WO2014126580A1 - Compositions pesticides et processus associés à celles-ci - Google Patents

Compositions pesticides et processus associés à celles-ci Download PDF

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Publication number
WO2014126580A1
WO2014126580A1 PCT/US2013/026317 US2013026317W WO2014126580A1 WO 2014126580 A1 WO2014126580 A1 WO 2014126580A1 US 2013026317 W US2013026317 W US 2013026317W WO 2014126580 A1 WO2014126580 A1 WO 2014126580A1
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Prior art keywords
alkenyl
alkynyl
alkyl
phenyl
heterocyclyl
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PCT/US2013/026317
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English (en)
Inventor
Mark A. Pobanz
William Hunter Dent
Zoltan L. Benko
W. Randal Erickson
Chaoxian Geng
Gerald B. Watson
Thomas C. Sparks
Akshay PATNY
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Dow Agrosciences Llc
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Priority to PCT/US2013/026317 priority Critical patent/WO2014126580A1/fr
Publication of WO2014126580A1 publication Critical patent/WO2014126580A1/fr

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    • 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
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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

Definitions

  • the invention disclosed in this document is related to the field of processes to produce molecules that are useful as pesticides (e.g., acaricides, insecticides, molluscicides, and nematicides), such molecules, and processes of using such molecules to control pests.
  • pesticides e.g., acaricides, insecticides, molluscicides, and nematicides
  • Alkenyl means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl.
  • Alkenyloxy means an alkenyl further consisting of a carbon-oxygen single bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.
  • Alkoxy means an alkyl further consisting of a carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and ieri-butoxy.
  • Alkyl means an acyclic, saturated, branched or unbranched, substituent consisting of carbon and hydrogen, for example, methyl, ethyl, (C3)alkyl which represents n-propyl and isopropyl), (C 4 )alkyl which represents n-butyl, sec-butyl, isobutyl, and ieri-butyl.
  • Alkynyl means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl.
  • Alkynyloxy means an alkynyl further consisting of a carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.
  • Aryl means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl.
  • (C x -C y ) where the subscripts "x” and “y” are integers such as 1, 2, or 3, means the range of carbon atoms for a substituent - for example, (Ci-C 4 )alkyl means methyl, ethyl, n- propyl, isopropyl, n-butyl, sec -butyl, isobutyl, and ieri-butyl.
  • Cycloalkenyl means a monocyclic or polycyclic, unsaturated (at least one carbon- carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl,
  • Cycloalkenyloxy means a cycloalkenyl further consisting of a carbon-oxygen single bond, for example, cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.
  • Cycloalkyl means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.
  • Cycloalkoxy means a cycloalkyl further consisting of a carbon-oxygen single bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and
  • Halo means fluoro, chloro, bromo, and iodo.
  • Haloalkoxy means an alkoxy further consisting of, from one to the maximum possible number of identical or different, halos, for example, fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy, chloromethoxy, trichloromethoxy, 1,1,2,2- tetrafluoroethoxy, and pentafluoroethoxy.
  • Haloalkyl means an alkyl further consisting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, trifluoromethyl, 2,2- difluoropropyl, chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.
  • Heterocyclyl means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, that atom can be in other oxidation states such as a sulfoxide and sulfone.
  • aromatic heterocyclyls include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzo thiazolyl, cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiadiazolyl, thiazolinyl, thiazolyl, thiazo
  • heterocyclyls examples include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, oxetanyl, oxiranyl, tetrahydrofuranyl, tetrahydrothienyl and tetrahydropyranyl.
  • partially unsaturated heterocyclyls include, but are not limited to, 1,2,3,4-tetrahydroquinolinyl, 4,5-dihydro- oxazolyl, 4,5-dihydro-lH-pyrazolyl, 4,5-dihydro-isoxazolyl, and 2,3-dihydro-[l,3,4]- oxadiazolyl. Additional examples
  • (A) (Al) X 1 is selected from N and CR 6 ;
  • (A2) X 2 is selected from N and CR 5 ;
  • R 1 and R 2 are (each independently) selected from
  • (h) of (Bl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e) and (f) of (Bl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) of (Bl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of (Bl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of (Bl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e3), (e4), (f3), and (f4) of (Bl) may (each independently) be substituted with one or more substituents selected from
  • R 1 and R 2 along with N 1 can instead form a 5- or 6- membered ring, where said ring may be saturated or unsaturated, where the additional atoms in said ring (ring atoms) are selected from C, S, S(O), S(0) 2 , N, or O (provided that two oxygen atoms are not bonded to each other), and where each C or N ring atom that can have non-ring bonds is bonded to one or more of the following excluding N-F, N-Cl, N-Br and N-I
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl in (b), (c), and (d) of (B2) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e) and (f) of (B2) may (each independently) be substituted with one or more substituents selected from
  • R 3 and R 4 are (each independently) selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl in (b), (c), (d) and (h) of (CI) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e) and (f) of (CI) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) of (Cl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of (CI) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of (CI) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e3), (e4), (f3), and (f4) of (CI) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl in (b), (c), (d), and (h) of (Dl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e) and (f) of (Dl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) of (Dl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of (Dl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of (Dl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e3), (e4), (f3), and (f4) of (Dl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl in (a), (b), (c), and (h) of (El) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (d) and (e) of (El) may (each independently) be substituted with one or more substituents selected from
  • (h2) (C 3 -C 8 )cycloalkyl, wherein each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) of (El) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of (El) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of (El) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e3), (e4), (f3), and (f4) of (El) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl in (b), (c), (d) and (g) of (Fl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e) and (f) of (Fl) may (each independently) be substituted with one or more substituents selected from (a2) F, CI, Br, I, CN, N0 2 , OH, SF 5 , OSi((Ci-C 8 )alkyl) 3 ,
  • each said phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of (Fl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of (Fl) may (each independently) be substituted with one or more substituents selected from (a5) F, CI, Br, I, CN, N0 2 , OH, OSi((Ci-C 8 )alkyl) 3 ,
  • each said phenyl and heterocyclyl in (e3), (e4), (f3), and (f4) of (Fl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b), (c), (d) and (g) of (Gl) may (each independently) be substituted with one or more substituents selected from (al) F, CI, Br, I, CN, N0 2 , OH, OSi((C C 8 )alkyl) 3 ,
  • each said phenyl and heterocyclyl in (e) and (f) of (Gl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (bl), (b2), (cl), (c2), (dl), (d2), (hi), and (h2) of (Gl) may (each independently) be substituted with one or more substituents selected from (a3) F, CI, Br, I, CN, N0 2 , OH, OSi((Ci-C 8 )alkyl) 3 ,
  • each said phenyl and heterocyclyl in (el), (e2), (fl), and (f2) of (Gl) may (each independently) be substituted with one or more substituents selected from
  • each said alkyl, alkenyl, alkynyl, and cycloalkyl, in (b3), (b4), (c3), (c4), (d3), (d4), (h3), and (h4) of (Gl) may (each independently) be substituted with one or more substituents selected from
  • each said phenyl and heterocyclyl in (e3), (e4), (f3), and (f4) of (Gl) may (each independently) be substituted with one or more substituents selected from
  • Embodiment Al Formula One with items (A)-(G) are hereafter referred to as Embodiment Al.
  • the molecules of Formula One will generally have a molecular mass of about 100 Daltons to about 1200 Daltons. However, it is generally preferred if the molecular mass is from about 120 Daltons to about 900 Daltons, and it is even more generally preferred if the molecular mass is from about 140 Daltons to about 600 Daltons.
  • R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more halos
  • the preparation of the compounds of Formula V wherein R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more halos can be accomplished in two steps from the compounds of Formula II, such as 2,2,2-trifluoroacetamide, or in one step from commercially available substituted acetonitriles (compounds of Formula III).
  • step a of Scheme 1 the R 3 - substituted nitrile, a compound of Formula III, is generated in situ as in Parker, M. H. et al. Synth. Commun.
  • R 3 -substituted amide a compound of Formula II
  • a solvent such as pyridine
  • the R 3 -substituted acetonitrile (compound of Formula III) is added directly to a solution of ethyl 3-oxobutanoate (compound of Formula IV) and a base, such as potassium ieri-butoxide, in a polar, aprotic solvent such as tetrahydrofuran (THF), at approximately 25 °C to provide the butenoate (compound of Formula V) as in Lee, L. F. et al.
  • step c of Scheme I the butenoate (compound of Formula V) is added to a solution of lithium diisopropylamide in a polar, aprotic solvent, such as THF, at low temperature such as -78 °C.
  • a polar, aprotic solvent such as THF
  • the mixture is stirred at low temperature for about 1 hour (h) and then is treated at low temperature with the appropriate alkyl ester such as ethyl ester, a compound of Formula VI, to provide a compound of Formula Vila as prepared in Lee, L. F.
  • the acid of Formula Villa can be transformed into the amide of Formula LXa, wherein X 1 is CR 5 , X 2 is N, R 3 is a (Ci-C 8 )alkyl substituted with at least 2 or more halos and R 4 is as previously disclosed in embodiment Al, in two steps.
  • step e of Scheme 1 the acid chloride is formed by reaction with a chlorinating reagent such as thionyl chloride at reflux temperature, and then the acid chloride is converted to the amide of Formula IXa, wherein X 1 is CR 5 , X 2 is N and R 4 is as previously disclosed in embodiment Al, by treatment with ammonium hydroxide (NH 4 OH) in a non-reactive solvent such as dichloromethane (CH 2 CI 2 ) at approximately 25°C , as in step / of Scheme 1.
  • a chlorinating reagent such as thionyl chloride at reflux temperature
  • Conversion of the hydroxy group to the chloride in conjunction with dehydration of the amide to form the cyano group is effected using a chlorinating reagent such as phosphorus oxychloride in the absence or presence of a base, such as l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), at reflux temperature as is steps gj or g 2 , respectively, of Scheme 1 to afford the compound of Formula Xa, wherein X 1 is CR 5 , X 2 is N, R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more halos and R 4 is as previously disclosed in embodiment Al.
  • a chlorinating reagent such as phosphorus oxychloride in the absence or presence of a base, such as l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), at reflux temperature as is steps gj or g 2 , respectively, of Scheme 1 to afford the compound
  • R 4 a mono halo alkyl such as C3 ⁇ 4F, of Formula Vila
  • saponification of the ester is accomplished with a base, such as NaOH, in a polar, protic solvent, such as CH 3 OH, at a higher temperature such as 40 °C, to afford the acid of Formula Vlllb, wherein X 1 is CR 5 , X 2 is N and R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more of halos, as in step ⁇ 3 ⁇ 4 of Scheme 2.
  • the acid of Formula Vlllb can be transformed into the amide of Formula FXb, wherein X 1 is CR 5 , X 2 is N and R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more halos in two steps.
  • step e 2 of Scheme 2 the acid chloride is formed by reaction with a chlorinating reagent such as thionyl chloride at reflux temperature, and then the acid chloride is converted to the amide of Formula IXb, wherein X 1 is CR 5 , X 2 is N and R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more halos by treatment with NH 4 OH in a non-reactive solvent such as CH 2 CI 2 at approximately 25°C, as in step 1 ⁇ 2 of Scheme 2.
  • a chlorinating reagent such as thionyl chloride at reflux temperature
  • Conversion of the hydroxy group to the chloride in conjunction with dehydration of the amide to form the cyano group is effected using a chlorinating reagent such as phosphorus oxychloride in the presence of a base, such as DBU, at reflux temperature as in step g 2 of Scheme 2.
  • a chlorinating reagent such as phosphorus oxychloride
  • a base such as DBU
  • step h of Scheme 2 the methyl group in Formula Xb is removed with a demethylating reagent such as boron tribromide in a non-reactive solvent such as CH 2 CI 2 at approximately 25°C to afford the hydroxymethyl compound of Formula Xc, wherein X 1 is CR 5 , X 2 is N and R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more of halos.
  • Fluorination of the compound of Formula Xc can be accomplished using a fluorinating reagent such as diethylaminosulfur trifluoride in a non-reactive solvent, such as CH 2 CI 2 , at lower temperature such as 0 °C to provide the compound of Formula Xd, wherein X 1 is CR 5 , X 2 is N and R 3 is a (Ci-Cs)alkyl substituted with at least 2 or more of halos as in step i in Scheme 2.
  • a fluorinating reagent such as diethylaminosulfur trifluoride in a non-reactive solvent, such as CH 2 CI 2
  • a non-reactive solvent such as CH 2 CI 2
  • step j of Scheme 3 reaction of a compound of Formula XI, with 2-cyanoacetamide, in the presence of a base, such as diethylamine or piperidine, in a polar, protic solvent such as ethyl alcohol (EtOH), at a higher temperature such as 50 to 70 °C as in Narsaiah, B. et al. Org. Prep. Proced. Int. 1993, 25, 116-117, provides the compounds of Formula XIII.
  • a base such as diethylamine or piperidine
  • a polar, protic solvent such as ethyl alcohol (EtOH)
  • EtOH ethyl alcohol
  • the hydroxyl group in Formula XIII is converted to a chloride in one of three ways: (1) via reaction with phosphorus oxychloride as in step gi of Scheme 3; (2) by reaction with phosphorus oxychloride in the presence of a base such as N,N- diethylbenzeneamine as in step g 3 of Scheme 3; or (3) via reaction with phenylphosphonic dichloride as in step g4 of Scheme 3 to provide the compounds of Formula Xe .
  • step k of Scheme 4 reaction of a compound of Formula XI with malonamide in a polar high boiling solvent such as dimethyl sulfoxide (DMSO) or sulfolane at a higher temperature such as 80 to 160 °C (as in Umemoto and Tomisawa, JP 10168061 A, June 23, 1998) provides the regioisomeric compounds of Formula XV (major is
  • Formula XVI (minor isomer).
  • the hydroxyl group in both Formula XV and Formula XVI can be converted to a chloride with concomitant amide dehydration to the nitrile in one of two ways: (1) by reaction with phosphorus oxychloride in the presence of a base such as N,N- diethylbenzeneamine as in step g 3 of Scheme 4; or (2) via reaction with phosphorus oxychloride in the presence of a base such as triethylamine as in step gs of Scheme 4 to provide the compounds of Formula Xe.
  • a base such as N,N- diethylbenzeneamine
  • a base such as triethylamine
  • step g of Scheme 5 the hydroxyl group in Formula XVIII is converted to a chloride via reaction with phosphorus oxychloride in a solvent such as acetonitrile at a temperature between 60 and 70 °C to provide the compounds of Formula Xf.
  • the molecules of Formula One are synthesized in one of six ways as shown in
  • step s of Scheme 7 reaction of compounds of Formula One, with electrophiles, such as but not limited to, alkyl halides, anhydrides, acid chlorides, isocyanates, and isothiocyanates, in the presence of a base, such as triethylamine, diisopropylethylamine, pyridine, N W-dimethylpyridin-4-amine, potassium carbonate and potassium phosphate tribasic, in a polar, aprotic solvent such as acetonitrile, THF or CH2CI2, between approximately 25°C and 60 °C to provide compounds of Formula One, wherein R 1 and R 2 are as previously disclosed.
  • a base such as triethylamine, diisopropylethylamine, pyridine, N W-dimethylpyridin-4-amine, potassium carbonate and potassium phosphate tribasic
  • a polar, aprotic solvent such as acetonitrile, THF or CH2CI2, between approximately 25°C and
  • a three-neck flask was equipped with a thermometer and gas inlet tube.
  • the reaction vessel was charged with potassium ieri-butoxide (1.78 grams (g), 0.016 moles (mol)) and dry tetrahydrofuran (THF; 500 milliliters (mL).
  • Ethyl 3-oxobutanoate (69 g, 0.53 mol) was added dropwise. The mixture was allowed to stir at room temperature for 1 hour (h).
  • a second three-neck flask was fitted with a gas outlet tube connected to the first three-neck flask. The flask was charged with 2,2,2-trifluoroacetamide (90 g, 0.796 mol) and pyridine (400 mL).
  • Example 14 Preparation of 2-chloro-6-isopropyl-4-(trifluoromethyl)nicotinonitrile (I- 30)
  • the orange suspension was heated at 60 °C for 1 h and then cooled to 5 °C with an ice bath.
  • a solution of tin (II) chloride (3.16 g, 16.67 mmol) in hydrochloric acid (37%; 2.5 mL, 82 mmol) dropwise causing an exotherm and forming a thick white precipitate.
  • the precipitate was filtered over a fritted glass funnel, and the solid was transferred in portions to a mixture of ammonium hydroxide (NH 4 OH, 28% in H 2 0; 30 mL, 770 mmol) and ice (50 g).
  • the white suspension was stirred for 30 min and then diluted with Et 2 0 (300 mL).
  • Example 20 Preparation of a library of 4-(trifluoromethyl)-2H-pyrazolo[4,3-c]- and - [3,5-ft]-pyridin-3-amines
  • a 2-chloro-6-(substituted)-4-(trifluoromethyl)nicotinonitrile such as 1-29, 1-30, 1-31,1-33 and 1-39, (0.7 mmol) in EtOH (4 rriL) was added an appropriate hydrazine, such as (4-(trifluoromethyl)phenyl)hydrazine, (4-fluoro-2- (trifluoromethyl)phenyl)hydrazine, (2-chloro-4-(trifluoromethyl)phenyl)hydrazine, (2,6- dichloro-4-(trifluoromethyl)phenyl)-hydrazine, 3,5-dichloro-2-hydrazinylpyridine, (4-chloro-
  • Example 21 Preparation of a library of 4,6-bis(trifluoromethyl)-2H-pyrazolo[4,3-c]- and -[3,5-6]-pyridin-3-amines
  • the hydrazines used include: (4-(trifluoromethyl)phenyl)hydrazine, (2,4- dichlorophenyl)hydrazine, (2-methoxyphenyl)hydrazine, (4-ieri-butylphenyl)hydrazine, p- tolylhydrazine, (4-(methylsulfonyl)phenyl)hydrazine, (2,6-dichlorophenyl)hydrazine, (4- chloro-2-methoxyphenyl)hydrazine, (4-chloro-2-methylphenyl)hydrazine, (2-chloro-4- methylphenyl)hydrazine, (2,6-dimethylphenyl)hydrazine, (2,6-dichloro-4- methylphenyl)hydrazine, (4-(trifluoromethoxy)phenyl)hydrazine, (2,6-dichloro-4- (methylsulfonyl)phenyl)hydr
  • the hydrazines used include: [2,6-dichloro-4-(pentafluoro ⁇ 6 - sulfanyl)phenyl]hydrazine (prepared as in Critcher, D. J. et al. WO 2005/090313), (2,3,5,6- tetrafluoro-4-(trifluoromethyl)phenyl)hydrazine, (2,6-dichloro-3,5-difluoro-4- (trifluoromethyl)phenyl)hydrazine, (2,6-dichloro-4-(trifluoromethyl)phenyl)hydrazine, (2- chloro-6-fluoro-4-(trifluoromethyl)phenyl)hydrazine, (2,4-dichlorophenyl)hydrazine, (2,5- dichlorophenyl)hydrazine, (2,4-difluorophenyl)hydrazine hydrochloride, (3- (trifluoromethyl)pheny
  • hydrochloride (2-(trifluoromethoxy)phenyl)hydrazine hydrochloride, (2,6- dimethylphenyl)hydrazine hydrochloride, (2,4,6-trichlorophenyl)hydrazine, (4-fluoro-2- (methylsulfonyl)phenyl)hydrazine, (4-(2,2,2-trifluoroethoxy)phenyl)hydrazine hydrochloride, 2-hydrazinyl-3-(trifluoromethyl)pyridine, (2,6-dichloro-4-
  • the hydrazines used include: (2-chlorophenyl)hydrazine hydrochloride, (4- (trifluoromethyl)phenyl)hydrazine, (2-chloro-4-(trifluoromethyl)phenyl)hydrazine, 3,6- dichloro-4-hydrazinylpyridazine.
  • Compounds 193 - 195 in Table 1 were made in accordance with the procedures disclosed in Example 23.
  • Argonaut PS-CHO resin (1.08 mmol/g; 100- 120 mg, 0.108-0.130 mmol) was added to scavenge the remaining hydrazine. The samples were heated at 50 °C for 1 h. The liquid was removed by pipette and filtered into a plate.
  • the hydrazines used include: 3,6-dichloro-4-hydrazinylpyridazine, 2-hydrazinyl-5- phenyl-l,3,4-thiadiazole, 3,5-dichloro-2-hydrazinylpyridin-4-amine, 4-hydrazinyl- benzenesulfonamide, 2-hydrazinylpyrimidine, 3,5,6-trichloro-4-hydrazinylpicolinonitrile, 5- hydrazinyl-6-methyl-3-(methylthio)-l,2,4-triazine, 6-hydrazinyl-l,3-dimethylpyrimidine- 2,4(lH,3H)-dione, 2-chloro-4-hydrazinyl-5-methoxypyrimidine, (4-chlorophenyl)hydrazine, (2-methoxyphenyl)hydrazine, 2-hydrazinylpyridine.
  • TFA trifluoroacetic acid
  • the mixture was heated at reflux for 1 h. More TFA (3 mL) was added, and heating was continued for 90 min.
  • the mixture was concentrated in vacuo and diluted with CH 2 C1 2 (150 mL).
  • the organic layer was washed with brine (2 x 150 mL) and water (50 mL) mixed with satd aq sodium bicarbonate (NaHCC ⁇ ) solution.
  • NaHCC ⁇ sodium bicarbonate
  • the organic layer was dried (MgS0 4 ), filtered and concentrated to give a yellow solid residue.
  • the electrophiles (1-9 equiv) used include: iodoethane, 2-iodopropane,
  • Example 26 Using the procedure of Example 26 with 2-(2,6-dichloro-4-(pentafluoro- ⁇ 6 - sulfanyl)phenyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-J
  • reaction mixture was diluted with diethyl ether (Et 2 0; 150 mL) and washed with a mixture of satd aq NaCl (50 mL) and H 2 0 (50 mL). The combined aqueous layer was extracted with Et 2 0 (1 x 25 mL). The combined organic layer was dried with Na 2 S0 4 , filtered and concentrated in vacuo to give a viscous orange/yellow material.
  • Et 2 0 diethyl ether
  • Compound 215 in Table 1 was made in accordance with the procedures disclosed in Example 29.
  • Example 29 Using the procedure of Example 29 with 2-(2,6-dichloro-4-(pentafluoro- ⁇ 6 - sulfanyl)phenyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-J
  • Electrophiles used in the above reaction 5-bromopentanenitrile, 5-bromopentan-l-ol, l-bromo-4-methoxybutane, 4-bromobut-l-ene, l-bromopent-2-yne, 4-bromo-2-methyl-2- butene, l-bromo-2-methylpentane, l-bromo-3-(ethylsulfanyl)propane, 2-[(2- bromoethyl)sulfanyl]propane, 2-(bromomethyl)thiazole.
  • Example 32 Preparation of V-(5-(tert-butyldimethylsilyloxy)pentyl)-2-(2,6-dichloro-4- (trifluoromethyl)phenyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-amine (Compound 232)
  • Electrophiles used in the above reaction 4-chlorobutyryl chloride, dichloroacetyl chloride, isopropyl chloroformate, 3-cyanopropanoyl chloride.
  • Example 37 Preparation of V-(2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4,6- bis(trifluoromethyl)-2H-pyrazolo[3,4-rf]pyrimidin-3-yl)- V-(3,3-dimethylbutanoyl)-3,3- dimethylbutanamide (Compound 237) and V-(2-(2,6-dichloro-4- (trifluoromethyl)phenyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-rf]pyrimidin-3-yl)- 3,3-dimethylbutanamide (Compound 238).
  • Example 38 Preparation of bis-2,2,2-trichloroethyl (2-(2,6-dichloro-4- (trifluoromethyl)phenyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-rf]pyrimidin-3- yl)carbamate (Compound 239).
  • Example 42 Preparation of 4-(iodomethyl)-l,2,3-thiadiazole (1-37) Procedure adapted from Van Zandt, M.C. et. al. WO2008/033455. To a solution of imidazole (148 mg, 2.17 mmol) and I 2 (270 mg, 1.08 mmol) in dichloromethane was added
  • Compound 294 in Table 1 was made in accordance with the procedure disclosed in Example 51 using 4,6-dichloro-5-cyanopyrimidine as the starting material.
  • reaction mixture was transferred to a 60 mL separatory funnel, diluted with Et 2 0 (40 mL), washed with H 2 0 (3 x 10 mL) and then brine (10 mL).
  • the organic phase was dried (MgS0 4 ) and then dry loaded onto a silica gel (5 g) for purification by column chromatography (Hexane-EtOAc gradient; 12 g column).
  • Example 22 Mixed 2-chloro-6-((3-chlorophenyl)thio)-4- (trifluoromethyl)nicotinonitrile (119 mg, 0.307 mmol) with a solution of (2-chloro-4- (trifluoromethyl)phenyl)hydrazine (137 mg, 0.644 mmol) in dioxane (2 mL) followed by triethylamine (47 ⁇ L ⁇ , 0.336 mmol) resulted in a mixture that was heated at 95 °C for 145 h.
  • reaction mixture was transferred to a 60 mL separatory funnel, diluted with Et 2 0 (40 mL), washed with H 2 0 (3 x 10 mL) and then brine (10 mL).
  • the organic phase was dried (MgS0 4 ) and then dry loaded onto a silica gel (5 g) for purification by column chromatography (Hexane-EtOAc gradient; 12 g column).
  • Example 56 6-((3-Chlorophenyl)thio)-2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4- (trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-amine (150 mg, 0.26 mmol) was dissolved in tetrahydrofuran (20 mL) and 3-chloroperoxybenzoic acid (46 mg, 0.26 mmol) was added. The reaction mixture was heated to 50 °C for 1 h. The reaction mixture was cooled to room temperature and washed with saturated sodium bicarbonate solution (20 mL).
  • Example 56 6-((3-Chlorophenyl)thio)-2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4- (trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-amine (150 mg, 0.26 mmol) was dissolved in tetrahydrofuran (20 mL) and 3-chloroperoxybenzoic acid (114 mg, 0.65 mmol) was added. The reaction mixture was heated to 50 °C for 1 h. The reaction mixture was cooled to room temperature and washed with saturated sodium bicarbonate solution (20 mL).
  • the nucleophiles (1-3 equiv) used include: 4-(trifluoromethyl)phenol, sodium methanolate, sodium ethanolate, sodium propan-2-olate, 5-methoxypyridin-3-ol, 3,4-dimethoxyphenol, 3,5-dichlorophenol, 2-methylquinolin-6-ol.
  • Example 60 Preparation of 2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-6-(methylthio)- 4- (trifluoromethyl)-2H-pyraz -d]pyrimidin-3-amine (Compound 365)
  • the nucleophiles (1-3 equiv) used include: sodium ethanethiolate, sodium propane-2- thiolate, 2-methoxybenzenethiol with NaH (60% dispersion, 1.2 eq), 3-chlorobenzenethiol with NaH (60% dispersion, 1.2 eq).
  • the nucleophiles (10-12 equiv) used include: 6-methoxypyridin-3 -amine.
  • Compound 349 was made in accordance with the procedures disclosed in Example 61.
  • the nucleophiles (1-5 equiv) used include: 2M ammonia in THF; cyclopropanamine, 2M methanamine in THF, 2M dimethylamine in THF, 2,4-dimethoxyaniline.
  • the following compounds 350, 354, 355, 356 and 357 were made in accordance with the procedures disclosed in Example 62 above.
  • Example 65 Preparation of fert-butyl (2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4- (methylsulfonyl)-6-(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-yl)carbamate (Compound 269) and fert-butyl (2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-hydroxy- 6-(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-yl)carbamate (Compound 270).
  • Example 68 Preparation of 2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-N-(3- (ethylsulfinyl)propyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-amine (Compound 288) and 2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-N-(3-(ethylsulfonyl)- propyl)-4,6-bis(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-amine (Compound 280)
  • Compound 290 in Table 1 was made in accordance with the procedure described in Example 69 using N-(but-3-en-l-yl)-2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4,6- bis(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-amine (Compound 230) as the starting material.
  • Example 72 Preparation of fert-butyl (2-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4- (methylthio)-6-(trifluoromethyl)-2H-pyrazolo[3,4-d]pyrimidin-3-yl)carbamate
  • the primary alkynes used include: 1-propyne, 1-heptyne, ethynylbenzene, 1-ethynyl- 4-ethoxy benzene, 5-chloro-l-pentyne, 3-methoxy- 1-propyne.
  • phenyl boronic acids used include: phenylboronic acid, (2-fluoro-4- (trifluoromethyl)phenyl)boronic acid, (3,5-dimethylphenyl)boronic acid, pyridin-3-ylboronic acid, (6-(trifluoromethyl)pyridin-3-yl)boronic acid, thiazol-5-ylboronic acid, (2-fluoro-4- methoxyphenyl)boronic acid and (4-acetylphenyl)boronic acid.
  • Example 76 Preparation of 2-(2,6-dichloro-4-amidophenyl)-4,6-bis(trifluoromethyl)- 2H-pyrazolo[3,4-d]pyrimidin-3-amines
  • the primary amines used include aniline, 4-methoxyaniline, 4-trifluoromethylaniline, tetrahydro-2H-pyran-4-amine, 3-aminothietane 1 -oxide, 3-aminothietane 1,1 -dioxide, 3- methoxypropan- 1 -amine, (2-chloropyridin-4-yl)methanamine, (6-chloropyridin-3- yl)methanamine and 2,2,2-trifluoroethanamine.
  • Compounds 309, 310, 311, 318, 319, 320, 321, 322, 323 and 324 were made in accordance with the procedure disclosed in Example 76.

Abstract

L'invention concerne des compositions pesticides comprenant des molécules ayant la formule suivante (« Formule Un »), les compositions comprenant de plus un ou plusieurs composants actifs pesticides supplémentaires. L'invention concerne aussi des processus d'application de la composition pesticide sur des plantes, des graines et du sol où les plantes seront plantées. Les compositions pesticides de l'invention sont efficaces pour l'éradication des organismes nuisibles tels que le légionnaire de la betterave, le ver de l'épi de maïs et le puceron vert du pêcher.
PCT/US2013/026317 2013-02-15 2013-02-15 Compositions pesticides et processus associés à celles-ci WO2014126580A1 (fr)

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WO2016087368A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
WO2016087363A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
WO2016087421A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
WO2016087422A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
WO2017134066A1 (fr) * 2016-02-05 2017-08-10 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre
CN112679467A (zh) * 2015-03-11 2021-04-20 Fmc公司 杂环取代的二环唑杀有害生物剂
US11161850B2 (en) 2018-07-05 2021-11-02 Incyte Corporation Fused pyrazine derivatives as A2A / A2B inhibitors
US11168089B2 (en) 2018-05-18 2021-11-09 Incyte Corporation Fused pyrimidine derivatives as A2A / A2B inhibitors
US11390624B2 (en) 2019-01-29 2022-07-19 Incyte Corporation Pyrazolopyridines and triazolopyridines as A2A / A2B inhibitors
US11673894B2 (en) 2018-02-27 2023-06-13 Incyte Corporation Imidazopyrimidines and triazolopyrimidines as A2A / A2B inhibitors
US11786528B2 (en) 2018-06-04 2023-10-17 Exscientia Ltd. Pyrazolopyrimidine compounds as adenosine receptor antagonists
US11889833B2 (en) 2022-01-14 2024-02-06 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

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JP2017537915A (ja) * 2014-12-02 2017-12-21 バイエル・クロップサイエンス・アクチェンゲゼルシャフト 有害生物防除剤としての二環式化合物
WO2016087421A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
WO2016087368A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
WO2016087422A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
CN107207466B (zh) * 2014-12-02 2020-09-08 拜耳作物科学股份公司 作为害虫防治剂的双环化合物
CN107207497A (zh) * 2014-12-02 2017-09-26 拜耳作物科学股份公司 作为害虫防治剂的双环化合物
CN107207495A (zh) * 2014-12-02 2017-09-26 拜耳作物科学股份公司 作为害虫防治剂的双环化合物
CN107207466A (zh) * 2014-12-02 2017-09-26 拜耳作物科学股份公司 作为害虫防治剂的双环化合物
CN107406443A (zh) * 2014-12-02 2017-11-28 拜耳作物科学股份公司 作为有害生物防治剂的双环化合物
US10131649B2 (en) 2014-12-02 2018-11-20 Bayer Cropscience Aktiengesellschaft Bicyclic compounds as pest control agents
WO2016087363A1 (fr) * 2014-12-02 2016-06-09 Bayer Cropscience Aktiengesellschaft Composés bicycliques utilisés en tant qu'agents de lutte contre les nuisibles
JP2017537914A (ja) * 2014-12-02 2017-12-21 バイエル・クロップサイエンス・アクチェンゲゼルシャフト 有害生物防除剤としての二環式化合物
US9832999B1 (en) 2014-12-02 2017-12-05 Bayer Cropscience Aktiengesellschaft Bicyclic compounds as pest control agents
CN112679467A (zh) * 2015-03-11 2021-04-20 Fmc公司 杂环取代的二环唑杀有害生物剂
WO2017134066A1 (fr) * 2016-02-05 2017-08-10 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre
US11673894B2 (en) 2018-02-27 2023-06-13 Incyte Corporation Imidazopyrimidines and triazolopyrimidines as A2A / A2B inhibitors
US11168089B2 (en) 2018-05-18 2021-11-09 Incyte Corporation Fused pyrimidine derivatives as A2A / A2B inhibitors
US11873304B2 (en) 2018-05-18 2024-01-16 Incyte Corporation Fused pyrimidine derivatives as A2A/A2B inhibitors
US11786528B2 (en) 2018-06-04 2023-10-17 Exscientia Ltd. Pyrazolopyrimidine compounds as adenosine receptor antagonists
US11161850B2 (en) 2018-07-05 2021-11-02 Incyte Corporation Fused pyrazine derivatives as A2A / A2B inhibitors
US11390624B2 (en) 2019-01-29 2022-07-19 Incyte Corporation Pyrazolopyridines and triazolopyridines as A2A / A2B inhibitors
US11884665B2 (en) 2019-01-29 2024-01-30 Incyte Corporation Pyrazolopyridines and triazolopyridines as A2A / A2B inhibitors
US11889833B2 (en) 2022-01-14 2024-02-06 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

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