WO2014149206A1 - Compositions insecticides à base de pyrazolopyrimidine et procédés associés - Google Patents

Compositions insecticides à base de pyrazolopyrimidine et procédés associés Download PDF

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WO2014149206A1
WO2014149206A1 PCT/US2014/014707 US2014014707W WO2014149206A1 WO 2014149206 A1 WO2014149206 A1 WO 2014149206A1 US 2014014707 W US2014014707 W US 2014014707W WO 2014149206 A1 WO2014149206 A1 WO 2014149206A1
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alkyl
alkenyl
alkynyl
phenyl
heterocyclyl
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William H. DENT
Mark A. Pobanz
Chaoxian Geng
Nick X. WANG
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Corteva Agriscience LLC
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Dow AgroSciences LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-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
    • A01N43/90—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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof

Definitions

  • aspects and embodiments relate generally to pesticidal compositions and to methods of preparing and using such pesticidal compositions. Particular aspects and embodiments generally relate to pyrazolopyrimidine-based pesticidal compositions and the methods of producing and using the pyrazolopyrimidine-based pesticidal compositions.
  • Controlling insect populations is essential to modern agriculture, food storage, and hygiene. There are more than ten thousand species of insects that cause losses in agriculture. The world-wide agricultural losses amount to billions of U.S. dollars each year. Accordingly, there exists a continuous need for new pesticides and for methods of producing and using such pesticides.
  • Embodiments of the present disclosure include pyrazolopyrimidine compounds, and the pesticidal compositions comprising such pyrazolopyrimidine compounds.
  • Embodiments of the present disclosure further include methods of producing pyrazolopyrimidine-based pesticidal compositions.
  • Further embodiments of the present disclosure include methods of controlling insects that include applying an pesticidal composition comprising a pyrazolopyrimidine -based compound near a population of insects.
  • alkyl means and includes a saturated, straight, or branched hydrocarbon. Examples may include, but are not limited to, methyl, ethyl, propyl, isopropyl, 1- butyl, isobutyl, t-butyl, 2-methylbutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, 3-methylpentyl, 2,2-dimethylbutyl, or 2,3-dimethylbutyl.
  • cycloalkyl means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, bicycle[2.2.2]octyl, and decahydronapthyl .
  • alkenyl means and includes a straight or branched hydrocarbon containing at least one carbon-carbon double bond. Examples may include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
  • cycloalkenyl means a cyclic hydrocarbon containing at least one carbon-carbon double bond, such as, for example, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and cyclodecenyl.
  • alkynyl means and includes a straight, branched, or hydrocarbon containing at least one carbon-carbon triple bond. Examples may include, but are not limited to, ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, or decynyl.
  • cycloalkynyl means a cyclic hydrocarbon containing at least one carbon-carbon triple bond.
  • aryl means and includes an aromatic ring compound with or without any substitution, such as, for example, phenyl and naphthyl.
  • alkoxy means and includes an alkyl group containing at least one carbon-oxygen single bond. Non-limiting examples may include methoxyl, ethoxy, propoxy, or butoxy.
  • alkylthio means and includes an alkyl group containing at least one carbon-sulfur single bond.
  • haloalkylthio means and includes an alkyl group containing at least one carbon-sulfur single bond and halogen atom.
  • halo and halogen mean and include fluorine, chlorine, bromine, or iodine.
  • heteroatom means and includes sulfur (S), oxygen (O) or nitrogen (N) atom.
  • heteroaryl means and includes an aromatic moiety containing at least one sulfur (S), oxygen (O), or nitrogen (N) atom in the aromatic ring.
  • Non-limiting examples may include furyl, pyridyl, pyrimidyl, thienyl, isothiazolyl, imidazolyl, tetrazolyl, pyrazinyl, benzofuranyl, benzothiophenyl, quinolyl, isoquinolyl, benzothienyl, isobenzoiuryl, pyrazolyl, indolyl, isoindolyl, benzimidazolyl, purinyl, carbozolyl, oxazolyl, thiazolyl, isothiazolyl, 1 ,2,4-thiadiazolyl, isooxazolyl, pyrrolyl, pyrazolyl, quinazolinyl, pyridazinyl, pyrazin
  • heteroalkyl means and includes an alkyl moiety as defined herein containing at least one sulfur (S), oxygen (O), or nitrogen (N) atom.
  • cyano means and includes a functional group containing a carbon-nitrogen triple bond.
  • nitro means and includes a functional group containing a nitrogen atom joined to two oxygen atoms.
  • “pesticidally effective amount” means and includes an amount of active material that causes an adverse effect to the at least one pest, wherein the adverse effect may include deviations from natural development, killing, regulation, or the like.
  • control means and includes regulating the number of living insects or regulating the number of viable eggs of the pests.
  • the pyrazolopyrimidine-based pesticidal composition may comprise a pyrazolopyrimidine compound of general formula I or any agriculturally acceptable salt thereof:
  • Ar may be any aryl group including, but are not limited to, phenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, pyrazolo, imidazolo, thiophenyl, or any other heteroaromatic rings.
  • Ar may be substituted or unsubstituted.
  • Ar may be substituted at any open position with hydrogen, halogen, alkyl, alkenyl, alkynyl, or combinations thereof.
  • Ar may be substituted with alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, halothio, cyano, nitro, sulfone, sulfoxide, unsubstituted amines, substituted amines, unsubstituted aryloxy, substituted aryloxy group, esters, acetates, amides, or combinations thereof;
  • X may be nitrogen (N), oxygen (O) or sulfur (S),
  • X is nitrogen
  • Y and Z may independently be hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, halothio, cyano amine, unsubstituted amine, or substituted amine;
  • the pyrazolopyrimidine compound of the general formula I may exist in various isomeric forms.
  • Non-limiting examples of such isomeric forms may include, but are not limited to, compounds I-A, I-B and I-C as shown below.
  • the pyrazolopyrimidine compound of the present disclosure may include at least one of these isomeric forms.
  • the pyrazolopyrimidine compound may have general formula II or any agriculturally acceptable salt thereof:
  • Ar may be a substituted phenyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, pyrazolo, imidazolo, triazole, thiophenyl, furyl, wherein the substituent group may include at least one of hydrogen, alkyl, alkoxy, halogen, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, halothio, nitro, sulfone, aryloxy, and any combination thereof;
  • R 1 , R 2 and R 5 may be independently selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl, in (b), (c), (d) and (h) may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (e) and (f) may independently be substituted with one or more substituents selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (el), (e2), (fl), and ( ⁇ ) may independently be substituted with one or more substituents selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) may independently be substituted with one or more substituents selected from:
  • R 8 may be selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl in (b), (c), (d) and (h) of R may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (e) and (f) of R may independently be substituted with one or more substituents selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) of R 8 may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of R may independently be substituted with one or more substituents selected from:
  • R 9 may be selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl, in (b), (c), (d) and (g) of R 9 may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (e) and (f) of R 9 may independently be substituted with one or more substituents selected from:
  • R 9 may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of R 9 may independently be substituted with one or more substituents selected from:
  • each of the alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of R 9 may independently be substituted with one or more substituents selected from:
  • each of the phenyl and heterocyclyl in (e3), (e4), ( ), and (f4) of R 9 may independently be substituted with one or more substituents selected from:
  • R 3 and R 4 may independently be hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, halothio, cyano amine, unsubstituted amine, or substituted amine.
  • the pyrazolopyrimidine compound of the general formula II may be produced by reducing the corresponding pyrazolopyrimidine compound of general formula III, as shown in Scheme 1.
  • the pyrazolopyrimidine compound III may be produced from 4-chloro-2,6-substituted pyrimidine-5-carbonitrile of formula IV- 1.
  • the compound 4-chloro-2,6- substituted pyrimidine-5-carbonitrile of formula IV-1 may be produced as shown in Scheme 2, wherein each substituent groups R 3 and R 4 is a Ci-C 8 alkyl group substituted with at least two or more halogen atoms.
  • cyanoalkyl compound IV-2 is reacted with ethyl 2-cyanoacetate (IV-3) in a solvent, such as tetrahydrofuran (THF), and a non-nucleophilic base, such as potassium tert-butoxide (KOiBu), at a temperature of approximately 25° C to provide the 4-hydroxy-2,6-substituted pyrimidine-5-carbonitrile salt of formula IV-4.
  • a solvent such as tetrahydrofuran (THF)
  • a non-nucleophilic base such as potassium tert-butoxide (KOiBu)
  • the hydroxyl substituent group at the 4-position of the pyrimidine compound IV-4 is converted to a chloride substituent group by reacting with phosphorus oxychloride (POCl 3 ) in a solvent, such as acetonitrile (MeCN), at a temperature between about 60 °C and about 70 °C to provide the 4-choloro-2,6-substituted pyrimidine-5-carbonitrile of formula IV-1.
  • a solvent such as acetonitrile (MeCN)
  • pyrazolopyrimidine compound V may be synthesized by reacting 4-choloro-2,6- substituted pyrimidine-5-carbonitrile compound IV-1 with a hydrazine-based compound as shown in Scheme 3.
  • compound 4-choloro-2,6-substituted pyrimidine-5-carbonitrile IV-1 may react with a hydrazine-based compound in the presence of a base, such as triethylamine (TEA), and a polar aprotic solvent, such as 1,4-dioxane or N,N- dimethylformamide (DMF), at a temperature from approximately 25° C to about 90° C.
  • a base such as triethylamine (TEA)
  • a polar aprotic solvent such as 1,4-dioxane or N,N- dimethylformamide (DMF)
  • compound 4-choloro-2,6-substituted pyrimidine-5-carbonitrile IV-1 may react with a feri-butoxycarbonyl (Boc)-protected hydrazine in the presence of a polar, aprotic solvent, such as 1 ,4-dioxane. Then, the resulting Boc- protected compound may react with triethylsilane and an acid, such as trifluoroacetic acid (TFA), in a non-reactive solvent, such as dichloromethane (CH 2 Cl 2 ) i at a temperature from approximately 25° C to about 50 °C.
  • a polar, aprotic solvent such as 1 ,4-dioxane.
  • TFA trifluoroacetic acid
  • compound 4-choloro-2,6-substituted pyrimidine-5-carbonitrile IV-1 may react with a hydrazine-based compound in the presence of a polar protic solvent, such as ethanol (EtOH), with or without a base, such as TEA, at an ambient temperature i.e. room temperature (RT, about 22 °C).
  • a polar protic solvent such as ethanol (EtOH)
  • EtOH ethanol
  • TEA room temperature
  • the amine group of the pyrazolopyrimidine compound V may be substitutented with at least one electrophile to provide the pyrazolopyrimidine compound of general formula VI, as shown in Scheme 4.
  • the pyrazolopyrimidine compound V may be reacted with at least one electrophile in the presence of a base in a polar aprotic solvent at a temperature from approximately 25° C to 60° C to provide the pyrazolopyrimidine compound VI.
  • electrophiles may include: alkyl halides, anhydrides, acid chlorides, isocyanates, isothiocyanate, or sulfonyl chlorides.
  • Suitable bases may include, but are not limited to, TEA, diisopropylethylamine (DIPEA), pyridine, NW-dimethylpyridin-4-amine (DMAP), potassium carbonate (K 2 C0 3 ), or potassium phosphate tribasic ( 3 P0 4 ).
  • polar aprotic solvents may include, but are not limited to, MeCN, THF, or CH 2 C1 2 .
  • the pyrazolopyrimidine compound VI may then be reduced by a hydride reducing agent, such as sodium borohydride (NaBH 4 ), in a polar protic solvent at a temperature from approximately 25° C to about 60° C to provide the pyrazolopyrimidine compound VII, as shown in Scheme 5.
  • a hydride reducing agent such as sodium borohydride (NaBH 4 )
  • NaBH 4 sodium borohydride
  • suitable polar protic solvents may include water, methanol (MeOH) or EtOH.
  • both R 3 and R 4 groups may be electron withdrawing groups, such as trifluoromethyl and trichloromethyl group.
  • the internal nitrogen atom of the pyrazolopyrimidine compound VII may be substituted with an electrophile (i.e., R 5 in Scheme 6) in the presence of a base in a polar aprotic solvent at a temperature from approximately 25° C to about 60° C to produce the pyrazolopyrimidine compound VIII, as shown in Scheme 6.
  • an electrophile i.e., R 5 in Scheme 6
  • Non-limiting examples of electrophiles suitable for Scheme 6 may include alkyl halides, anhydrides, acid chlorides, isocyanates, isothiocyanates, or sulfonyl chlorides.
  • suitable bases may include, but are not limited to, TEA, DIPEA, pyridine, DMAP, K 2 C0 3 , or K 3 P0 4 .
  • suitable polar protic solvents may include MeCN, THF, or
  • the R and R groups on the substutited amine of the pyrazolopyrimidine compound VIII may include an electron withdrawing group, such, for example, as carbamates, amides, ureas or sulfonamides. In one embodiment, both R 3 and R 4 groups may be electron withdrawing groups, such as trifluoromethyl. In one embodiment, the R 5 group on the nitrogen atom of the pyrazolopyrimidine compound VIII may be prepared using the same electrophiles as in R 1 and R 2 groups.
  • the pyrazolopyrimidine compound VI may be converted to the pyrazolopyrimidine compound VIII by Grignard reaction as shown in Scheme 7.
  • Pyrazolopyrimidine compound VI may react with an alkyl metal such methyl magnesium halide in the presence of metal halide, such as lithium chloride (LiCl), in a polar aprotic solvent, such as THF or ether, at a temperature from approximately -78° C to about 25° C to provide pyrazolopyrimidine compound VIII.
  • metal halide such as lithium chloride (LiCl)
  • a polar aprotic solvent such as THF or ether
  • both R 3 and R 4 groups may be electron withdrawing groups, such as trifluoromethyl.
  • W may be derived from a small alkyl magnesium halide such, for example, as methyl magnesium chloride (MeMgCl), /so-propyl magnesium chloride (z ' PrMgCl) and benzyl magnesium chloride (PhCH 2 MgCl).
  • a small alkyl magnesium halide such, for example, as methyl magnesium chloride (MeMgCl), /so-propyl magnesium chloride (z ' PrMgCl) and benzyl magnesium chloride (PhCH 2 MgCl).
  • the pyrazolopyrimidine compound may have general formula IX or any agriculturally acceptable salt thereof, wherein Ar, R 1 , R2 , R 5 and W may be as previously disclosed.
  • the pyrazolopyrimidine compound may have the general formula IX, wherein Ar represents 2,6-dichloro-4-(trifluoromethyl)phenyl group.
  • the pyrazolopyrimidine compound may have the general formula
  • R 1 , R 2 , R 5 and W may independently be hydrogen, alkyl, acyl, or alkylthioalkyl, or
  • R may be hydrogen and R may be alkyl, acyl, or alkylthioalkyl.
  • the pyrazolopyrimidine compound may have the general formula IX, wherein Ar, R 1 , R 2 and R 5 may be as previously disclosed, and W is hydrogen.
  • the method of Scheme 8 includes alkylating the amine substituent group of the pyrazolopyrimidine compound V-2 to produce ⁇ ', ⁇ '-bis-alkylated pyrazolopyrimidine compound VI-1, and then reducing Compound VI-1 to provide the pyrazolopyrimidine compound IX-1.
  • the reduction of the pyrazolopyrimidine compound VI-1 may be achieved using ethanolic NaBH 4 .
  • the pyrazolopyrimidine compound may have general formula X or any agriculturally acceptable salt thereof.
  • One embodiment of a method of producing the pyrazolopyrimidine compound X is shown in Scheme 9.
  • the method of Scheme 9 includes protecting the amine substitution group of the pyrazolopyrimidine compound V-2 with tert- butyloxycarbonyl (BOC) group to provide the bis-BOC protected compound V-3, and reducing Compound V-3 using NaBH 4 in EtOH to produce the pyrazolopyrimidine compound IX-2.
  • the substitution of the nitrogen at the 1 -position of the bis-BOC protected compound IX-2 may be achieved using Procedure A or B, depending on the substituent group.
  • Procedure A may be used when alkyl or benzyl halide is used the alkylating agent.
  • Procedure B may be used when substituted bromomethyl esters, chloroformates, sulfonyl chlorides, or acyl chlorides is employed as the alkylating agent.
  • An external base such as TEA, DMAP or DIPEA, may be used to affect the substitution of the amine group in an appropriate solvent (e.g., THF, acetone or CH 2 C1 2 ).
  • Procedure A may be performed as shown in Scheme 10, as follows: Scheme 10
  • the method of Scheme 10 includes alkylating the internal nitrogen at the 1 -position of the bis-BOC protected compound IX-2 with alkyl halide to provide compound IX-4, and then removing the bis-BOC protecting groups on the amine substituent group of compound IX-4 to provide the pyrazolopyrimidine compound X.
  • Procedure B may be performed as shown in Scheme 11, as follows:
  • the method of Scheme 11 includes substituting the internal nitrogen at the 1 -position of the pyrazolopyrimidine compound IX-5 with bromomethyl ester to provide compound IX-6, and then removing the bis-BOC protecting groups on the amine substituent group at the 3- position of compound IX-6 to provide the pyrazolopyrimidine compound X-l.
  • the BOC-deprotection of Compound IX-6 may provide compound X-2 in addition to the pyrazolopyrimidine compound X-l in resonance form I-A, I-B or I-C.
  • the pyrazolopyrimidine compound of the general formula I may be used to control a wide variety of pests.
  • the pyrazolopyrimidine compound I may be used to control one or more members of at least one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata, Subsphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla.
  • the method of the present disclosure may be used to control one or more members of at least one of Class Insecta and Class Arachnida.
  • the method of the present disclosure may be used to control one or more members of at least one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata, Subsphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla.
  • the method of the present disclosure may be used to control one or more members of at least one of Class Insecta and Class Arachnida.
  • the method of the present disclosure may be used to control members of the Order Coleoptera (beetles) including, but not limited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus (common bean weevil), Agrilus planipennis (emerald ash borer), Agriotes spp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle), Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidius spp., Apion spp. (weevils), Apogonia spp.
  • Acanthoscelides spp. (weevils)
  • Acanthoscelides obtectus common bean weevil
  • Agrilus planipennis emerald ash borer
  • Agriotes spp. wireworms
  • Ataenius spretulus Black Turfgrass Ataenius
  • Atomaria linearis pygmy mangold beetle
  • Aulacophore spp. Bothynoderes punctiventris (beet root weevil), Bruchus spp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp., Callosobruchus maculatus (southern cow pea weevil), Carpophilus hemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp., Cerotoma spp.
  • the method of the present disclosure may be used to control members of the Order Dermaptera (earwigs).
  • the method of the present disclosure may be used to control members of the Order Dictyoptera (cockroaches) including, but is not limited to, Blattella germanica (German cockroach), Blatta orientalis (oriental cockroach), Parcoblatta pennylvanica, Periplaneta americana (American cockroach), Periplaneta australoasiae (Australian cockroach), Periplaneta brunnea (brown cockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselus suninamensis (Surinam cockroach), and Supella longipalpa (brownbanded cockroach).
  • cockroaches including, but is not limited to, Blattella germanica (German cockroach), Blatta orientalis (oriental cockroach), Parcoblatta pennylvanica, Periplaneta americana (American cockroach), Periplaneta australoasiae (Australian cockroach), Periplan
  • the method of the present disclosure may be used to control members of the Order Diptera (true flies) including, but is not limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp.
  • Aedes spp. mosquitoes
  • Agromyza frontella alfalfa blotch leafminer
  • Agromyza spp. leaf miner flies
  • Anastrepha spp. fruit flies
  • Muscid flies Musca autumnalis (face fly), Musca domestica (house fly), Oestrus ovis (sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beet leafminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletis cerasi (cherry fruit fly), Rhagoletis pomonella (apple maggot), Sitodiplosis mosellana (orange wheat blossom midge), Stomoxys calcitrans (stable fly), Tabanus spp. (horse flies), and Tipula spp. (crane flies).
  • the method of the present disclosure may be used to control members of the Order Hemiptera (true bugs) including, but is not limited to, Acrosternum hilare (green stink bug), Blissus leucopterus (chinch bug), Calocoris norvegicus (potato mirid), Cimex hemipterus (tropical bed bug), Cimex lectularius (bed bug), Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturellus (cotton stainer), Edessa meditabunda, Eurygaster maura (cereal bug), Euschistus heros, Euschistus servus (brown stink bug), Helopeltis antonii, Helopeltis theivora (tea blight plantbug), Lagynotomus spp.
  • Acrosternum hilare green stink bug
  • Blissus leucopterus chinch bug
  • Calocoris norvegicus pot
  • the method of the present disclosure may be used to control members of the Order Homoptera (aphids, scales, whiteflies, leaflhoppers) including, but is not limited to, Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodes proletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixus floccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutella bigutella, Aphrophora spp. (leafhoppers), Aonidiella aiirantii (California red scale), Aphis spp.
  • Acrythosiphon pisum pea aphid
  • Adelges spp. Adelges spp.
  • Aleurodes proletella cabbage whitefly
  • Aleurodicus disperses Aleurothrixus floccos
  • Aphids Aphis gossypii (cotton aphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove aphid), Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci (sweetpotato whitefly), Brachycolus noxius (Russian aphid), Brachycorynella asparagi (asparagus aphid), Brevennia rehi, Brevicoryne brassicae (cabbage aphid), Ceroplastes spp.
  • Rhapalosiphum spp. aphids
  • Rhapalosiphum maida corn leaf aphid
  • Rhapalosiphum padi oat bird-cherry aphid
  • Saissetia spp. scales
  • Saissetia oleae black scale
  • Schizaphis graminum greenbug
  • Sitobion avenae English grain aphid
  • Sogatella furcifera white-backed planthopper
  • the method of the present disclosure may be used to control Myzus persicae.
  • the method of the present disclosure may be used to control members of the Order Hymenoptera (ants, wasps, and bees) including, but not limited to, Acromyrrmex spp., Athalia rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp. (sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant), Monomorium ssp., Monomorium minumum (little black ant), Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp.
  • Acromyrrmex spp. Athalia rosae
  • Atta spp. leafcutting ants
  • Camponotus spp. carpenter ants
  • Diprion spp. sawflies
  • the method of the present disclosure may be used to control members of the Order Isoptera (termites) including, but not limited to, Coptotermes spp., ⁇ Coptotermes curvignathus, Coptotermes frenchii, Coptotermes formosanus (Formosan subterranean termite), Cornitermes spp. (nasute termites), Cryptotermes spp. (drywood termites), Heterotermes spp. (desert subterranean termites), Heterotermes aureus, Kalotermes spp. (drywood termites), Incistitermes spp. (drywood termites), Macrotermes spp. (fungus growing termites), Marginitermes spp.
  • Coptotermes spp. ⁇ Coptotermes curvignathus, Coptotermes frenchii, Coptotermes formosanus (Formosan subterranean termite), Cornitermes spp. (nasute termites), Cryptotermes spp. (drywood termites),
  • the method of the present disclosure may be used to control members of the Order Lepidoptera (moths and butterflies) including, but not limited to, Achoea janata, Adoxophyes spp., Adoxophyes orana, Agrotis spp.
  • members of the Order Lepidoptera including, but not limited to, Achoea janata, Adoxophyes spp., Adoxophyes orana, Agrotis spp.
  • Pseud moths Pseudaletia unipunctata (armyworm), Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophaga incertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stem borer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella (Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.
  • the method of the present disclosure may be used to control Spodoptera exigua.
  • the method of the present disclosure may be used to control members of the Order Mallophaga (chewing lice) including, but not limited to, Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken body louse), and Menopon gallinea (common hen house).
  • the method of the present disclosure may be used to control members of the Order Orthoptera (grasshoppers, locusts, and crickets) including, but not limited to, Anabrus simplex (Mormon cricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplus spp. (grasshoppers), Microcentrum retinerve (angularwinged katydid), Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata (forktailed bush katydid), and Valanga nigricorni.
  • the method of the present disclosure may be used to control members of the Order Phthiraptera (sucking lice) including, but not limited to, Haematopinus spp. (cattle and hog lice), Linognathus ovillus (sheep louse), Pediculus humanus capitis (human body louse), Pediculus humanus humanus (human body lice), and Pthirus pubis (crab louse).
  • Haematopinus spp. cattle and hog lice
  • Linognathus ovillus seep louse
  • Pediculus humanus capitis human body louse
  • Pediculus humanus humanus humanus human body lice
  • Pthirus pubis crab louse
  • the method of the present disclosure may be used to control members of the Order Siphonaptera (fleas) including, but not limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea), and Pulex irritans (human flea).
  • members of the Order Siphonaptera including, but not limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea), and Pulex irritans (human flea).
  • the method of the present disclosure may be used to control members of the Order Thysanoptera (thrips) including, but not limited to, Frankliniella fusca (tobacco thrips), Frankliniella occidentalis (western flower thrips), Frankliniella shultzei, Frankliniella williamsi (corn thrips), Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp., Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow tea thrips), Taeniothrips rhopalantennalis, and Thrips spp.
  • Thysanoptera including, but not limited to, Frankliniella fusca (tobacco thrips), Frankliniella occidentalis (western flower thrips), Frankliniella shultzei, Frankliniella williamsi (
  • the method of the present disclosure may be used to control members of the Order Thysanura (bristletails) including, but not limited to, Lepisma spp. (silverfish) and Thermobia spp. (firebrats).
  • Thysanura bristletails
  • Lepisma spp. silverfish
  • Thermobia spp. firebrats
  • the method of the present disclosure may be used to control members of the Order Acari (mites and ticks) including, but not limited to, Acarapsis woodi (tracheal mite of honeybees), Acarus spp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mango bud mite), Aculops spp., Aculops lycopersici (tomato russet mite), Aculops pelekasi, Aculus pelekassi, Aculus convincedendali (apple rust mite), Amblyomma americanum (lone star tick), Boophilus spp.
  • Acarapsis woodi tracheal mite of honeybees
  • Acarus spp. food mites
  • Acarus siro grain mite
  • Aceria mangiferae mango bud mite
  • Aculops spp. Aculops lycopersici (tomato russet mite)
  • the method of the present disclosure may be used to control members of the Order Nematoda (nematodes) including, but not limited to, Aphelenchotdes spp. (bud and leaf& pine wood nematodes), Belonolalmus spp. (sting nematodes), Crlconemella spp. (ring nematodes), Dtrofilaria immltls (dog heartwom), Dltylenchusspp. (stem and bulb nematodes), Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella spp.
  • Aphelenchotdes spp. bud and leaf& pine wood nematodes
  • Belonolalmus spp. sting nematodes
  • Crlconemella spp. ring nematodes
  • Dtrofilaria immltls dog heartwom
  • root nematodes Hoplolalmus spp. (lance nematodes), Meloidogyne spp. (root knot nematodes), Meloidogyne Incognita (root knot nematode), Onchocerca volvulus (hook-tail worm), Pratylenchus spp. (lesion nematodes), Radopholus spp. (burrowing nematodes), and Rotylenchus renlformls (kidney-shaped nematode).
  • the method of the present disclosure may be used to control at least one insect in one or more of the Orders Lepldoptera, Coleoptera, Homoptera, Hemlptera, Thysanoptera, Isoptera, Orthoptera, Dlptera, Hymenoptera, and Slphonaptera, and at least one mite in the Order Acarl.
  • Example A Bioassays on Beet Armyworm (“BAW”) and Corn Earworm (“CEW”) and Cabbage Looper (“CL”)
  • BAW has few effective parasites, diseases, or predators to lower its population.
  • BAW infests many weeds, trees, grasses, legumes, and field crops, hi various places, it is of economic concern upon asparagus, cotton, corn, soybeans, tobacco, alfalfa, sugar beets, peppers, tomatoes, potatoes, onions, peas, sunflowers, and citrus, among other plants.
  • CEW is known to attack corn and tomatoes, but it also attacks artichoke, asparagus, cabbage, cantaloupe, collards, cowpeas, cucumbers, eggplant, lettuce, lima beans, melon, okra, peas, peppers, potatoes, pumpkin, snap beans, spinach, squash, sweet potatoes, and watermelon, among other plants.
  • CEW is also known to be resistant to certain insecticides.
  • CL feeds on a wide variety of cultivated plants and weeds. It feeds readily on crucifers, and has been reported damaging broccoli, cabbage, cauliflower, Chinese cabbage, collards, kale, mustard, radish, rutabaga, turnip, and watercress.
  • Other vegetable crops injured include beet, cantaloupe, celery, cucumber, lima bean, lettuce, parsnip, pea, pepper, potato, snap bean, spinach, squash, sweet potato, tomato, and watermelon.
  • CL is also known to be resistant to certain insecticides. Consequently, because of the above factors control of these pests is important. Furthermore, molecules that control these pests are useful in controlling other pests.
  • Bioassays on BAW were conducted using a 128-well diet tray assay.
  • One to five second instar BAW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 ⁇ g/cm 2 of the test compound (dissolved in 50 xL of 90:10 acetone- water mixture) had been applied (to each of eight wells) and then allowed to dry.
  • Trays were covered with a clear self-adhesive cover, and held at 25° C, 14: 10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the tables entitled "Table 1" (See Table Section).
  • Bioassays on CEW were conducted using a 128-well diet tray assay.
  • One to five second instar CEW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 ⁇ g /cm 2 of the test compound (dissolved in 50 of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry.
  • Trays were covered with a clear self-adhesive cover, and held at 25° C, 14: 10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled "Table 1" (See Table Section).
  • Bioassays on CL were conducted using a 128-well diet tray assay.
  • One to five second instar CL larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 ⁇ g /cm 2 of the test compound (dissolved in 50 ⁇ of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry.
  • Trays were covered with a clear self-adhesive cover, and held at 25° C, 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled "Table 1" (See Table Section).
  • Example B Bioassays on Green Peach Aphid (“GPA”) (Myzus persicae).
  • GPA is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other plants. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses. GPA has developed resistance to many pesticides.
  • the seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application.
  • Test compounds (2 mg) were dissolved in 2 mL of acetone/MeOH (1 :1) solvent, forming stock solutions of 1000 ppm test compound.
  • the stock solutions were diluted 5X with 0.025% Tween 20 in H 2 0 to obtain the solution at 200 ppm test compound.
  • a hand-held aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff.
  • Reference plants (solvent check) were sprayed with the diluent only containing 20% by volume of acetone/MeOH (1 : 1 ) solvent. Treated plants were held in a holding room for three days at approximately 25° C and ambient relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott's correction formula (W.S. Abbott, "A Method of Computing the Effectiveness of an Insecticide" J. Econ. Entomol. 18 (1925), pp.265-267) follows.
  • Example C BlOASSAYS ON Yellow Fever Mosquito "YFM" (Aedes aegypti).
  • YFM prefers to feed on humans during the daytime and is most frequently found in or near human habitations.
  • YFM is a vector for transmitting several diseases. It is a mosquito that can spread the dengue fever and yellow fever viruses. Yellow fever is the second most dangerous mosquito-borne disease after malaria. Yellow fever is an acute viral hemorrhagic disease and up to 50% of severely affected persons without treatment will die from yellow fever. There are an estimated 200,000 cases of yellow fever, causing 30,000 deaths, worldwide each year. Dengue fever is a nasty, viral disease; it is sometimes called "breakbone fever” or "break- heart fever” because of the intense pain it can produce. Dengue fever kills about 20,000 people annually. Consequently, because of the above factors control of this pest is important. Furthermore, molecules that control this pest (YFM), which is known as a sucking pest, are useful in controlling other pests that cause human and animal suffering.
  • Master plates containing 400 ⁇ g of a molecule dissolved in 100 of dimethyl sulfoxide (DMSO) (equivalent to a 4000 ppm solution) are used.
  • a master plate of assembled molecules contains 15 ⁇ , per well.
  • 135 xL of a 90:10 watenacetone mixture is added to each well.
  • a robot Biomek® NXP Laboratory Automation Workstation
  • a robot is programmed to dispense 15 aspirations from the master plate into an empty 96-well shallow plate ("daughter” plate).
  • mosquito eggs are placed in Millipore water containing liver powder to begin hatching (4 g. into 400 ml). After the daughter plates are created using the robot, they are infested with 220 of the liver powder/larval mosquito mixture (about 1 day-old larvae). After plates are infested with mosquito larvae, a non- evaporative lid is used to cover the plate to reduce drying. Plates are held at RT for 3 days prior to grading. After 3 days, each well is observed and scored based on mortality.
  • TABLE 1 shows the pesticidal activities of the pyrazolopyrimidine compounds against several insects: beet armyworm (BAW), corn earworm (CEW), cabbage looper (CL), green peach aphid (GPA), and yellow fever mosquitos (YFM).
  • BAW beet armyworm
  • CEW corn earworm
  • CL cabbage looper
  • GPA green peach aphid
  • YFM yellow fever mosquitos
  • TABLE 1 shows the mortality study results of the pyrazolopyrimidine compounds 1-96 against several insects: beet armyworm (BAW), corn earworm (CEW), cabbage looper (CL), green peach aphid (GPA), and yellow fever mosquitos (YFM).
  • BAW beet armyworm
  • CEW corn earworm
  • CL cabbage looper
  • GPA green peach aphid
  • YFM yellow fever mosquitos
  • Embodiments of the present disclosure further include methods of controlling pests that comprises applying an pesticidal composition comprising a pyrazolopyrimidine compound of the general formula I near a population of pests.
  • the pesticidal composition may comprise a pyrazolopyrimidine compound of the general formula I in a phytologically-acceptable inert carrier (e.g., solid carrier or liquid carrier), and may be applied near a population of pests.
  • a phytologically-acceptable inert carrier e.g., solid carrier or liquid carrier
  • the control of insects may be achieved by applying an pesticidally effective amount of the pyrazolopyrimidine-based composition in form of sprays, topical treatment, gels, seed coatings, microcapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols, dusts, or the like.
  • the pyrazolopyrimidine-based pesticidal compositions may be in the form of solid.
  • the solid forms may include power, dust or granular formulations.
  • the pyrazolopyrimidine-based pesticidal compositions may be in the form of liquid formulation.
  • the liquid forms may include, but not limited to, dispersion, suspension, emulsion or solution in appropriate liquid carrier.
  • the pyrazolopyrimidine-based pesticidal compositions may be in the form of liquid dispersion, wherein the pyrazolopyrimidine compound may be dispersed in water or other agriculturally suitable liquid carrier.
  • the pyrazolopyrimidine-based pesticidal compositions may be in the form of solution in an appropriate organic solvent.
  • the spray oils which are widely used in agricultural chemistry, may be used as the organic solvent for the pyrazolopyrimidine-based pesticidal compositions.
  • the pyrazolopyrimidine-based pesticidal compositions may be used in conjunction with at least one of other insecticides, fungicides and herbicides to obtain control of a wider variety of pests, diseases and weeds.
  • the pyrazolopyrimidine-based pesticidal compositions may be formulated with the other insecticides or fungicides or herbicide, or applied sequentially with the other insecticides or fungicides or herbicides.
  • the hydrazines may include: (2,6-dichloro-4-(trifluoromethyl)phenyl)hydrazine, (2- chloro-6-fluoro-4-(trifluoromethyl)phenyl)hydrazine, (2,4-dichlorophenyl)hydrazine, (3,5- dichlorophenyl)hydrazine hydrochloride, 3-chloro-2-hydrazinyl-5-(trifluoromethyl)pyridine, (2,4,6-trichlorophenyl)hydrazine, (2,6-dichloro-4-((trifluoromethyl)thio)phenyl)hydrazine (as prepared in WO 2005/090313 by Critcher, D. J.
  • Electrophiles for the above reaction were: 4-chlorobutyryl chloride, dichloroacetyl chloride, isopropyl chloroformate, 3-cyanopropanoyl chloride, or 3-methylbutanoyl chloride.
  • Electrophiles used in the above reaction may include: 5-bromopentanenitrile, 1 -bromo-
  • Electrophiles used (1-9 equivalents) may include the following: (iodomethyl)cyclopentane, l-iodo-4-methylpentane, or 2-(3-iodopropyl)-2-methyl-l,3- dioxolane.
  • V-2 V-39 Procedure was adapted from Yeom, C-E, et. al. Tetrahedron, 2006, 63, 904.
  • a solution of Compound V-2 (100 mg, 0.21 mmol), ethyl acrylate (22 mg, 0.22 mmol) and DBU (3 drops) in DMF (3 mL) was heated to 100 °C for 1 h.
  • the cooled mixture was diluted with water and extracted with EtOAc (2 x 10 mL).
  • Electrophiles used in th e a bove reaction may in c lude: 2-fluorobenzyl bromide, 4- trifluoromethylbenzyl bromide and 1 -(bromomethyl)-4- ( trifluoromethoxy)benzene.
  • the electrophiles used may include: bromomethylisobutyrate, bromomEtOAc, bromomethyl 2-ethoxyacetate.
  • the electrophiles used may include: 2-(bromomethyl)-l ,l-difluorocyclopropane.
  • Compound 57 in TABLE 9 was made in accordance with the procedure disclosed in Example 22.
  • Example 23
  • the electrophiles used may include: ethyl iodide, isopropyl iodide, l-(bromomethyl)-2- fiuorobenzene, l-(bromomethyl)-4-(trifluoromethoxy)benzene, 5-bromopentane nitrile, 1- bromopent-2-yne, 3-(iodomethyl)heptane.
  • the cooled reaction mixture was diluted with EtOAc (20 mL) and washed with water (10 mL), 0.1 N HC1 (10 mL) and brine (10 mL). The solution was dried over MgS0 4 , filtered and concentrated under vacuum.
  • the Grignard reagents used may include: isopropylmagnesium chloride, ethylmagnesium chloride, n-propylmagnesium chloride, benzylmagnesium chloride.

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Abstract

L'invention concerne une composition pesticide qui comprend un composé pyrazolopyrimidine de formule générale (I) ou tout sel acceptable dans l'agriculture de celui-ci, formule dans laquelle Ar, W, X, Y, Z et R sont tels que décrits dans la description. Une composition pesticide comprend un composé pyrazolopyrimidine de formule générale (II) ou tout sel acceptable dans l'agriculture de celui-ci, formule dans laquelle A, W, R1, R2, R3, R4 et R5 sont tels que décrits dans la description. Les procédés de préparation de telles compositions pesticides et les procédés de lutte contre les insectes comprennent l'utilisation de telles compositions pesticides.
PCT/US2014/014707 2013-03-15 2014-02-04 Compositions insecticides à base de pyrazolopyrimidine et procédés associés Ceased WO2014149206A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163846A (en) * 1976-05-15 1979-08-07 Fisons Limited Substituted pyrazolopyrimidine compounds
US20080312078A1 (en) * 2005-07-27 2008-12-18 Basf Aktiengesellschaft 6-Phenyl-Pyrazolopyrimidine-7-Ylamine Fungicides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163846A (en) * 1976-05-15 1979-08-07 Fisons Limited Substituted pyrazolopyrimidine compounds
US20080312078A1 (en) * 2005-07-27 2008-12-18 Basf Aktiengesellschaft 6-Phenyl-Pyrazolopyrimidine-7-Ylamine Fungicides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A. M. EL-REEDY ET AL.: "Azolopyrimidines and Pyrimidoquinazolines From 4-Chl oropyrimidines.", JOURNAL OF HETEROCYCLIC CHEMISTRY., vol. 26, no. 2, March 1989 (1989-03-01), pages 313 - 316 *
H. H. ABDEL-RAZIK ET AL.: "Enaminonitrile in Heterocyclic synthesis: Synthes is and Reactions of Some Pyrimidine Derivatives.", CHEMICAL PAPERS., vol. 58, no. 3, 2004, pages 209 - 213 *
RUTH BRENK ET AL.: "Virtual Screening for Submicromolar Leads of tRNA-guanin e Transglycosylase Based on a New Unexpected Binding Mode Detected by Crysta 1 Structure Analysis.", JOURNAL OF MEDICINAL CHEMISTRY, vol. 46, no. 7, 27 March 2003 (2003-03-27), pages 1133 - 1143 *

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