD-4.5-dihydro-4-oxazolyllbenzoate
  • Step B 4-f2-(2.6-Difluorophenyl)-4.5-dihydro-4-oxazolynbenzenemethanol
  • Step C 1 -Phenylethanone Q-. f4-.2-(2.6-difluorophenyl ⁇ -4.5-dihvdro-4- oxazolyl1phenyl]methynoxime
  • the title compound of Step B was dissolved in toluene (50 mL), cooled in an ice bath and treated with thionyl chloride (1.5 mL) in toluene (20 mL). The mixture was stirred for 3 h and then evaporated to dryness under reduced pressure. The unstable oil (2.0 g) was immediately dissolved in dimethylformamide (10 mL).
  • Step B 2-(2.6-Difluorophenyn-4.5-dihvdro-4-r4'-rrtris(l-methylethvnsUyllthioiri.l'- biphenyll-4-ynoxazole
  • Step A The title compound of Step A (4.3 g) was dissolved in 15 mL of THF under a nitrogen atmosphere and cooled below -65°C, and then n-BuLi in hexanes (4.7 mL of 2.5M solution) was added dropwise. After 15 minutes, 26 mL of a 0.5M solution of ZnCl 2 in THF was added dropwise. In a separate reaction flask, 67 mg of Pd(OAc) 2 was added to a solution of 201 mg of tri(o-tolyl)phosphine in 5 mL of THF, and this mixture was stirred for 5 min before its addition, via cannula, to the main reaction mixture.
  • Step C rr4'- .2-f 2.6-DifluorophenyD-4.5-dihydro-4-oxazolyll f 1.1 '-biphenyl -4- yllthiolacetonitrile
  • a solution of 0.54 g of the title compound of Step B in 10 mL of THF was added 1.0 mL of a 1.1 M THF solution of «-Bu 4 NF at 15 to 20 °C (water bath cooling) under a nitrogen atmosphere. After 5 min, 0.9 mL of iodoacetonitrile was added and th reaction mixture was stirred overnight at room temperature.
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, Alms, and the like which can be water-dispersible ("wettable") or water-soluble.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses.
  • All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NN-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, N-N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4, 144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Example A Wettable Powder Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B
  • Compound 4 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term “arthropods” includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active agains pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevi (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifer ⁇ ), green leafhopper (Nephotettix cincticeps), brown planthopper
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyida
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion, parathion-methyl, permethrin,
  • Preferred for better control of pests (use rate or spectrum) or resistance management are mixtures of a compound of this invention with an arthropodicide selected from the group abamectin, fenpropathrin, fipronil, imidacloprid, methomyl, propargite, pyridaben, tebufenozide and tebufenpyrad.
  • an arthropodicide selected from the group abamectin, fenpropathrin, fipronil, imidacloprid, methomyl, propargite, pyridaben, tebufenozide and tebufenpyrad.
  • Specifically preferred mixtures are selected from the group: compound 3 and abamectin; compound 3 and fenpropathrin; compound 3 and fipronil; compound 3 and imidacloprid; compound 3 and metiiomyl; compound 3 and propargite; compound 3 and pyridaben; compound 3 and tebufenozide; compound 3 and tebufenpyrad; compound 4 and abamectin; compound 4 and fenpropathrin; compound 4 and fipronil; compound 4 and imidacloprid; compound 4 and methomyl; compound 4 an propargite; compound 4 and pyridaben; compound 4 and tebufenozide; compound 4 and tebufenpyrad; compound 15 and abamectin; compound 15 and fenpropathrin; compound 15 and fipronil; compound 15 and imidacloprid; compound 15 and met
  • Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of the invention, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
  • Control efficacy represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding.
  • the pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-B for compound descriptions.
  • Test compounds were prepared by dissolving in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 50 ppm.
  • Two- week old red kidney bean plants infested with two-spotted spider mites eggs were sprayed to run-off (equivalent to 28 g/ha) with the test solution using a turntable sprayer. Plants were held in a chamber at 25 °C and 50% relative humidity.
  • the following gave mortality levels of 80% or higher seven days after spraying: 1, 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 23* and 24*.
  • test compounds were prepared by dissolving in a minimum of acetone and adding water containing a wetting agent until the concentration of the compounds was 10 ppm. Test compounds were then spray to run-off (equivalent to
  • Treated plants were dried, and fall armyworm (Spodopterafrugiperda) larvae were exposed to excised, treated leaves. Test units were held at 27°C and 50% relative humidity, and evaluated for larval mortality 120 h post-infestation. Of the compounds tested, the following gave mortality levels of 80% or higher: 2, 3, 4, 7*, 8**, 10*, 11*,

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
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  • Wood Science & Technology (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
EP95940807A 1995-01-20 1995-11-28 Insecticidal and acaricidal oxazolines and thiazolines Withdrawn EP0804423A1 (en)

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US376951 1995-01-20
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Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4401098A1 (de) * 1994-01-17 1995-07-20 Bayer Ag Diphenyloxazolin-Derivate
TW440429B (en) 1994-08-12 2001-06-16 Bayer Ag Substituted biphenyloxazolines
JP2000500755A (ja) * 1995-11-17 2000-01-25 バイエル・アクチエンゲゼルシヤフト ビフェニルエーテルオキサゾリン及びその有害生物防除剤としての使用
TW424089B (en) * 1996-01-16 2001-03-01 Du Pont Oxazoline arthropodicides
CA2283276A1 (en) * 1997-03-05 1998-09-11 Bayer Aktiengesellschaft Disubstituted biphenyloxazolines
DE19717228A1 (de) * 1997-04-24 1998-10-29 Bayer Ag Substituierte Oxazolin-Derivate
DE19727889A1 (de) * 1997-07-01 1999-01-07 Bayer Ag 2-(2-Methylphenyl)-oxazoline
CO5031296A1 (es) 1997-11-04 2001-04-27 Novartis Ag Derivados de azolina, compuestos que la contienen y metodo para la preparacion y aplicacion de dicho compuesto
DE19826671A1 (de) * 1998-06-16 1999-12-23 Hoechst Schering Agrevo Gmbh 1,3-Oxazolin- und 1,3-Thiazolin-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel
NZ514064A (en) * 1999-03-26 2004-01-30 Novartis Ag Pesticidal enantiomer-pure 2,4-disubstituted oxazolines
TWI275589B (en) * 2000-06-22 2007-03-11 Dow Agrosciences Llc 2-(3,5-disubstituted-4-pyridyl)-4-(thienyl, thiazolyl or arylphenyl)-1,3-oxazoline compounds
DE10114597A1 (de) * 2001-03-23 2002-10-02 Bayer Cropscience Gmbh Arylisoxazolin-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel
DE60215644T2 (de) * 2001-06-22 2007-02-15 Dow Agrosciences Llc, Indianapolis 2-(2,6-disubstituierte phenyl)-4-aryl-5-alkyl-1,3-oxazoline derivate zur verwendung als insektizide und acarizide
US6573286B1 (en) 2002-06-21 2003-06-03 Dow Agrosciences Llc 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline compounds
CN101998963B (zh) * 2008-02-12 2014-09-24 陶氏益农公司 杀虫组合物
TW201029997A (en) * 2008-12-23 2010-08-16 Basf Se Imine compounds for combating invertebrate pests
UA108619C2 (xx) * 2009-08-07 2015-05-25 Пестицидні композиції
WO2013169599A1 (en) * 2012-05-08 2013-11-14 Dow Agrosciences Llc 2,4-(substituted aromatic)-1,3-oxazoline compounds as a seed treatment to control pests
CN104910092B (zh) * 2014-03-12 2017-09-29 南开大学 4‑苯基对位含有醛肟醚结构的噁唑啉类化合物及其制备和在防治虫螨菌草方面的应用
CN104910093B (zh) * 2014-03-12 2017-09-29 南开大学 4‑苯基对位含有醇肟醚结构的噁唑啉类化合物及其制备和在防治虫螨菌草方面的应用
CN105348211B (zh) * 2015-09-25 2018-02-23 南开大学 4‑苯基对位含有硫醚及其衍生结构的噁唑啉类化合物、制备和作为杀虫杀螨剂的应用
CN117304127B (zh) * 2023-09-26 2025-08-08 南开大学 一种噁唑啉类衍生物及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4977171A (en) * 1988-06-09 1990-12-11 Yashima Chemical Industrial Co., Ltd. Oxa- or thia-zoline derivative
JP2613651B2 (ja) * 1989-05-17 1997-05-28 八洲化学工業株式会社 オキサー又はチアゾリン化合物及びこれを含有する殺虫、殺ダニ剤
AU634608B2 (en) * 1989-12-09 1993-02-25 Kyoyu Agri Co., Ltd. 2-substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insectides and acaricides containing the same
DE4401098A1 (de) * 1994-01-17 1995-07-20 Bayer Ag Diphenyloxazolin-Derivate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9622283A1 *

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