Abstract:
A pesticidal composition comprises a 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 12 , x, n, and Q are as described herein. A method of controlling pests comprises applying the pesticidal composition near a population of pests.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
       [0001]    This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/894,320, filed Oct. 22, 2013, the disclosure of which is hereby incorporated herein in its entirety by this reference. 
     
    
     TECHNICAL FIELD 
       [0002]    This disclosure relates to the field of compounds having pesticidal utility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca, processes to produce such compounds and intermediates used in such processes. These compounds may be used, for example, as nematicides, acaricides, insecticides, miticides, and/or molluscicides. 
       BACKGROUND 
       [0003]    Controlling pest populations is essential to human health, modern agriculture, food storage, and hygiene. There are more than ten thousand species of pests that cause losses in agriculture and the world-wide agricultural losses amount to billions of U.S. dollars each year. Accordingly, there exists a continuous need for new pesticides and for methods of producing and using such pesticides. 
       DISCLOSURE 
       [0004]    The examples given in the definitions are non-exhaustive and must not be construed as limiting the present disclosure. It is understood that a substituent should comply with chemical bonding rules and steric compatibility constraints in relation to the particular molecule to which it is attached. 
         [0005]    “Alkyl” means and includes an acyclic, saturated, branched or unbranched hydrocarbon. Non-limiting examples may include methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, or decyl. 
         [0006]    “Cycloalkyl” means and includes a monocyclic or polycyclic saturated hydrocarbon. Non-limiting examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, bicycle[2.2.2]octyl, or decahydronapthyl. 
         [0007]    “Alkenyl” means and includes an acyclic, branched or unbranched hydrocarbon containing at least one carboncarbon double bond. Non-limiting examples may include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. 
         [0008]    “Cycloalkenyl” means and includes a monocyclic or polycyclic hydrocarbon containing at least one carboncarbon double bond. Non-limiting examples may include cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, or cyclodecenyl. 
         [0009]    “Alkynyl” means and includes acyclic, branched or unbranched hydrocarbon containing at least one carboncarbon triple bond. Non-limiting examples may include ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, or decynyl. 
         [0010]    “Cycloalkynyl” means and includes a monocyclic or polycyclic hydrocarbon containing at least one carboncarbon triple bond. Non-limiting examples may include cycloheptynyl, cyclooctynyl, or cyclodecynyl. 
         [0011]    “Aryl” means and includes an aromatic compound with or without any substitution. Non-limiting examples may include phenyl or naphthyl. 
         [0012]    “Alkoxy” means and includes an alkyl group containing at least one carbonoxygen single bond. Non-limiting examples may include methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, or cyclop entoxy. 
         [0013]    “Alkenyloxy” means and includes an alkenyl containing at least one carbon-oxygen single bond. Non-limiting examples may include allyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy, nonenyloxy, or decenyloxy. 
         [0014]    “Alkynyloxy” means and includes an alkynyl containing at least one carbon-oxygen single bond. Non-limiting examples may include pentynyloxy, hexynyloxy, heptynyloxy, octynyloxy, nonynyloxy, or decynyloxy. 
         [0015]    “Cycloalkoxy” means and includes a cycloalkyl containing at least one carbon-oxygen single bond. Non-limiting examples may include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy, norbornyloxy, or bicyclo[2.2.2]octyloxy. 
         [0016]    “Cyclohaloalkyl” means and includes a monocyclic or polycyclic, saturated substituent comprising carbon, halogen, and hydrogen. Non-limiting examples may include 1-chlorocyclopropyl, 1-chlorocyclobutyl, or 1-dichlorocyclopentyl. 
         [0017]    “Cycloalkenyloxy” means and include a cycloalkenyl further consisting of a carbon-oxygen single bond. Non-limiting examples may include cyclobutenyloxy, cyclopentenyloxy, cyclohexenyloxy, cycloheptenyloxy, cyclooctenyloxy, cyclodecenyloxy, norbornenyloxy, or bicyclo[2.2.2]octenyloxy. 
         [0018]    “Alkylthio” means and includes an alkyl group containing at least one carbonsulfur single bond. 
         [0019]    “Haloalkylthio” means and includes an alkyl group containing at least one carbonsulfur single bond and halogen atom. 
         [0020]    “Halo” or “halogen” means and includes fluorine, chlorine, bromine, or iodine. 
         [0021]    “Haloalkyl” means and includes an alkyl group substituted with at least one halogen atom. 
         [0022]    “Haloalkoxy” means and includes an alkoxy group substituted with at least one halogen atom. 
         [0023]    “Heteroatom” means and includes sulfur (S), oxygen (O), or nitrogen (N) atom. 
         [0024]    “Heteroalkyl” means and includes an alkyl containing at least one sulfur (S), oxygen (O), or nitrogen (N) atom. 
         [0025]    “Heterocyclyl” means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, that atom can be in other oxidation states such as a sulfoxide and sulfone. Examples of aromatic heterocyclyls include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl, cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and triazolyl. Examples of fully saturated heterocyclyls include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl and tetrahydropyranyl. Examples of partially unsaturated heterocyclyls include, but are not limited to, 1,2,3,4-tetrahydroquinolinyl, 4,5-dihydro-oxazolyl, 4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and 2,3-dihydro-[1,3,4]-oxadiazolyl. Additional examples include the following 
         [0000]    
       
                 
         
             
             
         
       
     
         [0026]    “Pesticidally effective amount” means and includes an amount of active material that causes an adverse effect to the at least one insect, wherein the adverse effect may include deviations from natural development, killing, regulation, or the like. 
         [0027]    “Control” or grammatical variations thereof means and includes regulating the number of living insects or regulating the number of viable eggs of the insects. 
         [0028]    “Synergistic effect” or grammatical variations thereof means and includes a cooperative action encountered in a combination of two or more active agents in which the combined activity of the two or more active agents exceeds the sum of the activity of each active agent alone. 
       Pesticidal Compounds 
       [0029]    In one particular embodiment, a pesticidal composition comprises a 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein:
       R 1 , R 2 , and R 4  are independently selected from H, F, Cl, Br, I, substituted or unsubstituted C 1 -C 6  alkyl, or substituted or unsubstituted C 1 -C 6  haloalkyl,   wherein each said R 1 , R 2 , and R 4 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 3 -C 10  cycloalkyl, or C 3 -C 10  halocycloalkyl, (each of which that can be substituted, may optionally be substituted with R 10 );   R 3  is selected from H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1 -C 6  alkyl, substituted or unsubstituted C 2 -C 6  alkenyl, substituted or unsubstituted C 1 -C 6  alkoxy, substituted or unsubstituted C 3 -C 10  cycloalkyl, substituted or unsubstituted C 1 -C 6  haloalkyl, substituted or unsubstituted C 6 -C 20  aryl, substituted or unsubstituted C 1 -C 20  heterocyclyl, OR 11 , C(═X 1 )R 11 , C(═X 1 )OR 11 , C(═XON(R 11 ) 2 , N(R 11 ) 2 , N(R 11 )C(═X 1 )R 11 , SR 11 , S(O) n OR 11 , or R 11 S(O) n R 11 , wherein each said R 3 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 1 -C 6  haloalkyloxy, C 2 -C 6  haloalkenyloxy, C 3 -C 10  cycloalkyl, C 3 -C 10  cycloalkenyl, C 3 -C 10  halocycloalkyl, C 3 -C 10  halocycloalkenyl, OR 11 , S(O) n OR 11 , C 6 -C 20  aryl, or C 1 -C 20  heterocyclyl, (each of which that can be substituted, may optionally be substituted with R 10 );   R 5  is selected from H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1 -C 6  alkyl, substituted or unsubstituted C 2 -C 6  alkenyl, substituted or unsubstituted C 1 -C 6  alkoxy, C 3 -C 10  cycloalkyl, substituted or unsubstituted C 6 -C 20  aryl, substituted or unsubstituted C 1 -C 20  heterocyclyl, OR 11 , C(═X 1 )R 11 , C(═X 1 )OR 11 , C(═X 1 )N(R 11 ) 2 , N(R 11 ) 2 , N(R 11 )C(═X 1 )R 11 , SR 11 , S(O) n OR 11 , or R 11 S(O) n R 11 , wherein each said R 5 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 1 -C 6  haloalkyloxy, C 2 -C 6  haloalkenyloxy, C 3 -C 10  cycloalkyl, C 3 -C 10  cycloalkenyl, C 3 -C 10  halocycloalkyl, C 3 -C 10  halocycloalkenyl, OR 11 , S(O) n OR 11 , C 6 -C 20  aryl, or C 1 -C 20  heterocyclyl, (each of which that can be substituted, may optionally be substituted with R 10 );   R 6  is H, F, Cl, Br, I, substituted or unsubstituted C 1 -C 6  alkyl, or C 1 -C 6  haloalkyl, wherein each said R 6 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 1 -C 6  haloalkyloxy, C 2 -C 6  haloalkenyloxy, C 3 -C 10  cycloalkyl, C 3 -C 10  cycloalkenyl, C 3 -C 10  halocycloalkyl, or C 3 -C 10  halocycloalkenyl;   R 7  is selected from H, substituted or unsubstituted C 1 -C 6  alkyl, substituted or unsubstituted C 2 -C 6  alkenyl, substituted or unsubstituted C 2 -C 6  alkynyl, substituted or unsubstituted C 1 -C 6  alkoxy, substituted or unsubstituted C 3 -C 10  cycloalkyl, C 1 -C 6  alkyl, C 2 -C 6  alkynyl wherein the alkyl and alkynyl is independently substituted or unsubstituted, substituted or unsubstituted C 6 -C 20  aryl, substituted or unsubstituted C 1 -C 20  heterocyclyl, C 1 -C 6  alkyl C 6 -C 20  aryl wherein the alkyl and aryl is independently substituted or unsubstituted, C 1 -C 6  alkyl-(C 3 -C 10  cyclohaloalkyl) wherein the alkyl and cyclohaloalkyl is independently substituted or unsubstituted, C 1 -C 6  alkyl-(C 3 -C 10  cycloalkyl) wherein the alkyl and cycloalkyl is independently substituted or unsubstituted, wherein each said R 7 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 1 -C 6  haloalkyloxy, C 2 -C 6  haloalkenyloxy, C 3 -C 10  cycloalkyl, C 3 -C 10  cycloalkenyl, C 3 -C 10  halocycloalkyl, C 3 -C 10  halocycloalkenyl, OR 11 , S(O) n OR 11 , C 6 -C 20  aryl, C 1 -C 20  heterocyclyl, or R 11  aryl, (each of which that can be substituted, may optionally be substituted with R 10 );   R 9  is a bond or substituted or unsubstituted C 2 -C 12  alkenyl, substituted or unsubstituted C 1 -C 12  alkyl, or substituted or unsubstituted C 3 -C 10  cycloalkyl, wherein each said R 9 , when substituted, has one or more substituents selected from F, Cl, Br, I, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 3 -C 10  cycloalkyl, C 3 -C 10  halocycloalkyl, OR 11 , S(O) n R 11 , C 6 -C 20  aryl, or C 1 -C 20  heterocyclyl, (each of which that can be substituted, may optionally be substituted with R 10 );   R 10  is selected from H, substituted or unsubstituted C 1 -C 6  alkyl, substituted or unsubstituted C 1 -C 6  haloalkyl, substituted or unsubstituted C 2 -C 6  alkenyl, substituted or unsubstituted C 1 -C 6  alkoxy, substituted or unsubstituted C 3 -C 10  cycloalkyl, substituted or unsubstituted C 3 -C 10  halocycloalkyl, substituted or unsubstituted C 1 -C 6  alkyl-C 3 -C 10  halocycloalkyl, substituted or unsubstituted C 3 -C 10  cycloalkenyl, substituted or unsubstituted C 6 -C 20  aryl, or substituted or unsubstituted C 1 -C 20  heterocyclyl, wherein each said R 10 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 1 -C 6  haloalkyloxy, C 2 -C 6  haloalkenyloxy, C 3 -C 10  cycloalkyl, C 3 -C 10  cycloalkenyl, C 3 -C 10  halocycloalkyl, C 3 -C 10  halocycloalkenyl, oxo, OR 11 , S(O) n R 11 , C 6 -C 20  aryl, or C 1 -C 20  heterocyclyl, (each of which that can be substituted, may optionally be substituted with R 10 );   R 11  is H, CN, substituted or unsubstituted C 1 -C 6  alkyl, substituted or unsubstituted C 2 -C 6  alkenyl, substituted or unsubstituted C 1 -C 6  alkoxy, substituted or unsubstituted C 2 -C 6  alkenyloxy, substituted or unsubstituted C 3 -C 10  cycloalkyl, substituted or unsubstituted C 3 -C 10  cycloalkenyl, substituted or unsubstituted C 6 -C 20  aryl, substituted or unsubstituted C 1 -C 20  heterocyclyl, substituted or unsubstituted S(O) 11 C 1 -C 6  alkyl, or substituted or unsubstituted N(C 1 -C 6  alkyl) 2 , wherein each said R 11 , when substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 2 -C 6  haloalkenyl, C 1 -C 6  haloalkyloxy, C 2 -C 6  haloalkenyloxy, C 3 -C 10  cycloalkyl, C 3 -C 10  cycloalkenyl, C 3 -C 10  halocycloalkyl, C 3 -C 10  halocycloalkenyl, OC 1 -C 6  alkyl, OC 1 -C 6  haloalkyl, S(O) 11 C 1 -C 6  alkyl, S(O) n OC 1 -C 6  alkyl, C 6 -C 20  aryl, or C 1 -C 20  heterocyclyl;   R 12  is H, substituted or unsubstituted C 2 -C 12  alkenyl, substituted or unsubstituted C 1 -C 12  alkyl, substituted or unsubstituted C 2 -C 12  alkynyl, substituted or unsubstituted C 3 -C 10  cycloalkyl, C 6 -C 10  aryl, C 1 -C 20  heterocyclyl, R 9 C(═O)N(R 9 ) 2 , or R 9 C(═O)R 9 , wherein each said R 12 , when substituted, has one or more substituents selected from F, Cl, Br, I, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 1 -C 6  haloalkyl, C 3 -C 10  cycloalkyl, C 3 -C 10  halocycloalkyl, OR 11 , N(R 11 ) 2 , C 6 -C 20  aryl, or C 1 -C 20  heterocyclyl, (each of which that can be substituted, may optionally be substituted with R 10 );   Q is O or S;   n is 0, 1, or 2; and   x is 0 or 1.       
 
         [0043]    In another embodiment, and in any combination with any of the previous or following embodiments, R 1 , R 2 , and R 4  are H. 
         [0044]    In another embodiment, and in any combination with any of the previous or following embodiments, R 3  is selected from H, F, Cl, Br, or I, preferably, H and F. 
         [0045]    In another embodiment, and in any combination with any of the previous or following embodiments, R 5  F, Cl, Br, I, or unsubstituted C 1 -C 6  alkyl, preferably, Cl or CH 3 . 
         [0046]    In another embodiment, and in any combination with any of the previous or following embodiments, R 6  is H. 
         [0047]    In another embodiment, and in any combination with any of the previous or following embodiments, R 7  is H, CH 3 , CH 2 CH 3 CH 2 C≡CH, or CH(CH 3 )C≡CH. 
         [0048]    In another embodiment, and in any combination with any of the previous or following embodiments, R 9  is CH 2 . 
         [0049]    In another embodiment, and in any combination with any of the previous or following embodiments, R 10  is CH 2  (unsubstituted C 3 -C 10  halocycloalkyl), preferably, CH 2 -halocyclopropyl, C 3 -C 6  haloalkyl, preferably wherein said halos are only on the carbon atom furthest from the sulfur atom, such as CH 2 CH 2 CF 3 . 
         [0050]    In another embodiment, and in any combination with any of the previous or following embodiments, R 12  is OC 1 -C 6  alkyl, preferably OCH 3 . 
         [0051]    The 3-(1H-pyrazol)pyridine compound of formula I, when R 7  is H, may exist in various isomeric forms. Non-limiting examples of such isomeric forms may include, but are not limited to, compounds IA or IB as shown below. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0052]    In one embodiment, the 3-(1H-pyrazol)pyridine compound of formula 1-8 may be prepared as shown in Scheme 1. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0053]    In step A of Scheme 1, an oxime compound of formula 1-3, wherein R 12  is as previously defined, may be prepared via condensation of a pyruvate such as ethyl bromopyruvate (1-1), which is commercially available, with 0-substituted hydroxylamine compound of formula 1-2, wherein R 12  is as previously defined, according to procedures described by Noguchi et al. in Heterocycles 2002, 58, 471-504. 
         [0054]    In step B of Scheme 1, the bromide leaving group of the oxime compound (1-3) may be replaced with a thiol compound of formula 1-4, wherein R 10  is as previously defined, in the presence of a base, such as sodium hydride (NaH), and a polar aprotic solvent, such as tetrahydrofuran (THF), at a temperature from about 0° C. to about 30° C. to provide a corresponding oxime sulfide of formula 1-5. 
         [0055]    In step C of Scheme 1, an ethyl ester group of the oxime sulfide (1-5) may be hydrolyzed with a base, such as sodium hydroxide (NaOH), in a polar protic solvent, such as water and/or ethanol (EtOH), at a temperature from about 0° C. to about 30° C. to provide the corresponding carboxylic acid of formula 1-6. 
         [0056]    In step D of Scheme 1, the carboxylic acid (1-6) may react with 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula 1-7 or its HCl salt, prepared as described in the PCT Publication No. WO 2013/062981, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and x are as previously defined, in the presence of an amide coupling reagent, such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), in the presence of a base, such as diisopropylethylamine (DIPEA) and/or 4-dimethylaminopyridine (DHAP), in an aprotic solvent, such as dichloromethane (CH 2 Cl 2 ), at a temperature from about 0° C. to about 30° C. to provide a corresponding 3-(1H-pyrazol)pyridine compound of formula 1-8. 
         [0057]    Alternatively, as shown in step E of Scheme 1, the carboxylic acid (1-6) may be treated with a reagent, such as oxalyl chloride or thionyl chloride, in the presence of an initiator, such as N,N-dimethylformamide (DMF), in an aprotic solvent, such as CH 2 Cl 2 , at a temperature from about −20° C. to about 40° C. The resulting acid chloride may then be coupled with 1-(pyridin-3-yl)-1H-pyrazol-4-amine or corresponding HCl salt of the formula 1-7 in the presence of a base, such as DIPEA, and an aprotic solvent, such as CH 2 Cl 2 , at a temperature from about 0° C. to about 100° C. to provide a 3-(1H-pyrazol)pyridine compound of formula 1-8. 
         [0058]    In one embodiment, the 3-(1H-pyrazol)pyridine compound of formula 2-4 may be prepared as shown in Scheme 2. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0059]    In step A of Scheme 2, a 3-(1H-pyrazol)pyridine compound of formula 2-1, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 12  and x are as previously defined, may be converted to the corresponding thiol compound of formula 2-2 by reacting with an acid, such as trifluoroacetic acid (TFA), in the presence of a hydride source, such as triethylsilane, in an aprotic solvent, such as CH 2 Cl 2 , at a temperature from about 0° C. to about 30° C. 
         [0060]    In step B of Scheme 2, the thiol compound (2-2) may be coupled with an electrophile of formula 2-3, wherein R 10  is as previously defined and Y is a leaving group such as chloride, bromide, alkylsulfonate in the presence of a base, such as NaH or DIPEA, in an appropriate solvent, such as THF or DMF, at a temperature from about 0° C. to about 150° C. (when heating, reactions may be performed under either standard heating or microwave conditions) to afford 3-(1H-pyrazol)pyridine compound of formula 2-4. 
         [0061]    Alternatively, as shown in step C of Scheme 2, the thiol compound (2-2) may be coupled with an electrophile of formula 2-3, wherein Y is a leaving group such as bromide, and R 10  is either aryl or heteroaryl, in the presence of a catalyst, such as copper (I) oxide (Cu 2 O) or tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3 ), a base, such as potassium hydroxide or DIPEA, an appropriate ligand, such as 1,10-phenanthroline or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, in a suitable solvent, such as dioxane, under either standard heating or microwave conditions at a temperature from about 80° C. to about 110° C. to provide 3-(1H-pyrazol)pyridine compound of formula 2-4. 
         [0062]    In one embodiment, as shown in Scheme 3, the 3-(1H-pyrazol)pyridine compound (2-4), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 12 , and x are as previously defined, may be treated with a thionation reagent, such as Lawesson&#39;s reagent, in an aprotic solvent, such as 1,2-dichloroethane (DCE) or toluene, under either standard heating or microwave conditions at a temperature from about 80° C. to about 140° C. to provide the corresponding thioamide compound (3-1). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0063]    In one embodiment, as shown in step A of Scheme 4, the 3-(1H-pyrazol)pyridine compound of formula 4-1, wherein Q, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 12 , and x are as previously defined, may be oxidized with about 1 equivalent (eq) of an oxidant, such as mCPBA, hydrogen peroxide (H 2 O 2 ) or sodium perborate tetrahydrate, in an appropriate solvent, such as CH 2 Cl 2 , methanol (MeOH), or acetic acid (AcOH), at a temperature of from about 0° C. to about 60° C. to the corresponding sulfoxides (4-2). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0064]    In step C of Scheme 4, the sulfoxide (4-2) may be further oxidized with about one or more eq of an oxidant, such as sodium perborate tetrahydrate or mCPBA, in a suitable solvent system, such as AcOH or CH 2 Cl 2 , at a temperature from about 0° C. to about 60° C. to the corresponding sulfone compound (4-3). 
         [0065]    Alternatively, in step B of Scheme 4, the 3-(1H-pyrazol)pyridine compound 4-1 may be converted to the corresponding sulfone compound (4-3) by treating with about two or more eq of an oxidant, such as sodium perborate tetrahydrate or mCPBA, in the presence of a suitable solvent system, such as AcOH or CH 2 Cl 2 , at a temperature from about 0° C. to about 60° C. 
         [0066]    In one embodiment, as shown in step A of Scheme 5, commercially available ethyl 2-chloro-2-(hydroxyimino)acetate (5-1) may be treated with a thiol compound 5-2, wherein R 10  is as previously described, in the presence of base, such as triethylamine, and an aprotic solvent, such as THF, at a temperature from about 0° C. to about 30° C. to provide an N-hydroxyimidothioate compound 5-3. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0067]    In step B of Scheme 5, an N-hydroxyimidothioate compound 5-3 may be coupled with compound 5-4, wherein R 12  is as previously defined and Y is a leaving group such as bromide, in the presence of a base, such as NaH or DIPEA, in an appropriate solvent system, such as THF or DMF, at a temperature from about 0° C. to about 150° C. (when heating, the reaction may be performed under either standard heating or microwave conditions) to afford the corresponding 0-substituted N-oxyimidothioate compound of formula 5-5. 
         [0068]    Alternatively, as shown in step C of Scheme 5, an N-hydroxyimidothioate compound 5-3 may be coupled with a compound 5-4, wherein Y is a leaving group such as bromide, and R 12  is either aryl or heteroaryl, in a presence of a catalyst such as copper(I) iodide (CuI), a base such as cesium carbonate (Cs 2 CO 3 ), an appropriate ligand such as 1,10-phenanthroline, in a suitable solvent such as toluene, under either standard heating or microwave conditions at a temperature from about 80° C. to about 120° C. to afford the corresponding O-substituted N-oxyimidothioate compound of the formula 5-5. 
         [0069]    In step D of Scheme 5, the ethyl ester group of the 0-substituted N-oxyimidothioate compound 5-5 may be converted to the corresponding carboxylic acid (5-6) by treating with a base, such as lithium hydroxide, in a polar, protic solvent, such as water and/or EtOH, at a temperature from about 0° C. to about 30° C. 
         [0070]    In step E of Scheme 5, the carboxylic acid 5-6 may be reacted with 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula 1-7 or its HCl salt (prepared as described in the PCT Publication No. WO 2013062981), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and x are as previously defined, in the presence of an amide-coupling reagent, such as EDC, a base, such as DIPEA and/or DMAP, in an aprotic solvent, such as CH 2 Cl 2 , at a temperature from about 0° C. to about 30° C. to provide the corresponding 3-(1H-pyrazol-1-yl)pyridine compound of the formula 5-7. 
         [0071]    Alternatively, as shown in step F of Scheme 5, the carboxylic acid 5-6 may be reacted with a reagent, such as oxalyl chloride or thionyl chloride, in a presence of an initiator, such as DMF, in an aprotic solvent, such as CH 2 Cl 2 , at a temperature from about −20° C. to about 40° C. The resulting acid chloride may then be coupled with 1-(pyridin-3-yl)-1H-pyrazol-4-amine or corresponding salt of the formula 1-7 in the presence of a base, such as DIPEA, in an aprotic solvent, such as CH 2 Cl 2 , at a temperature from about 0° C. to about 40° C. to provide the corresponding 3-(1H-pyrazol-1-yl)pyridine compound of the formula 5-7. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0072]    In one embodiment, as shown in step A of Scheme 6, oxycarbamate 6-1, which is commercially available, may be converted to the corresponding 0-substituted oxycarbamate (6-3) by treating with a compound of the formula 6-2, wherein R 12  is as previously described and Y is a leaving group, such as bromide, in the presence of a base, such as NaH or DIPEA, in an appropriate solvent system, such as THF or DMF, at a temperature from about 0° C. to about 150° C. (when heating, reactions may be performed under either standard heating or microwave conditions). 
         [0073]    Alternatively, as shown in step B of Scheme 6, the oxycarbamate (6-1) may be coupled with compound 6-2, wherein Y is a leaving group, such as bromide, and R 12  is either aryl or heteroaryl, in a presence of a catalyst, such as CuI, a base, such as Cs 2 CO 3 , an appropriate ligand, such as 1,10-phenanthroline, in a suitable solvent, such as toluene, under either standard heating or microwave conditions at a temperature from about 80° C. to about 120° C. to provide an O-substituted oxycarbamate compound of the formula 6-3. 
         [0074]    In step C of Scheme 6, an O-substituted oxycarbamate compound of the formula 6-3 may be treated with an acid, such as TFA, in the presence of a solvent, such as CH 2 Cl 2 , at a temperature from about 0° C. to about 40° C. to provide the corresponding 0-substituted hydroxylamine compound of the formula 1-2. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0075]    In one embodiment, as shown in step A of Scheme 7, N-hydroxyphthalimide (7-1) may be reacted with a compound of the formula 7-2, wherein R 12  is as previously described and Y is a leaving group, such as bromide, in the presence of a base, such as NaH or DIPEA, in an appropriate solvent system, such as THF or DMF, at a temperature from about 0° C. to about 150° C. (when heating, reactions may be performed under either standard heating or microwave conditions) to provide the corresponding phthalimide compound of the formula 7-3. 
         [0076]    Alternatively, as shown in step B of Scheme 7, the hydroxyphthalimide compound 7-1 may be coupled with compound 7-2, wherein Y is a leaving group, such as bromide, and R 12  is either aryl or heteroaryl, in the presence of a catalyst, such as CuI, a base, such as Cs 2 CO 3 , an appropriate ligand, such as 1,10-phenanthroline, in a suitable solvent, such as toluene, under either standard heating or microwave conditions at a temperature from about 80° C. to about 120° C. to provide the phthalimide compound of the formula 7-3. 
         [0077]    In step C of Scheme 7, the phthalimide compound 7-3 may be treated with a nucleophile, such as hydrazine, in a polar protic solvent, such as water and/or EtOH, at a temperature from about 20° C. to about 80° C. to provide the corresponding 0-substituted hydroxylamine compound of the formula 1-2. 
       Pesticidally Acceptable Acid Addition Salts, Salt Derivatives, Solvates, Ester Derivatives, Polymorphs, Isotopes, Radionuclides and Stereoisomers 
       [0078]    In some embodiments, the 3-(1H-pyrazol-1-yl)pyridine compounds of formula I may be formulated into pesticidally acceptable acid addition salts. By way of 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, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, hydroxyethanesulfonic, and trifluoroacetic acids. Additionally, by way of a non-limiting example, an acid function can form salts including those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnesium. 
         [0079]    In some embodiments, the 3-(1H-pyrazol-1-yl)pyridine compounds of formula I may be formulated into salt derivatives. By way of a non-limiting example, a salt derivative can be prepared by contacting a free base with a sufficient amount of the desired acid to produce a salt. A free base may be regenerated by treating the salt with a suitable dilute aqueous base solution such as dilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia, and sodium bicarbonate. As an example, in many cases, a pesticide, such as 2,4-D, is made more water-soluble by converting it to its dimethylamine salt. 
         [0080]    In further embodiments, the 3-(1H-pyrazol-1-yl)pyridine compound of formula I may be formulated into stable complexes with a solvent, such that the complex remains intact after the non-complexed solvent is removed. These complexes are often referred to as “solvates.” However, it is particularly desirable to form stable hydrates with water as the solvent. 
         [0081]    In some embodiments, the 3-(1H-pyrazol-1-yl)pyridine compound of formula I may be made into ester derivatives. These ester derivatives can then be applied in the same manner as the invention disclosed in this document is applied. 
         [0082]    In some embodiments, the 3-(1H-pyrazol-1-yl)pyridine compound of formula I may be made as various crystal polymorphs. Polymorphism is important in the development of agrochemicals since different crystal polymorphs or structures of the same molecule can have vastly different physical properties and biological performances. 
         [0083]    In further embodiments, the 3-(1H-pyrazol-1-yl)pyridine compound of formula I may be made with different isotopes. Of particular importance are molecules having  2 H (also known as deuterium) in place of  1 H. 
         [0084]    In some embodiments, the 3-(1H-pyrazol-1-yl)pyridine compound of formula I may be made with different radionuclides. Of particular importance are molecules having  13 C or  14 C. 
         [0085]    In some embodiments, the 3-(1H-pyrazol-1-yl)pyridine compound of formula I may exist as one or more stereoisomers. Thus, certain molecules can be produced as racemic mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the other stereoisomers. Individual stereoisomers may be obtained by known selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures. Certain molecules disclosed in this document can exist as two or more isomers. The various isomers include geometric isomers, diastereomers, and enantiomers. Thus, the molecules disclosed in this document include geometric isomers, racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the present disclosure are drawn in only one geometric form for clarity, but are intended to represent all geometric forms of the molecule. 
       Pesticidal Compositions 
       [0086]    In one particular embodiment, a pesticidal composition comprises a 3-(1H-pyrazol-1-yl)pyridine compound of formula I or any agriculturally acceptable salt thereof. 
         [0087]    In some embodiments, a pesticidal composition comprises a 3-(1H-pyrazol-1-yl)pyridine compound of formula I or any agriculturally acceptable salt thereof, and a phytologically acceptable inert carrier (e.g., solid carrier, or liquid carrier). 
         [0088]    In one embodiment, the pesticidal composition may further comprise at least one additive selected from surfactant, a stabilizer, an emetic agent, a disintegrating agent, an antifoaming agent, a wetting agent, a dispersing agent, a binding agent, dyes, or fillers. 
         [0089]    In some embodiments, the pesticidal compositions may be in the form of solid. Non-limiting examples of the solid forms may include power, dust or granular formulations. 
         [0090]    In other embodiments, the pesticidal compositions may be in the form of liquid formulation. Examples of the liquid forms may include, but not limited to, dispersion, suspension, emulsion or solution in appropriate liquid carrier. 
         [0091]    In further embodiments, the pesticidal compositions may be in the form of liquid dispersion, wherein the 3-(1H-pyrazol-1-yl)pyridine compound may be dispersed in water or other agriculturally suitable liquid carrier. 
         [0092]    In yet further embodiments, the pesticidal compositions may be in the form of solution in an appropriate organic solvent. In one embodiment, the spray oils, which are widely used in agricultural chemistry, may be used as an organic solvent for the pesticidal compositions. 
         [0093]    The pesticidal composition may be used in conjunction (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more compounds having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, and/or virucidal properties. 
         [0094]    Furthermore, the pesticidal composition may be used in conjunction (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more compounds that are antifeedants, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammal repellents, mating disrupters, plant activators, plant growth regulators, and/or synergists. 
       Insecticides 
       [0095]    Non-limiting examples of insecticides that may be used in combination with the 3-(1H-pyrazol-1-yl)pyridine compound of formula I or any agriculturally acceptable salt thereof, may include 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, ctpw-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide (additionally resolved isomers thereof), flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, fufenozide, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, Aeto-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, or zolaprofos. 
       Acaricides 
       [0096]    Non-limiting examples of acaricides that may be used in combination with the 3-(1H-pyrazol-1-yl)pyridine compound of formula I or any agriculturally acceptable salt thereof, may include acequinocyl, amidoflumet, arsenous oxide, azobenzene, azocyclotin, benomyl, benoxafos, benzoximate, benzyl benzoate, bifenazate, binapacryl, bromopropylate, chinomethionat, chlorbenside, chlorfenethol, chlorfenson, chlorfensulphide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, clofentezine, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid, dicofol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenyl sulfone, disulfiram, dofenapyn, etoxazole, fenazaquin, fenbutatin oxide, fenothiocarb, fenpyroximate, fenson, fentrifanil, fluacrypyrim, fluazuron, flubenzimine, fluenetil, flumethrin, fluorbenside, hexythiazox, mesulfen, MNAF, nikkomycins, proclonol, propargite, quintiofos, spirodiclofen, sulfiram, sulfur, tetradifon, tetranactin, tetrasul, or thioquinox. 
       Nematicides 
       [0097]    Non-limiting examples of nematicides that may be used in combination with the 3-(1H-pyrazol-1-yl)pyridine compound of formula I or any agriculturally acceptable salt thereof, may include 1,3-dichloropropene, benclothiaz, dazomet, dazomet-sodium, DBCP, DCIP, diamidafos, fluensulfone, fosthiazate, furfural, imicyafos, isamidofos, isazofos, metam, metam-ammonium, metam-potassium, metam-sodium, phosphocarb, or thionazin. 
       Fungicides 
       [0098]    Non-limiting examples of fungicides that may be used in combination with the 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may include (3-ethoxypropyl)mercury bromide, 2-methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-S-methyl, acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol, ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril, benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S, Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole, copper acetate, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, dazomet-sodium, DBCP, debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine, diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, milneb, myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, orysastrobin, oxadixyl, oxine-copper, oxpoconazole, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothiocarb, prothiocarb hydrochloride, prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, salicylanilide, sedaxane, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, sulfur, sultropen, TCMTB, tebuconazole, tebufloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate, zineb, ziram, or zoxamide. 
       Herbicides 
       [0099]    Non-limiting examples of herbicides that may be used in combination the 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may include 2,3,6-TBA, 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl, 2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium, 2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D, 2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl, 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein, alachlor, allidochlor, alloxydim, alloxydim-sodium, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium, aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium, asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, benazolin-dimethylammonium, benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzoylprop-ethyl, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, borax, bromacil, bromacil-lithium, bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben, chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium, chloramben-sodium, chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorprocarb, chlorpropham, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clodinafop-propargyl, clofop, clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(2-hydroxypropyl)ammonium, cloransulam, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquat chloride, cyprazine, cyprazole, cypromid, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium, delachlor, desmedipham, desmetryn, di-allate, dicamba, dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P, dichlorprop-P-dimethylammonium, dichlorprop-potassium, dichlorprop-sodium, diclofop, diclofop-methyl, diclosulam, diethamquat, diethamquat dichloride, diethatyl, diethatyl-ethyl, difenopenten, difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate, diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat dibromide, disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl, endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenteracol, fenthiaprop, fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA, ferrous sulfate, flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupropanate-sodium, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, fosamine-ammonium, furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-monoammonium, glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium, halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb, medinoterb acetate, mefenacet, mefluidide, mefluidide-diolamine, mefluidide-potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, metam, metam-ammonium, metamifop, metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA, naproanilide, napropamide, naptalam, naptalam-sodium, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orb encarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, paraquat dichloride, paraquat dimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram-tris(2-hydroxypropyl)ammonium, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, primisulfuron-methyl, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, proglinazine-ethyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodium, prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron, saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, or xylachlor. 
       Biopesticides 
       [0100]    The 3-(1H-pyrazol-1-yl)pyridine compounds of formula I may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more biopesticides. The term “biopesticide” is used for microbial biological pest control agents that are applied in a similar manner to chemical pesticides. Commonly these are bacterial, but there are also examples of fungal control agents, including  Trichoderma  spp. and  Ampelomyces quisqualis  (a control agent for grape powdery mildew).  Bacillus subtilis  are used to control plant pathogens. Weeds and rodents have also been controlled with microbial agents. One well-known insecticide example is  Bacillus thuringiensis , a bacterial disease of Lepidoptera, Coleoptera, and Diptera. Because it has little effect on other organisms, it is considered more environmentally friendly than synthetic pesticides. Biological insecticides include products based on:
       1. entomopathogenic fungi (e.g.  Metarhizium anisopliae );   2. entomopathogenic nematodes (e.g.  Steinernema feltiae ); and   3. entomopathogenic viruses (e.g.  Cydia pomonella  granulovirus).       
 
         [0104]    Other examples of entomopathogenic organisms include, but are not limited to, baculoviruses, bacteria and other prokaryotic organisms, fungi, protozoa and Microsproridia. Biologically derived insecticides include, but not limited to, rotenone, veratridine, as well as microbial toxins; insect tolerant or resistant plant varieties; and organisms modified by recombinant DNA technology to either produce insecticides or to convey an insect resistant property to the genetically modified organism. In one embodiment, the molecules of Formula One may be used with one or more biopesticides in the area of seed treatments and soil amendments.  The Manual of Biocontrol Agents  gives a review of the available biological insecticide (and other biology-based control) products. Copping L. G. (ed.) (2004).  The Manual of Biocontrol Agents  (formerly the  Biopesticide Manual ) 3rd Edition. British Crop Production Council (BCPC), Farnham, Surrey UK. 
       Other Active Compounds 
       [0105]    The 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more of the following:
       1. 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;   2. 3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;   3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone;   4. 4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;   5. 3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;   6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;   7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide;   8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;   9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide;   10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide;   11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;   12. 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide;   13. 3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;   14. N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl) hydrazone;   15. N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl) hydrazone nicotine;   16. O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-methyl thiocarbonate;   17. (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;   18. 1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;   19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate; and   20. N-ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone.       
 
         [0126]    The 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more compounds in the following groups: algicides, antifeedants, avicides, bactericides, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammal repellents, mating disrupters, molluscicides, plant activators, plant growth regulators, rodenticides, or virucides. 
       Synergistic Mixtures and Synergists 
       [0127]    The 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may be used in combination with at least one other insecticides to form a synergistic mixture where the mode of action of such compounds compared to the mode of action of the 3-(1H-pyrazol)pyridine compound of formula I are the same, similar, or different. Examples of modes of action may include, but are not limited to: acetylcholinesterase inhibitor; sodium channel modulator; chitin biosynthesis inhibitor; GABA-gated chloride channel antagonist; GABA and glutamate-gated chloride channel agonist; acetylcholine receptor agonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholine receptor; Midgut membrane disrupter; oxidative phosphorylation disrupter, or ryanodine receptor (RyRs). 
         [0128]    Additionally, the 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may be used in combination with at least one of fungicides, acaricide, herbicides or nematicides to form a synergistic mixture. 
         [0129]    Furthermore, the 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may be used in combination with other active compounds, such as the compounds under the heading “OTHER ACTIVE COMPOUNDS,” algicides, avicides, bactericides, molluscicides, rodenticides, virucides, herbicide safeners, adjuvants, and/or surfactants to form a synergistic mixture. Moreover, the following compounds are known as synergists and may be used in combination with the 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof: piperonyl butoxide, piprotal, propyl isome, sesamex, sesamolin, sulfoxide, and tribufos. 
       Formulations 
       [0130]    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 at the required concentration and in an appropriate form, permitting ease of application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated emulsions, dusts, emulsifiable concentrates, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra low volume solutions. For further information on formulation types see “Catalogue of Pesticide Formulation Types and International Coding System” Technical Monograph no. 2, 5th Edition by CropLife International (2002). 
         [0131]    Pesticides are applied most often as aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrates, or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants. The concentration of the pesticide is usually from about 10% to about 90% by weight. The carrier is usually selected from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from 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 of alkyl phenols. 
         [0132]    Emulsifiable concentrates of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier that is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are selected from conventional anionic and non-ionic surfactants. 
         [0133]    Aqueous suspensions comprise suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. Ingredients, such as inorganic salts and synthetic or natural gums may also be added, to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer. 
         [0134]    Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size. 
         [0135]    Dusts containing a pesticide are prepared by intimately mixing the pesticide in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide. They can be applied as a seed dressing or as a foliage application with a dust blower machine. 
         [0136]    It is equally practical to apply a pesticide in the form of a solution in an appropriate organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry. 
         [0137]    Pesticides can also be applied in the form of an aerosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressure-generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve. 
         [0138]    Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When the pests eat the bait they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. They can be used in pest harborages. 
         [0139]    Fumigants are pesticides that have a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest&#39;s respiratory system or being absorbed through the pest&#39;s cuticle Fumigants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in special chambers. 
         [0140]    Pesticides can be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various types. By altering the chemistry of the polymer or by changing factors in the processing, microcapsules can be formed of various sizes, solubility, wall thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingredient within is released, which in turn, affects the residual performance, speed of action, and odor of the product. 
         [0141]    Oil solution concentrates are made by dissolving pesticide in a solvent that will hold the pesticide in solution. Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide. Other advantages of oil solutions include better storage stability, better penetration of crevices, and better adhesion to greasy surfaces. 
         [0142]    Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one compound which is agriculturally active, and is individually coated with a monolamellar or oligolamellar layer comprising: (1) at least one non-ionic lipophilic surface-active agent, (2) at least one non-ionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter of less than 800 nanometers. Further information on the embodiment is disclosed in U.S. patent publication 20070027034 published Feb. 1, 2007, having patent application Ser. No. 11/495,228. For ease of use, this embodiment will be referred to as “OIWE.” 
         [0143]    For further information consult “Insect Pest Management” 2nd Edition by D. Dent, copyright CAB International (2000). Additionally, for more detailed information consult “Handbook of Pest Control—The Behavior, Life History, and Control of Household Pests” by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc. 
       Other Formulation Components 
       [0144]    Generally, when 3-(1H-pyrazol)pyridine compounds of formula I or any agriculturally acceptable salt thereof, are used in a formulation, such 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, stickers, penetrants, buffers, sequestering agents, drift reduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith. 
         [0145]    A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauryl sulfate; sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates. 
         [0146]    A dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from reaggregating. Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersing agents have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of 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 suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Non-ionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersing agents. These have very long hydrophobic “backbones” and a large number of ethylene oxide chains forming the “teeth” of a “comb” surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersing agents used in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers. 
         [0147]    An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. A range of hydrophile-lipophile balance (“HLB”) values from 8 to 18 will normally provide good stable emulsions. Emulsion stability can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant. 
         [0148]    A solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobic part of the micelle. The types of surfactants usually used for solubilization are non-ionics, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyl oleate esters. 
         [0149]    Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to spray-tank mixes to improve the biological performance of the pesticide on the target. The types of surfactants used for bioenhancement depend generally on the nature and mode of action of the pesticide. However, they are often non-ionics such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates. 
         [0150]    A carrier or diluent in an agricultural formulation is a material added to the pesticide to give a product of the required strength. Carriers are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and water-dispersible granules. 
         [0151]    Organic solvents are used mainly in the formulation of emulsifiable concentrates, oil-in-water emulsions, suspoemulsions, and ultra low volume formulations, and to a lesser extent, granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are aliphatic paraffinic oils such as kerosene or refined paraffins. The second main group (and the most common) comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils. 
         [0152]    Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds or are synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum. 
         [0153]    Microorganisms can cause spoilage of formulated products. Therefore preservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt; methyl p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT). 
         [0154]    The presence of surfactants often causes water-based formulations to foam during mixing operations in production and in application through a spray tank. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane, while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface. 
         [0155]    “Green” agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection formulations. Green agents are biodegradable and generally derived from natural and/or sustainable sources, e.g. plant and animal sources. Specific examples are: vegetable oils, seed oils, and esters thereof, also alkoxylated alkyl polyglucosides. 
         [0156]    For further information, see “Chemistry and Technology of Agrochemical Formulations” edited by D. A. Knowles, copyright 1998 by Kluwer Academic Publishers. Also see “Insecticides in Agriculture and Environment Retrospects and Prospects” by A. S. Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag. 
       Pesticidal Activities 
       [0157]    The disclosed pesticidal compositions may be used, for example, as nematicides, acaricides, pesticides, insecticides, miticides, and/or molluscicides. 
         [0158]    In one particular embodiment, a method of controlling pests comprises applying a pesticidal composition comprising a 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, near a population of pests. 
         [0159]    The 3-(1H-pyrazol)pyridine compound of formula I are generally used in amounts from about 0.01 grams per hectare to about 5000 grams per hectare to provide control. Amounts from about 0.1 grams per hectare to about 500 grams per hectare are generally preferred, and amounts from about 1 gram per hectare to about 50 grams per hectare are generally more preferred. 
         [0160]    The area to which a 3-(1H-pyrazol)pyridine compound of formula I is applied can be any area inhabited (or maybe inhabited, or traversed by) a pest, for example: where crops, trees, fruits, cereals, fodder species, vines, turf and ornamental plants, are growing; where domesticated animals are residing; the interior or exterior surfaces of buildings (such as places where grains are stored), the materials of construction used in building (such as impregnated wood), and the soil around buildings. Particular crop areas to use a molecule of Formula One include areas where apples, corn, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets, beans and other valuable crops are growing or the seeds thereof are going to be planted. It is also advantageous to use ammonium sulfate with a 3-(1H-pyrazol)pyridine compound of formula I when growing various plants. 
         [0161]    Controlling pests generally means that pest populations, pest activity, or both, are reduced in an area. This can come about when: pest populations are repulsed from an area; when pests are incapacitated in or around an area; or pests are exterminated, in whole, or in part, in or around an area. Of course, a combination of these results can occur. Generally, pest populations, activity, or both are desirably reduced more than fifty percent, preferably more than 90 percent. Generally, the area is not in or on a human; consequently, the locus is generally a non-human area. 
         [0162]    The 3-(1H-pyrazol)pyridine compound of formula I may be used in mixtures, applied simultaneously or sequentially, alone or with other compounds to enhance plant vigor (e.g. to grow a better root system, to better withstand stressful growing conditions). Such other compounds are, for example, compounds that modulate plant ethylene receptors, most notably 1-methylcyclopropene (also known as 1-MCP). Furthermore, such molecules may be used during times when pest activity is low, such as before the plants that are growing begin to produce valuable agricultural commodities. Such times include the early planting season when pest pressure is usually low. 
         [0163]    The 3-(1H-pyrazol)pyridine compound of formula I can be applied to the foliar and fruiting portions of plants to control pests. The molecules will either come in direct contact with the pest, or the pest will consume the pesticide when eating leaf, fruit mass, or extracting sap, that contains the pesticide. The 3-(1H-pyrazol)pyridine compound of formula I can also be applied to the soil, and when applied in this manner, root and stem feeding pests can be controlled. The roots can absorb a molecule taking it up into the foliar portions of the plant to control above ground chewing and sap feeding pests. 
         [0164]    Generally, with baits, the baits are placed in the ground where, for example, termites can come into contact with, and/or be attracted to, the bait. Baits can also be applied to a surface of a building, (horizontal, vertical, or slant surface) where, for example, ants, termites, cockroaches, and flies, can come into contact with, and/or be attracted to, the bait. Baits can comprise a 3-(1H-pyrazol)pyridine compound of formula I. 
         [0165]    The 3-(1H-pyrazol)pyridine compound of formula I can be encapsulated inside, or placed on the surface of a capsule. The size of the capsules can range from nanometer size (about 100-900 nanometers in diameter) to micrometer size (about 10-900 microns in diameter). 
         [0166]    Because of the unique ability of the eggs of some pests to resist certain pesticides, repeated applications of the 3-(1H-pyrazol)pyridine compound of formula I may be desirable to control newly emerged larvae. 
         [0167]    Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying (for example by spraying an area) the 3-(1H-pyrazol)pyridine compound of formula I to a different portion of the plant. For example, control of foliar-feeding insects can be achieved by drip irrigation or furrow application, by treating the soil with for example pre- or post-planting soil drench, or by treating the seeds of a plant before planting. 
         [0168]    Seed treatment can be applied to all types of seeds, including those from which plants genetically modified to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as  Bacillus thuringiensis  or other insecticidal toxins, those expressing herbicide resistance, such as “Roundup Ready” seed, or those with “stacked” foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, drought resistance, or any other beneficial traits. Furthermore, such seed treatments with the 3-(1H-pyrazol)pyridine compound of formula I may further enhance the ability of a plant to better withstand stressful growing conditions. This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time. Generally, about 1 gram of the 3-(1H-pyrazol)pyridine compound of formula I to about 500 grams per 100,000 seeds is expected to provide good benefits, amounts from about 10 grams to about 100 grams per 100,000 seeds is expected to provide better benefits, and amounts from about 25 grams to about 75 grams per 100,000 seeds is expected to provide even better benefits. 
         [0169]    It should be readily apparent that the 3-(1H-pyrazol)pyridine compound of formula I compound may be used on, in, or around plants genetically modified to express specialized traits, such as  Bacillus thuringiensis  or other insecticidal toxins, or those expressing herbicide resistance, or those with “stacked” foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, or any other beneficial traits. 
         [0170]    The 3-(1H-pyrazol)pyridine compound of formula I may be used for controlling endoparasites and ectoparasites in the veterinary medicine sector or in the field of non-human animal keeping. The 3-(1H-pyrazol)pyridine compound of formula I are applied, such as by oral administration in the form of, for example, tablets, capsules, drinks, granules, by dermal application in the form of, for example, dipping, spraying, pouring on, spotting on, and dusting, and by parenteral administration in the form of, for example, an injection. 
         [0171]    The 3-(1H-pyrazol)pyridine compound of formula I may also be employed advantageously in livestock keeping, for example, cattle, sheep, pigs, chickens, and geese. They may also be employed advantageously in pets such as, horses, dogs, and cats. Particular pests to control would be fleas and ticks that are bothersome to such animals. Suitable formulations are administered orally to the animals with the drinking water or feed. The dosages and formulations that are suitable depend on the species. 
         [0172]    The 3-(1H-pyrazol)pyridine compound of formula I may also be used for controlling parasitic worms, especially of the intestine, in the animals listed above. 
         [0173]    The 3-(1H-pyrazol)pyridine compound of formula I may also be employed in therapeutic methods for human health care. Such methods include, but are limited to, oral administration in the form of, for example, tablets, capsules, drinks, granules, and by dermal application. 
         [0174]    Pests around the world have been migrating to new environments (for such pest) and thereafter becoming a new invasive species in such new environment. The 3-(1H-pyrazol)pyridine compound of formula I may also be used on such new invasive species to control them in such new environment. 
         [0175]    The 3-(1H-pyrazol)pyridine compound of formula I may also be used in an area where plants, such as crops, are growing (e.g. pre-planting, planting, pre-harvesting) and where there are low levels (even no actual presence) of pests that can commercially damage such plants. The use of such molecules in such area is to benefit the plants being grown in the area. Such benefits, may include, but are not limited to, improving the health of a plant, improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingredients), improving the vigor of a plant (e.g. improved plant growth and/or greener leaves), improving the quality of a plant (e.g. improved content or composition of certain ingredients), and improving the tolerance to abiotic and/or biotic stress of the plant. 
         [0176]    Before a pesticide can be used or sold commercially, such pesticide undergoes lengthy evaluation processes by various governmental authorities (local, regional, state, national, and international). Voluminous data requirements are specified by regulatory authorities and must be addressed through data generation and submission by the product registrant or by a third party on the product registrant&#39;s behalf, often using a computer with a connection to the World Wide Web. These governmental authorities then review such data and if a determination of safety is concluded, provide the potential user or seller with product registration approval. Thereafter, in that locality where the product registration is granted and supported, such user or seller may use or sell such pesticide. 
         [0177]    A 3-(1H-pyrazol)pyridine compound of formula I can be tested to determine its efficacy against pests. Furthermore, mode of action studies can be conducted to determine if said molecule has a different mode of action than other pesticides. Thereafter, such acquired data can be disseminated, such as by the internet, to third parties. 
         [0178]    The disclosed pesticidal composition comprising 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof, may be used to control a wide variety of pests. 
         [0179]    As a non-limiting example, in one or more embodiments, the method of the present disclosure may be used to control one or more members of  Lyriomiza sativae, Caliothrips phaseoli, Paratrioza cockerel, Spodoptera exigua, Nilaparvata lugens, Bemisia tabaci , and  Myzus persicae.    
         [0180]    In additional embodiments, the method of the present disclosure may be used to control one or more members of at least one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata, Subphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla. In at least some embodiments, the method of the present disclosure may be used to control one or more members of at least one of Class Insecta and Class Arachnida. 
         [0181]    In further embodiments, the method of the present disclosure may be used to control members of the Order Coleoptera (beetles) including, but not limited to,  Acanthoscelides  spp. (weevils),  Acanthoscelides obtectus  (common bean weevil),  Agrilus planipennis  (emerald ash borer),  Agriotes  spp. (wireworms),  Anoplophora glabripennis  (Asian longhorned beetle),  Anthonomus  spp. (weevils),  Anthonomus grandis  (boll weevil),  Aphidius  spp.,  Apion  spp. (weevils),  Apogonia  spp. (grubs),  Ataenius spretulus  (Black Turfgrass Ataenius),  Atomaria linearis  (pygmy mangold beetle), Aulacophore spp.,  Bothynoderes punctiventris  (beet root weevil),  Bruchus  spp. (weevils),  Bruchus pisorum  (pea weevil),  Cacoesia  spp.,  Callosobruchus maculatus  (southern cow pea weevil),  Carpophilus hemipteras  (dried fruit beetle),  Cassida vittata, Cerosterna  spp.,  Cerotoma  spp. (chrysomelids),  Cerotoma trifurcata  (bean leaf beetle),  Ceutorhynchus  spp. (weevils),  Ceutorhynchus assimilis  (cabbage seedpod weevil),  Ceutorhynchus napi  (cabbage curculio),  Chaetocnema  spp. (chrysomelids),  Colaspis  spp. (soil beetles),  Conoderus scalaris, Conoderus stigmosus, Conotrachelus nenuphar  (plum curculio),  Cotinus nitidis  (Green June beetle),  Crioceris asparagi  (asparagus beetle),  Cryptolestes ferrugineus  (rusty grain beetle),  Cryptolestes pusillus  (flat grain beetle),  Cryptolestes 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. (chrysomelids),  Epilachna varivestis  (Mexican bean beetle),  Faustinus cubae, Hylobius pales  (pales weevil),  Hypera  spp. (weevils),  Hypera postica  (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 beetlespowder 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 palm beetle),  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. (MayJune beetle),  Phyllophaga cuyabana  (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),  Tribolium castaneum  (red flour beetle),  Tribolium confusum  (confused flour beetle),  Trogoderma variabile  (warehouse beetle), and  Zabrus tenebioides.    
         [0182]    In other embodiments, the method of the present disclosure may also be used to control members of the Order Dermaptera (earwigs). 
         [0183]    In additional embodiments, the method of the present disclosure may be used to control members of the Order Dictyoptera (cockroaches) including, but is not limited to,  Blattella germanica  (German cockroach),  Blatta orientalis  (oriental cockroach),  Parcoblatta pennylvanica, Periplaneta americana  (American cockroach),  Periplaneta australoasiae  (Australian cockroach),  Periplaneta brunnea  (brown cockroach),  Periplaneta fuliginosa  (smokybrown cockroach),  Pyncoselus suninamensis  (Surinam cockroach), and  Supella longipalpa  (brownbanded cockroach). 
         [0184]    In further embodiments, the method of the present disclosure may be used to control members of the Order Diptera (true flies) including, but is not limited to,  Aedes  spp. (mosquitoes),  Agromyza frontella  (alfalfa blotch leafminer),  Agromyza  spp. (leaf miner flies),  Anastrepha  spp. (fruit flies),  Anastrepha suspensa  (Caribbean fruit fly),  Anopheles  spp. (mosquitoes),  Batrocera  spp. (fruit flies),  Bactrocera cucurbitae  (melon fly),  Bactrocera dorsalis  (oriental fruit fly),  Ceratitis  spp. (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). 
         [0185]    In other embodiments, the method of the present disclosure may be used to control members of the Order Hemiptera (true bugs) including, but is not limited to,  Acrosternum hilare  (green stink bug),  Blissus leucopterus  (chinch bug),  Calocoris norvegicus  (potato mirid),  Cimex hemipterus  (tropical bed bug),  Cimex lectularius  (bed bug),  Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturellus  (cotton stainer),  Edessa meditabunda, Eurygaster maura  (cereal bug),  Euschistus heros, Euschistus servus  (brown stink bug),  Helopeltis antonii, Helopeltis theivora  (tea blight plantbug),  Lagynotomus  spp. (stink bugs),  Leptocorisa oratorius, Leptocorisa varicornis, Lygus  spp. (plant bugs),  Lygus hesperus  (western tarnished plant bug), Maconellicoccus hirsutus, Neurocolpus longirostris, Nezara viridula (southern green stink bug),  Phytocoris  spp. (plant bugs),  Phytocoris californicus, Phytocoris relativus, Piezodorus guildingi, Poecilocapsus lineatus  (fourlined plant bug),  Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea , and  Triatoma  spp. (bloodsucking conenose bugs/kissing bugs). 
         [0186]    In additional embodiments, the method of the present disclosure may be used to control members of the Order Homoptera (aphids, scales, whiteflies, leaflhoppers) including, but is not limited to,  Actythosiphon 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),  Chrysomphalus  spp. (scales),  Coccus  spp. (scales),  Dysaphis plantaginea  (rosy apple aphid),  Empoasca  spp. (leafhoppers),  Eriosoma lanigerum  (woolly apple aphid),  Icerya purchasi  (cottony cushion scale),  Idioscopus nitidulus  (mango leafhopper),  Laodelphax striatellus  (smaller brown planthopper),  Lepidosaphes  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 aphid),  Mictis longicornis, Myzus  spp.,  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 perniciosus  (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 vaporariorum  (greenhouse whitefly),  Trialeurodes abutiloneus  (bandedwing whitefly),  Unaspis  spp. (scales),  Unaspis yanonensis  (arrowhead scale), and  Zulia entreriana . In at least some embodiments, the method of the present disclosure may be used to control  Myzus persicae.    
         [0187]    In other embodiments, the method of the present disclosure may be used to control members of the Order Hymenoptera (ants, wasps, and bees) including, but not limited to,  Acromyrrmex  spp.,  Athalia rosae, Atta  spp. (leafcutting ants),  Camponotus  spp. (carpenter ants),  Diprion  spp. (sawflies),  Formica  spp. (ants),  Iridomyrmex humilis  (Argentine ant),  Monomorium ssp., Monomorium minumum  (little black ant),  Monomorium pharaonic  (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). 
         [0188]    In certain embodiments, the method of the present disclosure may be used to control members of the Order Isoptera (termites) including, but not limited to,  Coptotermes  spp.,  Coptotermes curvignathus, Coptotermes frenchii, Coptotermes formosanus  (Formosan subterranean termite),  Cornitermes  spp. (nasute termites),  Ctyptotermes  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 tibialis, Reticulitermes virginicus, Schedorhinotermes  spp., and  Zootermopsis  spp. (rotten-wood termites). 
         [0189]    In additional embodiments, the method of the present disclosure may be used to control members of the Order Lepidoptera (moths and butterflies) including, but not limited to,  Achoea janata, Adoxophyes  spp.,  Adoxophyes orana, Agrotis  spp. (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 gemmatalis  (velvetbean caterpillar),  Archips argyrospila  (fruittree leafroller),  Archips rosana  (rose leaf roller),  Argyrotaenia  spp. (tortricid moths),  Argyrotaenia citrana  (orange  tortrix ),  Autographa gamma, Bonagota cranaodes, Borbo cinnara  (rice leaf folder),  Bucculatrix thurberiella  (cotton leafperforator),  Caloptilia  spp. (leaf miners),  Capua reticulana, Carposina niponensis  (peach fruit moth),  Chilo  spp.,  Chlumetia transversa  (mango shoot borer),  Choristoneura rosaceana  (obliquebanded leafroller),  Chrysodeixis  spp.,  Cnaphalocerus medinalis  (grass leafroller),  Colias  spp.,  Conpomorpha cramerella, Cossus cossus  (carpenter moth),  Crambus  spp. (Sod webworms),  Cydiafunebrana  (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),  Diatraea saccharalis  (sugarcane borer),  Diatraea graniosella  (southwester corn borer),  Earias  spp. (bollworms),  Earias insulata  (Egyptian bollworm),  Earias 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  (tobbaco moth),  Ephestia kuehniella  (Mediterranean flour moth),  Epimeces  spp.,  Epinotia aporema, Erionota thrax  (banana skipper),  Eupoecilia ambiguella  (grape berry moth),  Euxoa auxiliaris  (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  (bollwormcorn 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),  Metisa plana  (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 meal 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),  Rachiplusia nu, Scirpophaga incertulas, Sesamia  spp. (stemborers),  Sesamia inferens  (pink rice stem borer),  Sesamia nonagrioides, Setora nitens, Sitotroga cerealella  (Angoumois grain moth),  Sparganothis pilleriana, Spodoptera  spp. (armyworms),  Spodoptera exigua  (beet armyworm),  Spodoptera fugiperda  (fall 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 at least some embodiments, the method of the present disclosure may be used to control  Spodoptera exigua.    
         [0190]    The method of the present disclosure may be used to also control members of the Order Mallophaga (chewing lice) including, but not limited to,  Bovicola ovis  (sheep biting louse),  Menacanthus stramineus  (chicken body louse), and  Menopon gallinea  (common hen louse). 
         [0191]    In additional embodiments, the method of the present disclosure may be used to control members of the Order Orthoptera (grasshoppers, locusts, and crickets) including, but not limited to,  Anabrus simplex  (Mormon cricket), Gryllotalpidae (mole crickets),  Locusta migratoria, Melanoplus  spp. (grasshoppers),  Microcentrum retinerve  (angularwinged katydid),  Pterophylla  spp. (kaydids), chistocerca  gregaria, Scudderia furcata  (forktailed bush katydid), and  Valanga nigricorni.    
         [0192]    In other embodiments, the method of the present disclosure may be used to control members of the Order Phthiraptera (sucking lice) including, but not limited to,  Haematopinus  spp. (cattle and hog lice),  Linognathus ovillus  (sheep louse),  Pediculus humanus capitis  (human body louse),  Pediculus humanus humanus  (human body lice), and  Pthirus pubis  (crab louse). 
         [0193]    In particular embodiments, the method of the present disclosure may be used to control members of the Order Siphonaptera (fleas) including, but not limited to,  Ctenocephalides canis  (dog flea),  Ctenocephalides felis  (cat flea), and  Pulex irritans  (human flea). 
         [0194]    In additional embodiments, the method of the present disclosure may be used to control members of the Order Thysanoptera ( thrips ) including, but not limited to,  Frankliniella fusca  (tobacco  thrips ),  Frankliniella occidentalis  (western flower  thrips ),  Frankliniella shultzei, Frankliniella williamsi  (corn  thrips ),  Heliothrips haemorrhaidalis  (greenhouse  thrips ),  Riphiphorothrips cruentatus, Scirtothrips  spp.,  Scirtothrips citri  (citrus  thrips ),  Scirtothrips dorsalis  (yellow tea  thrips ),  Taeniothrips rhopalantennalis , and  Thrips  spp. 
         [0195]    The method of the present disclosure may be used to also control members of the Order Thysanura (bristletails) including, but not limited to,  Lepisma  spp. (silverfish) and  Thermobia  spp. (firebrats). 
         [0196]    In further embodiments, the method of the present disclosure may be used to control members of the Order Acari (mites and ticks) including, but not limited to,  Acarapsis woodi  (tracheal mite of honeybees),  Acarus  spp. (food mites),  Acarus siro  (grain mite),  Aceria mangiferae  (mango bud mite),  Aculops  spp.,  Aculops lycopersici  (tomato russet mite),  Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali  (apple rust mite),  Amblyomma americanum  (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 variabilis  (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 oleivora  (citrus 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  (twospotted spider mite), and  Varroa destructor  (honey bee mite). 
         [0197]    In additional embodiments, the method of the present disclosure may be used to control members of the Order Nematoda (nematodes) including, but not limited to,  Aphelenchoides  spp. (foliar 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). 
         [0198]    In at least some embodiments, the method of the present disclosure may be used to control at least one insect in one or more of the Orders Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Orthoptera, Diptera, Hymenoptera, and Siphonaptera, and at least one mite in the Order Acari. 
     
    
     DETAILED DESCRIPTION 
     Insecticidal Testing 
     Example A 
     Bioassays for Green Peach Aphid ( Myzus persicae ) (GPA) (MYZUPE) 
       [0199]    The green peach aphid ( Myzus persicae ) is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshadepotato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce, macadamia,  papaya , peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other plants. GPA also attacks many ornamental crops such as carnation,  chrysanthemum , flowering white cabbage, poinsettia, and roses. GPA has developed resistance to many pesticides. 
         [0200]    Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) true leaves, were used as test substrate. The seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application. Four pots with individual seedlings were used for each treatment. Test compounds (2 mg) were dissolved in 2 mL of acetonemethanol (1:1) solvent, forming stock solutions of 1000 ppm test compound. The stock solutions were diluted 5× with 0.025% Tween 20 in H 2 O to obtain the solution at 200 ppm test compound. A hand-held aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff. Reference plants (solvent check) were sprayed with the diluent only containing 20% by volume of acetonemethanol (1:1) solvent. Treated plants were held in a holding room for three days at approximately 25° C. and ambient relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent control was measured by using Abbott&#39;s correction formula (W. S. Abbott, “A Method of Computing the Effectiveness of an Insecticide,” J. Econ. Entomol. 18 (1925), pp. 265-267) as follows. 
         [0000]      Corrected % Control=100*( X−Y )/ X          where   X=No. of live aphids on solvent check plants and   Y=No. of live aphids on treated plants
 
The results are indicated in the table entitled “TABLE 2. Biological Data for Green Peach Aphid (MYZUPE) and Sweetpotato Whitefly-crawler (WF) (BEMITA)” (See Table Section).
         
       Example B 
     Insecticidal Test for Sweetpotato Whitefly-Crawler ( Bemisia tabaci ) (WF) (BEMITA) in Foliar Spray Assay 
       [0204]    The sweetpotato whitefly ( Bemisia tabaci ) has been reported as a serious pest of cultivated crops world-wide. It has an extremely wide host range attacking more than 500 species of plants from 63 plant families. Weeds often serve as alternate hosts of crop pests. Direct feeding damage is caused by the piercing and sucking sap from the foliage of plants. This feeding causes weakening and early wilting of the plant and reduces the plant growth rate and yield. Indirect damage results by the accumulation of honeydew produced by the whiteflies. Honeydew serves as a substrate for the growth of black sooty mold on leaves and fruit reducing photosynthesis and lessens the market value of the plant or yield. Damage is also caused when sweetpotato whitefly vectors plant viruses. The sweetpotato whitefly is considered the most common and important whitefly vector of plant viruses worldwide. 
         [0205]    Cotton plants ( Gossypium hirsutum ) grown in 3-inch pots, with 1 small (4-5 cm) true leaves, were used as test substrate. The plants were infested with 200-400 whitefly eggs 4-5 days prior to chemical application. Four pots with individual plants were used for each treatment. Test compounds (2 mg) were dissolved in 1 mL of acetone solvent, forming stock solutions of 2000 ppm test compound. The stock solutions were diluted 10× with 0.025% Tween 20 in H 2 O (diluents) to obtain the solution at 200 ppm test compound. A hand-held aspirator-type sprayer was used for spraying a solution to both sides of cotton leaves until runoff. Reference plants (solvent check) were sprayed with the diluent only containing 10% by volume of acetone solvent. Treated plants were held in a holding room for 9 days at approximately 25° C. and ambient relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live 3-4 nymph stage per plant under a microscope. Percent control was measured by using Abbott&#39;s correction formula (W. S. Abbott, “A Method of Computing the Effectiveness of an Insecticide,” J. Econ. Entomol. 18 (1925), pp. 265-267) as follows. 
         [0000]      Corrected % Control=100*( X−Y )/ X          where   X=No. of live nymphs on solvent check plants and   Y=No. of live nymphs on treated plants.         
         [0209]    The results are indicated in the table entitled “TABLE 2. Biological Data for Green Peach Aphid (MYZUPE) and Sweetpotato Whitefly-crawler (WF) (BEMITA)” (See Table Section). 
         [0210]    The mortality efficiency of the disclosed pesticidal compounds against GPA and WF insects was rated as shown in TABLE 1. 
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Mortality Rating for Green Peach Aphid and Whitefly 
               
             
          
           
               
                   
                 % Control (or Mortality) 
                 Rating 
               
               
                   
                   
               
               
                   
                 80-100 
                 A 
               
               
                   
                 More than 0-Less than 80 
                 B 
               
               
                   
                 Not Tested 
                 C 
               
               
                   
                 No activity noticed in this bioassay 
                 D 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
             
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Biological Data for Green Peach Aphid (GPA) (MYZUPE)and Sweet Potato 
               
               
                 Whitefly-Crawler (WF) (BEMITA) 
               
             
          
           
               
                   
                 Insect Species 
               
             
          
           
               
                   
                 GPA 
                 WF 
               
               
                 No. 
                 200 ppm 
                 200 ppm 
               
               
                   
               
               
                 F1 
                 D 
                 B 
               
               
                 F2 
                 A 
                 A 
               
               
                 F3 
                 A 
                 A 
               
               
                 F4 
                 D 
                 B 
               
               
                 F5 
                 A 
                 A 
               
               
                 F6 
                 A 
                 A 
               
               
                 F7 
                 A 
                 D 
               
               
                 F8 
                 A 
                 A 
               
               
                 F9 
                 A 
                 B 
               
               
                 F10 
                 C 
                 C 
               
               
                 F11 
                 A 
                 A 
               
               
                 F12 
                 B 
                 A 
               
               
                 F13 
                 B 
                 B 
               
               
                 F14 
                 A 
                 A 
               
               
                 F15 
                 A 
                 A 
               
               
                 F16 
                 A 
                 A 
               
               
                 F17 
                 A 
                 A 
               
               
                 F18 
                 A 
                 A 
               
               
                 F19 
                 A 
                 A 
               
               
                 F20 
                 A 
                 B 
               
               
                 F21 
                 A 
                 A 
               
               
                 F22 
                 A 
                 A 
               
               
                 F23 
                 B 
                 B 
               
               
                 F24 
                 A 
                 A 
               
               
                 P4 
                 A 
                 A 
               
               
                 P5 
                 A 
                 A 
               
               
                 P47 
                 A 
                 A 
               
               
                 FA1 
                 C 
                 C 
               
               
                 FA2 
                 C 
                 C 
               
               
                   
               
             
          
         
       
     
       EXAMPLES 
       [0211]    These examples are for illustration purposes and are not to be construed as limiting the disclosure to only the embodiments disclosed in these examples. 
         [0212]    Starting materials, reagents, and solvents that were obtained from commercial sources were used without further purification. Anhydrous solvents were purchased as SURESEAL™ from Aldrich and were used as received. Melting points were obtained on a Thomas Hoover Unimelt capillary melting point apparatus or an OptiMelt Automated Melting Point System from Stanford Research Systems and are uncorrected. Examples using “room temperature” were conducted in climate controlled laboratories with a temperature of from about 20° C. to about 24° C. Chemical compounds are given their known names, named according to naming programs within ISIS Draw, ChemDraw or ACD Name Pro. If such programs are unable to name a chemical compound, the chemical compounds named using conventional naming rules.  1 H NMR spectral data are in ppm (δ) and were recorded at 300, 400 or 600 MHz.  13 C NMR spectral data are in ppm (δ) and were recorded at 75, 100 or 150 MHz.  19 F NMR spectral data are in ppm (δ) and were recorded at 376 MHz, unless otherwise stated. 
       Example 1 
     Preparation of (Z)-ethyl 2-(ethoxyimino)-3-(tritylthio)propanoate 
     Compound C1 
       [0213]    
       
                 
         
             
             
         
       
     
         [0214]    To a solution of triphenylmethanethiol (5.80 g, 21.00 mmol) in THF (105 mL) at a temperature of 0° C. and under nitrogen (N 2 ) was added NaH (60% dispersion in oil, 0.840 g, 21.0 mmol). The mixture was stirred for 10 minutes at which point a solution of ethyl 3-bromo-2-(ethoxyimino)propanoate (5.00 g, 21.0 mmol) in THF (10 mL) was added. The reaction was warmed to room temperature (about 22° C.) and stirred overnight. Thin layer chromatography (TLC) analysis was used to indicate the complete consumption of starting thiol and formation of a UV-active product. The reaction was quenched with water (150 mL) and was diluted with ethyl acetate (EtOAc, 300 mL). The phases were mixed and separated. The aqueous phase was extracted with EtOAc (3×200 mL), and the combined organic extracts were dried over anhydrous sodium sulfate (Na 2 SO 4 ), filtered, and concentrated in vacuo. The crude residue was purified via normal phase flash chromatography (0 to 50% EtOAcHex) to provide compound C1 as a white solid (7.76 g, 84%) having a melting point of about 90° C. to about 96° C.  1 H NMR (400 MHz, CDCl 3 ) δ 7.50-7.37 (m, 6H), 7.35-7.26 (m, 6H), 7.25-7.18 (m, 3H), 4.39-4.16 (m, 4H), 3.20 (s, 2H), 1.38-1.28 (m, 6H);  13 C NMR (101 MHz, CDCl 3 ) δ 162.6, 147.7, 144.3, 129.7, 127.9, 126.8, 71.7, 67.3, 61.9, 25.7, 14.4, 14.2. 
         [0215]    The following molecules were made in accordance with the procedures disclosed in 
         [0000]    
       
                 
         
             
             
         
       
     
       Example 1 
       [0216]    Ethyl 2-(methoxyimino)-3-(tritylthio)propanoate (Compound C2) was isolated as clear oil (4.04 g, 43%).  1 H NMR (400 MHz, CDCl 3 ) δ 7.46-7.38 (m, 6H), 7.34-7.26 (m, 6H), 7.25-7.18 (m, 3H), 4.27 (q, J=7.1 Hz, 2H), 4.01 (s, 3H), 3.22 (s, 2H), 1.32 (t, J=7.1 Hz, 3H).  13 C NMR (101 MHz, CDCl 3 ) δ 162.5, 148.2, 144.3, 129.7, 127.9, 126.8, 67.5, 63.6, 62.0, 25.6, 14.2. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0217]    Ethyl 2-((allyloxy)imino)-3-(tritylthio)propanoate (Compound C3) was isolated as white solid (0.311 g, 78%): MP=67-68° C.;  1 H NMR (400 MHz, CDCl 3 ) δ 7.53-7.36 (m, 6H), 7.28 (ft, J=6.7, 0.9 Hz, 6H), 7.25-7.18 (m, 3H), 5.97 (ddt, J=17.3, 10.5, 5.7 Hz, 1H), 5.33 (dq, J=17.3, 1.6 Hz, 1H), 5.27 (dq, J=10.5, 1.3 Hz, 1H), 4.74 (dt, J=5.7, 1.4 Hz, 2H), 4.26 (q, J=7.1 Hz, 2H), 3.22 (s, 2H), 1.31 (t, J=7.1 Hz, 3H);  13 C NMR (101 MHz, CDCl 3 ) δ 162.5, 148.3, 144.3, 132.8, 129.7, 127.9, 126.8, 118.5, 76.8, 67.4, 62.0, 25.8, 14.2. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0218]    Ethyl 2-(methoxyimino)-3-((3,3,3-trifluoropropyl)thio)propanoate (Compound C4) was isolated as a yellow oil (1.08 g, 67%).  1 H NMR (400 MHz, CDCl 3 ) δ 4.36 (q, J=7.1 Hz, 2H), 4.07 (s, 3H), 3.60 (s, 2H), 2.71-2.62 (m, 2H), 2.48-2.33 (m, 2H), 1.37 (t, J=7.1 Hz, 3H). Oxime geometry was not determined. 
       Example 2 
     Preparation of 2-(ethoxyimino)-3-(tritylthio)propanoic acid 
     Compound C5 
       [0219]    
       
                 
         
             
             
         
       
     
         [0220]    To a solution of ethyl 2-(ethoxyimino)-3-(tritylthio)propanoate (4.00 g, 9.23 mmol) in EtOH (100 mL) and water (100 mL) was added a 2.0 M aqueous solution of NaOH (9.23 mL, 18.5 mmol). The reaction was stirred overnight and then acidified with hydrochloric acid (2 N HCl, 11.5 mL, 23.1 mmol). The resulting homogeneous solution was diluted in EtOAc (500 mL), and the phases were mixed and separated. The aqueous phase was extracted with EtOAc (3×250 mL), and the combined organic extracts were dried over anhydrous Na 2 SO 4 , filtered, and concentrated in vacuo to afford the desired compound C5 as a pale yellow semi-solid (3.83 g, 97%).  1 H NMR (400 MHz, CDCl 3 ) δ 7.52-7.37 (m, 6H), 7.32-7.25 (m, 6H), 7.25-7.18 (m, 3H), 4.29 (q, J=7.1 Hz, 2H), 3.22 (s, 2H), 1.32 (t, J=7.1 Hz, 3H);  13 C NMR (101 MHz, CDCl 3 ) δ 164.0, 147.0, 144.2, 129.7, 128.0, 126.9, 72.4, 67.5, 24.8, 14.4; ESIMS m/z 404 [(M-H) − ]. 
         [0221]    The following molecules were made in accordance with the procedures disclosed in Example 2: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0222]    2-(Methoxyimino)-3-(tritylthio)propanoic acid (Compound C6) was isolated as a white solid (3.33 g, 87%), having a melting point of about 152° C. to about 158° C.  1 H NMR (400 MHz, CDCl 3 ) δ 7.50-7.37 (m, 6H), 7.34-7.26 (m, 6H), 7.25-7.18 (m, 3H), 4.01 (s, 3H), 3.23 (s, 2H);  13 C NMR (101 MHz, CDCl 3 ) δ 162.7, 147.3, 144.1, 29.7, 128.0, 126.9, 67.6, 64.1, 24.5; ESIMS m/z 390 [(M-H) − ]. Oxime geometry was not determined. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0223]    2-((Allyloxy)imino)-3-(tritylthio)propanoic acid (Compound C7) was isolated in 88% yield (0.284 g).  1 H NMR (400 MHz, CDCl 3 ) δ 7.46-7.38 (m, 6H), 7.32-7.27 (m, 6H), 7.25-7.18 (m, 3H), 5.94 (ddt, J=17.3, 10.5, 5.8 Hz, 1H), 5.41-5.24 (m, 2H), 4.71 (dt, J=5.8, 1.4 Hz, 2H), 3.23 (s, 2H); ESIMS m/z 416 [(M-H) − ]. Oxime geometry was not determined. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0224]    2-(Methoxyimino)-3-((3,3,3-trifluoropropyl)thio)propanoic acid (Compound C8) was isolated as a yellow solid (980 mg, 89% [crude]).  1 H NMR (400 MHz, CDCl 3 ) δ 4.11 (s, 3H), 3.58 (s, 2H), 2.77-2.61 (m, 2H), 2.49-2.28 (m, 2H). Oxime geometry was not determined. 
       Example 3 
     Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-(tritylthio)propanamide 
     Compound F12 
       [0225]    
       
                 
         
             
             
         
       
     
         [0226]    To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (prepared as described in the PCT Publication No. WO 2013062981) (0.117 g, 0.525 mmol) and 2-(ethoxyimino)-3-(tritylthio)propanoic acid (0.224 g, 0.552 mmol) in DCE (5.25 mL) at room temperature were added DMAP (0.0960 g, 0.788 mmol) and EDC (0.121 g, 0.631 mmol). The reaction was capped and stirred for 18 hours, after which it was concentrated in vacuo and purified via normal phase flash chromatography (0% to 100% EtOAcHex) to afford the desired compound F12 as mixture of interconverting oxime isomers. The title compound F12 was isolated as white foam (0.144 g, 43%). 
         [0227]    The following molecules were made in accordance with the procedures disclosed in Example 3: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0228]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(methoxyimino)-3-(tritylthio)propanamide (Compound F10) was isolated as white foam (1.23 g, 76%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0229]    2-((Allyloxy)imino)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(tritylthio)propanamide (Compound F13) was isolated as a sticky white foam (0.110 g, 27%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0230]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-(prop-2-yn-1-yl)-3-(tritylthio)propanamide (Compound F4) was prepared from 3-chloro-N-(prop-2-yn-1-yl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine (as described in the PCT Publication No. WO 2013062981) and isolated as sticky white foam (1.67 g, 61%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0231]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-(prop-2-yn-1-yl)-3-(tritylthio)propanamide (Compound F1) was isolated as an off-white solid (0.351 g, 61%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0232]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(methoxyimino)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound F14) was isolated as yellow oil (0.459 g, 50%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0233]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-methyl-3-(tritylthio)propanamide (Compound FA1) from 3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (U.S. Application Publication No. 20120110702) was isolated as a white foam (3.39 g, 57%). 
       Example 4 
     Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-mercaptopropanamide 
     Compound F20 
       [0234]    
       
                 
         
             
             
         
       
     
         [0235]    To a solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-(tritylthio)propanamide (1.05 g, 1.721 mmol) in CH 2 Cl 2  (8.60 mL) at room temperature were added triethylsilane (2.75 mL, 17.2 mmol) and TFA (0.663 mL, 8.60 mmol), sequentially. The reaction was stirred for two hours at which point UPLC-MS analysis indicated excellent conversion to a product of the desired mass. The reaction was diluted in CH 2 Cl 2  (100 mL) and quenched with the careful addition of saturated, aqueous sodium bicarbonate (NaHCO 3 , 100 mL). The layers were separated. The aqueous phase was extracted with CH 2 Cl 2  (3×100 mL), and the combined organic extracts were dried over anhydrous Na 2 SO 4 , filtered, and concentrated in vacuo. The crude residue was purified via normal phase flash chromatography (0% to 100% EtOAcCH 2 Cl 2 ) to afford the desired product F20 as a mixture of interconverting oxime isomers. The title compound F20 was isolated as a white solid (0.605 g, 91%). 
         [0236]    The following molecules were made in accordance with the procedures disclosed in Example 4: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0237]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-mercapto-2-(methoxyimino)propanamide (Compound F9) was isolated as a white solid (0.701 g, 94%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0238]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-mercapto-2-(methoxyimino)-N-(prop-2-yn-1-yl)propanamide (Compound F23) was isolated as pale yellow oil (0.934 g, 94%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0239]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-3-mercapto-N-(prop-2-yn-1-yl)propanamide (Compound F7) was isolated as pale yellow oil (0.160 g, 91%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0240]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-mercapto-2-(methoxyimino)-N-methylpropanamide (Compound FA2) was isolated as a white solid (1.55 g, 95%). 
       Example 5 
     Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide 
     Compound F24 
       [0241]    
       
                 
         
             
             
         
       
     
         [0242]    To a solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-mercaptopropanamide (0.136 g, 0.370 mmol) in THF (3.70 mL) at a temperature of 0° C. and under nitrogen atmosphere was added NaH (60% dispersion in oil, 0.0180 g, 0.444 mmol). The reaction was stirred for 10 minutes, during which time the solution turned bright yellow. To the reaction was added 3-bromo-1,1,1-trifluoropropane (0.0850 g, 0.481 mmol). The reaction was then warmed to room temperature and stirred for 18 hours. The reaction was quenched with water (5 mL) and diluted in EtOAc (10 mL). The layers were mixed and then separated. The aqueous phase was extracted with EtOAc (3×10 mL), and the combined organic extracts were dried over anhydrous Na 2 SO 4 , filtered, and concentrated in vacuo. The crude residue was purified via normal phase flash chromatography (0% to 100% EtOAcHex) to afford the desired product as a mixture of interconverting oxime isomers. The title compound F24 was isolated as pale, pink oil (0.0810 g, 45%). 
         [0243]    The following molecules were made in accordance with the procedures disclosed in Example 5: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0244]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluorocyclopropyl)methyl)thio)-2-(ethoxyimino)-N-ethylpropanamide (Compound F11) was isolated as a pale pink solid (0.082 g, 46%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0245]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-((2,2,2-trifluoroethyl)thio)propanamide (Compound F17) was isolated as yellow oil (0.029 g, 17%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0246]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-ethyl-3-((4,4,4-trifluorobutyl)thio)propanamide (Compound F15) was isolated as pale pink oil (0.081 g, 44%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0247]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluoro cyclopropylmethyl)thio)-N-ethyl-2-(methoxyimino)propanamide (Compound F5) was isolated as clear oil (0.488 g, 57%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0248]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound F21) was isolated as clear oil (0.438 g, 75%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0249]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluorocyclopropyl)methyl)thio)-2-(methoxyimino)-N-(prop-2-yn-1-yl)propanamide (Compound F2) was isolated as pink oil (0.077 g, 40%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0250]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-(prop-2-yn-1-yl)-3-((2,2,2-trifluoroethyl)thio)propanamide (F6) was isolated as yellow oil (0.028 g, 15%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0251]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-(prop-2-yn-1-yl)-3-((4,4,4-trifluorobutyl)thio)propanamide (Compound F19) was isolated as pale pink oil (0.108 g, 54%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0252]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(ethoxyimino)-N-(prop-2-yn-1-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound F16) was isolated as clear oil (0.107 g, 69%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0253]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-methyl-3-((3,3,3-trifluoropropyl)thio)propanamide (Compound P4) was isolated as clear viscous oil (0.561 g, 94%). 
         [0254]    The following compounds in TABLE 4 may be prepared according to the procedures disclosed in Example 5: P1, P4, P6, P8, P10, P12, P14, P16, P26, P28, P30, P32, P34, P36, P38, P59, P62, P65 
       Example 6 
     Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-4(2,2-difluorocyclopropyl)methyl)sulfinyl)-N-ethyl-2-(methoxyimino)propanamide (Compound F22) and N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluorocyclopropyl)methyl)sulfonyl)-2-(ethoxyimino)-N-ethylpropanamide 
     Compound F3 
       [0255]    
       
                 
         
             
             
         
       
     
         [0256]    To a solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(((2,2-difluorocyclopropyl)methyl)thio)-N-ethyl-2-(methoxyimino)propanamide (0.360 g, 0.811 mmol) in AcOH (8.11 mL) at room temperature was added sodium perborate, tetrahydrate (0.187 g, 1.22 mmol). The reaction was fitted with a condenser and heated to 55° C. for 1 hour. The reaction was allowed to cool and was diluted (carefully) in saturated, aqueous NaHCO 3  (50 mL) and EtOAc (100 mL). The layers were separated and the aqueous layer was extracted with EtOAc. The combined organic extracts were washed with brine, dried over anhydrous Na 2 SO 4 , filtered, and concentrated in vacuo. The crude residue was purified via normal phase flash chromatography (0% to 100% acetone/Hexanes) to afford the separated products, each of which was shown to be a mixture of interconverting oxime isomers: the sulfoxide compound F22 was isolated as clear viscous oil (0.172 g, 44%), and the sulfone compound F3 was isolated as clear viscous oil (0.0800 g, 20%). 
         [0257]    The following molecules were made in accordance with the procedures disclosed in Example 6: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0258]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(methoxyimino)-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (Compound F18) was isolated as red oil (0.130 g, 34%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0259]    N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(methoxyimino)-3-((3,3,3-trifluoropropyl)sulfonyl)propanamide (Compound F8) was isolated as opaque oil (0.162 g, 40%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0260]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-methyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (Compound P5) was isolated as a clear viscous oil (0.178 g, 41%). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0261]    N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methoxyimino)-N-methyl-3-((3,3,3-trifluoropropyl)sulfonyl)propanamide (Compound F47) was isolated as a clear semi-solid (0.187 g, 39%). 
         [0262]    The following compounds in TABLE 4 may be prepared according to the procedures disclosed in Example 6: P2, P3, P5, P7, P9, P11, P13, P15, P17, P19, P21, P23, P25, P27, P29, P31, P33, P35, P37, P39, P41, P46, P47, P48, P49, P50, P51, P52, P53, P54, P55, P56, P57, P58, P60, P61, P63, P64, P66, P67. 
       Example 7 
     Preparation of ethyl 3-bromo-2-(methoxyimino)propanoate 
     Compound C9 
       [0263]    
       
                 
         
             
             
         
       
     
         [0264]    Ethyl 3-bromo-2-(methoxyimino)propanoate was prepared according to procedures described in: Noguchi, H; Aoyama, T; Shioiri, T. Heterocycles 2002, 58, 471-504. The title compound C9 was isolated as a mixture of oxime isomers. 
         [0265]    The following molecules were made in accordance with the procedures disclosed in Example 7: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0266]    Ethyl 3-bromo-2-(ethoxyimino)propanoate (Compound 10) was isolated as clear oil (7.51 g, 88%).  1 H NMR (400 MHz, CDCl 3 ) δ 4.50-4.30 (m, 6H), 1.46-1.30 (m, 6H). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0267]    Ethyl 2-((allyloxy)imino)-3-bromopropanoate (Compound C11) was isolated as clear oil (0.216 g, 94%):  1 H NMR (400 MHz, CDCl 3 ) δ 6.01 (ddtd, J=17.3, 10.5, 5.7, 1.2 Hz, 1H), 5.45-5.33 (m, 1H), 5.33-5.26 (m, 1H), 4.94-4.82 (m, 2H), 4.43-4.32 (m, 3.3H), 4.23 (s, 0.7H), 1.41-1.34 (m, 3H). 
       Example 8 
     Prophetic preparation of 3,3,3-trifluoropropyl 2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-N-methoxy-2-oxoethanimidothioate 
     Compound P40 
       [0268]    
       
                 
         
             
             
         
       
     
         [0269]    To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (about 1 eq) and 2-(methoxyimino)-2-(3,3,3-trifluoropropyl)thio)acetic acid (from about 1 eq to about 1.5 eq) in a solvent, such as DCE (at a concentration between about 0.01 M to about 1 M) at room temperature may be added a base, such as DMAP (from about 1.5 eq to about 2.0 eq), and an amide coupling reagent, such as EDC (from about 1.2 eq to about 1.75 eq). The reaction may be capped and stirred until it is determined to be completed. The title compound P40 may then be obtained using standard organic chemistry techniques for workup and purification. 
         [0270]    The following compounds in TABLE 4 may be prepared according to the procedures disclosed in Example 8: P40, P42, P43, P44, P45. 
       Example 9 
     Prophetic preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(methoxyimino)-3-((3,3,3-trifluoropropyl)thio)propanethioamide 
     Compound P18 
       [0271]    
       
                 
         
             
             
         
       
     
         [0272]    To a solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(methoxyimino)-3-((3,3,3-trifluoropropyl)thio)propanamide (about 1 eq) in a solvent, such as toluene, (at a concentration between about 0.01 M to about 1 M) at room temperature may be added a thionation reagent, such as Lawesson&#39;s reagent (from about 0.5 eq to about 1 eq). The reaction may be capped in a microwave vial and heated at a temperature of from about 100° C. to about 150° C. in a microwave reactor with external IR-sensor monitoring the temperature from the side of the vessel until it is determined to be complete. The title compound P18 may then be obtained using standard organic chemistry techniques for workup and purification. 
         [0273]    The following compounds in TABLE 4 may be prepared according to the procedures disclosed in Example 9: P18, P20, P22, P24. 
         [0274]    TABLE 3 and TABLE 4 show non-limiting examples of the 3-(1H-pyrazol)pyridine compound of formula I or any agriculturally acceptable salt thereof. Compounds F1, F4, F10, F12, F13, F14, and FA1 were prepared according to Example 3. Compounds F2, F5, F6, F11, F15, F16, F17, F19, F21, F24, and P4 were prepared according to Example 5. Compounds F3, F8, F18, F22, P5, and P47 were prepared according to Example 6. Compounds F7, F9, F20, F23, and FA2 were prepared according to Example 4. 
         [0000]    
       
         
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                 Appear- 
                   
                   
                   
               
               
                   
                   
                 ance, 
                   
                   
                   
               
               
                   
                   
                 Melting 
                 ESIMS 
                   
                   13 C NMR, 
               
               
                 No. 
                 Structure 
                 Point 
                 (m/z) 
                   1 H NMR 
                   19 F NMR 
               
               
                   
               
             
             
               
                 F1 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Off White Solid 133° C.− 141° C. 
                 620 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.89 (d = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.4 Hz, 1H), 8.05-7.84 (m, 2H), 7.48-7.33 (m, 7H), 7.32-7.26 (m, 6H), 7.25- 7.18 (m, 3H), 4.51 (s, 2H), 3.93 (q, J = 7.0 Hz, 2H), 3.25 (s, 2H), 2.27 (t, J = 2.5 Hz, 1H), 1.03 (t, J = 7.1 Hz, 3H)  
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.5, 148.3, 147.7, 144.2, 141.2, 140.1, 135.7, 129.6, 128.0, 127.5, 126.9, 126.1, 124.0, 123.3, 78.0, 73.1, 70.9, 67.4, 38.4, 26.2, 14.3 
               
               
                   
               
               
                 F2 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pink Oil 
                 454 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 9.01-8.88 (m, 1H), 8.61 (dd, J = 4.7, 1.5 Hz, 1H), 8.07 (s, 1H), 8.02 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 4.53 (s, 2H), 3.72 (s, 3H), 3.61 (s, 2H), 2.59 (dd, J = 13.9, 7.5 Hz, 1H), 2.47 (ddd, J = 14.3, 8.0, 3.1 Hz, 1H), 2.28 (t, J = 2.5 Hz, 1H), 1.91-1.70 (m, 1H), 1.56-1.38 (m, 
                   19 F NMR (376 MHz, CDCl 3 ) δ −127.9 (d, J = 157.4 Hz), −143.3 (d, J =  157.4 Hz) 
               
               
                   
                   
                   
                   
                 1H), 1.18-0.97 (m, 1H) 
                   
               
               
                   
               
               
                 F3 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear, Viscous Oil 
                 476 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 9.02 (d, J = 2.6 Hz, 0.2H), 8.96 (d, J = 2.6 Hz, 0.8H), 8.59 (dd, J = 4.7, 1.6 Hz, 1H), 8.40 (s, 0.2H), 8.08-8.00 (m, 1H), 7.98 (ddd, J = 8.3, 2.7, 1.5 Hz, 0.8H), 7.42 (dd, J = 8.4, 4.7 Hz, 1H), 4.47 (s, 1.6H), 4.14 (s, 0.4H), 4.01-3.60 (m, 5H), 3.40 (dd, J = 14.6, 6.7 Hz, 0.2H), 3.30 (dd, J = 14.6, 6.4 Hz, 0.8H), 3.22-  
                   19 F NMR (376 MHz, CDCl 3 ) δ −130.5 (d, J = 159.1 Hz), −140.9 (d, J = 159.1 Hz) 
               
               
                   
                   
                   
                   
                 3.09 (m, 0.2H), 3.09-2.91 (m, 0.8H), 
                   
               
               
                   
                   
                   
                   
                 2.14-1.92 (m, 1H), 1.86-1.68 (m, 
                   
               
               
                   
                   
                   
                   
                 1H), 1.54-1.35 (m, 1H), 1.24 (t, J = 
                   
               
               
                   
                   
                   
                   
                 7.1 Hz, 2.4H), 1.17 (t, J = 7.2 Hz, 
                   
               
               
                   
                   
                   
                   
                 0.6H) 
                   
               
               
                   
               
               
                 F4 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Sticky White Foam 
                 606 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.89 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.5 Hz, 1H), 7.95 (s, 1H), 7.93-7.82 (m, 1H), 7.55-7.32 (m, 7H), 7.32-7.26 (m, 6H), 7.25-7.15 (m, 3H), 4.50 (s, 2H), 3.68 (s, 3H), 3.24 (s, 2H), 2.28 (t, J = 2.5 Hz, 1H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.4, 148.3, 148.0, 144.1, 141.3 140.1, 135.7, 129.6, 128.1, 127.7, 127.0 126.1, 124.0, 123.0, 77.9, 73.2, 67.6, 62.8, 38.4, 26.1 
               
               
                   
               
               
                 F5 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear Oil 
                 444 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.91 (d, J = 2.8 Hz, 1H), 8.60 (dd, J = 4.6, 1.5 Hz, 1H), 8.01 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 7.96 (s, 1H), 7.44 (dd, J = 8.3, 4.7 Hz, 1H), 3.79 (q, J = 7.1 Hz, 2H), 3.71 (s, 3H), 3.59 (s, 2H), 2.57 (dd, J = 13.8, 7.4 Hz, 1H), 2.45 (ddd, J = 14.0, 7.6, 3.2 Hz, 1H), 1.86-1.69 (m, 1H), 1.56-1.38 (m, 1H), 1.23 (t, J =  
                   19 F NMR (376 MHz, CDCl 3  δ −127.9 (d, J = 157.5 Hz), −143.4 (d, J = 157.4 Hz) 
               
               
                   
                   
                   
                   
                 7.2 Hz, 3H), 1.14-0.98 (m, 1H) 
                   
               
               
                   
               
               
                 F6 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Yellow Oil 
                 446 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.93 (d, J = 2.8 Hz, 1H), 8.62 (dd,J = 4.8, 1.5 Hz, 1H), 8.09-7.98 (m, 2H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.53 (s, 2H), 3.72 (s, 3H), 3.66 (s, 2H), 3.14 (q, J = 9.9 Hz, 2H), 2.41-2.23 (m, 1H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.8 
               
               
                   
               
               
                 F7 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pale Yellow Oil 
                 378 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.92 (d, J = 2.6 Hz, 1H), 8.60 (dd,J = 4.7, 1.4 Hz, 1H), 8.07 (s, 1H), 8.01 (ddd,J = 8.4, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H), 4.53 (s, 2H), 3.96 (q, J = 7.1 Hz, 2H), 3.51 (d, J = 8.9 Hz, 2H), 2.29 (t, J = 2.5 Hz, 1H), 2.02 (t, J = 8.8 Hz, 1H), 1.03 (t, J = 7.0 Hz, 3H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.3, 150.4, 148.4, 141.1, 140.0, 135.8, 126.9, 126.2, 124.1, 123.8, 77.9, 73.1, 71.0, 38.7, 17.2, 14.4 
               
               
                   
               
               
                 F8 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Opaque Oil 
                 482 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.95 (d, J = 2.6 Hz, 1H), 8.60 (dd, J = 4.8, 1.4 Hz, 1H), 8.02 (s, 1H), 7.99 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.43 (dd, J = 8.5, 4.7 Hz, 1H), 4.48 (s, 2H), 3.81 (d, J = 1.2 Hz, 5H), 3.26-3.04 (m, 2H), 2.69- 2.47 (m, 2H), 1.24 (t, J = 7.1 Hz, 3H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.1 
               
               
                   
               
               
                 F9 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 White Solid 
                 354 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.92 (d, J = 2.7 Hz, 1H), 8.60 (dd,J = 4.8, 1.5 Hz, 1H), 8.01 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 7.97 (s, 1H), 7.44 (dd, J = 8.4, 4.7 Hz, 1H), 3.80 (q, J = 7.0 Hz, 2H), 3.71 (s, 3H), 3.47 (d,J = 8.9 Hz, 2H), 1.97 (t, J = 8.9 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.3, 151.2, 148.4, 141.3, 139.9, 135.8, 126.7, 126.1, 124.3, 124.1, 62.7, 44.5, 17.3, 12.7 
               
               
                   
               
               
                 F10 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 White foam 
                 596 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.88 (d, J = 2.7 Hz, 1H), 8.58 (dd, J = 4.8, 1.4 Hz, 1H), 7.95-7.86 (m, 1H), 7.82 (s, 1H), 7.40-7.32 (m, 7H), 7.32-7.26 (m, 6H), 7.25-7.19 (m, 3H), 3.75 (q, J = 7.2 Hz, 2H), 3.67 (s, 3H), 3.22 (s, 2H), 1.22 (t, J = 7.2 Hz, 3H)  
                   13 C NMR (151 MHz , CDCl 3 ) δ 164.4, 148.4, 148.1, 144.1, 141.3, 139.9, 135.6, 129.4, 127.9, 127.1, 126.8, 125.8, 123.9, 123.8, 67.3, 62.5, 44.1, 
               
               
                   
                   
                   
                   
                   
                 26.1, 12.5 
               
               
                   
               
               
                 F11 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pale Pink Solid 
                 458 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.90 (d, J = 2.7 Hz, 1H), 8.60 (dd,J = 4.7, 1.4 Hz, 1H), 7.99 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.94 (s, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.95 (q, J = 7.0 Hz, 2H), 3.80 (q, J = 7.4, 6.9 Hz, 2H), 3.62 (s, 2H), 2.57 (dd, J = 13.9, 7.3 Hz, 1H), 2.44 (ddd, J = 13.5, 7.4, 1.9 Hz, 1H), 1.90-1.71 (m, 1H), 1.57- 1.39 (m, 1H), 1.38-1.15 (m, 4H), 
                   19 F NMR (376 MHz, CDCl 3 ) δ −127.9 (d, J = 157.4 Hz), −143.4 (d, J = 157.4 Hz) 
               
               
                   
                   
                   
                   
                 1.03 (t, J = 7.0 Hz, 3H) 
                   
               
               
                   
               
               
                 F12 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Sticky White Foam 
                 610 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.88 (d, J = 2.5 Hz, 1H) 8.61-8.55 (m, 1H) 7.89 (ddd, J = 8.4, 2.9, 1.5 Hz, 1H), 7.83 (s, 1H), 7.47-7.33 (m, 8H), 7.32- 7.27 (m, 5H), 7.25-7.17 (m, 3H), 3.92 (q, J = 7.0 Hz, 2H), 3.76 (q, J = 7.2 Hz, 2H), 3.23 (s, 2H), 1.22 (t, J = 7.1 Hz, 3H), 1.03 (t, J = 7.1 Hz, 3H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.7, 148.2 (2C), 144.3, 141.3, 140.0, 135.7, 129.6, 128.0, 127.0, 126.9, 125.9, 124.3, 124.0, 70.6, 67.3, 44.2, 26.3, 14.3, 12.7 
               
               
                   
               
               
                 F13 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Sticky White Foam 
                 622 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.89 (s, 1H), 8.58 (d, J = 4.1 Hz, 1H), 7.90 (dt, J = 8.6, 1.6 Hz, 1H), 7.82 (s, 1H), 7.50- 7.32 (m, 8H), 7.32-7.27 (m, 5H), 7.25-7.18 (m, 3H), 5.67 (ddt, J = 16.3, 10.8, 5.5 Hz, 1H), 5.06 (dq, J = 17.2, 1.6 Hz, 1H), 4.97 (dd, J = 10.6, 1.6 Hz, 1H), 4.37 (dt, J = 5.6, 1.5 Hz, 2H), 3.75 (q, J = 7.1 Hz, 2H), 3.25 (s, 2H), 1.21 (t, J = 7.1 Hz, 3H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.5, 148.8, 148.2, 144.2, 141.2, 140.0, 135.7, 133.2, 129.6, 128.0, 127.0, 126.9, 125.9, 124.1, 124.0, 117.7, 75.6, 67.4, 44.2, 26.4, 12.6 
               
               
                   
               
               
                 F14 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Yellow Oil 
                 450 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.90 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz 1H), 8.01 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.95 (s, 1H), 7.44 (dd, J = 8.3, 4.7 Hz, 1H), 3.80 (q, J = 8.4, 7.9 Hz, 2H), 3.70 (s, 3H), 3.57 (s, 2H), 2.48- 2.38 (m, 2H), 2.38-2.23 (m, 2H), 1.24 (t, J = 7.2 Hz, 3H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.3, 149.5, 148.5, 141.5, 139.7, 135.7, 127.1, 126.1, 124.4, 124.1, 124.1, 62.5, 44.5, 34.4 (q, J = 28.5 Hz), 24.1, 23.9, 12.7  19 F NMR (376 MHz, CDCl 3 ) δ −66.6 
               
               
                   
               
               
                 F15 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pale Pink Oil 
                 478 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.90 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.4 Hz, 1H), 8.00 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.95 (s, 1H), 7.44 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H), 3.94 (q, J = 7.1 Hz, 2H), 3.79 (q, J = 7.1 Hz, 2H), 3.56 (s, 2H), 2.40 (t, J = 7.2 Hz, 2H), 2.21- 2.02 (m, 2H), 1.80 (dq, J = 10.3, 7.4 Hz, 2H), 1.23 (t, J = 7.2 Hz, 3H), 1.04 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.1 
               
               
                   
                   
                   
                   
                 (t, J = 7.0 Hz, 3H) 
                   
               
               
                   
               
               
                 F16 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear Oil 
                 474 ([M + H] + ) 
                 δ 8.90 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz, 1H), 8.04 (s, 1H), 8.00 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.53 (s, 2H), 3.95 (q, J = 7.0 Hz, 2H), 3.61 (s, 2H), 2.58-2.45 (m, 2H), 2.45-2.31 (m, 2H), 2.29 (t, J = 2.5 Hz, 1H), 1.05 (t, J = 7.1 Hz, 3H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.5 
               
               
                   
               
               
                 F17 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Yellow Oil 
                 450 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.91 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz, 1H), 8.00 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.90 (s, 1H), 7.44 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 3.94 (q, J = 7.1 Hz, 2H), 3.80 (q, J = 7.1 Hz, 2H), 3.67 (s, 2H), 3.14 (q, J = 9.9 Hz, 2H), 1.24 (t, J = 7.1 Hz, 3H), 1.02 (t, J = 7.0 Hz, 3H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.7 
               
               
                   
               
               
                 F18 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Red Oil 
                 466 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.96 (d, J = 2.6 Hz, 1H), 8.60 (dd, J = 4.8, 1.5 Hz, 1H), 8.08 (s, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.43 (ddd, J = 8.3, 4.7, 0.7 Hz, 1H), 4.06 (d, J = 12.4 Hz, 1H), 3.98 (d, J = 12.4 Hz, 1H), 3.90- 3.65 (m, 5H), 3.07-2.95 (m, 1H), 2.95-2.83 (m, 1H), 2.69-2.49 (m, 2H), 1.23 (t, J = 7.2 Hz, 3H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −65.8 
               
               
                   
               
               
                 F19 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pale Pink Oil 
                 474 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.92 (d, J = 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.07 (s, 1H), 8.02 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.45 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H), 4.53 (s, 2H), 3.72 (s, 3H), 3.55 (s, 2H), 2.40 (t, J = 7.2 Hz, 2H), 2.29 (t, J = 2.5 Hz, 1H), 2.22- 2.05 (m, 2H), 1.90-1.72 (m, 2H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.0 
               
               
                   
               
               
                 F20 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 White Solid 
                 368 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.91 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.7, 1.5 Hz, 1H), 8.09-7.92 (m, 2H), 7.44 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.94 (q, J = 7.0 Hz, 2H), 3.80 (d, J = 7.1 Hz, 2H), 3.49 (d, J = 8.9 Hz, 2H), 2.00 (t, J = 8.9 Hz, 1H), 1.24 (t, J = 7.1 Hz, 3H), 1.02 (t, J = 7.0 Hz, 3H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.4, 150.9, 148.3, 141.2, 139.9, 135.8, 126.5, 126.1, 124.6, 124.1, 70.7, 44.5, 17.3, 14.4, 12.6 
               
               
                   
               
               
                 F21 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear Oil 
                 460 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.91 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz, 1H), 8.05 (s, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 4.53 (s, 2H), 3.72 (s, 3H), 3.59 (s, 2H), 2.56-2.40 (m, 2H), 2.40-2.22 (m, 3H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.5 
               
               
                   
               
               
                 F22 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear, Viscous Oil 
                 460 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.97 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.4 Hz, 1H), 8.12 (d, J = 2.3 Hz, 1H), 8.01 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 7.43 (dd, J = 8.3, 4.8 Hz, 1H), 4.23-3.93 (m, 2H), 3.93-3.64 (m, 5H), 2.99 (ddd, J = 22.6, 13.7, 7.1 Hz, 1H), 2.92-2.70 (m, 1H), 2.07-1.83 (m, 1H), 1.67 (dddd, J = 19.7, 13.0, 
                   19 F NMR (376 MHz, CDCl 3 ) δ −129.2 (d, J = 157.4 Hz), −130.2 (d, J = 158.4 Hz), −140.7 (d, J = 157.4 Hz), −141.8 (d, J = 158.5 Hz) 
               
               
                   
                   
                   
                   
                 7.2, 3.9 Hz, 1H), 1.46-1.10 (m, 4H) 
                   
               
               
                   
               
               
                 F23 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pale Yellow Oil 
                 364 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.93 (dd, J = 2.8, 0.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz, 1H), 8.09 (s, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.53 (s, 2H), 3.73 (s, 3H), 3.49 (d, J = 8.9 Hz, 2H), 2.30 (t, J = 2.5 Hz, 1H), 2.00 (t, J = 8.9 Hz, 1H) 
                   13 C NMR (101 MHz, CDCl 3 ) δ 164.2, 150.7, 148.4, 141.1, 140.0, 135.8, 127.2, 126.2, 124.1, 123.5, 77.9, 73.2, 62.9, 38.7, 17.1 
               
               
                   
               
               
                 F24 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Pale Pink Oil 
                 464 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.89 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.5 Hz, 1H), 7.99 (ddd, J = 8.4, 2.8, 1.5 Hz, 1H), 7.92 (s, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.94 (q, J = 7.1 Hz, 2H), 3.87-3.76 (m, 2H), 3.60 (s, 2H), 2.59-2.42 (m, 2H), 2.42-2.23 (m, 2H), 1.24 (t, J = 7.1 Hz, 3H), 1.04 (t, J = 7.0 Hz, 3H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.5 
               
               
                   
               
               
                 P4 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear Viscous Oil 
                 436 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.88 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.9, 1.5 Hz, 1H), 8.07-7.93 (m, 2H), 7.44 (ddd, J = 8.3, 4.6, 0.8 Hz, 1H), 3.71 (s, 3H), 3.58 (s, 2H), 3.35 (s, 3H), 2.50-2.20 (m, 4H) 
                   19 F NMR (376 MHz, CDCl 3 ) δ −66.6 
               
               
                   
               
               
                 P5 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear Viscous Oil 
                 452 ([M + H] + ) 
                 (500 MHz, CDCl 3 ) δ 9.01-8.86 (m, 1H), 8.66-8.51 (m, 1H), 8.31 (s, 0.2H), 8.11 (s, 0.8H), 8.06-7.92 (m, 1H), 7.50-7.36 (m, 1H), 4.24-3.93 (m, 2H), 3.88-3.65 (m, 3H), 3.60- 3.25 (m, 3H), 3.06-2.96 (m, 1H), 2.96-2.81 (m, 1H), 2.73-2.47 (m, 2H) 
                   19 F NMR (471 MHz, CDCl 3 ) δ −65.75 (t, J = 10.2 Hz) 
               
               
                   
               
               
                 P47 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Clear semi- solid 
                 468 ([M + H] + ) 
                 (500 MHz, CDCl 3 ) δ 8.99 (d, J = 2.5 Hz, 0.2H), 8.93 (d, J = 2.7 Hz, 0.8H), 8.67-8.51 (m, 1H), 8.34 (d, J = 1.0 Hz, 0.2H), 8.04 (d, J = 1.1 Hz, 0.8H), 8.03-7.93 (m, 1H), 7.51-7.36 (m, 1H), 4.48 (s, 2H), 3.99-3.71 (m, 3H), 3.53-3.27 (m, 3H), 3.27-3.03 (m, 2H), 2.85-2.48 (m, 2H) 
                   19 F NMR (471 MHz, CDCl 3 ) δ −65.99 (t, J = 9.9 Hz), −66.11 (t, J = 9.9 Hz) 
               
               
                   
               
               
                 FA1 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 White foam 
                 583 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 9.01-8.80 (m, 1H), 8.58 (dd, J = 4.7, 1.4 Hz, 1H), 7.95-7.85 (m, 1H), 7.80 (s, 1H), 7.50-7.16 (m, 16H), 3.67 (s, 3H), 3.30 (s, 3H), 3.25 (s, 2H) 
                   
               
               
                   
               
               
                 FA2 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 White solid, mp 116- 121° C. 
                 340 ([M + H] + ) 
                 (400 MHz, CDCl 3 ) δ 8.90 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.5 Hz, 1H), 8.11-7.91 (m, 2H), 7.44 (dd, J = 8.4, 4.7 Hz, 1H), 3.72 (s,3H), 3.48 (d, J = 8.9 Hz, 2H), 3.35 (s, 3H), 1.97 (t, J = 8.9 Hz, 1H) 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
             
           
               
                 TABLE 4 
               
               
                   
               
               
                   
                   
                 May be 
               
               
                   
                   
                 Prepared 
               
               
                   
                   
                 according to 
               
               
                 No. 
                 Structure 
                 Example: 
               
               
                   
               
             
             
               
                 P1 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P2 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P3 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P4 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P5 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P6 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P7 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P8 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P9 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P10 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P11 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P12 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P13 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P14 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P15 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P16 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P17 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P18 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 9 
               
               
                   
               
               
                 P19 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P20 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 9 
               
               
                   
               
               
                 P21 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P22 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 9 
               
               
                   
               
               
                 P23 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P24 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 9 
               
               
                   
               
               
                 P25 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P26 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P27 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P28 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P29 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P30 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P31 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P32 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P33 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P34 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P35 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P36 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P37 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P38 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P39 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P40 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 8 
               
               
                   
               
               
                 P41 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P42 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 8 
               
               
                   
               
               
                 P43 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 8 
               
               
                   
               
               
                 P44 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 8 
               
               
                   
               
               
                 P45 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 8 
               
               
                   
               
               
                 P46 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P47 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P48 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P49 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P50 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P51 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P52 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P53 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P54 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P55 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P56 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P57 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P58 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P59 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P60 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P61 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P62 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P63 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P64 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P65 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5 
               
               
                   
               
               
                 P66 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
               
                 P67 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 6 
               
               
                   
               
             
          
         
       
     
         [0275]    While this invention has been described in certain embodiments, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.