Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/70—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
  • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/62—Oxygen or sulfur atoms
  • C07D213/70—Sulfur atoms
  • C07D213/71—Sulfur atoms to which a second hetero atom is attached
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D277/36—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
  • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

• This invention pertains to compounds of Formula I, including all geometric and stereoisomers,
• R 1 is selected from the group C 1 -C 3 alkyl and C 1 -C 3 haloalkyl;
• R 2 is selected from the group H, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfinyl, C 1 -C 2 haloalkylsulfinyl, C 1 -C 2 alkylsulfonyl, C 1 -C 2 haloalkylsulfonyl, amino, C 1 -C 2 alkylamino, C 2 -C 4 dialkylamino, C 2 -C 3 alkoxycarbonyl; phenyl optionally substituted with halogen, CN or NO 2 ; halogen; NO 2 ; and CN;
• R 3 is selected from the group C 1 -C 6 alkyl
• R 6 substituted with R 6 , C 3 -C 6 alkenyl substituted with R 6 , C 3 -C 6 alkynyl substituted with R 7 and C 4 -C 7 cycloalkylalkyl optionally substituted with R 8 ; wherein when R 3 is C 3 -C 6 alkenyl substituted with R 7 and R 7 is 1 to 3 halogens, then n is 0 or 1;
• R 4 and R 5 are independently selected from the group C 1 -C 6 alkyl substituted with R 9 , C 2 -C 6 alkenyl substituted with R 10 , and C 2 -C 6 alkynyl
• R 6 is selected from the group CN, SCN, NO 2 , OH,
• R 7 is selected from the group 1-3 halogens, C 1 -C 3 alkyl, CN, SCN, NO 2 , OH, OR 11 , SR 11 , S(O)R 11 , SO 2 R 11 , OC(O)R 11 , OSO 2 R 11 , Si(R 11 ) (R 12 ) (R 13 ), CO 2 R 11 , C(O)N(R 11 )R 12 , C(O)R 11 and N(R 11 )R 12 ;
• R 8 is selected from the group 1-3 halogens, CN and C 1 -C 2 alkyl;
• R 9 is selected from the group CN, SCN, NO 2 , OH,
• R 10 is selected from the group 1-3 halogens, C 1 -C 3 alkyl, CN, SCN, NO 2 , OH, OR 11 , SR 11 , S(O)R 11 , SO 2 R 11 , OC(O)R 11 , OSO 2 R 11 , Si (R 11 ) (R 12 ) (R 13 ), CO 2 R 11 , C(O)N(R 11 )R 12 , C(O)R 11 and N(R 11 )R 12 ; R 10 is selected from the group 1-3 halogens, C 1 -C 3 alkyl, CN, SCN, NO 2 , OH, OR 11 , SR 11 , S(O)R 11 , SO 2 R 11 , OC(O)R 11 , OSO 2 R 11 , Si (R 11 ) (R 12 ) (R 13 ), CO 2 R 11 , C(O)N(R 11 )R 12 , C(O)R 11 and N(R 11 )
• R 14 is selected from C 1 -C 3 haloalkyl
• n 0, 1 or 2.
• Preferred Compounds A are compounds of Formula I wherein:
• R 1 is CH 3 ;
• R 2 is selected from the group H, CH 3 , halogen, CF 3 and CN;
• R 6 is selected from the group CN, SCN,
• R 7 is selected from the group 1-3 halogens, CN,
• R 9 is selected from the group CN, SCN,
• R 10 is selected from the group 1-3 halogens, CN,
• Preferred Compounds B are compounds of Preferred A wherein Q is Q-1.
• Preferred Compounds C are compounds of Preferred A wherein Q is Q-2.
• Preferred Compounds D are compounds of Preferred A wherein Q is Q-3.
• stereoisomers include enantiomers, diastereomers and geometric isomers.
• One skilled in the art will appreciate that one stereoisomer may be more active than the others and how to separate said
• the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
• alkyl used either alone or in compound word such as “haloalkyl”, denotes straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl or hexyl isomers.
• Alkoxy denotes methoxy and ethoxy.
• Alkenyl denotes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers.
• Alkynyl denotes straight chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers.
• Cycloalkylalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl attached to a straight or branched C 1 -C 4 alkylene group.
• 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 or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH 2 CH 2 F, CF 2 CF 3 and CH 2 CHFCl.
• haloalkenyl and “haloalkynyl” are defined analogously to the term “haloalkyl”.
• C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 7. For example, C 2
• alkoxycarbonyl designates C(O)OCH 3 and C 3
• alkoxycarbonyl designates C(O)OCH 2 CH 3 .
• Compounds of Formula I can be prepared by the reaction of hydroxyaryl compounds of Formula II with an alkylsulfonylating reagent such as an alkylsulfonyl halide or an alkylsulfonic acid anhydride.
• This reaction is generally conducted in a solvent and typically employs a base to initiate the reaction and quench the liberated acid by-product.
• Suitable solvents include, tetrahydrofuran, diethyl ether, methylene chloride, chloroform, benzene and toluene.
• Examples of typical bases include triethylamine and pyridine. The reactions are usually run at
• Oxidation to the sulfoxide can be achieved with a variety of oxidative reagents such as hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate and t-butylhypochlorite.
• stoichiometric amounts of the oxidative reagent can be employed. For example, one equivalent of 30% hydrogen peroxide at room temperature is usually sufficient to convert a sulfide to a sulfoxide.
• Sulfoxides can be further oxidized to the sulfone by an additional equivalent of 30% hydrogen peroxide and may require higher
• Intermediate hydroxyaryl compounds of Formula II can be prepared as depicted in Schemes 3, 4 and 5.
• the key step in the synthesis of each of these intermediates is the alkylation of an aryl or heteroaryl mercaptan (III, VI and VII) with a substituted alkyl, alkenyl or alkynyl halide (i.e. R 3 X, R 4 X and R 5 X) where X is a halogen leaving group such as chlorine, bromine or iodine.
• Step A 2-Methoxy-6-[[(4-methoxyphenyl)methyl]thio]- pyridine
• Step C 2-Methoxy-6-[[(trimethylsilyl)methyl]thio]- pyridine
• Example 6 1 H NMR (CD C l 3 ) ⁇ 2.8-2.9 (m,2H), 3.54 (s,3H), 3.57, (t,2H), 7.41 (d, 1H), 8.08 (d,1H), 8.15 (t,1H).
• Example 7 1 H NMR (CDCl 3 ) ⁇ 2.4-2.7 (m,1H), 2.7-3.0 (m, 1H) 3.15 (m,1H), 3.35 (m,1H), 3.46 (s,3H), 7.22 (d,1H), 7.98 (d,1H), 8.10 (t, 1H).
• compositions of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent.
• the arthropodicidal compositions of the present invention comprise an effective amount of a .compound of Formula I and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
• Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
• 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
• compositions Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New
• Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
• Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example. Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259.
• Suspensions are prepared by wet-milling; see, for example, U.S.
• Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See
• Pellets can be prepared as described in U.S.
• Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
• Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
• arthropods includes insects, mites and nematodes which are pests of growing and stored agronomic crops, forestry, greenhouse crops,
• the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Pscoptera;
• the compounds are particularly active against southern corn rootworm (Dia-brotica undecij ⁇ punctata howardi), aster leafhopper
• rice leaf beetle Olema oryzae
• whitebacked planthopper Sogatella furcifera
• green leafhopper Nephotettix cincticeps
• brown planthopper Naparvata lugens
• Compounds of this invention can also be mixed with one or more other insecticides, fungicides,
• nematocides bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding
• insecticides such as avermectic B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate,
• insecticides such as avermectic B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumur
• azinphosmethyl chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone,
• methoxychlor methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate,
• fungicides such as carbendazim, thiuram, dodine, maneb,
• ipconazole metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox,
• blasticidin S blasticidin S, diclomezine, edifenphos
• tebufenpyrad and fenbutatin oxide tebufenpyrad and fenbutatin oxide
• biological agents such as Bacillus thuringiensis and baculovirus.
• Arthropod pests are controlled and protection of agronomic 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
• 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 Formula I, 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.
• 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.
• suitable carriers diluents, and surfactants
• 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
• TESTS demonstrate the control efficacy of compounds of this invention on specific pests.
• the pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A, B and C for compound descriptions.
• the units each consisting of an 8-ounce (230 mL) plastic cup containing a one-inch square of a soybean- wheat germ diet were prepared. Solutions of each of the test compounds (acetone/distilled water 75/25) were sprayed into the cup. Spraying was accomplished by passing the cup, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds active ingredient per acre (about 0.55 kg/ha) at 30 psi (207 kPa).
• Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat (Avena sativa) seedlings in a 1-inch (2.5 cm) layer of sterilized soil and a 1/2-inch layer of sand.
• the test units were sprayed as described in Test A with individual solutions of spraying, between 10 and 15 adult aster leafhoppers (Macrosteles fascifrons) were aspirated into each of the cups covered with vented lids.
• the cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 2, 4, 5, 6, 7, 8, 11, 12, 13, 17, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 33, 46, 51, 52, 53, 55.
• test units Five adult boll weevils (Anthonomus grandis grandis) were placed into each of a series of 9-ounce (260 mL) cups. The test units were sprayed as
• Test D The test procedure for Test D was used for Test D.
• Test E is read at 48 hours for mortality. Of the compounds tested, the following gave mortality level of 80% or higher: 1, 2, 4, 11, 12, 14, 17, 18, 19, 23, 27, 29, 30, 31, 49, 50.
• the treated cups were held in a vented enclosure to dry for about 2 h. After drying, the cups were placed into conical shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) were transferred into the test units using an aspirator. The test units were held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs were taken at 24 and 48 h post-infestation.
• the turntable completes 7.5 rotations during the 45 second spray interval.
• treated cups were held in a vented enclosure to dry for about 2 h. After drying, the cups were placed into conical shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the brown planthopper (Nilaparvata lugens) were then transferred into the test units using an
• test units were held at 27°C and
• test chemical was added directly into 10 mL of distilled water and dissolved completely. This chemical solution was poured into a conical shaped test unit. Three rice seedlings were then positioned in the unit by a notched sponge disk.
• the sponge disk allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The sponge also prevents the test nymphs from accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of the sponge disk, prevents accidental
• the rice seedlings were allowed to absorb the chemical from the solution for 24 h in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) were then transferred into the test units using an
• test chemical was added directly into 10 mL of distilled water and dissolved completely. This chemical solution was poured into a conical shaped test unit. Three rice seedlings were then positioned in the unit by a notched sponge disk.
• the sponge disk allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The sponge also prevents the test nymphs from accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of the sponge disk, prevents accidental
• the rice seedlings were allowed to absorb the chemical from the solution for 24 h in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the brown planthopper (Nilaparvata lugens) were then transferred into the test units using an

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• 1993
  • 1993-03-09 TW TW082101796A patent/TW235903B/zh active
  • 1993-04-06 WO PCT/US1993/003205 patent/WO1993021150A2/en active Application Filing
  • 1993-04-06 AU AU42789/93A patent/AU4278993A/en not_active Abandoned
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