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    pesticide compositions. The present invention relates to novel heteroaryl-n-aryl thiosemicarbazones and their uses in pest control, such as insecticides and acaricides. The present invention further relates to the preparation of pesticidal compositions containing the compounds and to insect control methods using the compounds.
    公开号:BR112012002676B1
    申请号:R112012002676-3
    申请日:2010-08-05
    公开日:2018-02-06
    发明作者:Brown Annette；Crouse Gary；Sparks Thomas；Mcleod Casandra；Rigsbee Emily；Lambert William；Niyaz Noormohamed
    申请人:Dow Agrosciences Llc；
    IPC主号:
    专利说明:

    (54) Title: MOLECULES, PROCESSES FOR ITS APPLICATION, AND COMPOSITION (51) Int.CI .: A01N 43/64 (30) Unionist Priority: 07/08/2009 US 61 / 232,152 (73) Holder (s): DOW AGROSCIENCES LLC (72) Inventor (s): ANNETTE BROWN; GARY CROUSE; THOMAS SPARKS; CASANDRA MCLEOD; EMILY RIGSBEE; WILLIAM LAMBERT; NOORMOHAMED NIYAZ
    1/109
    Descriptive Report of the Invention Patent for MOLECULES, PROCESSES FOR ITS APPLICATION, AND COMPOSITION.
    FIELD OF THE PRESENT INVENTION
    This patent application claims the benefit of the United States Provisional Pa5 trial Serial Number 61 / 232,152, filed on August 7, 2009, the entire contents of which are incorporated into the present invention by reference. The present invention relates to the field of pesticides and their use in pest control.
    BACKGROUND OF THE INVENTION
    Pests cause millions of human deaths worldwide each year. In addition, there are more than ten thousand species of pests that cause damage to agriculture. These agricultural losses mean billions of dollars for the United States of America each year. Termites damage various structures, such as houses. These termites cause damage that means billions of dollars in losses to the United States of America each year. As a final note, many stored food pests eat and adulterate stored food. These stored foods mean billions of dollars in losses to the United States of America each year, but more importantly, they deprive people of the necessary foods.
    There is an urgent need for new pesticides. Insects are developing resistance to the pesticides used today. Hundreds of insect species are resistant to one or more pesticides. The development of resistance to some of the oldest pesticides, such as
    DDT, carbamates and organophosates, is well known. But resistance has even developed some of the more recent pesticides. Therefore, there is a need for new pesticides and particularly for pesticides that have new modes of action.
    SUBSTITUTES (NON-EXHAUSTIVE LIST)
    The examples given for the substituents are (except halo) not exhaustive and should not be construed as limiting the present invention described in this document.
    Petition 870170071853, of September 25, 2017, p. 5/28
    2/109 alkenyl means an acyclic substituent, unsaturated (at least one carbon - carbon double bond), branched or unbranched, consisting of carbon and hydrogen, for example, vinyl, ally, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl.
    alkenyloxy means an additional alkenyl consisting of a single carbon-oxygen bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy, nonenyloxy, and decenyloxy.
    alkoxy means additional alkyl consisting of a single carbon-oxygen bond, for example, methoxy, ethoxy, propoxy, isopropoxy, 1-butoxy, 2-butoxy, isobutoxy, ether-butoxy, pentoxy, 2-methylabutoxy, 1,1dimethylpropoxy, hexoxy , heptoxy, octoxy, nonoxy, and decoxy.
    alkyl means an acyclic substituent, saturated, branched or unbranched, consisting of carbon and hydrogen, for example, methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, ether-butyl, pentyl, 2methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl.
    alkynyl means an acyclic substituent, unsaturated (at least one carbon-carbon triple bond, and any double bond), branched or unbranched, consisting of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptinyl, octinyl, noninyl, and decinyl.
    alkynyloxy means an additional alkynyl consisting of a single carbon-oxygen bond, for example, pentynyloxy, hexynyloxy, heptinyloxy, octinyloxy, noninyloxy, and decinyloxy.
    aryl means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl.
    cycloalkenyl means an unsaturated monocyclic or polycyclic substituent (at least one carbon - carbon double bond) consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, norbornenyl, bicyclo [2.2.2] octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.
    cycloalkenyloxy means an additional cycloalkenyl consisting of a single carbon-oxygen bond, for example, cyclobutenyloxy, cyclopentenyloxy, cyclohexenyloxy, cycloheptenyloxy, cyclooctenyloxy, cyclodece3 / 109 niloxy, norbornenyloxy, and bicyclo [2.2.2] octenyl
    cycloalkyl means a monocyclic or polycyclic substituent, saturated consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, bicycle [2.2.2] octyl, and deca -hydronaftila.
    cycloalkoxy means an additional cycloalkyl consisting of a single carbon-oxygen bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy, norbornyloxy, and cyclo [2.2.2] octyloxy.
    halo means fluorine, chlorine, bromine, and iodine.
    haloalkyl means additional alkyl consisting of, from one to the maximum possible number, identical or different, for example, halos, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoromethyl, 2fluorethyl, 2,2,2-trifluorethyl, chloromethyl, trichloromethyl , and 1,1,2,2-tetrafluorethyl.
    heterocyclyl means a cyclic substituent that can be fully saturated, partially unsaturated, or totally unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen, for example, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, 1,3,4-oxazazolyl, 1,3,4-oxazazolyl , pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, 1,2,3,4tetrazolyl, thiazolinyl, thiazolyl, thienyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5triazinyl, 1 , 2,3-triazolyl, and 1,2,4-triazolyl.
    DETAILED DESCRIPTION OF THE PRESENT INVENTION
    The compounds of the present invention have the following formula:
    on what:
    4/109 (a) Ar is (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl, or (2) substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl, where said substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl, has one or more substituents independently selected from H, F, Cl, Br, I, CN, NO2, C1-C6 alkyl, Ci-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocicloalquila, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C1-C6 alkoxy, C ^ Ce haloalkoxy, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, S (= O) n (C 1 -C 6 alkyl), S (= O) n (C 1 -C 6 haloalkyl), OSO 2 (C 1 -C 6 alkyl), OSO 2 (C 1 -C 6 haloalkyl), C (= O) NR x R y , (C 1 -C 6 alkyl) NR x R y , C (= O) (C 1 -C 6 alkyl), C (= O) O (C 1 -C 6 alkyl), C (= O) (C 1 -C 6 haloalkyl), C (= O) O (C 1 -C 6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C3-C 6 cycloalkyl), C (= O) ( C 2 -C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (CrC 6 alkyl) O (C 1 -C 6 alkyl), (C 1 -C 6 alkyl) S (C 1 -C 6 alkyl), 0 (= 0) (0 ^ 06 alkyl) C (= O) O (C 1 -C 6 alkyl), phenyl, phenoxy, substituted phenyl, and substituted phenoxy, wherein such substituted phenyl and substituted phenoxy has one or more substituents selected independently from H, F, Cl, Br, I, CN, NO2, Ci-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocicloalquila, C3 -C6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, C1-C6 alkoxy, C1-C6 haloalkoxy, C 2 -C6 alkenyl, C 2 -C 6 alkynyl, S (= O) n (C 1 -C 6 alkyl), S (= O) n ( -C6 haloalkyl), OSO 2 (-C6 alkyl), OSO 2 (C-C6 haloalkyl), C (= O) NR x R y, (Ci-C6 alkyl) NR x R y, C (= O) (Ci-C 6 alkyl), C (= O) O (Ci-C 6 alkyl), C (= O) (CiC 6 haloalkyl), C (= O) O (Ci-C 6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C3-C6 cycloalkyl), C (= O) (C 2 -C6 alkenyl), C (= O) O (C 2 -C 6 alkenyl ), (Ci-C 6 alkyl) O (Ci-C 6 alkyl), (Ci-C 6 alkyl) S (Ci-C 6 alkyl), C (= O ) (C 1 -C 6 alkyl) C (= O) O (C 1 -C 6 alkyl) phenyl, and phenoxy;
    (b) Het is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing one or more heteroatoms independently selected from nitrogen, sulfur, or oxygen, and where Αη and Ar 2 are not ortho for each one (but it can be goal or for, like, for
    5/109 a five-membered ring they are 1,3 and for a 6-membered ring they are both 1,3 and 1,4), and where said heterocyclic ring can also be replaced with one or more substituents selected from independently from H, OH, F, Cl, Br, I, CN, NO2, oxo, Ci-C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocicloalquila C 3 -C 6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, C ^ C alkoxy, C-C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, S (= O) n (Ci-C 6 alkyl ), S (= O) n (C 1 -C 6 haloalkyl), OSO 2 (C r C 6 alkyl), OSO 2 (C-C 6 haloalkyl), C (= O) NR x R y , (Ci- C 6 alkyl) NR x R y , C (= O) (C 1 -C 6 alkyl), 0 (= 0) 0 (0 ^ 6 alkyl), 0 (= 0) (^ - 06 haloalkyl), C (= O) O (C ^ -C 6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= 0) 0 (C 3 -C 6 cycloalkyl), C (= O) (C 2 C 6 alkenyl), C (= 0) 0 (C 2 -C 6 alkenyl), (C 1 -C 6 alkyl) O (C 1 -C 6 alkyl), (C 1 -C 6 alkyl) S (C 1 -C 6 alkyl) , C (= O) (C 1 -C 6 alkyl) C (= O) O (C 1 -C 6 alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy in which such substituted phenyl and substituted phenoxy has one or more substituents independently selected from H, F, Cl, Br, I, CN, NO 2 , CrCe alkyl, Ci-C 6 haloalkyl, C 3 - C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, C-C 6 alkoxy, C ^ Ce haloalkoxy, C 2 -C6 alkenyl, C 2 -C6 alkynyl, S ( = O) n (Ci-C 6 alkyl), S (= O) n (C r C 6 haloalkyl), OSO 2 (Ci-C 6 alkyl), OSO 2 (Ci-C 6 haloalkyl), C (= O ) H, C (= O) NR x R y , (C 1 -C 6 alkyl) NR x R y , C (= O) (C 1 -C 6 alkyl), C (= O) O (Cd-C 6 alkyl) ), C (= O) (C 1 -C 6 haloalkyl), C (= O) O (C 1 -C 6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O ( C 3 -C 6 cycloalkyl), C (= O) (C 2 -C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (C 1 -C 6 alkylJOÍC-i-Ce alkyl), (Ci-C6 alkyl) O (Ci-C6 alkyl), C (= O) (Ci-C6 alkyl) C (= O) O (Ci-C6 alkyl), phenyl, and phenoxy;
    (c) Ar 2 is (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl, or (2) substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl, in which said substituted furanyl , substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl, has one or more substituents independently selected from H, F, Cl, Br, I, CN, NO 2 , Ci-C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl / 109 la, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, Ci-C 6 alkoxy, CrC 6 haloalkoxy, C 2 - C 6 alkenyl, C 2 -C 6 alkynyl, S (= O) n (Ci-C 6 alkyl), SGCOníCb-Ce haloalkyl), OSO 2 (Ci-C 6 alkyl), OSO 2 (Ci-C 6 haloalkyl) , C (= O) NR x R y , (CrCs alkyl) NR x R y , C (= O) (C 1 -C 6 alkyl), C (= O) O (C 1 -C 6 alkyl), C (= O) (C 1 -C 6 haloalkyl), C (= O) O (C 1 -C 6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C 3 -C 6 cycle here la), C (= O) (C 2 -C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (CrC 6 alkyl) O (C 1 -C 6 alkyl), (CrCe alkyl) S (CiC 6 alkyl), C (= O) (Ci-C 6 alkyl) C (= O) O (Ci-C 6 alkyl), phenyl, phenoxy, substituted phenyl and substituted phenoxy in which such substituted phenyl and substituted phenoxy It has one or more substituents independently selected from H, F, Cl, Br, I, CN, NO2, Ci-C6 alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 hydroxycycloalkyl, C 3 -C 6 cycloalkoxy, C 3 -C6 halocycloalkoxy, Ci-C 6 alkoxy, Ci-C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, S (= O) n (C 1 -C 6 alkyl), S (= O) n (C 1 -C 6 haloalkyl), OSO 2 (C 1 -C 6 alkyl), OSO 2 (C 1 -C 6 haloalkyl), C (= O) H , C (= O) NR x R y , (C 1 -C 6 alkyl) NR x R y , C (= O) (C 1 -C 6 alkyl), C (= O) O (C 1 -C 6 alkyl), C (= O) (C1-C 6 haloalkyl), C (= O) O (CrC6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C 3 -C 6 cycloalkyl), C (= O) (C 1 -C 6 haloalkyl), C (= O) (C 2 -C 6 alkenyl), C (= O) O (C 2 - C 6 alkenyl), (C 1 -C 6 alkyl) O (C 1 -C 6 alkyl), (C 1 -C 6 alkyl) S (C- | C 6 alkyl), C (= O) (CrC 6 alkyl) C (= O) O (C 1 -C 6 alkyl), phenyl, and phenoxy);
    (d) X is O or S;
    (e) R1 is selected from H, CN, Ci-C 6 alkyl, Ci-Cô haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C 6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, Ci-C 6 alkoxy, Ci-C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, S (= O) n (Ci-C 6 alkyl), S (= O) n (Ci -C 6 haloalkyl), OSO 2 (C 1 -C 6 alkyl), OSO 2 (C 1 -C 6 haloalkyl), C (= O) NR x R y , (C ^ Ce alkyl) NR x R y , C (= O) (Ci-C6 alkyl), C (= O) O (Ci-C6 alkyl), C (= O) (C 1 -C 6 haloalkyl), C (= O) O (Ci-C6 haloalkyl ), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C 3 -C 6 cycloalkyl), C (= O) (C 2 C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (C 1 -C 6 alkyl) O (C 1 -C 6 alkyl), (C 1 -C 6 alkyl) S (C 1 -C 6 alkyl), C (= O) (C 1 - C 6 alkyl) C (= O) O (C 1 -C 6 alkyl), phenyl, phenoxy;
    7/109 (f) R2, R3 and R4 are independently selected from H, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C ( = O) (C 1 -C 6 alkyl), C (= O) O (C 1 -C 6 alkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C 3 -C 6 cycloalkyl) ), C (= O) (C 2 -C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (C- | -C 6 alkyl) O (C 1 -C 6 alkyl), (Ci -C 6 alkyl) S (CrC 6 alkyl), C (= O) (C 1 -C 6 alkyl) C (= O) O (C 1 -C 6 alkyl), C (= O) phenyl, phenyl, C 1 -C 6 alkylphenyl, C 1 -C 6 alkylphenoxy, indanyl, C (= O) Het-1, Het-1, (C 4 -Ce alkyl) Het-1, or C 1 -C 6 alkylO-Het-1, where each alkyl, cycloalkyl, cycloalkoxy, halocycloalkoxy, alkoxy, haloalkoxy, alkenyl, alkynyl, C- | -C 6 alkylphenyl, phenyl, phenoxy, and Het-1, are optionally substituted with one or more substituents independently selected from F, Cl, Br, I, CN, NO 2 , NR x R y , Ci-C 6 alkyl, Ci-C 6 haloalkyl, C 3 -C6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 3 -C6 cycloalkoxy, C 3 - C 6 halocycloalkoxy, C alkoxy rCg, C1-C6 haloalkoxy, C 2 -C6 alkenyl, C 3 -C 6 cycloalkenyl, C 2 -C6 alkynyl, C 3 -C 6 cycloalkynyl, S (= O) n (CiC 6 alkyl), S (= O ) n (C 1 -C 6 haloalkyl), S (= O) 2 N (C 1 -C 6 alkyl) 2 , OSO 2 (C 1 -C 6 alkyl), OSO 2 (C 1 -C 6 haloalkyl), C (= O) H, C (= O) NR x R y , (C 1 -C 6 alkyl) NR x R y , C (= O) (C 1 -C 6 alkyl), C (= O) O (C 1 -C 6 alkyl), C (= O) (C 1 -C 6 haloalkyl), C (= O) O (C 1 -C 6 haloalkyl), C (= O) (C 3 -C 6 cycloalkyl), C (= O) O (C 3 -C 6 cycloalkyl) ), C (= O) (C 2 -C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (C 1 -C 6 alkyl) O (C 1 -C 6 alkyl), (Ci- C 6 alkyl) S (C 1 -C 6 alkyl), C (= O) (C 1 -C 6 alkyl) C (= O) O (C 1 -C 6 alkyl), phenyl, phenoxy, O-Het-1, and Het -1, where Het-1 is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing one or more heteroatoms independently selected from nitrogen, sulfur or oxygen,
    R3 and R4 together where it can optionally form a cyclic group, saturated or unsaturated, with 3 to 8 members that can contain one or more heteroatoms selected from nitrogen, sulfur and oxygen;
    (g) n = 0, 1 or 2;
    (h) R x and R y are independently selected from H, Ci-C 6 alkyl, Ci-Ce haloalkyl, C 3 -C6 cycloalkyl, C 3 -C6 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C6 alkynyl, S (= O) n (C 1 -C 6 alkyl), S (= O) n (C 1 -C 6
    8/109 haloalkyl), OSO 2 (C 1 -C 6 alkyl), OSO 2 (CrC 6 haloalkyl), C (= O) H, 0 (= 0) ((^ - 06 alkyl), C (= O) O ( Ci-C6 alkyl), C (= O) (Ci-C6 haloalkyl), C (= O) O (Ci-C6 haloalkyl), C (= O) (C3-C6 cycloalkyl), C (= O) O (C 3 -C 6 cycloalkyl), C (= O) (C 2 -C 6 alkenyl), C (= O) O (C 2 -C 6 alkenyl), (C 1 -C 6 alkyl) O (CiC 6 alkyl), (C- | -C 6 alkyl) S (C 1-6 alkyl), C (= O) (C 1-6 alkyl) C (= O) O (C 1-6 alkyl), and phenyl.
    In another embodiment, Ar 1 is a substituted phenyl wherein said substituted phenyl has one or more substituents independently selected from Ci-C6 alkyl, Ci-C6 haloalkyl, and Ci-C6 haloalkoxy. In a more preferred embodiment, Αη is a substituted phenyl in which said substituted phenyl has one or more substituents independently selected from OCF 3 , OCF 2 CF 3 , CF 3 ,
    In another modality, Het is triazolyl, imidazolyl, pyrrolyl, or pyrazolyl.
    In another embodiment, Het is a substituted pyrazolyl in which said substituted pyrazolyl has one or more substituents selected independently from H, C (= O) O (C 1 -C 6 alkyl), or C (= O) NR x R y .
    In another embodiment, Ar 2 is phenyl.
    In another embodiment, R1 is H or a Ci-Οβ alkyl.
    In another embodiment, R2 is H or a Ci-Οθ alkyl.
    In another mode, R3 is H.
    In another mode, X is S.
    In another embodiment, R4 is a Οι-Οβ alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C (= O) phenyl, Ci-C 6 alkylphenyl, Het-1, or (Ci-C 6 alkyl) Het-1.
    In another embodiment, R4 is an Οι-Οθ alkyl, Ci-Οβ alkylphenyl, phenyl, or Het-1, where each is substituted with one or more substituents independently selected from F, Cl, Br, I , CN, NO 2 , NR x R y , Ci-C 6 alkyl, haloalkyl, Ci-C 6 alkoxy, Ci-C 6 haloalkoxy, C 3 -C 6 cycloalkenyl, S (= O) n (Ci-C 6 alkyl ), S (= O) n (C 1 -C 6 haloalkyl), S (= O) 2 N (C 1 -C 6 alkyl) 2 , C (= O) (C 1 -C 6 alkyl), C (= O) O (C 1 -C 6 alkyl),
    9/109
    C (= O) (C- | -C 6 haloalkyl), (C1-C6 alkyl) O (C1-C6 alkyl), phenyl, O-Het-1, and Het-1.
    Although these modalities have been expressed, other modalities and combinations of these modalities and other expressed modalities are possible.
    PREPARATION OF TRIARILLA INTERMEDIARIES
    The compounds of the present invention can be prepared by making a triaryl intermediate, ARi-Het-AR 2 , and then linking it to the desired intermediate to form the desired compound. A wide variety of triaryl intermediates can be used to prepare the compounds of the present invention, provided that such triaryl intermediates contain a suitable functional group in AR 2 so that the rest of the desired intermediate can be attached. Suitable functional groups include an oxoalkyl or a formyl group. These triaryl intermediates can be prepared using methods previously described in the chemical literature. Several of these methods are described below.
    Intermediates in which Het is a disubstituted pyridine, pyrimidine, pyrazine or pyridizine can be made by coupling a haloalkyl substituted pyridine, pyrazine or pyrimidine with an aryl boronic acid or borate ester, under Suzuki arylation conditions. See, for example, the following.
    For pyridines: Cabbage-Bonnaire and others. Tetrahedron 2003, 59, 2793 and Puglisi et al. Eur. J. Org. Chem. 2003, 1552.
    For pyrazines: Schulteiss and Bosch Heterocicles 2003, 60, 1891.
    For pyrimidines: Qing and others. J. Fluorine Chem. 2003, 120, 21 and Ceide and Montalban Tetrahedron Lett. 2006, 47, 4415.
    For 2,4-diaryl pyrimidines: Schomaker and Delia, J. Org.Chem. 2001, 66, 7125.
    In this way, successive arylations of catalyzed palladium, using 4-formylphenyl boronic acid and 4-trifluormethoxyphenyl boronic acid, can virtually generate any particular substitution pattern, as shown in the scheme below:
    10/109
    (WO 2007003604)
    Conditions: a) 4-trifluormethoxyphenyl boronic acid b) 4-formylphenylboronic acid

    Similarly, diaryl pyridines and pyrazines and other aromatic, heterocyclic, dihalogenated compounds can be prepared from dihalogenated pyridines and pyrazines and other aromatic, heterocyclic, dihalogenated compounds using the same protocol:
    10/119
    (EJC2003, 8. 1152-1558)
    Conditions: a) 4-trifluormethoxyphenyl boronic acid b) 4-formylphenylboronic acid
    The halo- or alkylathiopyrimidine and pyridine precursors are both commercially available, and can be synthesized by means of routes described in the literature (Rorig and Wagner, US patent 3,149,109, 1964; Kreutzberger andTesch Arzneim.-Forsch. 1978, 28, 235).
    Intermediate compounds in which 'Het' is a 1,3,4-substituted 1,2,4-triazole can be prepared according to one of the following schemes.
    Route A: 1,3-Diaryl 1,2,4-triazoles were prepared for the corresponding -NH 3aryl 1,2,4-triazoles using the following published route for N-arylation of imidazoles (Lin et al. J. Org Chem. 1979, 44, 4160). The coupling of 1,2,4-triazoles to the aryl halides was done under thermal conditions or, preferably, Microwave (Antilla et al. J. Org. Chem. 2004, 69, 5578). (DIBAL is diisobutylaluminum hydride.)
    10/129
    CN
    H 2 NOC ^ //
    I.Br.F]
    1.DMF-DMA, 100 ° C. 3 am
    2. H 2 NNH 2 AcOH, 80 ° C, 30 min
    1. Cs 2 CO 3 , Cul 8-hydroxyquinoline dmf / h 2 o 150 ° C, 30 min Microwave
    NN / =
    CN
    Or
    1. NaH. DMSO (Where R is superimposed electron)
    2. DIBAL, CH 2 CI 2
    R
    Route B: Hydrazone bromination followed by treatment of bromohydrazone with tetrazole results in the formation of 1,3-diaryl 1,2,4-triazole (Butler and Fitzgerald J. Chem. Soc., Perkin Trans. 1 1988, 1587 ).
    R

    CN
    1. NBS
    2. tetrazole. EtOH
    3. DIBAL, CH 2 CI 2
    The compounds where 'Het' is an imidazole can be prepared according to one of the following schemes:
    Route A (Step 1: Linch et al. J. Am. Chem. Soc. 1994, 116, 11030. Step 2: Liu et al. J. Org. Chem. 2005, 70, 10135):
    Rr H 2 NCOH r | Rrl
    160 »C.4h OAC / CN
    1. Cs 2 CO 3
    Cul, 8-hydroxyquinoline
    -> bdmf / h 2 o
    150 ° C, 30 min, microwave
    2. DIBAL, CH 2 CI 2
    Route B. For halo-aryl groups which also contain an activation group such as nitro or cyano, displacement of an aryl halide with an imidazole, using a base such as potassium carbonate in a polar aprotic solvent, such as A /, A / -dimethylformamide (DMF) or sulfoxy13 / 109 of dimethyl (DMSO), can be achieved as follows (Bouchet et al. Tetrahedron 1979, 35, 1331):
    Via C: Following the first procedure described by Porretta et al. (Pharmaco, Edizione Scientifíca 1985, 40, 404), a / V-phenacyl aniline is treated with potassium thiocyanate in an acidic medium (HCI), and the resulting imidazole 2mercapto is then converted to a diary imidazole by treatment with acid nitric acid in acetic acid.
    CN
    KSCN, HCI
    CN
    1. HNO 3 , AcOH
    Ν ~ ξ 2. DIBAL, CH 2 CI 2 SH
    N ^
    Route D. N-Arylation of 4-bromoimidazole under Microwave irradiation conditions (Route A, Step 2) equipping the intermediate 1-aryl-410 bromoimidazole, which was converted into triaryl intermediates by means of an acid treatment boronic aryls under palladium catalyzed conditions.
    cf 3 o + Ar-B (OR) 2
    Br
    8-hydroxyquinoline (10%) Cul (10%), Cs 2 CO 3
    DMF-H 2 O (10: 1)
    130 ° C, 4 hours or microwave 150 ° C, 30 min
    CF 3 O
    Br
    Bis (triphenylphosphine) palladium (II) dichloride
    Or
    Tetrakis (triphenylphosphine) Pd cf 3 oA4
    NaHCO 3 or KjCC ^
    DME / H 2 O (1: 1) Or microwave dioxane 20-30 min, 100-190 ° C
    10/149
    Compounds where ‘Het’ is a 1,4,3-disubstituted 1,2,3-triazole can be prepared according to the following scheme (Feldman et al. Org Lett. 2004, 6, 3897):
    1. NaN 3 CuS0 4 Na 2 S0 4 | -proline sodium ascorbate
    DMSO, 65 ° C, 24 h
    N ~ N
    2. DIBAL, CH 2 CI 2

    Compounds where ‘Het’ is a 3,5,4-disubstituted 1,2,4-triazole can be prepared according to the following scheme (Yeung et al. Tetrahedron Lett. 2005, 46, 3429):
    iW n-BuOH 150 ° C, 30 min microwave 2. DIBAL, CH 2 CI 2
    X
    N-N
    Compounds where 'Het' is a 1,2,4-substituted 1,2,4-triazolin-5-one can be prepared according to the following scheme (Pirrung eTepper J. Org. Chem. 1995, 60, 2461 and Liga Synt. Commun. 1986, 16, 163). (DPPA is diphenyl phosphoryl azide.):
    + x
    HCI
    Compounds where ‘Het’ is a 1,3-diaryl pyrazoline can be prepared according to the following scheme. The terephthalaldehyde monohydrazone is treated with / V-chlorosuccinimide (NCS) in isopropyl alcohol (/ PrOH), and the resulting chlorohydrazone intermediate is treated, directly, with the base and a substituted olfine to generate the pyrazoline:
    10/159
    Compounds where ‘Het’ is a 3,5-disubstituted isoxazole can be prepared according to the following scheme:
    Compounds where 'Het' is a 1,3-disubstituted pyrazole can be prepared according to the following scheme. The coupling of pyrazole to aromatic halogenates was achieved by means of the microwave conditions described by Liu et al., Via A, Step 2 above. (DMA is dimethyl acetal.)
    150-190 'C, 30 min Microwave 2. DIBAL, CH 2 CI 2
    Compounds where 'Het' is a 1,4-disubstituted pyrazole can be prepared according to the following scheme. 4- Bromopyrazole is first coupled with an iodophenyl analog, and the resulting 1-aryl-4-bromopyrazole is
    16/109 then coupled with a phenylboronic acid using the conditions described above for arylation of imidazoles.
    dioxane
    150 ° C
    CHO
    Compounds where 'Het' is a 2,4-disubstituted thiazole are prepared by condensing a thioamide to an α-halo acetophenone in a solvent such as ethanol (for example, Potts and Marshall J. Org. Chem. 1976, 41 , 129).
    s
    1. EtOH, Rt Ar - <
    N
    Br
    2. DIBAL, CH, CI 9 CN
    CHO
    Compounds where ‘Het’ is a 2,4-disubstituted oxazoline are prepared starting from α-bromoacetophenone according to the following scheme (Periasamy et al. Syntesis 2003,
    1965 and Liu et al. J.
    Am. Chem. Soc. 2007, 129, 5834).
    Not AC
    TBAB
    ° C, 3 h
    MeONH 3 CI
    Not AC
    80 ° C EtOH, 3 h
    Et 3 N, PS-PPh 3
    Compounds where ‘Het’ is a 2,5-disubstituted oxazoline are
    17/109 prepared according to the following scheme (Favretto et al. Tetrahedron Lett. 2002, 43, 2581 and Liu et al. J. Am. Chem. Soc. 2007, 729, 5834):
    O
    Compounds where 'Het' is a 3,5-disubstituted 1,2,4-triazine 5 are prepared according to the following scheme (Reid et al. Bioorg. Med. Chem. Lett. 2008, 18, 2455 and Saraswati and Srinivasan Tetrahedron Lett.
    1971, 2315):
    PREPARATION OF HYDRAZONE-CONNECTED COMPOUNDS
    Hydrazone-linked compounds can be prepared from the corresponding aryl aldehydes or ketones by one of three methods: (A) by reaction with hydrazine, followed by reaction with an aryl isothiocyanate in tetrahydrofuran ( THF), at temperatures between 0 and 100 ° C; (B) by reaction with methyl hydrazinacarbodithioate, followed by reaction with an amine in a polar aprotic solvent such as DMF, at temperatures between 25 and 150 ° C, or (C) by
    18/109 means of reaction with an alkyl or aryl semicarbazide or thiosemicarbazide, which is both commercially available and can be prepared by someone skilled in the art, in a polar protic solvent such as ethyl alcohol (ethanol), at temperatures between 0 and 100 ° C.
    O 1. R2NHNH, R2
    A, 'R4
    Het
    Air <-Ar.
    2. R4-NCS, THF, 65 ° C
    Het / N N,
    Air / Air 2 N
    Het
    Air / -Ar,
    H, r <X „R4 2 NN ι ι R2 R3
    Η, Ν, or „R4
    R1 R2 R3
    I 1 1
    Het JT, ΓΤ
    R2 R3 Air / Air, X '“R4
    EtOH, 80 ° C
    X
    X = O OR S
    EXAMPLES
    The examples are for illustrative purposes and are not to be construed as limiting the present invention described only to the modalities described in these examples.
    The starting materials, reagents and solvents that were obtained from commercial sources were used without further purification. Anhydrous solvents were purchased as Claro / Seal ™ from Aldrich and were used as received. Melting points were obtained on a Hopor Tomas Unimelt capillary melting point device or an OptiMelt Automated Melting Point System from Sanford Research and have not been corrected.
    Step 1. 1- (4-Trifluoromethoxyphenyl) -1W-pyrrole. The compound was prepared according to Colotta et al. J. Med. Chem. 2006, 49, 6015.
    10/199
    A solution of 4-trifluoromethoxyphenyl amine (500 milligrams (mg), 2.82 millimols (mmol), 1.00 equivalent (eq)) and 2.5-diethoxy tetrahydrofuran (452 mg, 2.82 mmols, 1.00 eq ) in a glacial acetic acid (20 milliliters (mL)) was heated to 90 ° C for 1 hour (h) before being dried with silica gel. The residue was then suspended in a reflux hexane, filtered hot, and concentrated to dryness to generate the desired intermediate (519 mg, 81%).
    Step 2. 3-Bromo-1- (4-trifluoromethoxyphenyl) -1H-pyrrole. The compound was prepared according to Bray et al. J. Org. Chem. 1990, 55, 6317. A A solution of 1- (4-trifluoromethoxyphenyl) -1 / 7-pyrrole (519 mg, 2.29 mmol, 1.00 eq) in THF (250 mL) at -78 ° C was added A solution of 0.05 M / V-bromosuccinimide (NBS; 408 mg, 2.29 mmol, 1.00 eq) in THF for 45 minutes (min). The vessel was slowly warmed to room temperature before the concentration generated the crude bromopyrrole, which was shown to consist of 55% of the desired intermediate by means of GC-MS. The material was used in the subsequent reaction without further purification.
    Step 3. 4- [1- (4-Trifluoromethoxyphenyl) -1 / 7-pyrrol-3-ylbenzaldehyde. A suspension of crude 3-bromo-1- (4-trifluoromethoxyphenyl) -1H-pyrrole (356 mg, 1.26 mmol, 1.00 eq), 4-formylphenylboronic acid (283 mg, 1.89 mmol, 1.50 eq), bis (triphenylphosphine) palladium (ll) dichloride (27 mg, 0.04 mmol, 0.03 eq), 2 M Na 2 CO 3 (aq) (1.26 mL, 2.52 mmol, 2 , 0 eq), and 1,4dioxane (5 mL) were heated to 150 ° C in a microwave reaction vessel for 45 min. A cooled solution was then diluted with EtOAc (20 mL), filtered with Celite®, concentrated to dryness, and purified by chromatography (2: 2: 1, hexane: EtOAc: acetone) to generate the intermediate desired (79 mg, 21%).
    Example 2: Preparation of 4- [1- (4-trifluoromethoxyphenyl) -4,5-dihydro-1H-pyrazol-3-yl] -benzaldehyde.
    Step 1. 1- (4-Trifluoromethoxyphenyl) -pyrazolidin-3-one: The compound was prepared according to Rees and Tsoi Chem. Commun. 2000, 415.
    10/20
    A suspension of (4-trifluoromethoxyphenyl) -hydrazine hydrochloride (300 mg, 1.32 mmol, 1.00 eq), 3-chloropropionyl chloride (167 mg, 1.32 mmol, 1.00 eq), and PS-DIEA (1, 30 grams (g), 5.28 mmols, 4.00 eq) in THF (20 ml) was stirred at room temperature 12 h. A solution was then stirred, concentrated to dryness, and purified by means of chromatography (2: 2: 1, hexane: EtOAc: acetone) in order to generate the desired intermediate (120 mg, 37%).
    Step 2. 3-Chloro-1- (4-trifluoromethoxyphenyl) -4,5-dihydro-1Hpyazole: The general procedure was taken from Wang et al. Tetrahedron Lett. 2005, 46, 2631. A A solution of 1- (4-trifluoromethoxyphenyl) pyrazolidin-3-one (120 mg, 0.49 mmol, 1.00 eq) in toluene (20 mL) was slowly added to phosphoryl chloride (22 , 5 mg, 1.47 mmol, 3.00 eq). The mixture was then heated to 80 ° C for 1 h before cooling to room temperature and quenched with H 2 O (10 mL). The vessel was stirred under a nitrogen atmosphere (N 2 ) for 8 h before the product was extracted in EtOAc (200 ml), dried (MgSO 4 ), and concentrated under reduced pressure. GCMS provided 88% of the desired intermediate formation, which was used in the subsequent reaction without further purification.
    Step 3. 4- [1- (4-Trifluoromethoxyphenyl) -4,5-dihydro-1H-pyrazol3-yl] -benzaldehyde: A suspension of 3-chloro-1- (4-trifluoromethoxyphenyl) -4,5di- hydro-1H-pyrazole (114 mg, 0.43 mmol, 1.00 eq), 4-formylphenylboronic acid (97 mg, 0.65 mmol, 1.50 eq), bis (triphenylphosphine) palladium (ll) dichloride (10 mg, 0 , 01 mmol, 0.03 eq), 2 M Na 2 CO 3 (aq) (0.43 mL, 0.86 mmol, 2.0 eq), and 1.4 dixane (5 mL) were heated to 150 ° C in a microwave reaction vessel for 45 min. A cooled solution was then diluted with EtOAc (20 mL), filtered with Celite®, concentrated to dryness, and purified by chromatography (2: 2: 1, hexane: EtOAc: acetone) to generate the intermediate desired (50 mg, 0.15 mmol, 31%).
    Example 3: Preparation of 4- [1- (4-trifluoromethoxyphenyl) -1Hpyrazol-4-yl] -benzaldehyde
    10/21
    Step 1. 4-Bromo-1- (4-trifluoromethoxyphenyl) -1H-pyrazole. 4 Bromopyrazole (1.5 g, 10 mmols) and 4-iodotrifluoromethoxybenzene (3.0 g, 10.3 mmol) were stirred with DMF (8 mL) and treated with potassium phosphate (6.3 g, 30 mmols) and Cul (0.5 g, 2.6 mmols). A solution was stirred and heated to 130 ° C for 30 min, then it was cooled to room temperature and poured into 1 N NH 4 OH (50 mL). The solid precipitate was isolated by filtration, redissolved in ether, filtered and concentrated to a brown solid. Recrystallization from EtOH gave an off-white solid (2.1 g): mp 63-65 ° C; LCMS 308.6 (M + 1).
    Step 2. 4- [1- (4-Trifluoromethoxyphenyl) -1H-pyrazol-4-yl] - benzaldehyde. A suspension of bromopyrazole (0.31 g, 1 mmol) and 4formylboronic acid (0.15 g, 1 mmol), 2 M aqueous potassium carbonate solution (1 mL), and tetrakis (triphenyphosphine) -paladium (0) (35 mg, cat) in dioxane (6 mL) was heated to 150 ° C in a microwave reactor. The residue was then concentrated in vacuo and purified by chromatography (ΟΙ 00% EtOAc-hexanes) to give the title compound (175 mg) as a brown solid: mp 107-109 ° C; LCMS 332.8 (M + 1).
    Example 4: Preparation of 4- [5- (4-propylphenyl) -isoxazol-3-yl] benzaldehyde.
    Ο-Ν
    Step 1. 4- (Hydroxy-iminomethyl) -benzonitrile. The compost was prepared according to Biasotti et al. Bioorg. Med. Chem. 2003, 11, 2247. A suspension of 4-formylbenzonitrile (500 mg, 3.81 mmols, 1.00 eq), Hydroxylamine hydrochloride (290 mg, 4.19 mmols, 1.10 eq), and sodium acetate ( 1.56 g, 19.05 mmols, 5.00 eq) in MeOH (50 ml) was heated to 70 ° C for 4 h before concentration to dryness. The residue was then suspended in Et 2 O, filtered, and concentrated to generate the desired intermediate (496 mg, 3.39 mmol, 89%).
    10/22
    Step 2. 4- (Hydroxy-imino-bromomethyl) -benzonitrile. The compound was prepared according to Tanaka and others. Bull. Chem. Soc. Jpn. 1984, 57, 2184. A 0.05 M solution of / V-bromosuccinimide (724 mg, 4.07 mmol, 1.20 eq) in CH2 Cl2 was added dropwise at 0 ° C of a solution of 4- (Hydroxy- iminomethyl) -benzonitrile (496 mg, 3.39 mmol, 1.00 eq) in CH 2 CI 2 (50 mL). A solution was warmed to room temperature before being volumetrically divided between two different reaction vessels. Each vessel was then concentrated and the crude waste was used without further purification.
    Step 3. 4- [5- (4-Propylphenyl) -isoxazol-3-yl] -benzonitrile. A solution of 4- (Hydroxy-imino-bromomethyl) -benzonitrile (381 mg, 1.70 mmol), triethylamine (0.71 mL, 5.10 mmol, 3.0 eq), and 1-ethynyl-4-propylbenzene (1.23 g, 8.50 mmols, 5.0 eq) in toluene (20 ml) was heated to 100 ° C for 1 h before concentration to dryness. Purification through the normal phase by means of chromatography generated the desired intermediate (108 mg, 22%). The reduction of nitrile to the corresponding aldehyde was achieved following the DIBAL procedure described above.
    Example 5: Preparation of 4- {1- [4- (1-Hydroxypropyl) -phenyl] -1Hpyazol-3-yl} -benzaldehyde.
    Step 1. 3- (4-Cyanophenyl) pyrazole. To a round-bottom flask equipped with a mechanical rotating bar and the reflux condenser were added p-cyanoacetophenone (5 g, 34.44 mmols) and dimethylacetal dimethylformamide (DMF-DMA; 40 ml). The mixture was stirred at reflux for 5 h before concentration under reduced pressure to generate the crude dimethylamino-acryloyl benzonitrile intermediate. The residue was then suspended in a minimum volume of EtOH (~ 20 mL), loaded with hydrazine monohydrate (1.67 mL, 34.4 mmols), and heated to 80 ° C for 30 min before concentration. The crude material 3- (4-cyanophenyl) pyrazole (5.59 g, 33 mmols, 96%) which was isolated was of sufficient purity for use in the subsequent reaction.
    10/23
    Step 2. 4- [1- (4-Propionyl-phenyl) -1H-pyrazol-3-yl] -benzonitrile.
    4- (1 / - / - Pyrazol-3-yl) -benzonitrile (100 mg, 0.591 mmol), 1- (4-bromophenyl) propan-1-one (126 mg, 0.591 mmol), CS2CO3 (770 mg, 2 ., 64 mmols), Cul (4 mg, 0.018 mmol), 8-Hydroxyquinoline (3 mg, 0.018 mmol), and DMF / H 2 O (2 mL; 10: 1 solution) were combined in 10 mL of a microwave EMC reaction with a mechanical stir bar and subjected to microwave irradiation at 150 ° C for 30 min. The contents were then filtered and concentrated to dryness generating nitrile (158 mg, 0.508 mmol, 86%). The reduction of nitrile to the corresponding aldehyde was achieved following the DIBAL procedure described above.
    Example 6: Preparation of 5- (4formylphenyl) -2- (4-trifluoromethoxyphenyl) -3,4-dihydro-2/7-pyrazole-3,4dicarboxylic acid diethyl ester.
    Step 1. Preparation of 4 - [(4-trifluoromethoxyphenyl) Hydrazonomethyl-benzaldehyde. The compound was prepared according to Paulvannan and others. Tetrahedron 2000, 56, 8071. To a stirred solution of benzene-1,4-dicarbaldehyde (1.50 g, 11.2 mmol, 1.0 eq) in / -PrOH (250 mL) was added 4-trifluoromethoxyphenylhydrazine hydrochloride (2.55 g, 11.2 mmols, 1.0 eq) in portions under 5 min. A solution was stirred at room temperature 1 h before concentration to dryness and purification by chromatography (2: 2: 1 hexane: EtOAc: acetone) to generate the intermediate (2.48 g, 72%).
    Step 2. Synthesis of Chlorohydrazone. The intermediate was prepared according to Lokanatha Rai and Hassner Synth. Commun. 1989, 19, 2799. A solution of 4 - [(4-trifluoromethoxyphenyl) -Hidrazonomethyl] -benzaldehyde (2.48 g, 8.05 mmol, 1.00 eq) and / V-chlorosuccinimide (1.61 g, 12 , 08 mmols, 1.5 eq) in / -PrOH (100 mL) was heated to 80 ° C for 1 h. A solution was then cooled and volumetrically divided evenly between six different reaction vessels, each containing 1.34 mmol of the termediate in24 / 109.
    Step 3. Synthesis of pyrazoline. The compounds were prepared according to Paulvannan and others. Tetrahedron 2000, 56, 8071. For each reaction vessel, triethylamine (0.56 mL, 4.02 mmols, 3.00 eq) and the respective acrylates (6.70 mmols, 5.00 eq) were added. The reaction mixtures were then heated to 70 ° C for 90 min before concentration to dryness and purification by chromatography (2: 2: 1, hexane: EtOAc: acetone). The reduction of nitriles to the corresponding aldehyde was achieved following the DIBAL procedure described above.
    Example 7: Preparation of 4- {1- [4- (2,2,2-trifluoroethoxy) -phenyl] 1 H-imidazol-4-yl} -benzaldehyde.
    / = Ν χ v
    CHO
    4- (2-Bromoacetyl) -benzonitrile (58 mg, 0.21 mmol) and 4- (2,2,2trifluoroethoxy) -phenylamine (50 mg, 0.21 mmol) were combined in a 100 mL Erlenmeyer flask adjusted with the mechanical stir bar. The contents were dissolved in EtOH (1 mL) and stirred at room temperature for 2 h. The crude intermediate was then transferred to a 100 ml round bottom flask containing KSCN (21 mg, 0.21 mmol) and HCI conc. (18 pL, 0.21 mmol). The vessel was heated to 80 ° C for 1 h before its contents were poured into a 1: 1 H2O / NH4OH solution (5 mL). A solution was allowed to rest for 24 h, and then the solid was filtered and maintained with ether to generate the imidazoltiol intermediate (32 mg, 0.086 mmol, 33%). An aqueous solution of HNO 3 (1.35 ml, 0.387 mmol) and KNO3 (1 mg, 0.003 mmol) was then added dropwise over 10 min to a suspension of imidazole ethyl in acetic acid (2 ml). After stirring for 2 h at room temperature, a solution was poured onto crushed ice and neutralized (pH = 7) with 0.1 N sodium hydroxide (NaOH, aq). The nitrile intermediate was isolated by vacuum filtration and dried in a vacuum oven at 45 ° C for 12 h (23 mg, 78%), mp 179 ° C. The reduction to the corresponding aldehyde was achieved using DIBAL under the conditions described above.
    Example 8: Preparation of 4- [i- (4-propylphenyl) -1Á / -imidazole-4yl] -benzaldehyde.
    4-Propylaniline (2.70 g, 20 mmol) was added dropwise to a solution of 4-cyanophenacyl bromide (2.0 g, 10 mmol) in DMF (5 ml). This solution was then added to the hot formamide (20 mL) (180 ° C) for 5 min, and the combined solution was allowed to stir at 180 ° C for 2 h. A cooled solution was then poured onto ice (100 ml), and extracted with ether (2 x 75 ml). After drying and concentration, the resulting dark oil was purified by means of chromatography (3: 1: 2 hexanes: EtOAc: CH 2 CI 2 ). The first product (510 mg) was identified as 4- (5propyl-1 / - / - indol-3-yl) -benzonitrile, mp 140 ° C. The second fraction (275 mg) was identified as the desired imidazole: mp 133 ° C; 1 H NMR (400 MHz, CDCb) δ 7.95 (d, J = 6 Hz, 2H), 7.90 (s, 1H), 7.70 (d, J = 6 Hz, 2H), 7.68 (s, 1H), 7.38 (d, J = 4 Hz, 2H), 7.31 (d, J = 4 Hz, 2H), 2.69 (t, J = 8.9 Hz, 2H), 1.68 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H); ESIMS m / z 288.1 (M + H).
    The reduction to the corresponding aldehyde was achieved using DIBAL under the conditions described above: mp 97 ° C; 1 H NMR (300 MHz, CDCI3) δ 10.02 (s, 1H), 8.03 (d, J = 6 Hz, 2H), 7.92 (d, J = 6 Hz, 2H), 7.90 (s, 1H), 7.72 (s, 1H), 7.38 (d, J = 4 Hz, 2H), 7.31 (d, J = 4 Hz, 2H), 2.69 (t, J = 8.9 Hz, 2H), 1.68 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H); ESIMS m / z 291.1 (M + H).
    Example 9: Preparation of 4- [1- (4-trifluoromethoxyphenyl) -1Himidazol-4-yl] -benzaldehyde.
    / = / ^ N CF 3 °
    4-Trifluoromethoxyaniline (2.20 g, 12.4 mmol) was added dropwise to a solution of 4-cyanopenacil bromide (1.50 g, 6.7 mmol) in DMF (5 mL). This solution was then added to hot (180 ° C) formamide
    26/109 (20 mL) for 5 min, and the combined solution was allowed to stir at 180 ° C for 2 h. A cooled solution was then poured onto ice (100 ml), and extracted with ether (2 x 75 ml). After drying and concentration, the resulting semi-solid was crystallized from MeOH / H 2 O. The second recrystallization from MeOH / H 2 O removed the impurity traces of the formanilide and provided a pure product (200 mg): mp 155 ° C. Anal. Calcd. for C17H10F3N3O: C, 62.01; H, 3.06; N, 12.76. Found: C. 61.53; H, 3.13; N, 12.55. The reduction to the corresponding aldehyde was achieved using DIBAL under the conditions described above: mp 112 ° C; 1 H NMR (300 MHz, CDCl3) δ 10.0 (s, 1H), 8.05-7.90 (m, 5H), 7.70 (s, 1H), 7.50 (d, J = 6 Hz, 2H), 7.42 (d, J = 6 Hz, 2H); ESIMS m / z 333.0 (M + H).
    Example 10: Preparation of 4- [4- (4-trifluoromethylphenyl) -1H-imidazol-1-yl] benzaldehyde.
    4-Trifluoromethylphenyl imidazole (4.0 g, 19 mmol), 4 fluorobenzonitrile (1.2 g, 8.5 mmol) and potassium carbonate (1.5 g, 10.9 mmol) were combined in DMSO (15 mL) and heated to 100 ° C for 6 h. A cooled solution was then poured into water (H 2 O; 100 ml), and the resulting solid was filtered and dried to give the imidazole nitrile (4.65 g) as a white solid: mp 252 ° C; 1 H NMR (300 MHz, CDCl3) δ 8.05 (s, 1H), 7.95 (d, J = 8 Hz, 2H), 7.85 (d, J = 8 Hz, 2H), 7.72 (s, 1H), 7.72 (d, J = 8 Hz, 2H), 7.62 (d, J = 8 Hz, 2H); ESIMS m / z 314.1 (M + H). Anal. Calcd. for C16H10F3N3O2: C, 65.18; H, 3.22; N, 13.41. Found: C, 64.49; H, 3.23; N, 13.08. A portion of the nitrile (3.8 g) was reduced to the presence of DIBAL under the conditions described above to give the corresponding aldehyde (2.41 g): mp 141 ° C; 1 H NMR (300 MHz, CDCl3) δ 10.1 (s, 1H), 8.10 (d, J = 8 Hz, 2H), 8.05 (s, 1H), 7.95 (d, J = 8 Hz, 2H), 7.75 (s, 1H), 7.7 (m, 4H); ESIMS m / z 317.1 (M + H).
    Example 11: Preparation of 4-bromo-1- (4-trifluoromethoxyphenyl) -1H-imidazole.
    27/109 CF 3 0 A = /
    A round bottom flask was loaded with 4-bromoimidazole (1.15 g, 7.81 mmol), Cul (0.07 g, 0.36 mmol), 8-Hydroxyquinoline (0.05 g, 0.36 mmol), carbonate cesium (3.39 g, 10.4 mmols) and 4trifluoromethoxyiodobenzene (1.50 g, 5.21 mmols). A 10: 1 mixture of DMF (15 mL) and H 2 O (1.5 mL) was added to the reaction mixture, and a solution was heated at 130 ° C for 4 h. The reaction mixture was then diluted with EtOAc and maintained sequentially with H 2 O, ammonium chloride (NH 4 CI, saturated), H 2 O and sodium bicarbonate (NaHCOa). The organics were dried over MgSO 4 , filtered and purified through the reverse phase column by means of chromatography to give the imidazole (820 mg) as a white solid: mp 139 at 141 ° C; ESIMS m / z 308.0 (M + H).
    Example 12: Preparation of 4-methoxy-2- [1- (4trifluoromethoxyphenyl) -1H-imidazol-4-yl] -benzaldehyde.
    4-Bromo-1- (4-trifluoromethoxyphenyl) -1 / 7-imidazole (100 mg, 0.326 mmol), 2-formyl-5-methoxyphenylboronic acid (73 mg, 0.41 mmol), bis (triphenylphosphine) dichloride (2 mg, 0.003 mmol), NaHCC> 3 (49 mg, 0.59 mmol) and 1: 1 DME / H 2 O (8: 8 mL) were combined and added to a microwave vessel. The reaction mixture was heated in the microwave with stirring at 100 ° C for 12 min. The microwave took 5 min to reach 100 ° C, then kept at 100 ° C for 12 min, and then cooled. TLC (1: 1 EtOAc: cyclohexane) showed the presence of starting materials, thus, the sample was heated to 100 ° C for another 8 min. After cooling, the precipitate was formed; it was filtered and maintained with H 2 O to give a gray solid (86 mg): ESIMS m / z 363.0 (M + H).
    The following intermediary was also prepared using this procedure:
    10/28
    Example 13: Preparation of oromethoxyphenyl) -1H-imidazol-4-yl] -benzaldehyde.
    2-fluorine-4- [1 - (4-triflu-
    ESIMS m / z 351.0 (M + H).
    Example 14: Preparation of 1- {4-fluor-3- [1- (4trifluoromethoxyphenyl) -1H-imidazol-4-yl] -phenyl} -ethanone.
    4-Bromo-1- (4-trifluoromethoxyphenyl) -1H-imidazole (200 mg, 0.651 mmol), 5-acetyl-2-fluorophenylboronic acid (178 mg, 0.977 mmol), tetrakis (triphenylphosphine) -paladium (0) (7) mg, 0.007 mmol), a 2 N aqueous potassium carbonate solution (0.651 ml) and dioxane (8 ml) were combined and added to a microwave vessel. The reaction mixture was heated in the microwave with stirring at 150 ° C for 20 min. LC-MS indicated 88% of the anticipated product; TLC (1: 1 hexanes: EtOAc) indicated the presence of starting material plus 3 other materials. EtOAc and H2O were added to the reaction mixture. The aqueous layer was extracted with EtOAc, and the organic extracts were kept with brine, dried over MgSO 4 , and concentrated in vacuo. The crude product was purified by means of gradient elution chromatography (100% hexanes to 100% EtOAc) resulting in an off-white solid (90 mg): mp 129 ° C; ESIMS m / z 265.0 (M + H).
    Example 15: Preparation of 4- [1- (4-trifluoromethoxyphenyl) -1H [1,2,4] triazol-3-yl] -benzaldehyde.
    Step 1. 4- (1H- [1,2,4] Triazol-3-yl) -benzonitrile. The general procedure outlined by Lin and others. (J. Org. Chem. 1979, 44, 4163) through the preparation of 3- (4-nitrophenyl) -1 / 7- [1,2,4] triazole was used. 4 Cyanobenzamide (21.63 g, 0.148 mol) was dissolved in DMF-DMA (100 mL)
    29/109 and was stirred at reflux under N 2 for 8 h. The mixture was concentrated to dryness and suspended in AcOH (50 ml). The vessel was then charged with hydrazine monohydrate (7.18 mL, 0.148 mmol) and stirred at reflux for 1 h before concentration. The desired 4- (1 / - / - [1,2,4] triazol-3-yl) -benzonitrile was obtained in 98% purity by trituration with Et 2 O followed by filtration (12,17 g, 0.072 mol, 48%).
    Step 2. 4- [1- (4-Trifluoromethoxyphenyl) -1H- [1,2,4] tríazol-3-yl] benzonitrile. Triazole (70 mg, 0.41 mmol), 1-iodo-4-trifluoromethoxybenzene • (142 mg, 0.493 mmol), Cs 2 CO 3 (535 mg, 1.644 mmol), Cul (3 mg, 0.012 mmol), 8 -Hydroxyquinoline (2 mg, 0.012 mmol), and DMF / H 2 O (2 mL; 10: 1 solution) were combined in a 10 mL EMC microwave reaction vessel with mechanical stir bar and subjected to irradiation of microwave at 150 ° C for 30 min. The contents were then filtered and concentrated to dryness yielding the intermediate 1,3-diphenyl triazole (18 mg, 13%).
    Step 3. 4- [1- (4-Trifluoromethoxyphenyl) -1H- [1,2,4] triazol-3-yl] benzaldehyde. The nitrile was reduced with previously described DIBAL conditions: mp 137-140 ° C; 1 H NMR (300 MHz, CDCI 3 ) δ 10.1 (s, 1H), 8.61 (s, 1H), 8.37 (d, J = 9 Hz, 2H), 8.0 (d, J = 8.4 Hz, 2H), 7.8 (d, J = 9 Hz, 2H), 7.4 (d, J = 8.4 Hz, 2H); ESIMS m / z 334.2 (M + H).
    Example 16: Preparation of 4- [1- (4-pentafluoroethylsulfanylphenyl) -1H- [1,2,4] triazol-3-yl] -benzaldehyde.
    Step 1. 1-Bromo-4-pentafluoroethylsulfanylbenzene. The title compound was prepared using perfluoroalkylation conditions originally described by Popov and others J. Fluoríne Chem. 1982, 21,
    365. To a solution of 4-bromobenzenethiol (500 mg, 2.64 mmol, 1.00 eq) and triethylbenzyl ammonium chloride (60 mg, 0.26 mmol, 0.10 eq) in 10 mL of 1: 1 Et 2 O / NaOH (25% aq) at 0 ° C, 1,1,1,2,2-pentafluor-2-iodoethane gas was bubbled for 30 min (> 5eq). During this time, a UV lamp was directed into the reaction vessel while the temperature was kept below
    30/109 of 10 ° C through intermittent use of an ice bath. The contents were then warmed to room temperature, extracted in Et 2 O (300 ml), dried (MgSO 4 ), and concentrated under reduced pressure. A portion of this crude material was used in a subsequent reaction without further purification (200 mg residue: 120 mg product, 0.39 mmol, 1.2 eq).
    Step 2. 4- [1- (4-Pentafluoroethylsulfanylphenyl) -1H- [1,2,4] triazol3-yl] -benzonitrile. Coupling with 4- (1 / 7- [1,2,4] triazol-3-yl) -benzonitrile as described above gave 4- [1- (4-pentafluoroethylsulfanylphenyl) -1 / 7- [1,2,4 ] triazol3-yl] -benzonitrile (70 mg, 46%). The reduction with DIBAL, as previously described, gave the corresponding aldehyde.
    Example 17: Preparation of 4- [1- (4-pentafluoroethyloxy-phenyl) 1 H- [1,2,4] triazol-3-yl] -benzaldehyde.
    Step 1. A solution of 3-p-tolyl-1 / 7- [1,2,4] triazole (4.85 g, 30.5 mmols), 4-bromophenyl pentafluoroethyl ether (10.0 g, 34.4 mmols), CS2CO3 (25 g, 77 mmols), Cul (1.25 g, 6.5 mmols) and 8-Hydroxyquinoline (0.35 g, 2.4 mmols) in 9: 1 DMF / H 2 O (50 mL) was vigorously stirred and heated to 130 ° C (internal temperature) for 20 h. A solution was then cooled, poured into H 2 O, and acidified with 2 N HCI to pH 2. Ether (250 ml) was then added and a solution was stirred and filtered before separating the layers. The organic layer was dried and concentrated, and the resulting gummy solid was heated with hexanes (100 ml). The hot hexane layer was decanted from insoluble residue, the resulting solution cooled to 0 ° C and the precipitated solid was filtered and dried to yield 1- (4pentafluoroethyloxy-phenyl) -3-p-tolyl-1W- [1, 2.4] triazole (7.0 g, 61% based on the starting triazole) as an off-white solid: mp 130-132 ° C; ESIMS m / z 370.8 (M + H).
    Step 2. The product from Step 1 (70 g, 18.7 mmols) was dissolved in acetonitrile (200 mL) and stirred at room temperature while the amount of ceric ammonium nitrate (32 g, 58 mmols) in
    10/319
    Η 2 Ο (60 mL) was added in portions for 10 min. A solution was then heated to reflux for 4 h, cooled, and diluted with H 2 O (200 ml). A solution was extracted with ether (2 x 200 ml), and the combined organic layer was dried and concentrated to give an orange oil. This material was dissolved in dioxane (40 ml) and treated with a solution of potassium hydroxide (KOH; 5 g, 90 mmols) in H 2 O (20 ml). A solution was heated to reflux for 2 h, then cooled and diluted with H 2 O (100 ml). The precipitated aldehyde was collected by filtration. Recrystallization from MeOH / H 2 O gave the pure aldehyde as a white solid (2.2 g, 30%): mp 137-144 ° C; 1 H NMR (300 MHz, CDCI 3 ) δ 10.1 (s, 1H), 8.65 (s, 1H), 8.40 (d, J = 8.4 Hz, 2H), 8.0 (d , J = 8.4 Hz, 2H), 7.85 (d, J = 9 Hz, 2H), 7.45 (d, J = 9 Hz, 2H); ESIMS m / z 384.2 (M + H).
    Example 18: Preparation of 4- [1- (4-butylphenyl) -1H- [1,2,4] triazol-3-yl] -benzaldehyde.
    N '^ AZ> - cho
    Step 1. 4- [1 - (4-Butiphenyl) -1 H- [1,2,4] triazol-3-yl] -benzonitrile.
    A solution of 4-n-butyl phenyl hydrazine (1.0 g, 5 mmol) and 4-cyanobenzaldehyde (0.8 g, 6.0 mmol) in / -PrOH (15 mL) was heated in a steam bath for 2 h then it was heated and diluted with H 2 O (5 ml). The orange solid was filtered and dried to give Hydrazone (1.30 g) as a yellow solid, mp 107 ° C. A solution of this Hydrazone (1.1 g, 4.0 mmols) and NCS (0.67 g, 5 mmols) in / -PrOH (20 mL) was stirred under nitrogen at room temperature for 2 h, during which time original solid was dissolved and a new solid was formed. The resulting orange solution was then treated with tetrazole (0.45 g, 6.4 mmols) and triethylamine (960 pL, 7.0 mmols). The orange - brown solution was heated to reflux for 2 h. A solution was then cooled, diluted with H 2 O (25 mL), extracted with EtOAc, dried, concentrated, and purified by chromatography (Biotage, 4: 1 hexane: EtOAc) to give the triazole (0, 42 g, 35%) as an off-white solid: mp 124 ° C; 1 H NMR (300 MHz, CDCI 3 ) δ 8.58 (s, 1H), 8.33 (d, J = 8 Hz, 2H),
    10/32
    7.78 (d, J = 8 Hz, 2H), 7.64 (d, J = 8.2 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 2.70 ( t, J = 7.8 Hz, 2H), 1.63 (m, 2H), 1.38 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H); ESIMSm / z 303.1.
    Step 2. 4- [1- (4-Butylphenyl) -1H- [1,2,4] triazol-3-yl] -benzaldehyde.
    The reduction with DIBAL, as previously described, gave the corresponding aldehyde: mp 124 ° C; 1 H NMR (300 MHz, CDCI 3 ) δ 10.08 (s, 1H), 8.58 (s, 1 H), 8.37 (d, J = 8 Hz, 2H), 7.98 (d, J = 8 Hz, 2H), 7.62 (d, J = 8.2 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 2.70 (t, J = 7, 8 Hz, 2H), 1.63 (m, 2H), 1.38 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H); ESIMS m / z 306.1.
    Example 19: Preparation of 4- [1- (4-pentafluoroethylphenyl) -1H [1,2,4] triazol-3-yl] -benzaldehyde.
    Step 1. 1- (4-Pentafluoroethylphenyl) -3-p-tolyl-1H- [1,2,4] triazole.
    pentafluoroethyl lodide (521 mg, 2.12 mmol) was condensed in a vial containing 1-bromo-4-iodobenzene (300 mg, 1.06 mmol), copper (0) powder (135 mg, 2.12 mmol) , and DMSO (5 ml). The flask was then sealed and subjected to microwave irradiation at 150 ° C for 60 min. GC-MS proved a consumption of the starting material yielding both intermediates 1bromo-4-pentafluoroethylbenzene and 1-iodo-4-pentafluoroethylbenzene. The mixture (1.06 mmol) was transferred to a 250 mL round-bottom flask of 3-p-tolyl-1A7- [1,2,4] triazole (169 mg, 1.06 mmol), CS2CO3 (1 , 38 g, 4.24 mmol), Cul (202 mg, 1.06 mmol), 8-Hydroxyquinoline (2 mg, 0.011 mmol), and DMF / H2O (12 mL; 10: 1 solution) were added. A solution was stirred at reflux at 160 ° C for 6 h. After completion, the contents were poured into H2O and precipitation was allowed for 1 h. The precipitate was collected by vacuum filtration and dried overnight in a vacuum oven at 45 ° C. The intermediate 1- (4-pentafluoroethylphenyl) -3-p-tolyl-1 H [1,2,4] crude triazole was used in Step 2 without further purification.
    Step 2. Oxidation of the aldehyde. Ammonium (IV) cerium nitrate (3.32 g, 4.24 mmols) and the intermediate from Step 1 were combined
    33/109 in a round-bottom flask with acetonitrile and H 2 O (20 mL; 1: 1). A solution was stirred at reflux at 110 ° C for 4 h, yielding the mixture of intermediates 3- (4-nitrooxymethyl-phenyl) -1- (4-pentafluoroethyl-phenyl) -1 / - / - [1,2,4 ] triazole and 4- [1- (4-pentafluoroethyl-phenyl) -1 / - / - [1,2,4] triazol-3-yl] -benzaldehyde. Acetonitrile was removed in vacuo and the precipitate of the crude intermediate was collected by filtration. The material was then combined with powdered KOH (178 mg, 3.18 mmol) in dioxane and H 2 O (10 mL; 1: 1) and was stirred at reflux at 105 ° C for 90 min before dioxane have been removed under vacuum allowing the precipitation of the intermediate from H 2 O. Intermediate 4- [1- (4-pentafluoroethylphenyl) -1 / - / - [1,2,4] triazol-3-yl] -benzaldehyde was collected by filtration (35 mg, 0.095 mmol, 9% from 4-tolyl triazole).
    Example 20: Preparation of 4- [3- (4-formylphenyl) - [1,2,4] triazol1 -yl] -phenyl ester of trifluoromethanesulfonic acid.
    Step 1. 1- (4-Methoxyphenyl) -3-p-tolyl-1H- [1,2,4] triazole was prepared by coupling 3-p-tolyl-1H- [1,2,4] triazole with 4-iodoanisole under conditions described in Step 1 of the previous Example. This material was then demethylated using the conditions described in Hitchcock et al. Synlett 2006, 2625. Boron tribromide (1 M solution in hexanes; 1.67 mL, 1.67 mmol) was added dropwise to a solution of 1- (4 methoxyphenyl) -3-p-tolyl-1 / - / - [1,2,4] triazole (300 mg, 1.28 mmol) in CH 2 CI 2 (10 mL) at 0 ° C under N 2 . After the addition was complete, the vessel was warmed to room temperature before refluxing at 40 ° C for 6 h. The cooled contents were then quenched with H 2 O before the removal of CH 2 CI 2 and the division between EtOAc and H 2 O. The organic layer was collected, washed with brine, dried (MgSO 4 ), concentrated, and purified by chromatography (3: 1: 1, hexanes: EtOAc: acetone) to generate intermediate 4- (3-p-tolyl [1,2,4] triazol-1-yl) -phenol (219 mg, 0.872 mmol, 68%). Trifluoromethanesulfonic anhydride (0.16 mL, 0.96 mmol) was added dropwise to a solution of the phenol and 4-fer-butyl-2,6-dimethylpyridine (142 mg, 0.872 mmol) over
    10/34
    CH 2 Cl2 (10 mL) at 0 ° C under N 2 . The vessel was warmed to room temperature before the solvent was removed under reduced pressure and the residue purified by chromatography (2: 2: 1, hexanes: EtOAc: acetone) generating the intermediate of 4- (3-p-tolyl- [1,2,4] triazol-1-yl) -phenyl ester of trifluoromethanesulfonic acid (304 mg, 0.794 mmol, 91%).
    Step 2. Oxidation of the above 4-methyl intermediate to the corresponding aldehyde was carried out using ammonium (IV) cerium nitrate under the conditions described in Step 2 of the previous Example.
    Example 21: Preparation of 4- [5- (4-trifluoromethylphenyl) -1H [1,2,4] triazol-3-yl] -benzaldehyde.
    N-N
    Terephthalonitrile (115 mg, 0.90 mmol), 4trifluoromethylbenzoic acid hydrazide (92 mg, 0.450 mmol), K 2 CO 3 (31 mg, 0.225 mmol), and n-butyl alcohol (~ 2 mL) were combined in a 10 mL of a CEM microwave reaction flask with mechanical stir bar and subjected to microwave irradiation at 150 ° C for 30 min. The contents were then filtered and concentrated to dryness. Chromatography (3: 1 hexanes / EtOAc) generated 1,2,4-triazole nitrile (72 mg, 0.230 mmol, 51%). The reduction with DIBAL then generated the corresponding aldehyde.
    Example 22: Preparation of 4- [1- (3,4-dichlorophenyl) -5-oxo-4,5dihydro-1 H- [1,2,4] triazol-3-yl] -benzaldehyde.
    CHO
    Step 1. 4-cyanophenyl-oxo-acetic acid. A round-bottom flask equipped with a mechanical stirrer and the reflux condenser was charged with p-cyanoacetophenone (5 g, 34.44 moles), selenium dioxide (SeO 2 ; 9.55 g, 86.1 mmols), and pyridine (~ 100 mL). A mixture was stirred at reflux for 6 h before the precipitates were removed by filtration and the filtrate was charged with 10% HCI (aq) (20 ml). The filtrate was
    35/109 extracted in EtOAc (3 x 50 mL) and the combined organic layer was extracted further in saturated NaHCO 3 . The aqueous layer was then made acidic carefully (pH = 1) with conc. HCI yielding a smaller cut of the desired product. The remainder of oxo acetic acid was obtained by extraction in EtOAc, drying (MgSO 4 ), and concentration (1.69 g, 28%).
    Step 2. 4- [1- (3,4-Dichlorophenyl) -5-oxo-4,5-dihydro-1H- [1,2,4] triazol-3-yl] -benzonitrile. A suspension of 4-cyanophenyl oxo-acetic acid (100 mg, 0.571 mmol), (3,4-dichlorophenyl) hydrazine hydrochloride (122 mg, 0.571 mmol), 12.1 N HCI (5 pL, 0.057 mmol) , and H 2 O (~ 10 mL) in a 25 mL reaction vessel was stirred vigorously at room temperature for 24 h. The hydrazone was obtained by means of vacuum filtration and placed in a 100 mL round-bottom flask with a mechanical stir bar. The flask was then supplemented with triethylamine (0.08 mL, 0.571 mmol), diphenylphosphoryl azide (157 mg, 0.571 mmol), and toluene (20 mL) before heating at 110 ° C for 1 h. After cooling, the contents were extinguished with 10% NaOH (aq) and made acidic (pH 1) with HCI conc. The precipitation was left for 15 min before the intermediate was obtained by means of vacuum filtration and dried overnight in a vacuum oven at 45 ° C (16 mg, 8%). Nitrile was reduced to aldehyde using DIBAL under conditions previously described.
    Example 23: Preparation of 4- [1- (4-Chlorophenyl) -1H- [1,2,3] triazol-4-yl] -benzaldehyde.
    Following the procedure published by Feldman and others. (Org Lett. 2004, 6, 3897), a suspension of 4-ethynylbenzonitrile (50 mg, 0.393 mmol), 1-chloro-4-iodobenzene (94 mg, 0.393 mmol), L-proline (9 mg, 0.079 mmol) , ascorbic acid (7 mg, 0.039 mmol), NaN 3 (31 mg, 0.472 mmol), CuSO 4 (3 mg, 0.020 mmol), and Na 2 SO 4 (11 mg, 0.079 mmol) in DIVISION (1.5 mL ) was heated to 65 ° C for 24 h. After cooling, the mixture was diluted with H 2 O and stirred for 30 min at room temperature. Intermediate 36/109 4- [1- (4-chlorophenyl) -1 / - / [1,2,3] triazol-4-yl] -benzonitrile (54 mg, 48%) was then obtained by of vacuum filtration after washing with copious volumes of H 2 O and 20% NH 4 OH (~ 20 mL). The aldehyde reduction was then carried out under conditions previously described.
    Example 24: Preparation of 4- [5- (4-trifluoromethyl-phenyl) tetrazol-2-yl] -benzaldehyde.
    N = N
    This aldehyde was prepared from 4-trifluoromethylbenzaldehyde using the following route described in Roppe et al. J. Med Chem. 2004, 47, 4645.
    Example 25: Preparation of 4- [5- (4-trifluoromethoxyphenyl) pyridin-3-yl] -benzaldehyde.
    CHO
    Step 1. 3,5-Dibromopyridine (4.4 mmol), 4trifluoromethoxyphenyl boronic acid (5.1 mmol), tetrakis (triphenylphosphine) palladium (0) (0.04 mmol), 2 M potassium carbonate (8.44 mmols) and dioxane (21 mL) were combined in a flask and heated by microwave for 10 min at 150 ° C. The reaction mixture was taken up in ether and washed with brine. The ether layer was dried over magnesium sulfate, filtered and the solvent removed in vacuo. The crude mixture was purified by silica gel using chromatography to yield 3-bromo-5- (4-trifluoromethoxyphenyl) -pyridine (130 mg) as a yellow solid: 1 H NMR (400 MHz, CDCl3) δ 8 , 71 (m, 2H), 8.00 (t, J = 2.1 Hz, 1H), 7.58 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 8, 0 Hz, 2H); EIMS m / z 317 (M + ).
    Step 2. The compound was prepared by palladium-catalyzed arylation of the Step 1 product with 4-formylphenyl boronic acid.
    Example 26: Preparation of 4- [4- (4-trifluoromethoxyphenyl) pyridin-2-yl] -benzaldehyde.
    37/109
    CHO
    Step 1. The compound was prepared by palladium-catalyzed arylation of 2-chloro-4-iodopyridine with 4-trifluoromethoxyphenyl boronic acid.
    Step 2. 2-Chloro-4- (4-trifluoromethoxyphenyl) -pyridine (0.55 mmol) starting from 2-chloro-4-iodopyridine, 4-formylphenyl boronic acid (0.82 mmol), tetrakis (triphenylphosphine) palladium (0) (0.005 mmol), 2 M potassium carbonate (0.55 mL) and dioxane (3 mL) were combined in a flask and irradiated by microwave for 15 min at 150 ° C. The reaction mixture was taken up in EtOAc and washed with brine. The organic layer was dried over magnesium sulfate, filtered and the solvent removed in vacuo. Purification by silica gel using chromatography (EtOAc / hexanes) yielded the product (120 mg) as an off-white solid: 1 H NMR (400 MHz, CDCI 3 ) δ 10.11 (s, 1H), 8 , 81 (d, J = 4.8 Hz, 1H), 8.24 (d, J = 8.7 Hz, 2H), 8.03 (d, J = 8.4 Hz, 2H), 7.96 (m, 1H), 7.73 (d, J = 9.0 Hz, 2H), 7.49 (dd, J = 5.3, 1.8 Hz, 1H), 7.37 (d, J = 8.1 Hz, 2H); EIMS m / z 343 (M + ).
    Example 27: Preparation of 4- [6- (4-trifluoromethoxyphenyl) pyridin-2-yl] -benzaldehyde.
    CHO
    Step 1. 4- (6-Bromopyridin-2-yl) -benzaldehyde (0.31 mmol) was prepared as in Puglisi et al. Eur. J. Org. Chem 2003, 8, 1552-1558.
    Step 2. 4- [6- (4-Trifluoromethoxyphenyl) -pyridin-2-yl] - benzaldehyde. 4- (6-Bromo-pyridin-2-yl) -benzaldehyde (0.31 mmol), 4trifluoromethoxyphenyl boronic acid (0.46 mmol), tetrakis (triphenylphosphine) palladium (0) (0.003 mmol), 2 M potassium carbonate ( 0.31 mL) and dioxane (2 mL) were combined in a flask and irradiated by microwave for 10 min at
    150 ° C. The reaction mixture was taken up in ether and washed with brine. THE
    38/109 organic layer was dried over magnesium sulfate, filtered and the solvent removed in vacuo. Purification by silica gel using chromatography (EtOAc / hexanes) yielded the product (80 mg) as an off-white solid: mp 109-112 ° C; 1 H NMR (400 MHz, CDCI 3 ) δ 10.11 (s, 1H), 8.32 (d, J = 8.5 Hz, 2H), 8.19 (d, J = 8.1 Hz, 2H ), 8.03 (d, J = 8.4 Hz, 2H), 7.89 (t, J =
    7.9 Hz, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8, 3 Hz, 2H); EIMS m / z 343 (M + ).
    Example 28: Preparation of 4- [6- (4-trifluoromethoxyphenyl) pyrimidin-4-yl] -benzaldehyde.
    Etapa0 Step 1. 4-Chloro-6- (4-trifluoromethoxyphenyl) -pyrimidine was prepared by palladium-catalyzed arylation of 4,6-dichloropyrimidine and 4-trifluoromethoxyphenyl boronic acid: 1 H NMR (400 MHz, CDCI 3 ) δ 9.05 (s, 1H), 8.14 (d, J = 9.8 Hz, 2H), 7.74 (m, 1H), 7.36 (d, J = 8.4 Hz, 2H); EIMS m / z 274 (M + ).
    Step 2. The compound was prepared by palladium-catalyzed arylation of the Step 1 product with 4-formylphenyl boronic acid: 1 H NMR (400 MHz, CDCI 3 ) δ 10.15 (s, 1H), 9.38 ( d, J = 0.9 Hz, 1H), 8.33 (d, J = 8.4 Hz, 2H), 8.23 (d, J = 8.5 Hz, 2H), 8.16 (d, J = 0.8 Hz, 1H), 8.08 (d, J = 8.8 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H); EIMS m / z 344 (M + ).
    Example 29: Preparation of 4- [2- (4-trifluoromethoxyphenyl) pyrimidin-4-yl] -benzaldehyde.
    title was prepared by means of palladium-catalyzed arylation of
    2,4-dichloropyrimidine and 4-trifluoromethoxyphenyl boronic acid: mp 70-73 ° C; 1 H
    NMR (400 MHz, CDCI 3 ) δ 8.68 (d, J = 5.6 Hz, 1H), 8.16 (d, J = 9.1 Hz, 2H), 7.65 (d, J = 5 , 3 Hz, 1H), 7.36 (dd, J = 9.2, 0.9 Hz, 2H); EIMS m / z 274 (M + ).
    10/39
    Step 2. The compound was prepared by palladium-catalyzed arylation of the Step 1 product with 4-formylphenyl boronic acid: 1 H NMR (400 MHz, CDCI 3 ) δ 10.13 (s, 1H), 8.91 ( d, J = 4.8 Hz, 1H), 8.74 (d, J = 8.5 Hz, 2H), 8.28 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 5.3 Hz, 1H), 7.39 (d, J = 8.6 Hz, 2H); EIMS m / z 344 (M + ).
    Example 30: Preparation of 4- [4- (4-trifluoromethoxyphenyl) pyrimidin-2-yl] -benzaldehyde.
    Step 1. 4- (4-Chloropyrimidin-2-yl) -benzaldehyde. The compound was prepared by means of arylation catalyzed by palladium of 2,4dichloropyrimidine and 4-formylphenyl boronic acid: 1 H NMR (400 MHz, CDCl3) δ 10.13 (s, 1H), 8.74 (d, J = 5 , 0 Hz, 1H), 8.27 (d, J = 7.8 Hz, 2H), 8.04 (d, J = 7.9 Hz, 2H), 7.74 (m, 1H); EIMS m / z 218 (M + ).
    Step 2. The compound was prepared by palladium-catalyzed arylation of the Step 1 product with 4-trifluoromethoxyphenyl boronic acid: 1 H NMR (400 MHz, CDCI 3 ) δ 10.14 (s, 1H), 8.91 ( d, J = 4.2 Hz, 1H), 8.63 (d, J = 8.5 Hz, 2H), 8, 37 (d, J = 8.4 Hz, 2H), 8.06 (d, J = 8.8 Hz, 2H), 7.67 (d, J = 5.4 Hz, 1H), 7.35 (d, J = 8.7 Hz, 2H); EIMS m / z 344 (M + ).
    Example 31: Preparation of 4- [6- (4-trifluoromethoxyphenyl) pyrazin-2-yl] -benzaldehyde.
    Step 1. 2-Chloro-6- (4-trifluoromethoxyphenyl) -pyrazine. The compound was prepared by palladium-catalyzed arylation of 2,6dichloropyrazine and 4-trifluoromethoxyphenyl boronic acid: mp 58-60 ° C; 1 H NMR (400 MHz, CDCl3) δ 8.94 (s, 1H), 8.57 (s, 1H), 8.10 (d, J = 9.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H); EIMS m / z 274 (M + ).
    10/40
    Step 2. The compound was prepared by palladium-catalyzed arylation of the Step 1 product with 4-formylphenyl boronic acid: 1 H NMR (400 MHz, CDCI 3 ) δ 10.13 (s, 1H), 9.07 ( s, 1H), 9.03 (s, 1H), 8.33 (d, J = 8.1 Hz, 2H), 8.21 (d, J = 8.7 Hz, 2H), 8.07 ( d, J = 7.6 Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H); EIMS m / z 344 (M + ).
    Example 32: Preparation of 4- [2- (4-trifluoromethoxyphenyl) pyrimidin-5-yl] -benzaldehyde.
    Step 1. 4- (2-Chloropyrimidin-5-yl) -benzaldehyde. The compound was prepared by means of arylation catalyzed by 2.5dichloropyrimidine palladium and 4-formylphenyl boronic acid.
    Step 2. 4- (2-Chloropyrimidin-5-yl) -benzaldehyde (0.92 mmol), 4-trifluoromethoxyphenyl boronic acid (1.10 mmol), dichlorobis (triphenylphosphine) palladium (ll) (0.01 mmol), 2 M potassium carbonate (0.92 ml) and dioxane (5 ml) were combined in a flask and irradiated by microwave for 10 min at 150 ° C. The organic layer from the reaction mixture was loaded directly onto silica and dried under vacuum. Purification by silica gel using chromatography (EtOAc / hexanes) yielded the product (140 mg) as a white solid: 1 H NMR (400 MHz, CDCI 3 ) δ 10.11 (s, 1H), 9 , 07 (s, 2H), 8.57 (d, J = 9.0 Hz, 2H), 8.07 (d, J = 8.5 Hz, 2H), 7.82 (d, J = 8, 3 Hz, 2H), 7.35 (d, J = 8.3 Hz, 2H); EIMS m / z 344 (M + ).
    Example 33: Preparation of 4- [5- (4-trifluoromethoxyphenyl) pyrimidin-2-yl] -benzaldehyde.
    Step 1. 2-Chloro-5- (4-trifluoromethoxyphenyl) -pyrimidine The compound was prepared by palladium-catalyzed arylation of 2,5dichloropyrimidine with 4-trifluoromethoxyphenyl boronic acid.
    Step 2. 2-Chloro-5- (4-trifluoromethoxyphenyl) -pyrimidine (4.22 mmol), 4-formylphenyl boronic acid (5.1 mmol), dichlorobis (triphenylphosphine) palladium (ll) (0.05 mmol), 2 M potassium carbonate (4.2
    41/109 mL) and dioxane (21 mL) were combined in a flask and irradiated by microwave for 20 min at 150 ° C. The organic layer from the reaction mixture was loaded directly onto silica and dried under vacuum. Purification by silica gel using chromatography (EtOAc / hexanes) yielded the product (75 mg) as a white solid: 1 H NMR (400 MHz, CDCl 3 ) δ 10.13 (s, 1H), 9 , 06 (s, 2H), 8.68 (d, J = 8.8 Hz, 2H), 8.03 (d, J = 8.3 Hz, 2H), 7.68 (d, J = 8, 8 Hz, 2H), 7.40 (d, J = 8.7 Hz, 2H); EIMS m / z 344 (M + ).
    Example 34: Preparation of (£) -A / - (4-dimethylamino) phenyl) -2- (4 (1- (4- (trifluoromethoxy) phenyl) -1H-1,2,4triazol-3-yl) benzylidene) hydrazinacarbothioamide (Compound 1) [Synthesis Method A].
    Step 1. (E) -3- (4- (Hydrazonomethyl) phenyl) -1- (4- (trifluoromethoxy) phenyl) -1H-1,2,4-triazole. To a 250 ml round-bottom flask containing hydrazine hydrate (64% aq; 7.27 ml, 15.0 mmols) in EtOH (100 ml) at 80 ° C was added 4- [1- (4- trifluoromethoxyphenyl) -1 / 7- [1,2,4] triazol3-yl] -benzaldehyde (5.00 g, 1.50 mmol) in dropwise portions over 5 min. A solution was stirred at reflux for an additional 3 h and was diluted with H 2 O (300 mL) and cooled to 0 ° C. The precipitated product was collected by means of vacuum filtration as a white solid (4.89 g, 93%) mp 222-226 ° C; 1 H NMR (400 MHz, DMSO-cfe) δ 8.59 (s, 1H), 8.22 (d, J = 8.2 Hz, 2H), 7.84-7.79 (m, 2H), 7.66 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 7.29 (s, 1H), 5.63 (br s, 2H) ; ESIMS m / z 348 (M + H).
    Step 2. To a 25 mL round-bottom flask containing (E) 3- (4- (Hydrazonomethyl) phenyl) -1 - (4- (trifluoromethoxy) phenyl) -1 / - / - 1,2,4-triazole (250 mg, 0.720 mmol) in THF (10 mL) 4-isothiocyanate- / V, / Vdimethylaniline (385 mg, 2.16 mmol) was added. The contents were heated to 65 ° C with stirring for 2 h before the solvent was removed under reduced pressure. The residue was suspended in CH 2 CI 2 (10 mL) resulting in precipitation of the product material. The desired product was obtained as a yellow solid by vacuum filtration (350 mg, 93%); mp 205-208 ° C; 1 H NMR (400 MHz, DMSO-cfe) δ 11.78 (s, 1H), 10.02 (s, 1H), 9.42 (s, 1H), 8.19-7.99 (m, ' 6H), 7.64 (d, J = 8.3 Hz, 2H), 7.28 (d, J = 8.3 Hz, 2H), 7.73 (d, J = 8.3 Hz, 2H) , 2.92 (s, 6H); ESIMS m / z 526 (M + H).
    Example 35: Preparation of N- (3- (dimethylamino) phenyl) -2- (4- (1- (4 (trifluoromethoxy) phenyl) -1H-1,2,4-triazol-3-yl) benzylidene) hydrazinacarbothioamide ( Compound 2) [Synthesis Method B].
    Step 1. (£) -Methyl 2- (4- (1- (4- (trifluoromethoxy) phenyl) -1H-1,2,4-triazol-3yl) benzylidene) hydrazinacarbodithioate. To a bottom flask
    -10 round of 250 mL containing methyl ester of hydrazinecarbodithioic acid (2.38 g, 1.95 mmol) in EtOH (100 mL) was added 4- [1- (4trifluoromethoxyphenyl) -1 / 7- [1,2,4 ] triazol-3-yl] -benzaldehyde (5.00 g, 1.50 mmol). The vessel was heated to 80 ° C for 3 h before being diluted with H 2 O (300 ml) and cooled to 0 ° C. The precipitated product was collected by means of vacuum filtration as an off-white solid (6.13 g, 93%) mp 204-206 ° C; 1 H NMR (400 MHz, DMSO-cfe) δ 13.39 (s, 1H), 9.43 (s, 1H), 8.38 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 8.09 (d, J = 8.4 Hz, 2H), 7.88 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 8.3 Hz, 2H), 2.57 (s, 3H); ESIMS m / z 438 (M + H).
    Step 2. To a 50 mL round-bottom flask containing 2- (420 (1- (4- (trifluoromethoxy) phenyl) -1H-1,2,4-triazol-3-yl) benzylidene) (E) hydrazinacarboditioate -methyl (250 mg, 0.571 mmol) in DMF (3 mL) was added / V1, A / 1-dimethylbenzene-1,3-diamine (195 mg, 1.43 mmol). The contents were heated to 150 ° C with stirring for 5 h before a solution was allowed to cool overnight. The mixture was filtered, and the filtrate purified through RP-HPLC to yield the desired material (235 mg, 78%) as an off-white solid: mp 192-194 ° C; 1 H NMR (400 MHz, DMSO-cfe) δ 11.82 (s, 1H), 10.04 (s, 1H), 9.41 (s, 1H), 8.19 (s, 1H), 8, 16-7.99 (m, 6H), 7.61 (d, J = 8.3 Hz, 2H), 7.16 (t, J = 7.2 Hz, 1H), 7.01 (m, 1H ), 6.87 (m, 1H), 6.58 (m, 1H), 2.88 (s, 6H); ESIMS m / z 526 ([M + H] + ).
    43/109
    Example 36: Preparation of N-benzyl-2- (4- (1- (4 (trifluoromethoxy) phenyl) -1 H-1,2,4-triazoI-3-yl) benzylidene) hydrazinacarbothioamide (Compound 3) [ Synthesis C].
    To a 50 ml round bottom flask containing 4- [1- [45 (trifluoromethoxy) phenyl] -1,2,4-triazol-3-yl] benzaldehyde (500 mg, 1.5 mmol) in EtOH (3 ml ) 4-benzylthiosemicarbazide (650 mg, 3.6 mmol) was added. The reaction mixture was heated to 80 ° C overnight. H 2 O was added after the reaction was complete and the crude product material was isolated by means of vacuum filtration. The title compound was isolated via RP10 HPLC as a white solid (390 mg, 52% yield): mp 220-224 ° C; 1 H NMR (400 MHz, CDCI 3 ) δ 9.29 (s, 1H), 8.59 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 7,857.79 (m , 3H), 7.71 (d, J = 8.4 Hz, 2H), 7.46-7.30 (m, 8H), 5.01 (d, J = 5.8 Hz, 2H); ESIMS 497.2 (M + H).
    Compounds 4 to 159 in Table 1 were synthesized according to the examples above.
    The compounds were tested against beet caterpillar and corn moth larva using procedures described in the following examples and shown in Table 2.
    In each case in Table 2, the rating scale is as follows:
    % Control (or Mortality) Classification 50-100 THE less than 50 B not tested Ç
    Example 37: Insecticide testing for beet caterpillar (Spodoptera exigua)
    Bioassays on beet caterpillars (BAW; Spodoptera exigua: Lepidoptera) were performed using a 128-well feed tray assay. Three to five seconds later, BAW larvae were placed in each well (3 mL) of the feed tray that had been previously filled with 1 mL of artificial diet which contained 50 pg / cm 2 of the test compound (dissolved in 50 90: 10 ml of the acetone-water mixture) had been applied (to each of the eight wells) and then allowed to dry. The trays were covered with a transparent self-adhesive lid, and held at 25 ° C, 14:10 chiaroscuro for six days. The mortality percentage was recorded for the larvae in each well; the activity in the eight wells was then measured. The results for both bioassays are shown in Table 2.
    Example 38: Insecticide test for moth larvae that eats corn (Helicporpa zea)
    The bioassays with the moth larvae that eats corn (CEW; Helicporpa zea: Lepidoptera) were carried out using a 128-well feed tray assay. Three to five second instars of CEW larvae were placed in each well (3 mL) of the feed tray that had previously been filled with 1 mL of artificial diet to which 50 pg / cm 2 of the test compound (dissolved in 50 mL of 90 : 10 acetone-water mixture) had been applied (to each of the eight wells) and then allowed to dry. The trays were covered with a transparent self-adhesive lid, and held at 25 ° C, 14:10 chiaroscuro for six days. The mortality percentage was recorded for the larvae in each well; the activity in the eight wells was then measured. The results for both bioassays are shown in Table 2.
    The compounds were tested against the green aphid using a procedure described in the following example and shown in Table 2.
    In each case in Table 2, the rating scale is as follows:
    % Control (or Mortality) Classification 80-100 THE less than 80 B not tested Ç
    Example 39: Insecticide test for green aphid (Myzus persicaé) in a leaf spray test
    45/109
    The cabbage seedlings grown in 7.62 cm (3 inch) pots, with 2 to 3 small natural leaves (3 to 5 cm), were used as a test substrate. The seedlings were infested with 20 to 50 green aphids (adult aphids and nymphs) one day before chemical application. Four individual pots with seedlings were used for each treatment. The compounds (2 mg) were dissolved in 2 ml of acetone / methanol (1: 1) of solvent, forming stock solutions of 1000 ppm. The stock solutions were diluted 5X with 0.025% Tween 20 in H 2 O to obtain a test solution at 200 ppm. A hand-held Devilbiss sprayer was used to spray a solution onto both sides of the cabbage leaves until runoff. The reference plants (solvent checked) were sprayed with the diluent only. The treated plants were carried out in a detention room for three days, at approximately 25 0 C and 40% relative humidity (RH) before classification. The evaluation was performed by counting the number of live aphids per plant under a microscope. Data on insecticidal activity, measured using Abbott's correction formula, are shown in Table 2:
    Control% corrected = 100 * (X - Y) / X where X = n of aphids that live in solvent selection plants
    Y = No. of aphids live on treated plants
    ACID AND SALT DERIVATIVES AND SOLVATQS
    The compounds described in the present invention can be in the form of pesticide-acceptable acid addition salts.
    As a non-limiting example, an amine function can form salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, ascorbic, gluconic, acids. maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic and hydroxyethanesulfonic.
    In addition, as a non-limiting example, an acid function can form salts, including those derived from alkaline earth metals or
    46/109 alkali and derivatives of ammonia and amines. Examples of preferred cations are: sodium, potassium, magnesium and amine cations.
    The salts are prepared by contacting the free base form with a sufficient amount of the desired acid to produce a salt. The free base forms can be regenerated by treating the salt with a dilute aqueous solution of suitable base, such as diluting aqueous NaOH, potassium carbonate, ammonia and sodium bicarbonate. As an example, in many cases, a pesticide is modified to a more water-soluble form, for example 2,4-dichlorophenoxy acetic acid of dimethyl amine salt is a more water-soluble form of 2,4 dichlorophenoxy-acetic acid as a known herbicide.
    The compounds described in the present invention can also form stable complexes with the solvent molecules that remain intact after the uncomplexed solvent molecules have been removed from the compounds. These complexes are often referred to as solvates.
    Stereoisomers
    Certain compounds described in the present invention can exist as one or more stereoisomers. Stereoisomers include several geometric isomers, diastereoisomers, and enantiomers. Accordingly, the compounds described in the present invention include racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that a stereoisomer can be more active than the others. Individual stereoisomers and optically active mixtures can be obtained through synthetic selective procedures, through conventional synthetic procedures using resolved starting materials, or through conventional resolution procedures.
    SEA
    In another embodiment, the present invention described in this document can be used to control pests.
    In another embodiment, the present invention described in this document can be used to control Phylum Nematoda pests
    47/109
    In another embodiment, the present invention described in this document can be used to control Phylum Artropoda pests
    In another embodiment, the present invention described in this document can be used to control the pests of SubPhylum Chelicerata
    In another embodiment, the present invention described in this document can be used to control pests of the Arachnida Class.
    In another embodiment, the present invention described in this document can be used to control pests of SubPhylum Myriapoda.
    In another embodiment, the present invention described in this document can be used to control pests of the Symfilaa Class.
    In another embodiment, the present invention described in this document can be used to control SubPhylum Hexapoda pests.
    In another embodiment, the present invention described in this document can be used to control pests of the Insecta class.
    In another embodiment, the present invention described in this document can be used to control Coloptera (beetles). A non-exhaustive list of these pests includes, but is 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. (grubs), Ataenius spretulus (Black Turgrass 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, Cerostema spp., Cerotoma spp. (chrysomeids), Cerotoma trifurcata (bean leaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpod weevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp. (chrysomelids), Colaspis
    48/109 spp. (soil beetles), Conoderus scalarís, Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinus nitidis (Green June beetle), Críoceris asparagi (asparagus beetle), Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pellets turcicus (Turkish grain beetle), Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp. (grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporaus marginatus (mango leaf-cutting weevil), Dermestes lardarius (larder beetle), Dermestes maculates (hide beetle), Diabrotica spp. (chrysolemids), Epilachna varivestis (Mexican bean beetle), Faustinus cubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hypera false (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil), Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers), Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata (Colorado potato beetle), Liogenys fuscus, Liogenys suturalis, Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (wood beetles / powder post beetles), Maecolaspis joliveti, Megascelis spp., Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle), Melolontha melolontha (common European cockchafer), Oberea brevis, Oberea linearis, Oryctes rhinoceros (date ), Oryzaephilus mercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothed grain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cereal leaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp. (May / June beetle), Phyllophaga cuyabana, Phyllotreta spp. (chrysomelids), Phynchites spp., Popillia japonica (Japanese beetle), Prostephanus truncates (larger grain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogus spp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp. (wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granary weevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstore beetle), Tribolium spp. (flour beetles), Tríbolium castaneum (red flour beetle), Tríbolium confusum (confused flour beetle), Trogoderma varíabile (warehouse beetle), and Zabrus tenebioides.
    In another embodiment, the present invention described in this
    49/109 document can be used to control Dermaptera (tesourintem).
    In another embodiment, the present invention described in this document can be used to control Dictioptera (cockroaches). A non-exhaustive list of these pests includes, but is not limited to, Germanic blattella (German cockroach), Blatta orientalis (oriental cockroach), Parcoblatta pennylvanica, American periplaneta (American cockroach), Peripianeta australoasiae (Australian cockroach), Periplaneta brunnea (brown cockroach) ), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselus suninamensis (Surinam cockroach), and Supella longipalpa (brownbanded cockroach).
    In another embodiment, the present invention described in this document can be used to control Diptera (flies). A non-exhaustive list of these pests includes, but is not limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp. (fruit flies), Anastrepha suspended (Caribbean fruit fly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp. (fruit flies), Ceratitis capitata (Mediterranean fruit fly), Chrysops spp. (deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (gall midges), Culex spp. (mosquitoes), Dasineura spp. (gall midges), Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura (seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filth flies), Fannia canicularis (little house fly), Fannia scalaris (latrine fly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypoderma lineatum (common cattle grub), Liriomyza spp. (leafminer flies), Liriomyza brassica (serpentine leafminer), Melophagus ovinus (sheep ked), Musca spp. (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).
    In another embodiment, the present invention described in this
    50/109 document can be used to control Hemiptera (bed bugs). A non-exhaustive list of these pests includes, but is not limited to, Acrosternum hilare (green stink bug), B / issus leucopterus (chinch bug), Calocorís 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 theivug (spight blightpn . (stink bugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp. (plant bugs), Lygus hesperus (western tarnished plant bug), Maconellicoccus hirsutus, Neurocolpus longirostrís, Nezara viridula (Southern green stink bug), Phytocorís spp. (plant bugs), Phytocorís californicus, Phytocorís relativus, Piezodorus guildingi, Poecilocapsus lineatus (fourlined plant bug), Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea, and Triatoma spp. (bloodsucking conenosis bugs / kissing bugs).
    In another embodiment, the present invention described in this document can be used to control Homoptera (aphids, scales, whiteflies, cigarrintem). A non-exhaustive list of these pests includes, 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 aurantii (California red scale), Aphis spp. (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. (scales), Ceroplastes rubens (red wax scale), Chionaspis spp. (scales), Chrysomphaius spp. (scales), Coccus spp. (scales), Dysaphis plantaginea (rosy apple aphid), Empoasca spp. (leafhoppers), Eríosoma lanigerum (woolly apple aphid), Icerya purchasi (cottony cushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphax striatellus (smaller brown planthopper), Lepidosaphes
    51/109 spp., Macrosiphum spp., Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae (rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarva frimbiolata, Metopolophium dirhodum (rose grain) Mictis longicornis, Myzus persicae (green peach aphid), Nephotettix spp. (leafhoppers), Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (brown planthopper), Parlatoria pergandii (chaff scale), Parlatoria ziziphi (ebony scale), Peregrinus maidis (corn delphacid), Philaenus spp. (spittlebugs), Phylloxera vitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale), Planococcus spp. (mealybugs), Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pine apple mealybug), Quadraspidiotus pemiciosus (San Jose scale), 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), Therioaphis spp. (aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies), Trialeurodes vaporaríorum (greenhouse whitefly), Trialeurodes abutiloneus (bandedwing whitefly), Unaspis spp. (scales), Unaspis yanonensis (arrowhead scale), and Zulia entreríana.
    In another embodiment, the present invention described in this document can be used to control Himenoptera (ants, wasps and beetles). A non-exhaustive list of these pests includes, but is 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., Monomoríum minumum (little black ant), Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp. (harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fire ants), Tapoinoma sessile (odorous house ant), Tetranomorium spp. (pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp. (carpenter bees).
    In another embodiment, the present invention described in this document can be used to control Isoptera (termites). A list does not
    An exhaustive 52/109 of these pests includes, but is 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. (drywood termites), Microcerotermes spp. (harvester termites), Microtermes obesi, Procornitermes spp., Reticulitermes spp. (subterranean termites), Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes (eastern subterranean termite), Reticulitermes hageni, Reticulitermes hesperus (western subterranean termite), Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes, Schedichermes and spherichermes, tericulitermes. (rotten-wood termites).
    In another embodiment, the present invention described in this document can be used to control Lepidoptera (moths and butterflies). A non-exhaustive list of these pests includes, but is not limited to, Acredea janata, Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana, Amyelosis transitella (navel orangeworm), Anacamptodes defectaria, Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper), Anticarsia gembean Caterpillar), Archips argyrospila (fruit tree leafroller), Archips rosaria (rose leaf roller), Argyrotaenia spp. (tortricid moths), Argyrotaenia citrana (orange tortrix), Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder), Bucculatrix thurberiella (cotton leaf perforator), Caloptilia spp. (leaf miners), Capua reticulana, Carposina niponensis (peach fruit moth), Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneura rosaceana (oblique banded leaf roller), Chrysodeixis spp., Cnaphalocerus medinalis (grass leafroller), Colias ., Conpomorpha cramerella, Cossus cossus (carpenter moth), Crambus spp. (Sod webworms), Cydia funebrana (plum fruit moth), Cydia molesta (oriental fruit moth), Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darna diducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),
    53/109
    Diatraea saccharalis (sugarcane borer), Diatraea graniosella (southwestern corn borer), Earias spp. (bollworms), Earias insulata (Egyptian bollworm), Earías vitella (rough northern bollworm), Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalk borer), Epiphysias postruttana (light brown apple moth), Ephestia spp. (flour moths), Ephestia cautella (almond moth), Ephestia elutella (tobacco moth), Ephestia kuehniella (Mediterranean flour moth), Epimeces spp., Epinotia aporema, Erionota thrax (banana skipper), Eupoecilia ambiguella (grape berry moth), Euxoa auxiliary (army cutworm), Feltia spp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (oriental fruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp. (noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (bollworm / corn earworm), Heliothis spp. (noctuid moths), Heliothis virescens (tobacco budworm), Hellula undalis (cabbage webworm), Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm), Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella, Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp. (noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantria dispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasena corbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars), Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean pod borer), flat metisa (bagworm), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis (rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis (European corn borer), Oxydia vesulia, Pandemis cerasana (common currant tortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus, Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms), Peridroma saucia (variegated cutworm), Perileucoptera coffeella (white coffee leafminer), Phthorimaea operculella (potato tuber moth), Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae (imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indian meai moth), Plutella xylostella (diamondback moth), Polychrosis viteana (grape berry moth), Prays endocarpa, Prays oleae (olive moth), Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm), Pseudoplusia includens (soybean looper), Ra54 / 109 naked chiplusia, Scirpophaga incertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stem borer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella (Angoumois grain moth), Sparganothis pilleríana, Spodoptera spp. (armyworms), Spodoptera exigua (beet armyworm), Spodoptera frugiperda (fali armyworm), Spodoptera oridania (Southern armyworm), Synanthedon spp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineola bisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper), Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), and Zeuzera pyrina (leopard moth).
    In another embodiment, the present invention described in this document can be used to control to control Mallofaga (chewing lice). A non-exhaustive list of these pests includes, but is not limited to, Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken body louse), and Menopon gallinea (common hen louse).
    In another embodiment, the present invention described in this document can be used to control Ortoptera (grasshoppers, and crickets). A non-exhaustive list of these pests includes, but is not limited to, Anabrus simplex (Mormon cricket), Gryllotalpidae (mole crickets), Migratory Localta, Melanoplus spp. (grasshoppers), Microcentrum retinerve (angular winged katydid), Pterophylla spp. (katydids), schistocerca gregaria, Scudderia furcata (fork tailed bush katydid), and Valanga nigricorni.
    In another embodiment, the present invention described in this document can be used to control Ftiraptera (sucking lice). The non-exhaustive list of these pests includes, but is 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).
    In another embodiment, the present invention described in this document can be used to control to control Sifonaptera (fleas). A non-exhaustive list of these pests includes, but is not limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea), and Pulex irritans (human flea).
    55/109
    In another embodiment, the present invention described in this document can be used to control Tisanoptera (tripods). A non-exhaustive list of these pests includes, but is not limited to, Frankliniella fusca (tobacco thrips), Frankliniella occidentalis (western flower thrips), Frankliniella shultzei Frankliniella williamsi (corn thrips), Heliothríps haemorrhaidalis (greenhouse thrips), Riphiphorothríps cruentatus, Scirtpotspsirt ., Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow tea thrips), Taeniothrips rhopalantennalis, and Thrips spp.
    In another embodiment, the present invention described in this document can be used to control to control Tisanura (bristletails). A non-exhaustive list of these pests includes, but is not limited to, Lepisma spp. (silverfish) and Thermobia spp. (firebrats).
    In another embodiment, the present invention described in this document can be used to control to control Acarina (mites and ticks). A non-exhaustive list of these pests includes, but is 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 schlechtendali (apple rust mite), Amblyomma amerícanum (lone star tick), Boophilus spp. (ticks), Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and black flat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks), Dermacentor varíabilis (American dog tick), Dermatophagoides pteronyssinus (house dust mite), Eotetranycus spp., Eotetranychus carpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodes spp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (Southern red mite), Panonychus spp., Panonychus citri (citrus red mite), Panonychus ulmi (European red mite), Phyllocoptruta oleiv (Phyllocoptruta oleiv rust mite), Polyphagotarsonemun latus (broad mite), Rhipicephalus sanguineus (brown dog tick), Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite), Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae (two-spotted spider mite), and Varroa destructor (honey bee mite).
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    In another embodiment, the present invention described in this document can be used to control Nematodes (nematodes). A non-exhaustive list of these pests includes, but is not limited to, Aphelenchoides spp. (bud and leaf & pine wood nematodes), Belonolaimus spp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilaria immitis (dog heartworm), Ditylenchus spp. (stem and bulb nematodes), Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella spp. (root nematodes), Hoplolaimus 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 reniformis (kidney-shaped nematode).
    In another embodiment, the present invention described in this document can be used to control to control Symphyla (symphylans). A non-exhaustive list of these pests includes, but is not limited to, Scutigerella immaculata.
    For more detailed information see the Handbook of Pest Control - The Behavior, Life History and Control of Household Pests, Arnold Mallis, 9th Edition, Copyright 2004 by GIE Media Inc.
    MIXTURES
    The present invention described in this document can also be used with various insecticides, both for reasons of economy and synergy. Insecticides include, but are not limited to, antibiotic insecticides, macrocyclic lactone insecticides (eg avermectin insecticides, milbemycin insecticides and spinosyn insecticides), arsenical insecticides, botanical insecticides, carbamate insecticides (eg benzofuran methylcarbamate insecticides, carbofuran insecticides, dimethyl insecticides, oxime carbamate insecticides, and phenyl methylcarbamate insecticides), diamide insecticides, desiccant insecticides, dinitrophenol insecticides, fluorine insecticides, formamidine insecticides, fumigant insecticides, inorganic insecticides, insect growth regulators (for example, inhibitor inhibitors , youth hormone mimics, youth hormones, agonists
    57/109 mutable hormones, mutable hormones, mutable inhibitors, precocenes, and other unclassified insect growth regulators), analogue nereistoxin insecticides, nicotinoid insecticides (eg nitroguanidine oxadiazolone insecticides, nitromethylene insecticides and pyridylmethylamine insecticides) organochlorines, organophosphorus insecticides, oxadiazine insecticides, oxadiazolone insecticides, phthalimide insecticides, pyrazole insecticides, pyrethroid insecticides, pyrimidinamine insecticides, pyrrole insecticides, tetramic acid insecticides, thetronic acid insecticides, aunt insecticides thiourea, urea insecticides, as well as other unclassified insecticides.
    Some of the insecticides in particular that can be used advantageously in combination with the present invention described in this document include, but are not limited to, the following 1,2dichloropropane, 1,3-dichloropropene, abamectin, acephate, acetamipride, acetone, acetoprol, acrinatrine , acrylonitrile, alanicarb, aldicarb, aldoxicarb, aldrin, aletrine, allosamidine, allixicarb, alpha-cypermethrin, alpha-endosulfan, amiditiona, aminocarb, Amiditiona, amitraz, Anabasine, atidation, azadiractin, azinfetate, azamethos , Barium hexafluorsilicate, bartrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, betacypermethrin, bifenthrin, Bioalethrin, bioethanometrine, biopermethrin, biormethrin, bistrifluronaa, borax, boric acid, bromofenic, bromine, bromine, bromine, bromine, bromine, bromine ethyl, bufencarb, buprofezina, butacarb, butatiofos, butocarboxim, butonato, butoxicarboxim, cadusafos, calcium arsenate, calcium polysulfide, canfecloro, carbanolato, carbarila, carbofuranoo, carbon disulfide, carbon tetrachloride, carbofenothione, carbosulfam, cartap, clorantraniliprol, chlorbicyclene, chlordane, chlordecone, chlordimeform, chlorethoxy, chlorfenoxy, chloroform, chloroform, chloro chlorpyrifos, chlorpyrifosmethyl, chlortiofos, chromafenozide, cinerin I, cinerin II, cyismetrin, cloetocarb, closantel, clothianidin.copper arsenate, copper arsenate, copper naphthenate, copper olate, coumafos, kymothomate, crotifox, crotoxy, cryptotoxide, cryptotoxide, cryptotoxide, cryptotoxide, cryptotoxide, crotoxide, cryptide cyanophos, cyantraniliprol cyantoate, cycletrin,
    58/109 cycloprotrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenotrin, cyromazine, DDT.decarbofuran, deltamethrin, demefion, demefion-O, demefion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-O-methyl, demeton-O-methyl, S, demeton-S-methyl, demeton-S-methylsulfon, diafentiurone, dialiphs, diatomaceous, diazinon, dicapton, dichlofention, dichlorvos, dicresila, dicrotofos, dicyclanyl, dieldrin, diflubenzurone, Dilor, dimoxetin, dimeflutrin, dimeflutrin, dimeflutrin dimethylavinfos, dimethilan, dinex, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxation, disulfoton, dithrophos, dlimonene, DNOC, doramectin, ecdisterone, emamectin, EMPC, empentrin, endentin, endentin, endosan, endosan, endosan, endosan, endosan, endosan esfenvalerate, etafos, etiofencarb, etion etiprol, etoate-methyl, etoprofos, ethyl formate, ethyl-DDD, ethylene dibromide, dichloroethane, ethylene oxide, etofenprox, etrimphos, EXD, famfur, fenfen, fenfen, fenfen otion, fenobucarb, fenoxacrim, fenoxicarb, fenpiritrin, fempropatrina, fensulfotion, fention, fention-ethyl, fenvalerato, fipronil, flonicamid, flubendiamide, flucofurone, flucicloxurone, flucitrinate, flufenerin, flufenoxurate, flufenoxurone, flufenoxurone, flufenoxurone, flufenoxurone, flufenoxurone, flufenoxurone, flufenoxurone, formulinate fosmetilane, fostietano phospirate, furatiocarb, furetrin, gamma-cyhalothrin, gamma HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumurone, HHDN, hydramethylone, hydroprene, cyanide, imidine, hydroxy, imidine iodomethane, IPSP, isazofos, isobenzan, isocarbofos, isodrine, isofenfos, isoprocarb, isoprothiolane, isothioate Isoxation, ivermectin, jasmolin I, jasmolin II, jodfenfos, juvenile hormone I, juvenile hormone II, juvenile hormone, juvenile hormone, kevinan, youthful hormone, juvenile hormone, kylamine lead, lepimectin, leptophos, lindane, lirimphos, lufenurone, litidation, malation, malonoben, mazidox, mecarbame, mecarfon, menazon , mefosfolan, mercury chloride, mesulfenphos, metaflumizone, methacrifos, metamidophos, metidation, metiocarb, metocrotophos, metomil, metoprene, metoxichlor, methoxyfenozide, methyl bromide, methylachloroform, methylene chloride, methacrylone, methacrylone, methacrylone oxime, mipafox, mirex, monocrotofós, morfotion, moxidectin, naphthalophos, nalede, naphthalene, nicotine, nifluridide, nitenpiram,
    59/109 nitiazine, nitrilacarb, novaluron, noviflumurone, ometoate, oxamil, oxidemeton-methyl, oxideprofos, oxidisulfoton, para-dichlorobenzene, paration, parationmethyl, penflurone, pentachlorophenol, permethrin, phenkapton, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphatone, phosphenol fosnichlor, phosfamidão, phosfina, foxima, foxima-methyl, pirimetafos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp 'DDT, pralletrin, early I, early II, early III, primophils, profidophines, primophines , proflutrin, promacila, promecarb, propafos, propetamfos, propoxur, protidation, protiofos, protrifenbute protoate, piraclofos, pirafluprol, pirazofos piresmetrin, pyrethrin, pyridaben, piridalil, piridifen, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine , quinalfos, quinalfos-methyl, quinotion, rafoxanida, resmetrina, rotenona, ryania, sabadilla, schradan, selamectina, silafluofen, silica gel, sodium arsenite, sodium fluoride, hexafluorsilicate, sodium thiocyanate, sofamide, spinetoram, spinosad, spiromesifene, spirotetramato, sulcofurone, sulfoxaflor, sulfluramide, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarbene, tzimcarbide, tzimcarbide, tzimcarbide, tzimcarbide, tzimcarbide, tzimcarbide, tzimcarbide, tzimfeb teflutrin, temefos, TEPP, teralletrin, terbufos, tetrachloroethane, tetrachlorvinfos, tetramethrin, theta-cypermethrin, thiacloprid, thiamethoxy, ticrofos, tiocarboxime, tiocyclam, tiodicarb, tiofanox, transametin, tetrachin, triazamate, triazophos, trichlorfon, trichloromethane-3, trichloronat, triphenophones, triflumurone, trimetacarb, triprene, vamidotion, vaniliprol, XMC, xylailacarb, zeta-cypermethrin, zolaprofos, and a-ecdysone.
    In addition, any combination of the above insecticides can be used.
    The present invention described in this document can also be used, for reasons of economy and synergy, with acaricides, algaecides, antifeedants, avicides, bactericides, bird repellents, Chemical sterilizers, fungicides, herbicidal agents, herbicides, attractive insects, insect repellents, mammalian repellents, mating disrupters, molluscicides, plant activators, growth regulators, rodenticides, synergists, defoliants, desiccants, disinfectants, semi-chemicals, and viru60 / 109 acids (these categories are not necessarily mutually exclusive).
    For more information, see Compendium of Pestícíde Common Names, located at http://www.alanwood.net/ pesticides / index.html. See also The Pesticide Manual Edition 14, edited by CDS Tomlin, Copyright 2006 by the British Crop Production Council.
    SYNERGIC MIXTURES
    The present invention described in this document can be used to control with other compounds, such as those mentioned under the title Mixtures to form synergistic mixtures, where the mode of action of the compounds in the mixtures are the same, similar or different.
    Examples of the mode of action include, but are not limited to: acetylcholinesterase inhibitors; sodium channel modulator; chitin inhibitor of biosynthesis; antagonist of the chloride channels linked to GABA; chlorine channel linked to GABA and glutamate; acetylcholine receptor agonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholine receptor; membrane-disrupting midgut; oxidative phosphorylation disruptor; and ryanodine receptor (RyRs).
    In addition, the following compounds are known to be synergistic and can be used with the present invention described in this document: piperonyl butoxide, piprotal, propyl isoma, sesamex, sesamoline and sulfoxide.
    FORMULATIONS
    A pesticide is rarely suitable for application in its pure form. It is usually necessary to add other substances so that the pesticide can be used in the concentration, and in an appropriate form, allowing ease of application, handling, maximum activity of the pesticide, transport, and storage. Thus, pesticides are formulated in, for example, baits, concentrated emulsions, dust, emulsifiable concentrates, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water-soluble liquids, water-dispersible granules or dry flakes, wettable powders, and ultra-low volume solutions.
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    For more information on types of formulation see Catalog of Pesticide Formulation Types and International Coding System Technical Monograph n ° 2, 5 a Edited by CropLife Internacional (2002).
    Pesticides are applied most often as aqueous suspensions or emulsions prepared from concentrated pesticide formulations. Such water-soluble, suspended water or emulsion formulations are either solid, generally known as wettable powders or water-dispersible granules, or are liquids generally known as emulsifiable concentrates, or aqueous suspensions. Wettable powders, which can be compacted to form water-dispersible granules, comprise an intimate mixture of the pesticide, a vehicle and surfactant. The concentration of the pesticide is generally from about 10% to about 90% by weight. The vehicle is generally chosen from atapulgite clays, montmorillonite clays, diatomaceous earth, or purified silicates. Effective surfactants, composed of about 0.5% to about 10% of the wettable powder, are found among sulfonated lignins, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants, such as ethylene oxide adducts. alkyl phenols.
    Emulsifiable pesticide concentrates comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a vehicle that is a miscible solvent water or a mixture of water, immiscible organic solvent and emulsifiers. Useful aromatic organic solvents include, especially xylenes and oil fractions, especially the high-boiling portions of naphthalene and olefinic oil, such as heavy aromatic naphtha. Other organic solvents can also be used, such as terpenic solvents including rosin derivatives, aliphatic ketones, such as cyclohexanone and complex alcohols, such as 2-ethoxyethanol. Emulsifiers suitable for emulsifiable concentrates are chosen from conventional anionic and non-ionic surfactants.
    Aqueous suspensions comprise pesticide suspensions
    62/109 water insoluble dispersed in an aqueous vehicle at a concentration in the range of about 5% to about 50% by weight. The suspensions are prepared by finely grinding a pesticide and vigorously mixing a mixture composed of water and surfactants. The ingredients, such as inorganic salts and synthetic or natural gums, can also be added, to increase the density and viscosity of the aqueous vehicle. It is often more effective to grind and mix pesticides at the same time, preparing the aqueous mixture and homogenization in an implement such as a sand mill, ball mill, or piston-type homogenizer.
    Pesticides can also be applied as granular compositions that are particularly useful for soil applications. Granular compositions generally contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a vehicle comprising clay or similar substance. Such compositions are generally prepared by dissolving the pesticide in a suitable solvent and applying it to a vehicle. granular which has been preformed to the appropriate particle size, in the range of about 0.5 to about 3 mm. Such compositions can also be formulated, making a mass or paste of the vehicle and compounds and crushing and drying to obtain the desired granular size.
    Dusts containing a pesticide are prepared by intimately mixing the pesticide in powder form with a suitable dusty agricultural vehicle, such as kaolin clay, volcanic stone soil, and the like. Dusts can conveniently contain from about 1% to about 10% of pesticides. They can be applied as a seed treatment or as a leaf application with an air blowing machine.
    It is equally practical to apply a pesticide in the form of a solution of an organic solvent in an appropriate manner, usually oil, petroleum, such as spray oils, which are widely used in agricultural chemistry.
    Pesticides can also be applied in the form of an aerosol composition. In such compositions, the pesticide is dissolved or dispersed in a vehicle, which is a propellant mixture generating pressure. THE
    63/109 aerosol composition is packed in a container where the mixture is dispensed through an atomization valve.
    Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When pests eat the bait they also consume the pesticide. The baits can take the form of granules, gels, fluid powder, liquid or solid. They are used in territories where there are pests.
    Fumigants are pesticides that have a relatively high vapor pressure and therefore can exist as a gas in sufficient concentrations to kill pests in the soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and exposure time. They are characterized by a good diffusion capacity and act by penetrating the respiratory system of the pest, or being absorbed through the cuticle of the pest. Fumigants are applied to control pests of products stored in gas-proof foliage, in sealed gas rooms or buildings or in special chambers.
    Pesticides can be microencapsulated, suspending pesticidal particles or droplets of plastic polymers of various types. By changing polymer chemistry or changing factors in processing, microcapsules can be formed in various sizes, solubility, thicknesses and degrees of penetrability. These factors regulate the speed with which the active ingredient is released inside, which in turn affects the residual performance, the speed of action, and the odor of the product.
    The oil solution concentrates are made by dissolving pesticides in a solvent that will contain the pesticide in solution. Oil solutions of a pesticide generally provide faster knockdown and kill pests faster than other formulations, due to the action of solvents if there is pesticide and the dissolution of the wax-like coating of the object increasing the speed of absorption of the pesticide. Other advantages of oil solutions include better storage stability, better crack penetration, and better adhesion to fatty surfaces.
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    Another embodiment is an oil-in-water emulsion, in which the emulsion comprises oily globules which are each with a lamellar liquid crystal coating and are dispersed in an aqueous phase, in which each oily globule comprising at least one compound which is active agriculture and is individually coated comprising a monolamellar or oligolamellar layer: (1) at least one nonionic lipophilic surfactant, (2) at least one nonionic hydrophilic surfactant and (3) at least one ionic surfactant, where the globules has an average particle diameter of less than 800 nanometers. More information on the incorporation is described in the publication of the patent U. S. 20070027034 published February 1, 2007, with the number of patent application series 11/495, 228. For ease of use of this modality it will be referred to as OIWE.
    For more information see Insect Pest Management 2nd Edition by D. Dent, copyright CAB International (2000). Also, for more detailed information see Handbook of Pest Control - The Behavior, Life History, and Control of Household Pests Arnold Mallis, 9th Edition, Copyright 2004 by GIE Media Inc.
    OTHER COMPONENTS OF THE FORMULATION
    Generally, the present invention described in this document when used in a formulation, such a formulation can also contain other components. These components include, but are not limited to, (this is a non-exhaustive and non-mutually exclusive list) Wetters, spreaders, adhesives, penetrants, buffers, sequestering agents, drift reduction agents, compatibility agents, antifoaming agents, cleaning, and emulsifiers. Some components are described immediately.
    A wetting agent is a substance that when added to a liquid increases the diffusion or penetration power of the liquid, reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in pesticide formulations: during processing and manufacturing for
    65/109 increase the rate of wetting of powders in water to make concentrates for soluble liquids or concentrates in suspension, and when mixing a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the water penetration into water-dispersible granules. Examples of wetting agents used in wettable powder, concentrated suspension, water-dispersible formulations and granules are: sodium lauryl sulfate, sodium dioctyl sulfosuccinate; ethoxylated alkyl phenol and aliphatic alcohol ethoxylates.
    A dispersing agent is a substance that adsorbes on the surface of particles and helps to preserve the dispersion state of the particles and prevents them from re-aggregating. Dispersing agents are added to pesticide formulations to facilitate dispersion and suspension during manufacture, and to ensure that particles re-disperse in water in a spray tank. They are widely used in wettable powders, concentrated in suspension and water-dispersible granules. Surfactants that are used as dispersing agents have the ability to strongly adsorb on a particle surface and provide a charged or steric barrier for the re-aggregation of the particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For concentrates in the suspension, very good adsorption and stabilization are achieved using polyelectrolytes, such as condensed naphthalene sodium formaldehyde sulfonate. Tristyrylphenol ethoxylated phosphate esters are also used. Non-ionics such as condensed alkylaryl ethylene oxide and EO-PO copolymer block are sometimes combined with anionic dispersants for concentrated suspension. In recent years, new types of surfactants with a high molecular weight of polymers have been developed as dispersing agents. These have a very long hydrophobic main structure and a large number of ethylene oxide chains that form the teeth of a 'comb' surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because
    66/109 hydrophobic main structures have many attachment points on particle surfaces. Examples of dispersing agents used in pesticide formulations are: sodium lignosulfonates, condensed naphthalene sodium formaldehyde sulfonate; ethoxylated phosphate tristyrylphenol esters; ethoxylate of aliphatic alcohol; alkyl ethoxylate; block of EO-PO copolymers and grafted copolymers.
    An emulsifying agent is a substance that stabilizes a suspension of droplets from one liquid phase to another liquid phase. Without the emulsifying agent the two liquids separate into two liquid immiscible phases. The most commonly used emulsifying mixture contains alkylphenols or aliphatic alcohol with twelve or more units of ethylene oxide and oil soluble in calcium salt of dodecylbenzenesulfonic acid. A range of lipophilic hydrophilic equilibrium (HLB) values from 8 to 18 usually provide good stable emulsions. The stability of the emulsion can sometimes be improved with the addition of a small amount of an EO-PO copolymer block surfactant.
    A solubilizing agent is a surfactant that will form micelles in water at concentrations above the critical micellar concentration. The micelles are then able to dissolve or solubilize water-insoluble materials within the hydrophobic part of the micelle. The type of surfactants normally used for non-ionic solubilization are: sorbitan monoolates; sorbitan ethoxylate and methyl oleate esters.
    Surfactants are sometimes used, alone or with other additives, such as mineral or vegetable oils as adjuvants to spray mixtures to improve the biological performance of the target pesticide. The types of surfactants used for biological improvement generally depend on the nature and mode of action of the pesticide. However, they are often non-ionic, such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates.
    A vehicle or diluent in an agricultural formulation is a material added to the pesticide to provide a product with the necessary strength. The vehicles are usually materials with a high absorption capacity, en67 / 109 as the diluents are generally materials with a low absorption capacity. The vehicles and diluents are used in the formulation of dust, wettable powders, granules and water dispersible granules.
    Organic solvents are used mainly in the formulation of emulsifiable concentrates, (ultra low volume) ULV formulations and, in smaller granular formulations. Sometimes, solvent mixtures are used. The first major groups of aliphatic solvents are paraffinic oils, such as kerosene or refined paraffins. The second main and most common group comprises aromatic solvents, such as xylene and higher molecular weight of C9 and C10 fractions of aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified in water. Alcohols are sometimes used as cosolvents to increase solvent power.
    Thickeners or gelling agents are mainly used in the formulation of suspended concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and prevent the separation and sedimentation of the dispersed particles or droplets. Thickeners, gelling and anti-sedimentation agents generally fall into two categories, namely, water-insoluble particles and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silica. Examples of these types of materials include, but are limited to, montmorillonite, for example, bentonite; aluminum, magnesium silicate, and atapulgite. Water-soluble polysaccharides have been used as thickening and gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and algae or are synthetic cellulose derivatives. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum; carrageenan; alginates, methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of antifeeding agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-sedimentation agent is
    68/109 xanthan gum.
    Microorganisms cause deterioration of formulated products. Therefore, preservative agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salts, sorbic acid and its sodium or potassium salts, benzoic acid and its sodium salt; sodium salt of hydroxybenzoic acid; methyl p-hydroxybenzoate and 1,2-benzisothiazalin-3-one (BIT).
    The presence of surfactants, which reduce interfacial tension, often makes water-based foam formulations available during mixing operations in production and application through a spray tank. In order to reduce the foam tendency, antifoam agents are often added, either during the production phase or before filling bottles. Generally, there are two types of antifoam agents, namely, silicones and non-silicones. Silicones are generally aqueous emulsions of dimethylpolysiloxane while non-silicone antifoam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the antifoam agent is to move the surfactant from the air-water interface.
    For more information, see Chemistry and Technology of Agrochemical Formulations, edited by DAKnowles copyright, 1998 by Kluwer Academic Publishers. See also Insecticides in Agriculture and Environment - Retróspects and Prospects by AS Perry, I. Yamamoto, I. Ishaaya, and R. Perry, Copyright 1998 by Spaneler-Verlag.
    APPLICATIONS
    The actual amount of pesticides applied to pest sites is generally not critical and can easily be determined by those skilled in the art. In general, concentrations of about 0.01 grams of pesticides per hectare to about 5000 grams of pesticides per hectare are expected to provide good control.
    The place where a pesticide is applied can be anywhere inhabited by a pest, for example, vegetables, fruits and trees, vines, ornamental plants, domesticated animals, the interior or exterior surfaces of buildings and the surrounding soil of buildings. Pest control in general means that pest populations, activity, or both, are reduced in one location. This can happen when: pest populations are repelled from one place, when pests are disabled or around a location, or pests are exterminated, in whole or in part, or around a location. It is clear that a combination of these results can occur. Generally, pest populations, activity, or both are desirably reduced by more than fifty percent, preferably more than 90 percent.
    Generally, with baits, the baits are placed on the ground, where, for example, termites can come into contact with the bait. Baits can also be applied to a building surface, (horizontal, vertical, or sloping surface), where, for example, ants, termites, cockroaches and flies, can come into contact with the bait.
    Because of the unique ability of eggs in some pests to withstand repeated applications of pesticides, it may be desirable to control newly emerged larvae.
    The systemic movement of pesticides in plants can be used to control pests in one portion of the plant by applying pesticides to a different part of the plant. For example, insect control in the feed foliage can be controlled by drip irrigation or furrow application, or by treating the seed before planting. Seed treatment can be applied to all types of seeds, including those from genetically transformed plants to express specialized traits that will germinate. Representative examples include proteins expressed toxic to invertebrate pests, such as Bacillus tuaneliensis or other insecticidal toxins, those expressing resistance to herbicides, such as seed Roundup Ready, or those with foreign genes stacked expressing insecticidal toxins, resistance to nutrition, improved nutrition or any other beneficial features. In addition, seed treatments, such as the present in70 / 109 invention described in this document, can further increase a plant's ability to better withstand stressful growing conditions. This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time.
    It should be readily apparent that the present invention can be used with genetically transformed plants to express specialized characteristics, such as Bacillus tuaneliensis or other insecticidal toxins, or those expressing herbicide resistance, or those with foreign genes stacked expressing insecticidal toxins, herbicide resistance, enhancement nutrition or any other beneficial features.
    The present invention described in this document is suitable for controlling endoparasites and ectoparasites in the veterinary medicine sector or in the animal field. Compounds are applied in a known manner, such as orally in the form of, for example, tablets, capsules, drinks, granules, by dermal application in the form of, for example, dipping, spraying, spotting, and cleaning the dust, and by parenteral administration in the form of, for example, an injection.
    The present invention described in this document can also be used advantageously in the breeding of cattle, for example, cattle, sheep, pigs, chickens and geese. Suitable formulations are administered orally to animals with drinking water or food. The dosages and formulations that are appropriate depend on the species.
    Before a pesticide can be used or sold commercially, that pesticide undergoes lengthy assessment processes by various government authorities (local, state, regional, national, international). Bulky Requirements data are specified by regulatory authorities and must be addressed through data generation and submission by the holder or another product on behalf of the product registrant. These government officials then review this data and if a security determination is completed, it provides the potential user or seller with product registration approval. After that, in that location where product registration is granted and supported, that user or seller
    71/109 can use or sell such pesticides.
    The titles in this document are for convenience only and should not be used to interpret any part of them.
    TABLES
    Table 1
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    105/109 1 All NMR data measured in DMSO - d 6 are at 300 or 400 MHZ unless otherwise noted Table 2
    Compound Mortality CEW 50 pg / cm2 BAW mortality 50 pg / cm2 Mortality GPA 200 ppm 1 THE THE B 2 THE THE B 3 B THE B 4 THE THE B 5 THE THE B 6 THE THE B 7 THE B B 8 THE THE B 9 THE THE B 10 THE THE B 11 THE THE B 12 THE THE B 13 THE THE B 14 THE THE B 15 THE THE B 16 THE THE B 17 THE THE B 18 THE THE B 19 B B B 20 THE THE B 21 THE THE B 22 THE THE B 23 THE THE B 24 B THE B 25 THE THE B 26 THE THE B 27 THE THE B 28 THE THE B 29 THE THE B 30 THE THE B 31 B B B 32 B B B 33 THE THE B 34 THE THE B 35 B B B
    106/109
    Compound Mortality CEW 50 pg / cm2 BAW mortality 50 pg / cm2 Mortality GPA 200 ppm 36 THE THE B 37 THE THE B 38 THE THE B 39 THE THE B 40 THE THE B 41 THE THE B 42 THE THE B 43 THE THE B 44 B B B 45 THE THE B 46 THE THE B 47 THE THE B 48 THE THE Ç 49 THE THE B 50 THE THE B 51 THE THE B 52 THE THE B 53 THE THE B 54 B B B 55 B B B 56 THE THE B 57 THE THE B 58 THE THE B 59 B B B 60 THE THE Ç 61 THE THE B 62 THE THE B 63 THE THE B 64 THE THE B 65 THE THE B 66 THE THE B 67 THE THE B 68 THE THE B 69 THE THE B 70 THE THE B 71 THE THE B 72 THE THE B 73 THE THE B 74 THE THE B
    107/109
    Compound Mortality CEW 50 pg / cm2 BAW Mortality50 pg / cm2 Mortality GPA 200 ppm 75 THE THE B 76 THE THE B 77 THE THE B 78 THE THE B 79 THE THE B 80 THE THE Ç 81 THE THE B 82 THE THE Ç 83 B B Ç 84 B B Ç 85 THE THE Ç 86 THE THE Ç 87 B B Ç 88 THE THE Ç 89 THE THE Ç 90 THE THE Ç 91 THE THE Ç 92 THE THE Ç 93 THE THE Ç 94 THE THE Ç 95 THE THE Ç 96 THE THE Ç 97 THE THE B 98 THE THE Ç 99 THE THE Ç 100 THE THE Ç 101 THE THE Ç 102 THE THE Ç 103 THE THE Ç 104 THE THE Ç 105 THE THE Ç 106 THE THE Ç 107 THE THE Ç 108 THE THE Ç 109 THE THE B 110 THE THE Ç 111 THE THE Ç 112 THE THE Ç 113 B B Ç
    108/109
    Compound Mortality CEW 50 pg / cm2 BAW mortality 50 pg / cm2 Mortality GPA 200 ppm 114 THE THE Ç 115 THE THE Ç 116 THE THE Ç 117 THE THE Ç 118 THE THE Ç 119 THE THE B 120 THE THE B 121 THE THE Ç 122 THE THE Ç 123 THE THE Ç 124 THE THE Ç 125 THE THE B 126 THE THE B 127 THE THE B 128 THE THE B 129 THE THE B 130 THE THE Ç 131 THE THE Ç 132 THE THE B 133 THE THE B 134 THE THE Ç 135 THE THE Ç 136 THE THE Ç 137 THE THE Ç 138 THE THE Ç 139 THE THE Ç 140 THE THE Ç 141 THE THE Ç 142 THE THE Ç 143 THE THE Ç 144 THE THE Ç 145 THE THE Ç 146 THE THE Ç 147 THE THE Ç 148 THE THE Ç 149 THE THE Ç 150 THE THE Ç 151 THE THE Ç 152 THE THE Ç
    109/109
    Compound Mortality CEW 50 pg / cm2 BAW Mortality50 pg / cm2 Mortality GPA 200 ppm 153 THE THE Ç 154 THE THE Ç 155 THE THE Ç 156 THE THE Ç 157 THE THE Ç 158 THE THE Ç 159 THE THE Ç
    V
    1/19
    权利要求:
    Claims (19)
    [1]
    5 1. Molecule, characterized by the fact that it has one of the following structures:
    # Structure 1 F F = N | 2 Λ N N ^ Xr-N. 1 WN- ^ JY - F ^ = N íS> 3 > The nn Vn-o n ^^ JP n -n 4 F FF ^ 10 = N 5 F V = N N ^ l 6 7 f ^ f O ^ K N ^ T NM r ^ = N 8 = N 9 nP N V N 'i F N ^ S ÃÕ = / VN N ^ b 10 / - N / Υ ^ ΥΥΊ F ^ 'F N N F F
    Petition 870170071853, of September 25, 2017, p. 6/28
    [2]
    2/19
    # Structure 11F FF = N 12 = / y = n 13F FF ^ = N 14N ίΎ ^ ΎΥΊ su F F 15F fY ^ Y F ^ = / = N 16 / ¾. .N ^ /%F F \ S /q 17S 0 x = / -sN 18 fV S z = / ^ n 19 fV, γνγγ SN = / ^ n 20 = / ^ N 21 howling F F
    Petition 870170071853, of September 25, 2017, p. 7/28
    [3]
    3/19
    # Structure 22 ^ y 23 F / Á / - X S F F 24 ^ y JTTú F F 25F F 26 rvvvv> A Vq FF F F 27 ΑΧ γτ ^ -ύίXo' ^ h = / 28 ^ y -ΧΤ'ΎΟ. F y A> n ι ^^ o X ' ss- | F F 29 The va 'Xj)ONi cAú 30 fV πρύί ^ Vh-W S ° Λ ° ^ == / = - / 31 /The . XV - ' - ^ rv- ° f / O-cX - χ> °
    Petition 870170071853, of September 25, 2017, p. 8/28
    [4]
    4/19
    # Structure 32 ,% ^ / ni FF Γ JJ 'ΦΟΓ F F 33 XX ^ N 'X ° 34 35 - fJ X F / FX n> ^ . 36 // N ^ V F F v ° / “N 1 1 Ί F 1 37 FF / r ~ A XVXX ^ X vjhn n ^ x yN v = N x 38 FF F X.! S V>! ^ RN N 39 FF '' Λ '', · V ^ / n n ^ χχ 'N X> 40 / -¾ N S V '- /'! 'f ^ ('
    Petition 870170071853, of September 25, 2017, p. 9/28
    [5]
    5/19
    # Structure 41 F F> 0 42F FF II N. F XX / A = / ... / 43 -N ^ P S FF 1 N. F 'X // l 1' N 0 ^ N Τ ζ II = / V'N N ^ ^ / 44 V 0t 45 46 -N ^ V S ° O N U kA 47 -N ^ S c ^ O ^ N ^ N FÒ 48 2'Vn F F 'N S b' Ϋ) O <ib 49 F 'O F o ^ yX; f ^ F 1
    Petition 870170071853, of September 25, 2017, p. 10/28
    [6]
    6/19
    # Structure 50N xx ° ΟΎ av 51 / <,, N ^ S Y- NY FF Γ \ N > ^ F ° YYYí 52 AY Y ^ NY F, F O 'VXT 0 ^ ° 53 -N ^ Y YYA n τ FFO N. ^ K F S YY .n ^ A / T fl o OYN 54 - · ν ν - X YY Ν ΧΊ) cA ^ 55 r ^ NV f ^ F _y N ^ J ^ z N pp) ° ^) - όν ci ^ a ci 56 f f OP N Y ^ Y ^^ - or shah 57 , αΑνΥ fF F O SÁ^ ΚΧ3Υ op 58 Y > S fF O N F / Υν'Υ ° ογγ ^ Ν γ 59 , N ^ Y YiP N ι Fj ÁJ N Y * S Ύγγ / ^^ XX ° YY ' ^ N Cl
    Petition 870170071853, of 09/25/2017, p. 11/28
    [7]
    7/19
    # Structure 60FFf ° O-0 ^ N X) 61 A - Y F FV 8 N F VXsr F F FF 62 -N ^ z> S 63FSf ° O-0 ^ 64 -N ^ A S c F 65 χΤ'ΤΛ& 66 F, N ^> S ° Χψ FF J0Ã NN V, 67 , N ^ S / X - Z NT F F O N > ^ F ° YãOi ÃX ° 68 d ΧΤΓΛ
    Petition 870170071853, of September 25, 2017, p. 12/28
    [8]
    8/19
    # Structure 69F 'jNL · Fd U F = / N ^ O 70F Λ 71 -N ^ S 72 -N ^ z> S r ^^ NTI F F 15 N - ^^ Jv f N Nís <^ T |) O OUí 73 -N ^ S X) 74F X τΤΛ N ^ J ^ Ν ΧΊ) <Xí w 75f X λλ n ^ j ^ N n 76 , N ^ S / FFL jJ Ν ^^ λ f N Nís / ^ / T / 1 <Κί 77 fs Q F N, »^ ~ NO = S ~ N - ' N ^ V * N NON ^ N = / 78 -N ^ S
    Petition 870170071853, of September 25, 2017, p. 13/28
    [9]
    9/19
    # Structure 79 80 -N ^ S FF í 1J N ^ v <KÍ x < 81 ^ 5> S XxX N n = / = * N nh 2 82 -N ^ S FFL jJ N. ^^ F X n ^ A / - T 1 83 / ¾ -N ^ S f ^ âX ^ NT F F l U 'ΦΟΓ 84 x xi vNAt z N x ° ^ N = / 85 1 S _ .N ^ S ΧχΧ W X&N 86 X S -N ^ S (^ i ^ N 'Χ ^ Χ Xl 87S -N ^ S (^ i ^ N 'ΧκΧ Xl
    Petition 870170071853, of September 25, 2017, p. 14/28
    [10]
    10/19
    # Structure 88 A N Ό . n 89 F F Γ JJ 90 -N ^ S 91 ΖΎ T F F l JJ N - ^^ k Ύ / “Λ T (1 ° O N U 92 -N ^ S FÍ W ^ XK 93 -N ^ S 94 / <s -N ^ Y F, F O N ^^ O ^ F A [Y oY Vn j, ay - / ^ N 95 -N ^ Y 96 .NY h- NT F F UN ^; = / ^ n γ 97F F Ύ ,,,, G
    Petition 870170071853, of September 25, 2017, p. 15/28
    [11]
    11/19
    # Structure 98FU C ^ - N ~ NNF 99 _ U N ^ N = / 100F / 'O PT 101 Clιό n PP^ N = / 102 ιό. _ cRfWVZN 103 f f y o ^ ctí FNO 104 ιό. PÍixy 105 F {$ F N _ ^ N Br ιΗΧ
    Petition 870170071853, of 09/25/2017, p. 16/28
    [12]
    12/19
    # Structure 106 <g. . 22 107 108 O F u c ^ - < nN F 109 O f ^ XX N Vn ^ ÍKK 110 'XXX n Victim 111 O F ^ Xl n _ Vn ^ L 112 <o .. 22 113 Cl F m _ cP fW ZN ^ N = /
    Petition 870170071853, of September 25, 2017, p. 17/28
    [13]
    13/19
    # Structure 114 Cl = / 115 O u o n F __ ^ N Cl νηκ 116 O 117 FM F no 118F. _ ϊΚκ ' 119 The F ^ XX. _ 120 f <tQ F. _ ^ N Cl 121 The F. v. ^ L ζΚΧ
    Petition 870170071853, of September 25, 2017, p. 18/28
    [14]
    14/19
    # Structure 122 F F 123 00À „vNÓ 124 O-,.L 125 n vH 126  „&^ N = / 127F FO ^ Tlv, N '»Z N * n ~ n 128 F, F O 0- tj <y · 129 OL '^^ W ~ n
    Petition 870170071853, of September 25, 2017, p. 19/28
    [15]
    15/19
    # Structure 134 IV — V _ ^ N-n 135 ipi. 0P n ^^ ~ Wn Cl 136 S -n 137: > Pi n op ci 138A vp N ^ vZY 139 > —P% / N ~ NNV γ V— & 142 ^ ΎνΎ NN ^ N = / 143 Y ^ yVi = P 144 VnVjl F < À r ^^ V ' NW ''
    Petition 870170071853, of September 25, 2017, p. 20/28
    [16]
    16/19
    # Structure 145F 'N = Z 146FW Er l / y— ' 147 VV ^ Fp) N'WP f ^ n 'n;: N 148 1 θ 'VnAA 149 s mL ·Ν 'N 150 s Yí /Ν 'N 151 y-K5- < r, Ν 'N 152 y ^ O r, Ν ' F x O ^ L, n JV FF ^ / ^ N b - , ^ / F M
    Petition 870170071853, of September 25, 2017, p. 21/28
    [17]
    17/19
    # Structure 153 f f x ° yy n - v n F M 154 f> z o ^^,, F F ^ / ^ A - CT ^ = 155 F> z O ^^,. F F ^ = t / ^ NA — CT ^ = 156 F> Z O ^^,, ' F YVY - F F ^ / ^ A— / ^ = 157 ’'A-o-Y’ ^- O 158 s n ' F x O ^ L -yyTV f FY = / ãYJ F M 159 V ^ Ãj - O '^ XKnvO'' FF =
    2. Molecule, according to claim 1, characterized by the fact that it has one of the following structures:
    Petition 870170071853, of September 25, 2017, p. 22/28
    [18]
    18/19
    Petition 870170071853, of September 25, 2017, p. 23/28
    [19]
    19/19 dication 1 or 2, characterized by the fact that it comprises the application of a molecule, as defined in claim 1 or 2, to an area to control a pest, in sufficient quantity for the control of such pests.
    4. Process, according to claim 3, characterized by the fact that said pests are beet caterpillars (BAW), corn cob caterpillar (CEW), or green aphid (GPA).
    5. Molecule, characterized by the fact that it is a pesticidably acceptable acid addition salt, a salt derivative, a solvate, or an ester derivative, of a molecule, as defined in claim 1 or 2.
    6. Molecule according to claim 1 or 2, characterized by the fact that at least one H is 2 H or at least one C is 14 C.
    7. Composition, characterized by the fact that it comprises a molecule, as defined in claim 1 or 2, and at least one other compound with insecticides, herbicides, acaricidal, nematicidal, or fungicidal activity.
    8. Composition, characterized by the fact that it comprises a molecule, as defined in claim 1 or 2, and a seed.
    9. Process, characterized by the fact that it comprises the application of a molecule, as defined in claim 1 or 2, to a genetically modified plant, or a genetically modified seed, which has been genetically modified to express one or more specialized characteristics.
    Petition 870170071853, of September 25, 2017, p. 24/28
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    US20120172217A1|2012-07-05|
    RU2012108622A|2013-09-20|
    EP2461687B1|2015-09-16|
    ES2551387T3|2015-11-18|
    AR077818A1|2011-09-28|
    MX2012001619A|2012-04-11|
    IL217949A|2015-01-29|
    WO2011017504A1|2011-02-10|
    PL2461687T3|2016-02-29|
    EP2461687A1|2012-06-13|
    AU2010279373B2|2014-05-01|
    ZA201200816B|2013-05-29|
    BR112012002676A2|2015-09-15|
    DK2461687T3|2015-12-21|
    NZ597543A|2013-08-30|
    US8680269B2|2014-03-25|
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    法律状态:
    2016-05-31| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2017-09-19| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2018-01-02| B09A| Decision: intention to grant|
    2018-02-06| B16A| Patent or certificate of addition of invention granted|
    优先权:
    申请号 | 申请日 | 专利标题
    US23215209P| true| 2009-08-07|2009-08-07|
    US61/232,152|2009-08-07|
    PCT/US2010/044525|WO2011017504A1|2009-08-07|2010-08-05|Pesticidal compositions|
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