Indian Patents
Title of Invention

A ZIRCONIUM COMPLEX
Abstract A compund of Formula I, an N-oxide thereof or suitable salt thereof whereim A and B are idependently O or S; each J is independently a phenyl ring, a naphthyl ring system,a 5-or 6-membered heteroaromatic ring or an aromatic 8-,9-or 10-membered fused heterobicyclic ring system wherein each or ring system is optionally substitued with 1 to 4 R5
Full Text FORM 2
THE PATENTS ACT, 1970
COMPLETE SPECIFICATION
Section 10
E.I. DU PONT DE NEMOURS AND COMPANY, a corporation organized and existing under the laws of the State of Delaware, USA of 1007 Market Street, Wilmington, Delaware 19898, USA.
The following specification particularly describes invention and the manner In which it is to be performed:
1
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8 FEB 2008


BACKGROUND OF THE INVENTION This invention relates to certain heterocyclic diamides, their N-oxides, suitable salts and compositions, and a method of their use for controlling invertebrate pests in both agronomic and nonagronomic environments.
" The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
NL 9202078 discloses N-acyl anthranilic acid derivatives of Formula i as insecticides

R1 Z
wherein, inter alia, X is a direct bond; Y is H or CrC6 alkyl; Z is NH2, NH(CrC3 alkyl) or N(C1C3 alkyl)2; and R1 through R9 are independently H, halogen, C1C6 alkyl, phenyl, hydroxy. C1-C6 alkoxy or C1-C7 acyloxy.
WOO 1/070671 discloses 7V-acyl anthranilic acid derivatives of Formula i as arthropodicides

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R^NvR3
wherein, inter alia, A and B are independently 0 or S; J is an optionally substituted phenyl ring, 5- or 6-membered heteroaromatic ring, naphthyl ring system or an aromatic 8-s 9- or 10-membered fused heterobicyclic ring system; R1 and R3 are independently H or optionally substituted CrC6 alkyl; R2 is H or CrC6 alkyl; each R4 is independently H, CrC6 alkyl, CrC6 haloalkyl, halogen or CN; and n is I to 4.
SUMMARY OF THE INVENTION This invention pertains to compounds of Formula I, and jV-oxides or suitable salts thereof



10

15
20

wherein
A and B are independently O or S;
each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4
R5;
K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered heteroaromatic ring optionally substituted with 1 to 3 R4:
n is 1 to 3:
R1 is H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N02, hydroxy, C1-C4 alkoxyC1-C4 alkylthio, C1-C4

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aikylsulfinyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl,C1-C4 alkylamino, C2-C8 dialkyiamino and C3-C6 cycioalkylamino; or R1 is 0,-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C-3-C8
dialkylaminocarbonyl or C(=A)J; R2 is H, CrC6 alkyl C2-C6 alkenyl, C2-C6 alkynyL C3-C6 cycloalkyl, CrC4 alkoxy, CrC4 alkylamino, C2-C8 dialkyiamino, C3-C6 cycioalkylamino, C2-C6 alkoxycarbonyl or C2-C6 alkylcarbonyl; R3 is H; G; or CrC6 alkyl, C2-C6 alkenyl C2-C6 alkynyl, C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of G, halogen, CN, N02, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 aikylsulfinyl, CrC4 alkylsulfonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl, or a phenyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6; or R2 and R3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring may be optionally substituted with one to four substituents selected from R12; and G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=0), SO or S(0)2 and optionally substituted with one to four substituents selected from R12; each R4 is independently H, CrC,5 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, CrC6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, N02, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C3-C4 aikylsulfinyl,C1-C4 alkylsulfonyl, C1-C4 haloalkylthio., C1-C4 haloalkylsulfmyl, CrC4 haloalkylsulfonylC1-C4 alkylamino, C2~C& dialkyiamino, C3-C6 cycioalkylamino, C1-C4 alkoxyalkyl, C1-C4 hydroxyalkyl, C(0)R10, C02R10, CCONR^Rl^NR^Ri^NCRl^^R10; or each R4 is independently a phenyl, benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6; each R5 is independently H, CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, CrC6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C2-C6 halocycloalkyl, halogen, CN, C02H, CONH2, N02, hydroxy, CrC4 alkoxy, ■ C1-C4 haloalkoxy C1-C4 alkylthio, C1-C4 aikylsulfinyl, CrC4 alkylsulfonyl, C1-C4 haloalkylthioC1-C4 haloalkylsulfmyl, C1-C4 haloalkylsulfonyl,C1-C4 alkylamino, C2-C^ dialkylammo, C3-C6 cycioalkylamino, C2-C6 alkylcarbonyl.

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C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyL C3-Cg dialkylaminocarbonyl,
C3-C6 trialkylsiiyl; or
each R5 is independently a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered
heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic
5 ring system, each ring or ring system optionally substituted with one to three
substituents independently selected from R6; or (R5)2 when attached to adjacent carbon atoms can be taken together as -OCF2O-,
-CF2CF20-> or -OCF2CF20-; and
each R6 is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6
10 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl,C1-C4 haloalkynyl, C3-C6
halocycloalkyl, halogen, CN, N02, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4
alkylthio, C1-C4 alkylsulfmyl,C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C.g
dialkylamino, C3-C6 cycloalkyl amino, C4-C6 (alkyl)cycloalkylamino,C1-C4
alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C%
15 dialkylaminocarbonyl or C3-C6 trialkylsiiyl;
each R10 is independently H, C1-C4 alkyl or C1-C4 haloalkyl; each R1 T is independently H or C1-C4 alkyl; and
each R12 is independently C]-C2 alkyl, halogen, CN, N02 or Ci~C2 alkoxy. This invention also pertains to a method for controlling an invertebrate pest comprising 20 contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I, an TV-oxide thereof or a suitable salt of the compound (e.g., as a composition described herein). This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula I or a composition comprising a compound of Formula I, an TV-oxide 25 thereof or a suitable salt of the compound and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an TV-oxide thereof or a suitable salt of the compound and at least one additional component selected from the 30 group consisting of surfactants, solid diluents and liquid diluents. This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I, an TV-oxide thereof or a suitable salt of the compound and an effective amount of at least one additional biologically active compound or agent.
DETAILS OF THE INVENTION
35 In the above recitations, the term "alky!", used either alone or in compound words such
as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, . propyl, z-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different

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butenyl. pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such asethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2.5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyldxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2CH2 and CR3CH2CH22CH2 "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers. "Alkylsulfmyl" includes both enantiomers of an alkylsulfmyl group. Examples of "alkylsulfmyl" include CH3S(0), CH3CH2S(0)5 CH3CH2CH2S(0), (CH3)2CHS(0) and the different butylsulfmyl isomers. Examples.of "alkylsulfonyl" include CH3S(0)2, CH3CH2S(0)2, CH3CH2CH2S(0)2, (CH3)2CHS(0)2 and the different butylsulfonyl isomers. "Alkylamino", "dialkylamino", "alkenylthio", "alkenylsulfmyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl"., and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. "Aromatic" indicates that each of the ring atoms is essentially in the same plane and has a^-orbital perpendicular to the ring plane, and in which (4n + 2) 71 electrons, when n is 0 or a positive integer, are associated with the ring to comply with Hiickel"s rule. The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic. The term "aromatic carbocyclic ring or ring system" includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (e.g. phenyl and naphthyl). The term "nonaromatic carbocyclic ring or ring system" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Hiickel rule is not satisfied by any of the rings in the ring system. The term "hetero" in connection with rings or ring systems refers to a ring or ring system in which at least one ring atom is not carbon and which can contain I to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. The terms "heteroaromatic ring or ring system" and "aromatic fused heterobicyclic ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Kuckel rule is satisfied). The term "nonaromatic heterocyclic ring or ring system" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hiickel rule is not satisfied by any of the rings in the ring system. The heterocyclic ring or ring system can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

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The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms"which may¬be the same or different. Examples of "haloalkyl" include F3C, C1CH2, CF3CH2 and 5 CF3CC12. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C-CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HOCCHCL CF3CsC, CC13C=C and FCH2C=CCE2- Examples of "haloalkoxy" include CF30, CC13CH20, HCF2CH2CH20 and CF3CH20. Examples of "haloalkylthio" include CCl3S, 10 CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfinyl" include CF3S(0), CC13S(0), CF3CH2S(0) and CF3CF2S(0). Examples of "haloalkylsulfonyl" include CF3S(0)2, CC13S(0)2, CF3CH2S(0)2 and CF3CF2S(0)2.
Examples of "alkylcarbonyl" include C(0)CH3, C(0)CH2CH2CH3 and C(0)CH(CH3)2. Examples of "alkoxycarbonyl" include CH30C(=O),"CH3CH20C(=0), 15 CH3CH2CH2OC(=0), (CH3)2CHOC(=0) and the different butoxy- or pentoxycarbonyl isomers. Examples of "alkylaminocarbonyl" include CH3NHC(=0), CH3CH2NHC(=0), CH3CH2CH2NHC(=0), (CH3)2CHNHC(=0) and the different butylamino- or pentylaminocarbonyl isomers. Examples of "dialkylaminocarbonyl" include (CH3)2NC(=0), (CH3CH2)2NC(=0), CH3CH2(CH3)NC(=0), CH3CH2CH2(CH3)NC(=0) 20 and (CH3)2CHN(CH3)C(=0).
The total number of carbon atoms in a substituent group is indicated by the "CiCj" prefix where i and j are numbers from 1 to 6. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(O.CH3), CH3OCH2CH2 or CH3CH2OCH2; 25 and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2.
In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or 30 nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a compound is. substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_j, then the number of substituents may be selected from the 55 integers between i and j inclusive.
The term "optionally substituted with one to three substituents" and the like indicates that one to three of the available positions on the group may be substituted. When a group contains a substituent which can be"hydrogen, for example R1 or ~R5, then, when this

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suhstituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, TV-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
One skilled in the art will appreciate that not all nitrogen containing heterocycles can form TV-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form //-oxides. One skilled in the art will also recognize that tertiary amines can form TV-oxides. Synthetic methods for the preparation of TV-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and w-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alky! hydroperoxides such as /-butyl hydroperoxide, sodium perborate, and^dioxiranes such as dimethydioxirane. These methods for the preparation of TV-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimrnett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, furnaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.

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As noted above, J is a phenyl ring, a naphthyl ring system, a 5- or 6-membered
heteroaromatic ring or an aromatic 8-. 9- or 10-membered fused heterobicyclic ring system
wherein each ring or ring systsm is optionally substituted with 1 to 4 R5. The term
"optionally substituted" in connection with these J groups refers to groups which are
unsubstituted or have at least one non-hydrogen substituent that does not extinguish the
biological activity possessed by the unsubstituted analog. An example of phenyl optionally
substituted with 1 to 4 R5 is the ring illustrated as U-l in Exhibit 1, wherein Rv is R5 and r is
an integer from 1 to 4. An example of a naphthyl group optionally substituted with 1 to 4 R5
is illustrated as U-85 in Exhibit 1, wherein Rv is R5 and r is an integer from 1 to 4.
Examples of 5- or 6-membered heteroaromatic rings optionally substituted with 1 to 4 R5
include the rings U-2 through U-53 illustrated in Exhibit 1 wherein Rv is R5 and r is an
integer from 1 to 4. Note that J-l through J-13 below also denote 5- or 6-membered
heteroaromatic rings. Note that U-2 through U-20 are examples of J-l, U-21 through U-35
and U-40 are examples of J-2, U-36 through U-39 are examples of J-3, U-41 through U-48
are examples of J-4 and U-49 through U-53 are examples of J-5. Note that J-6 is a subset of
U-l 1, J-7 or J-10 are a subset of U-26, J-8 is a subset of U-42, J-9 is a subset of U-45, J-l 1 is
a subset ofXJ-4 and J-12 or J-13 are a subset of U-24. Also note that in J-6 through J-13 that
R7 and R9 are subsets of R5. Examples of aromatic 8-, 9- or 10-membered fused
heterobicyclic ring systems optionally substituted with 1 to 4 R5 include U-54 through U-84
illustrated in Exhibit 1 wherein Rv is R5 and r is an integer from 1 to 4.
Although Rv groups are shown in the structures U-l through U-85, it is noted that they
do not need to be present since they are optional substituents. Note that when Rv is H when
attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that
require substitution to fill their valence are substituted with H or Rv. Note that some U
groups can only be substituted with less than 4 Rv groups (e.g. U-14, U-15, U-l 8 through
U-21 and U-32 through U-34 can only be substituted with one Rv). Note that when the
attachment point between (Rv)r and the U group is illustrated as floating, (Rv)r can be .
attached to any available carbon atom of the U group. Note that when the attachment point
on the U group is illustrated as floating, the U group can be attached to the remainder of
Formula I through any available carbon of the U group by replacement of a hydrogen atom.
Exhibit 1


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4 3


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11



As noted above, K is, together with the two contiguous linking carbon atoms, a 5-or 6-5 membered heteroaromatic ring optionally substituted with 1 to 3 R4. Examples of said K rings wherein said rings are optionally substituted with 1 to 3 R4include the ringsystems illustrated as K-l to K-37 in Exhibit 2, wherein n is an integer from 1 to 3 and R4 is as defined above. The term "optionally substituted" in connection with these K groups refers to K groups which are unsubstituted or have at least one non-hydrogen substituent that does not 10 extinguish the biological activity possessed by the unsubstituted analog. As with the carbon
atoms in the ring, the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R4. Although (R4)n groups are shown in the structures K-l to K-37, it is noted that R4 does not need to be present since it is an optional substituent. Note that some K groups can only be substituted with less than 3 R4 groups (e.g. K-7 15 through K-10, K-15, K-16, K-20, K-21, K-23, K-24, K-26 and K-27 can only be substituted with one R4). In the exemplified K groups, the upper right bond is attached through the available linking carbon atom to the nitrogen atom of the NR1(=A)J portion of Formula I and the lower right bond is attached through the available linking carbon atom to the carbon

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12 atom of the C(=B)NR2R3 portion of Formula I. The wavy line indicates that the K ring is attached to the remainder of Formula I as illustrated below.


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Preferred K rings include optionally substituted thiophene, isoxazole, isothiazole, pyrazole, pyridine and pyrimidine rings. More preferred K rings include K-l, K-14, K-15, K-18, K-23, K-28, K-29, K-30, K-31 and K-33. Most preferred are K-28, K-31 and K-33.
As noted above, R3 can be (among others C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of a phenyl ring, or 5- or 6-memberedheteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6. Examples of such rings incorporated into said R3 groups include the rings illustrated as U-l through U-53 and U-86 illustrated in Exhibit 1, except that such rings are optionally substituted with 1 to 3 substituents independently selected from R6 rather than (Rv)r and are attached.to an R3 group selected from the list immediately above.
As noted above, R3 can"be (among others) G, or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, each optionally substituted with G; wherein G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=0). SO or S(0)2 and optionally substituted with 1 to 4 substituents selected, from R12. The term "optionally substituted" in connection with these G groups refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the

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10

unsubstituted analog. Note that when the attachment point on the G group is illustrated as floating, the G group can be attached to the remainder of Formula I through any available carbon of the G group by replacement of a hydrogen atom. The optional substituents can be attached to any available carbon by replacing a hydrogen atom. Examples of 5- or 6-membered nonaromatic carbocyclic rings as G include the rings illustrated as G-1 through G-8 of Exhibit 3. Examples of 5- or 6-membered nonaromatic heterocyclic rings as G include the rings illustrated as G-9 through G-48 of Exhibit 3. Note that when G comprises a ring selected from G-31 through G-34, G-37 and G-38, Q} is selected from O, S or N. Note that when G is G-11, G13, G-14, G16, G-23, G-24, G-30 through G-34, G-37 and G-38 and Q1 is N5 the nitrogen atom can complete its valence by substitution with either H or C1-C2 ■alkyl.
Exhibit 3





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As noted above, each R4 can be independently (among others) a phenyl, benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6. Examples of such R4 groups include the rings or ring systems illustrated as U-1 through U-53, U-86 and U-87 illustrated in 5 Exhibit 1, except that such rings are optionally substituted with 1 to 3 substituents independently selected from R6 rather than (Rv)r.
As noted above, each R5 can be independently (among others) a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring optionally substituted with one to 10 three substituents independently selected from R6. Examples of such R3 groups include the rings or ring systems illustrated as U-1 through U-88 illustrated in Exhibit 1, except that such rings are optionally substituted with 1 to 3 substituents independently selected from R6 rather than (Rv)r
Preferred compounds for reasons of better activity and/or ease of synthesis are:
15 Preferred 1. Compounds of Formula I above, and TV-oxides and suitable salts thereof,
wherein A and B are both O and J is a phenyl ring optionally substituted with 1 to 4 R5. Preferred 2. Compounds of Preferred 1 wherein
each R4 is independently C1-C4 alkyl C]-C4 haloalkyl, halogen, CN, N02 or
20 C1-C4 alkoxy, and one R4 group is attached to the K ring at the atom
adjacent to either the NR! C(=A) J moiety or the C(=B)NR2R3 moiety;
and
each R5 is independently H, halogen,C1-C4 allcyl, Cy-O^ alkoxy, C1-C4
haloalkyl, CN, N02, C1-C4haloalkoxyC1-C4 alkylthio, C3-C4
25 alkylsulfinyl, C1-C4 alkylsulfonyl, CrC4 haloalkylthio, CrC4
haloalkylsulfinyl,C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; or

each R5 is independently a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6; or
(R5)2 when attached to adjacent carbon atoms can be taken together as -0CF2O-, -CF2GF20- or -OCF2CF20-. Preferred 3. Compounds of Preferred 2 wherein
Rl"isHj/;- ;"
R2isHorC%
R3 is 0^04 alkyl optionaUy substituted with one or more substituents
independently selected from halogen, CN, QCH3or S(0)pGH3; •
each R4 is independently CH3, C^.CN or halogen, and one R4 group is attached to the Kring at the atom adjacentto me NRk^A^ moiety;
each R5 is independently H, halogen, methyl, CF3, OCF3, OCHF2, S(0)peF3, S(0)pCHF2, OCH2CF3, QCF2CHF2, S(0)pCI^CI^orS(0)p(^CHF2r^ or aphenyl, pyrazole, imidazole; triazole, pyridine or pyrimidine ring, each ring optionally substituted with; one to three substituents independently selected from C1-C4 alkyl, C1-C4haloalkyl, halogen or CN;and
pisO, 1 or 2. Preferred 4. Compounds of Preferred 3 wherein R3 is C2-C4 alkyl. Preferred 5. Compounds of Formula I wherein
A and B are both O;
J is a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-l, J-2, J-3, J-4 and J-5, each J optionally
J-l J-2 J-3 J-4 J-5 .
Q is O, S or NR5; and
W, X, Y and Z are independently N or CR5, provided that in J-4 and J-5 at
least one of W, X, Y or Z is N. Preferred 6. Compounds of Preferred 5 wherein
each R4 is independently CrC4 alkyl, CrC4 haloalkyl, halogen, CN, N02 or
C1-C4 alkoxy, and one R4 group is attached to the K ring at the atom

17

10

adjacent to either die NR1C(=A)J moiety or the C(=B)NR2R3 moiety; : and each R5 is independently H,C1-C4 alkyl* C1-C4 haloalkyl, halogen, CN, NQ2, C1-C4 haloalkoxy, C1-C4 all^lthio, C2-C4 alkylsulfinyl, C1-C4 alkylsulfonyl,C1-C4 haloalkylthio, C1-C4 halpalkylsulfiriyl,C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; or a phenyl or a 5- or 6~membered heteroaromatic ring, each ring optionally substituted with
: R6. .,."
Preferred 7. Compounds of Preferred 6 wherein r
J is selected from the group consisting of J-6,K7.-J-8, J-9, J-10, J-ll, J-12 and^
1-13 "■";■.


N-^.

R9




and

R5 is H, CrC4 alkyl, CrC4 haloalkyl, or




15

V is N, CH, CF, CC1, CBr or CI;
each R6 and R7 is independently H, C1-C6 alkyl, C3-C6 cycloalkyl, Cj-Cg.
haloalkyl, halogen, CN, C1-C4 alkoxy, C1-C4 haloalkoxy orC1-C4
haloalkylthio; and

18 ...:""":
R9 is H, CrC6 alkyl, CrC6 haloalkyl, C3-C6 alkenyl, C3-C6 haloaJkenylJ ■ C3~C6alkynylor C3-C6 haloalkynyl; provided R7 and R9 are not both
H. .".■■". .;,:.;■;"":"■". :?:i
Preferred 8. Compounds of Preferred 7 wherein VisN.
5 Preferred9. Compounds of Preferred 7 whferem Vis CH.CF, CClor CBr.
Preferred 10. Compounds of Preferred 8 or Preferred 9 wherein • Rfis"H; R2isHorCH3;
R3 is C1-C4 alkyl optionally substituted with one or more substituents
10 independently selected from halogen, CN, OCH3 or S(0)pCH3;
each R4 is mdependenfly CH3, CF3, CN or halogen, and one R4 group is
attached to the Kring at the atom adjacent to the NR1C(=A)J moiety;
R6 is CJ-C4 alkyl, C!-C4 haloalkyl, halogen or CN;
R7 is H, CH3, CF3, OCH2CF3, OCHF2 or halogen; and
15 pis0,lor2.
Preferred 11. Compounds of Preferred 10 wherein R? is C1-C4 alkyl; one R4 group is
independently CH3, CI, Br or I and is attached to the K ring at the atom adjacent
to the NRiC^A)! moiety; and a second optional R4 is H, F, CI, Br, f or CF3. i
Preferred 12. Compounds of Preferred 11 wherein J is J-6; R6 is CI or Br; and R7 is
20 halogen, 6CH2CF3 or CF3.
Preferredl3. Compound^ of Preferred 12 wherem VisN; R3 is methyl, ethyl,
isopropyl, tertiary butyl or; and R7 is Br, CI, OCH2CF3 or CF3.
Preferred 14. Compounds of Preferred 11 wherein J is J-7; R6 is CI or Br; and R9 is
CF3, CHF2, CH2CF3 or CF2CHF2.
25 Preferred 15. Compounds of Preferred 11 wherein J is J-8; R6 is. CI or Br; and R7 is
halogen, OCH2CF3 or CF3. Preferred 16. Compounds of Preferred 11 wherein J is J-9; R6 is Cl or Br; and R7 is
OCH2CF3orCF3.
Preferred 17. Compounds of Preferred 11 wherein J is J-10; R6 is Cl or Br; and R9 is
30 CF3,CHF2,CH2CF3orCF2CHF2.
Preferred 18. Compounds of Preferred 11 wherein J is J-l 1; R6 is Cl or Br; and R7 is
halogen, GCH2CF3, or CF3.
Preferred^19. Compounds of Preferred 11 wherein J is J-12; R6 is Cl or Br; R7 is H,
halogen or CF3, and R9 is H, CF3, CHF2, CH2CF3, or CF2CHF2.
35 Preferred 20. Compounds of Preferred 11 wherein J is J-13; R6 is Cl or Br; and R9 is H,
CF3, CHF2, CH2CF3 or CF2CHF2.

r WO 02/070483

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19 Most preferred is the compound of Formula I selected from the group consisting of:
4-[[[l-(2-Chlorophenyl)-3-(1xifluoromemyI)4i7-pyra2ol-5-yiJcarbonyl]amirio]-5-methyl-jV-1 -methylethyl)-3-pyridincarboxamide.
4-Methyl-A^-(l-methylethyl)-3-[[2--methyl-4-(triiluoromethyI)ben2oyl]amino]-2" thiophencarboxamide,
l-Methyl-iV-(l-memylethyl>5-[[4^trifluoromemyl)benzoyl]ammo]4ii/"-pyrazole-4-carboxamide;
4-[[[3-Bromo-1 -(3-chloro-2-pyridinyl)- l#-pyrazol~5-yI]carbonyl]amino]-5-chloro-7V-methyl-3-pyridinecarboxamide;
3-[[[3-Bromo-l-(3-chloro-2-pyridinyl)-lif-pyrazol-5-yl]carbonyl]ammo]-2,6-dichloro-Ar-methyl-4-pyridinecarboxarmde;
2.6-dichloro-3 -[[[ 1 -(3-chloro-2-pyri dinyl)-3 -(trifluoromethyl)- lff-pyrazol- 5 -yl]carbonyI]amino]-7V-(l -methylethyl)- 4-pyridinecarboxamide; 3-[[[3-Brorno-1 -(3-chloro-2-pyridinyI)- li7-pyrazol-5-yl]carbonyIjamino]-6-chioro-A/,4-dimethyl-2-pyridinecarboxamide;
3-[[[3-Bromo4-(3-chloro-2-pyridinyl)-lF-pyrazol-5-yl]carbonyl]amino]-4,6-dichloro-N-methyl-2-pyridinecarboxamide;
5-[[[3-Chloro-1-(3-chloro-2-pyridinyl)-li7-pyrazol-5-yl]carbonyI]amino]-A^,6-dimethyl-4-pyrimidinecarboxamide; and , .5-[[[3-BromoT-(3-chloro-2-pyridinyl)T/^-pyrazol-5-3^1}carbonyl]amino]-A?;Ar:,2,6-
tetramethyl-4-pyridinecarboxamide. This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an vY-oxide thereof or a suitable salt thereof and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I, an Tv-oxide thereof or a suitable salt thereof and an effective amount of at least one additional biologically active compound or agent. The preferred compositions of the present invention are those which comprise the above preferred compounds.
This invention also pertains to a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I, an .iV-oxide thereof or a suitable salt thereof (e.g., as a composition described herein). This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula! or a composition comprising a compound of Formula I. anjV-oxide thereof or a suitable salt thereof and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests. The preferred methods of use are those involving the above preferred compounds.

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20
Of note are compounds of Formula 1 (a subset of Formula I) and A^-oxides or suitable salts thereof

J
R2^ ^R3
1
wherein
5 A and B are independently 0 or S;
each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4
R5;
10 K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered
heteroaromatic ring optionally substituted with 1 to 3 R4; n is 1 to 3;
R1 is H; or C2-C6alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl each
optionally substituted with one or more substituents selected from the group
15 consisting of halogen, CN, N02, hydroxy, C 1-C4 alkoxyC 1-C4 alkylthio,C 1-C4
alkylsulfinyl,C 1-C4 alkylsulfonyl, C2-C4 alkoxycarbonylC 1-C4alkylamino,
C2-C8 dialkylamino and C3-C6 cycloalkylamino; or
R1 is C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6alkylarninocarbonyl, C3-Cg
dialkylaminocarbonyl or C(=A)J;
20 R2 is H, CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 cycloalkyl,C 1-C4alkoxy,
25
C 1-C4alkylamino, C2-C6 dialkylamino, C3-C5 cycloalkylamino, C2-C6
alkoxycarbonyl or C2-C6 alkylcarbonyl;
R3 is H; G; CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, each
optionally substituted with one or more substituents selected from the group
consisting of halogen, G, CN, N02, hydroxyC 1-C4alkoxy, C 1-C4haloalkoxy,
C 1-C4 alkylthioC 1-C4 alkylsulfmyl, C 1-C4 alkylsulfonyl, C2-C6
alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl, or a phenyl; phenoxy
or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with
one to three substituents independently selected from the group consisting of
30 C 1-C4 alkyl, C2-C4alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyC2-C4haloalkyl,

21
C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN,
NO2, C1-C4alkoxy,C1-C4 haloalkoxyC1-C4 alkylthio, C1-C4 alkylsulfinyl,
C1-C4alkylsulfonyl, C1-C4 alkylamino, C2-C8dialkylarrmrc>, C3-C6
cycloalkylamino, C4-C6 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-C6
5 alkoxycarbonylvC2-C6alkylaminocarbQnyl,G3-Cgdiall£ylaminocOT
C3-C6trialkylsiiyl; C1-C4 alkoxy;C1-C4alkylamino;C2-C8 dialkylamino;
C3-C6cycloallcylamino;C2-C6 alkoxycarbonyl or/C2-C6 alkylcarbonyl; or
R2 and R3 can be taken together with-the nitrogeti to which they are attached to form a
ring containing 2 to 6 atoms of carbon and optionally one additional atom of
10 nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to4
substituents selected from the group consisting of C1-C2 alkyl, halogen, CN,
N02 and C1-C2 alkoxy;
G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally
, . including one or two ring members selected from the group consisting of C(=0),
15 SO or S(0>2 and optionally substituted with 1 to 4 substituents selected from the
group consisting of CrC2 alkyl, halogen, CN, NO2 and C2-C4 alkoxy;
each R4 is independently H,C2-C4 alkyl, C2-C4alkenyl, C^-Cg alkynyl, C3-C6
cycloalkyl, C!^ haloalkyl, C2-C6 haloalkenyl, C^-Cg haloalkynyl, C3-C6
halocycloalkyl, halogen, CN, NO2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy,
20 C!-C4 alkylthio, CrC4 alkylsulfinyl, C1-C4 alkylsulfonyl, CrC4 halodkylthio,
Cj^haloalkylsulfinyl,C2-C4 haloalkylsulfqnyl, C1-C4alkylaminoC2-C4
dialkylammo, C3-C6 cycloalkylammo, or C3-C6 Malkylsilyl; or
each R4 is independently phenyl, benzyl or phenoxy, each optionally substituted With
CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl,/C1-C4 haloalkyl,
25 C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C5 halocycloalkyl, halogen, CN,
N02, C1-C4 alkoxy, CrC4 haloalkoxy, CrC4 alkylthio, CrC4 alkylsulfinylj
CrC4 alkylsulfonyl, C1-C4alkylamino, C^-Cg dialkylamino, C3-C6
cycloallcylammo, C3-Cg (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-Cg
alkoxycarbonylC2-C6 alkylaminocarbonyl, Cs-Cg dialkylaminocarbonyl or
30 C3-C6 trialkylsiiyl;
each R5 is independently H, CrC6 alkyl,C2-C6 alkenyl, C2-C6alkynyl, C3-C6
cycloalkyl, C2-C6haloalkyl, C2-C6 haloalkenyl, C2-C6haloalkynyl, C3-C6
halocycloalkyl, halogen, CN, C02H, CONH2, NOz, hydroxy, CrC4 alkoxy,
C1-C4 haloalkoxy,C1-C4alkylthio, CrC4 alkylsulfinyl, C1-C4 alkylsulfonyl,
35 C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, CrC4 haloalkylsulfonyl, C1-C4
alkylamino, C2~C8 dialkylamino,C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6alkoxycarbonyl,C2-C6alkylaminocarbonyl, C3-C6 $aIkylaminocarbonyl, C3-C6 trialkylsiiyl; or

22
eachR5 is independently a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered
heteroarornatic ring or an aromatic 8-9- or 10-membered fused heterobicyclic
ring system, each ring optionally substituted with one to three substiuients ■
independently selected from the group consisting of C1-C4 alkyl, C2-C4 alkenyl,
C2-C4alkynyl,C3-C6Cycl6alkyl,C1-C4haloa^l,C2-C4hdoalkenyl,C2-C4.
haloalkynyl, C3-C6 halbeycloalkyl, halogen, CN, N02, C1-C4 alkoxy, C1-C4
haloalkoxy, C1-C4alkyithio, C1-C4 alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4
alkylarnino, C1-C4dialkylamino, C3-C6 cycloalkylamino, C3-Cg
(alkyl)cycloalkylamino,C2-C4 alkylcarbonyl, (C2-C6 alkoxycarbonyl, C2-C6
10 alkylaminbcarboriyl, C3-Cg dialkylaminocarbonyl orC3-C6 trialkylsilyl; or
(R5>2 when attached to adjacent carbon atoms can be taken together as-OCF2O-,
-CF2CF20-, or -OCF2CF2O-.
. Also of note are. selected compounds for reasons of cost, ease of synthesis and/or
biological efficacy:
15 Selection A. Compounds of Formula 1 wherein K is, together with the two linking
atoms, a thiophene, pyrazole, isoxazole, pyridine or pyrimidme optionally
substituted with 1 to 3 R4.
Selection B. Compounds of Selection A wherein J is independently a phenyl ring or a 5-
or 6-membered heteroaromatic ring wherein each ring is optionally substituted
20 with l to2R5.
Selection C. Compounds of Selection A wherein
J is a phenyl ring or a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-1, J-2, J-3,J-4and J-5; each ring optionally

25



Y
J-4 J.5
.

23
Selection D. Compounds of Selection B or Selection C wherein
A and Bare both O;
riislto2;
R1 is H, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cg cycloalkyl, C2-C6::;
5 alkylcarbonyl or C2-C6 alkoxycarbonyl;
R2 is H, C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, c
alkylcarbonyl orC2-C4 alkoxycarbonyl;
R3 is C1-C4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl each
optionally substituted with one or more substituents selected from the
10 group consisting of halogen, CN, C1-C2 alkoxy, C1-C2 alkylthio, C1-C2
alkylsurfmyl and C2-C6alkylsulfonyl;
one of the R4 groups is attached to the heteroaromatic ring at one of the two ,
positions ortho to the two linking; atoms, and said R4 is C1-C4 alkyl;; : *
C1-C4 haloalkyl; halogen, CN, NO2,C2-C6alkoxy, C1-C4 haloalkoxy,
15 C1-C4 alkylthio, C1-C4alkylsulfinyl,C1-C4 alkylsulfonyl, CrC4
haloalkylthio, C1-C4 haloalkylsulfinylorC1-C4 haloalkylsulfonyl;
each R5 is independently H,C1-C4 alkylC1-C4 haloalkyl, halogen, GN,NQ2,
C1-C4haloalkoxy, C1-C4 alkylmioC1-C4 alkylsulfinylC1-C4
alkylsulfonyl,C1-C4 haloalkylthio,C1-C4haloalkylsulfinylC1-C4
20 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; or a phenyl or a 5-or
6-membered heteroaromatic ring, each ring optionally substituted with
C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkylC1-C4
haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl,
halogen, CN.N02, , C1-C4alkoxy, , C1-C4haloalkoxyl C1C4 alkylthio,
25 C1-C4 alkylsiJfmyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino,C1-C4
dialkylamino, C3-C6 cycloalkylaminb, C4-C6 (alkyl)cycloalkyiamino,
C2-C4 alkylcarbonyl,C2-C6 alkoxycarbonyl, C2-C6
alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl or C3-C6 trialkylsilyU
or . ■■ "
30 (R5)2 when attached to adjacent carbon atoms can be taken together as-
OCF20-, -CF2CF20 or -OCF2CF20-. Selection E. Compounds of Selection D wherein
J is selected from the group consisting of phenyl, pyridine, pyrimidine,
pyrazole, imidazole, triazole, thiophene,thiazole arid oxazole, furan,
35 isotbiazole and isoxazole, each optionally substituted with 1 to 2 R5.
Selection F. Compounds of Selection E wherein

WO 02/070483 PCT/OS02/06582
24
J is selected from the group consisting of phenyl, pyridine, pyrimidine,
pyrazole, thiophene and thiazole, each optionally substituted with 1 to 2
R5;
R1 and R2 are both H;
5 H3 is CrC4 aJkyl optionally substituted with halogen, CN, OCH3, S(0)pCH3;
each R4 is independently CH3, CF3, OCF3J OCHF2, S(0)pCF3, S(0)pCHF2,
CN or halogen; each R5 is independently H, halogen, CH3, CF3, OCHF2, S(0)pCF3,
S(0)pCHF2, OCH2CF3, OCF2CHF2, S(0)pCH2CF3, S(0)pCF2CF£F2;
3 0 or phenyl, pyrazole, imidazole, triazole, pyridine or pyrimidine, each
ring optionally substituted with CrC4 alkyl, C] -C4 haloalkyl, C] -C4
alkoxy, CrC4 haloalkoxy, CrC4 alkylthio, CrCA alkylsulfinyl, CrC4
alkylsulfonyl, halogen or CN; and
p is 0, 1 or 2.
15 Selection G. Compounds of Selection F wherein R3 is CpC4 alkyl.
Selection H. Compounds of Selection G wherein J is a phenyl optionally substituted
with 1 to 2 R5.
Selection I. Compounds of Selection H wherein one R5 is a phenyl optionally
substituted with CrC4 alkyl, CrC4 haloalkyl, halogen or CN.
20 Selection J. Compounds of Selection H wherein one R5 is a pyrazole, imidazole.
triazole, pyridine or pyrimidine, each ring optionally substituted with CrC4
alkyl, C]-C4 haloalkyl, halogen or CN.
Selection K, Compounds of Selection I wherein J is a pyridine optionally substituted
with 1 to 2 R5.
25 Selection L. Compounds of Selection K wherein one R5 is a phenyl optionally
substituted with C]-C4 alkyl, C]-C4 haloalkyl, halogen or CN.
Selection M. Compounds of Selection K wherein one R5 is a pyrazole, imidazole,
triazole, pyridine or pyrimidine, each ring optionally substituted with C]~C4
alkyl, C1-C4 haloalkyl, halogen or CN.
30 Selection N. Compounds of Selection I wherein J is a pyrimidine optionally substituted
with 1 to 2 R5. Selection O. Compounds of Selection N wherein one R5 is a phenyl optionally
substituted with CrC4 alkyl, CrC4 haloalkyl halogen or CN.
Selection P. Compounds of Selection N wherein one R5 is a pyrazole. imidazole,
35 triazole, pyridine or pyrimidine, each ring optionally substituted with C1-C4
alkyl, CrC4 haloalkyl, halogen or CN. Selection Q. Compounds of Selection I wherein J is a. pyrazole optionally substituted with 1 to 2 R5.

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25 •
Selection R. Compounds of Selection Q wherein one R5 is a phenyl optionally •
substituted with C1 -C4 alkyl, C1 -C4 haloalkyl, halogen or CN. Selection S. Compounds of Selection Q wherein one R5 is a pyrazole, imidazole,
triazole, pyridine or pyrimidine, each ring optionally substituted with C|-C4
alkyl, CrC4 haloalkyl, halogen or CN. Selection T. Compounds of Selection S wherein one R5 is a pyridine optionally
substituted with CrC4 alkyl, CrC4 haloalkyl, halogen or CN.
Most select is the compound of Formula 1 selected from the group consisting of:
■ 4-[[[l -(2-Chlorophenyl)-3-(trifluoromethyI)- l#-pyrazol-5-yI]carbonyI]amino]-5-methyl-?vr-l-methylethyl)-3-pyridincarboxamide,
4-Memyl-7^-(l-memylemyl)-3-[[2-methyI-4-(trifiuoromemyI)benzoyI]ammo]-2-thiophencarboxamide, and
l-Memyl-AL(l-methylemyl)-5-[[4-(rrifluoromethyl)benzoyljamino]-l^/-pyrazole-4-carboxamide. The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-19. The definitions of A, B, J, K, R], R2, R3, R4, R5 and n in the compounds of Formulae I and 2-41 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-c, 2a-b and 4a-g are various subsets of the compounds of Formula I, 2 and 4, respectively. Of note are compounds of Formulae I, 2, 5, 6, 6a, 13, 14, 15. 40 and 41 wherein K is selected from the group consisting of optionally substituted thiophene, isoxazole, isothiazole, pyrazole, pyridine and pyrimidine rings. Also of note are compounds of Formulae I, 2, 5, 6, 6a, 13, 14, 15, 40 and 41 wherein K is K-1, K-14, K-15, K-18, K-23, K-28, K-29, K-30, K-31 and K-33. Of particular note are compounds of Formulae I, 2, 5, 6, 6a, 13, 14, 15, 40 and 41 wherein K is K-28, K-31 and K-33.
Compounds of Formula I can be prepared by procedures outlined in Schemes 1-19. A typical procedure is detailed in Scheme 1 and involves coupling of an ortho amino carboxylic acid amide of Formula 2 with an acid chloride of Formula 3 in the presence of an acid scavenger to provide the compound of Formula la. Typical acid scavengers include amine bases such as triethylamine, diisopropyl ethyl amine and pyridine; other scavengers include hydroxides such as sodium and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate. In certain instances it is useful to use-polymer-supported acid scavengers such as polymer-bound diisopropylefhylamine and polymer-bound dimethylaminopyridine. In a subsequent step, amides of Formula la can be converted to thioamides of Formula lb using a variety of standard thio transfer reagents including phosphorus pentasulfide and Lawesson"s reagent.

WO 02/070483

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26 "-Scheme 1



An alternate procedure for the preparation of compounds of Formula la involves • coupling of an amide of Formula 2 with an acid of Formula 4 in the presence of a dehydrating agent such as dicyclohex-ylcarbodiimide (DCC). Polymer supported reagents are useful here, such as polymer-bound cyclohexj^carbodiimide. Synthetic procedures of Schemes 1 and 2 are only representative examples of useful methods for the preparation of Formula I compounds as the synthetic literature is extensive for this type of reaction.
Scheme 2

+


O

OH

dehydrative coupling reagent

la

10

15

One skilled in the art will also realize that acid chlorides of Formula 3 may be prepared from acids of Formula 4 by numerous well-known methods.
An alternate procedure for the preparation of compounds of Formula la involves coupling of an ortho amino carboxylic acid ester of Formula 5 with an acid chloride of Formula 3 by a method similar to that described in Scheme 1, followed by transformation of the ester group into an amide functionality. This transformation can be achieved by an animation with an amine of Formula 7. A Lewis acid such-as trimethyl aluminum as shown in Scheme 3 may catalyze this reaction.


20

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27
Alternatively the ester 6 can be transformed to an amide (6a) as shown, in Scheme 4 by saponification with a base such as aqueous sodium hydroxide followed by dehydrative coupling with an amine of Formula 7 by a procedure similar to that described in Scheme 2.
Scheme 4

base

6a

C02H

R2R3NH
dehydrative coupling agent

la

Benzoic acids of Formula 4 (J is optionally substituted phenyl) are generally well known in the art as are procedures for their preparation. One particularly useful subset of benzoic acids of this invention are 2-methyl-4-perfluoroalkyl benzoic acids of Formula 4a (R5(a) equals e.g. CF3, C2¥^ C3F7). The synthesis for these compounds is outlined in
10 Schemes 5-9. Benzoic acids of Formula 4a may be prepared from the benzonitriles of Formula 8 by hydrolysis. The conditions used may involve the use of a base such as an alkaline metal hydroxide or alkoxide (e.g. potassium or sodium hydroxide) in a solvent such as water, ethanol or ethylene glycol (e.g. J. Chem. Soc. 1948, 1025). Alternatively, the hydrolysis may be carried out using an acid such as sulfuric acid or phosphoric acid in a
15 suitable solvent such as water (e.g. Org. Synth. 1955, Coll. vol. 3, 557). The choice of the conditions is contingent on the stability of R5 to the reaction conditions and elevated temperatures are usually employed to achieve this transformation.
Scheme 5


R5(a)
Hydrolysis


R (b) is Me
Nitciles of Formula 8 may be prepared from anilines of Formula 9 by the classical 20 sequence involving diazotization and treatment of the intermediate diazonrurn salt with a copper cyanide salt (e.g. J. Amer. Chem. Soc. 1902, 24, 1035).

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28 Scheme 6 R5(a)

9 R5(b) is Me
Anilines of Formula 9 may be prepared from compounds of Formula 10. This transformation may be achieved by a well-known procedure that employs Raney Nickel (Org. Synth. Coll. Vol. VI, 581). Alternatively, the same transformation may be effected by the use of a suitable catalyst such as palladium in the presence of hydrogen. The reaction is usually conducted at pressures of 104 to 107 kPa in a suitable organic solvent such as, but not limited to, toluene. Elevated temperatures of 80-110 °C are usually required to achieve the transformation. As one skilled in the art will realize, numerous chemical modifications of the thioether moiety are possible, and may be employed when necessary to facilitate this transformation..
Scheme 7

-SMe 10
Compounds of Formula 10 may be prepared from iminosulfuranes of Formula 11. The transformation may be achieved in a protic solvent such as methanol or water, in a non-protic solvent such as dichloromethane or toluene in the presence of a suitable base such as triethylamine (e.g. Org. Synth. Coll. Vol. VI, 581) or sodium methoxide, or in a combination of a protic solvent, a protic solvent and a base. The temperature at which the reaction is conducted is usually in the range 40-110 °C. As one skilled in the art will realize, suitable salts of compounds of Formula 11 such as, but not limited to a hydrochloride, a sulfate or a bisulfate may also be employed, provided that the appropriate amount of base is first used to generate the free base 11. This may be done as a separate step or as an integral part of the step involving the transformation of compounds of Formula 11 to compounds of Formula 10.

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Scheme 8


Rearrangement

10



10

Compounds of Formula 11 may be prepared from anilines of Formula 12 by reaction with dimethyl sulfide and a suitable chlorinating agent such as, but not limited to N-chlorosuccinimide (e.g. Org. Synth. Coll. Vol. VI, 581), chlorine or N-chlorobenzotriazole. Alternatively, anilines of Formula 12 may be treated with dimethyl sulfoxide which has been "activated" by treatment with an agent such as acetic anhydride, trifluoroacetic, .anhydride, trifluoromethanesulfonic anhydride, cyclohexylcarbodiirnide, sulfur trioxide, or phosphorus pentoxide. The reaction is conducted in a suitable organic solvent such as dichloromethane or dimethyl sulfoxide. The reaction is conducted at a temperature of-70°C to 25 °C and is dependent on the solvent and reagent used.
Scheme 9




HoN"

11

12

15
20

Intermediate ortho amino carboxylic acid amides of Formula 2a and 2b may also be prepared from isatoic anhydrides of Formula 13 and 14 (Scheme 10). Typical procedures involve combination of equimolar amounts of the amine 7 with the isatoic anhydride in polar aprotic solvents such as pyridine and dimethylformamide at temperatures ranging from room temperature to 100 °C. R1 substituents such as alkyl and substituted alkyl may be introduced by the base catalyzed alkylation of isatoic anhydride 13 with known alkylating reagents R1_Lg (wherein Lg is a leaving group such as halogen, alkyl or aryl suphonates or alkyl sulfates) to provide the alkyl substituted intermediates 14. Isatoic anhydrides of Formula 13 may be made by methods described in Coppola, Synthesis 1980, 505 and Fabis et al Tetrahedron, 1998, 10789.

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30 Scheme 10




10

An alternate procedure for the preparation of specific compounds of Formula I (wherein A is O, B is O and R1 is H) involves reaction of an amine 7 with a heterocyclic fused oxazinone of Formula 15. Typical procedures involve combination of the amine with the oxazinone in solvents such as tetrahydrofuran or pyridine at temperatures ranging from room temperature to the reflux temperature of the solvent. Oxazinones are well documented in the chemical literature and are available via known methods that involve the coupling of either an ortho amino carboxylic acid with an acid chloride. For references to the synthesis and chemistry of heterocyclic fused oxazinones see Jakobsen et al, Biorganic and Medicinal Chemistry, 2000, 8, 2803-2812 and references cited therein.
Scheme 11


Ic (A is O, B is O, R1 is H)
Heterocyclic acids of Formula 4, wherein J is an optionally substituted heterocycle, can be prepared by procedures outlined in Schemes 12-17. Both general and specific

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10
15

31
references to a wide variety of heterocyclic acids including thiophenes, furans. pyridines, pyrrolidines, triazoles, imidazoles, pyrazoles, thiazoles, oxazoles, isothiazoles, thiadiazoles. oxadiazoles, triazines, pyrazines, pyridazines, and isoxazoles can be found in the following compendia: Rodd"s Chemistry of Chemistry of Carbon Compounds, Vol. Wato IVL, S. Coffey editor, Elsevier Scientific Publishing, New York, 1973; Comprehensive Heterocyclic Chemistry, Vol. 1-7. A. R. Katritzky and C. W. Rees editors, Pergamon Press, New York, 1984; Comprehensive Heterocyclic Chemistry II, Vol. 1-9, A. R. Katritzky, C. W. Rees, and E. F. Scriven editors, Pergamon Press, New York, 1996; and the series, The Chemistry of Heterocyclic Compounds, E. C, Taylor, editor, Wiley, New York. Particularly useful heterocyclic acids of .this invention include pyridine acids, pyrimidine acids and pyrazole acids. Procedures for the synthesis of representative examples of each are detailed in Schemes 12-17. A variety of heterocyclic acids and general methods for their synthesis may be found in World Patent Application WO 98/57397.
The synthesis of representative pyridine acids (4b) is depicted in Scheme 12. This procedure involves the known synthesis of pyridines from P-ketoesters and 4-aminobutenones (19). Substituent groups R5(a) and R5(b) include e.g. alkyl and haloalkyl.
Scheme 12


The synthesis of representative pyrimidine acids, (4c) is depicted in Scheme 13. This 20 procedure involves the known synthesis of pyrimidines from vinylidene-(3-ketoesters (22) and amidines. Substituent groups R5(a) and R5(b) include e.g. alkyl and haloalkyl.

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10
15

The synthesis of representative pyrazole acids (4d-4g) is depicted in Schemes 14-17. Pyrazoles 4d are described in Scheme 14. The synthesis of Scheme 14 involves as the key step introduction of the R5(b) substituent via alkylation of the pyrazole. The alkylating agent R5(b)-Lg (wherein Lg is a leaving group such as CI, Br, I, sulfonates such as p-toluenesulfonate or methanesulfonate or sulfates such as -S02OR7(b)) includes R7(b) groups such as CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, CrC6 haloalkyl C2-C6 haloalkenyl, C2-Cg haloalkynyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2~C6 alkoxycarbonyl, C3-Cg dialkylaminocarbonyl, C3-C5 trialkylsilyl; or phenyl, benzyl, benzoyl, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted. Oxidation of the methyl group affords the pyrazole carboxylic acid. Some of the more preferred R5(a) groups include haloalkyl.
Scheme 14


Pyrazoles 4e are described in Scheme 15. These pyrazole acids may be prepared via metallation and carboxylation of pyrazoles of formula 28 as the key step. The R5(b) group is

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introduced in a manner similar to that of Scheme 14, i.e. via alkylation with a R5(b) alkylating agent. Representative R5(a) groups include e.g. cyano, and haloalkyl.
Scheme 15




10

Pyrazoles 4f are described in Scheme 16. These can be prepared via reaction of an optionally substituted phenyl hydrazine 29 with a pyruvate 30 to yield pyrazole esters 31. Hydrolysis of the ester affords the pyrazole acids 4f. This procedure is particularly useful for the preparation of compounds where R5(b) is optionally substituted phenyl and R5(a) is haloalkyl.
Scheme 16


Pyrazoles acids of Formula 4g are described in Scheme 17. These can be prepared via 3+2 cycloaddition of an appropriately substituted nitrilimine (32) with either substituted propiolates (33) or acrylates (36). Cycloaddition with acrylates requires additional oxidation
15 of the intermediate pyrazoline to the pyrazole. Hydrolysis of the ester affords the pyrazole acids 4g. Preferred iminohalides for this reaction include the trifluorornethyl iminochloride (38) and the irninodibromide (39). Compounds such as 38 are known (J. Heterocyd. Chem. 1985, 22(2), 565-8). Compounds such as 39 are available by known methods (Tetrahedron Letters 1999, 40, 2605). These procedures are particularly useful for the preparation of
20 compounds where R5(b) is optionally substituted phenyl and R5(a) is haloalkyl or bromo.

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Ort/zo-amino carboxylic acid esters of Formula 5 wherein R1 is H can be prepared from monoesters of ortho dicarboxylic acids of Formula 40 via rearrangement of the corresponding acyl azide and hydrolysis of the resulting isocyanate (or alternatively by trapping of the isocyanate with an alcohol and cleaving of the resulting carbamate) as shown in Scheme 18.
Scheme 18



1) (COCQ2
2) NaN3
3) heat
4) hydrolysis

or

40


1) (PhO^PCO)^, ROH
2) hydrolysis

5 (R1 is H)

Alternatively ortfio-amino carboxylic acid esters of Formula 5 can be prepared from ortho carboxamide carboxylic esters of Formula 41 by Hoffman rearrangement with reagents such as sodium hydroxide and bromine as shown in Scheme 19.

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Scheme 19




Compounds of Formulae 40 and 41 are known in the art or can be readily prepared from compounds known in the art. (For example, see Tetrahedron, 1997, 53,14497; J. Chem. Soc, Perkin Trans. 1, 1996,10, 1035; WO92/08724 and EP 418667).
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted b any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume .unless otherwise indicated. HNMR spectra are reported in ppm downfield from tetramethylsilane; s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, id is doublet of doublets, dt is doublet of triplets, brs is broad singlet.

36
EXAMPLE 1
Preparation of 5-methyl-N-f(l-memylemyi)-4-4-tfifluoromemoxy)benzoyl1amino1-3-
pyridmecarboxarnide
Step A: Preparation of ethyl 4-azido-5 methyl-3rpyridinecarboxylate
5 A slurry of 14.1 g (78 rnmol) of ethyl 1,4-dihydro-S>-methyl-4-oxo-3-
pyridinecarboxylate (prepared according to Horvath, G.; Dvortsak, P. J. Heterocycl. Chem, 1980, 359) in 30ml of phosphorous pxychloride was refiuxed for 1 hour. After cooling, the volatiles were removed with a rotary evaporator. The residue was poured into cold saturated aqueous sodium bicarbonate. Dichloromethane was added and the mixture was filtered 10 through celite. The layers were separated. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was dissolved in 150 inL of ^ diinethylformamide. 15.2g (234 rnmol) of sodium azide was added. The mixture was heated at 95°C for lhour. After cooling, the solvent was removed with a rotary evaporator. The residue was partitioned between ethyl acetate and water. The organic layer was dried 15 (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was passed through a plug of silica gel with 25% ethyl acetate in hexanes as eluant to afford 11.9g of the title compound as a cream colored solid.
!HNMR (CDCI3) S 1.41 (t,3H), 2.12 (s,3H), 4.36 (q,2H), 8.12 (s,lH), 8.83 (s,lH).
Step B: Preparation of ethyl 4-amino-5-methyl-3-pvridinecarboxvlate
20 0.50 g of materialprepared in Step A was dissolved in 15 mL of ethanol. 0.15gof
10% palladium on carbon was added. The reaction mixture was placed under one
atmosphere of hydrogen for 2 hours. The catalyst was removed by filtration. The solvent
was removed with a rotary evaporator to afford 0.43 g of the title compound as a white solid.
1H NMR (CDCI3) 5 1.42 (OH), 2.30 (s,3H)> 4.45 (q,2H), 8.47 (s,IK), 8.87 (s, 1H).
25 StepG; Preparation of ethyl 5-memvl-4-rr4-trifluoromethoxv)berizoyllammo1-3-
pvridinecarboxvlate l.Og (5.6 rnmol)""of material prepared in Step B was dissolved in 30 mL of dichloromethane. 0.77 mL (5.6 rnmol) of triethylamine, a catalytic amount of 4-dimethylaminopyridine and 0.88 mL (5.6 mmol) of 4-(trifluoromethoxy)benzoyl chloride 30 were added. The mixture was stirred overnight. The reaction mixture was washed with water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was purified by medium-pressure liquid chromatography (MPLC) with a gradient of 15-100% ethyl acetate in hexanes as eluant. The bisacylation product eluted first, then 0.42 g of the title compound as white solid. Starting material 35 (0.52 g) was also recovered.
!H NMR (CDCI3) 5 1.41 (t,3H), 2.32 (s,3H), 4.39 (q,2H), 7.37 (d,2H), 8.08 (d,2H), 8.63 (brs,lH), 9.04 (brs,lH), 10.78 (brs,lH).

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Step D: Preparation of 5-methvl-N-( 1-methyl ethvl)4-[T4-
trifluoromethoxv)benzovi1aminol-3-pvridinecarboxamide To a solution of 0.049 mL (0.57 mmol) of isopropylamine in 20 mL of dichloroethane at 0 °C was added 0.64 mL (1.3 mmol) of a 2M solution of trimethylaluminum in toluene 5 dropwise. A solution of 0.21 g (0.57 mmol) of the material prepared in Step C in 5 mL of dichloroethane was added dropwise. Four days later an additional 0.049 mL of isopropylamine and 0.64 mL of trimethylaluminum were added. The reaction was refluxed for 6h, After cooling 20 mL of IN HC1 was added. The layers were separated. The aqueous layer was made basic with a saturated sodium bicarbonate solution. Dichloromethane was
10 added and the mixture was filtered through celite. The dichloromethane was separated,
combined with the dichloroethane layer from above and dried (sodium sulfate). The solvent was removed with a rotary evaporator. The residue was purified by MPLC with a gradient of 25-50% ethyl acetate in hexanes as eluant to afford 0.047 g of the title compound, a compound of the invention, as a white solid; m.p. 202-204 °C.
15 ]HNMR (CDC13) 6 1.27 (d,6H), 2.33 (s,3H), 4.23 (m,lH), 6.46 (br.lH), 7.35 (d,2H),
8.07 (d,2H), 8.56(brs,lH), 8.69 (brs,lH), 11.15 (brs,lH).
EXAMPLE 2
Preparation of 1 -methyl-N-0-methvlethvl)-5-rf4-trifluoromethoxv)benzovl]amino]-lH-
pyrazole-4-carboxamide
20 Step A: Preparation of_5-amino-1 -methyl-N-Q -methylethyl)-lH-pyrazole-4-
carboxamide l.Og (8.0 mmol) of 2-cyano-A/-(l-methylethyl)acetamide (prepared according to the procedure of Cheikh et a] J. Org. Chem., 1991, 56, 970) was combined with 3.1 mL of triethylorthoformate, 5 mL of acetic anhydride and 0.01 g of anhydrous zinc chloride. The 25 mixture was refluxed for 1 hour. A distillation head was placed on the flask and the reaction was heated at 120 °C for 8 hours. After standing for two days the mixture was heated again for 12 hours at 120 °C for 12 hours. The volatiles were removed with a rotary evaporator. Ethanol was added and the volatiles were again removed with a •rotary evaporator. This material was dissolved in 15 mL of ethanol. 0.34 mL (6.4 mmol) of methyl hydrazine was 30 added. The reaction mixture was refluxed for 5 hours and then allowed to stand at room
temperature overnight. The solvent was removed with a rotary evaporator. The residue was purified by MPLC (ethyl acetate as eluant) to afford 0.14g of the title compound as a solid.
lHNMR (CDC\3) 5 1.23 (d,6H), 3.61 (s,3H), 4.21 (m..lH), 5.17 (brr2H), 5.34 (br/fH), 7.38 (s, 1H).

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StepB: Preparation of l-methvl-K(fl-methvlethvIV5-[[4-
trifluoromethoxvlbenzoyllaminol-1 H-pvrazole-4-carboxamide 0.14 g (0.77 mmol) of the material from Step A was dissolved in 20 mL of tetrahydrofuran and 0.12 mL (0.85 mmol) of triethylamine and 0.12 mL (0.77 mmol) of 5 4-(rrifluoromethoxy)benzoyl chloride were added. Three days later 0.12 mL (0.S5 mmol) of triethylamine and 0.12 mL (0.77 mmol) of 4-(trifluoromethoxy)benzoyl chloride were added. The reaction mixture was refluxed for two days. After cooling the reaction mixture was partitioned between ethyl acetate and water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was purified by 10 MPLC with 50% ethyl acetate in hexanes as eluant to afford 0.18 g of the title compound, a compound of the invention, as a white solid; m.p. 68-75 °C.
"H NMR (CDC13) 8 1.22 (d,6H), 3.91 (s,3H), 4.14 (m,lH), 5.92 (brd,lH), 7.32 (d,2H), 7.62 (s,lH), 8.08 (d,2H), 10.78 (brs,lH).
EXAMPLE 3
15 Preparation of 4-methvI-JV-d -methyiethyl)-3-rr4-trifluoromethvl")ben20vI]aminoj-2-
thiophenecarboxamide
Step A: Preparation of 7-methvi-2H-thienor3.2-d] IT ,3"|oxazine-2.4(l FD-dione
Phosgene in toluene (4.4 g, 20%, 8.88 mmol) was added to the sodium salt of 3-amino-
4-methyl-thiophene-2-carbocyclic acid (1 g, 5.58 mmol) in water (17 mL) at 0 C. The
20 mixture was allowed to warm to room temperature and was stirred for 1 hour. The mixture
was filtered. After drying in vacuum the product was obtained as a solid 0.49 g (47%).
IR (Nujol®) 1785, 1696,1580, 1513, 1236, 988, 918, 848, 826 cm-1.
m NMR (DMSO-d6) 8 2.20 (s,3H), 7.88 (s,lH).
StepB: Preparation of 7-methvl-244-(trifluoromethyl)phenyI]-4H-thieno|"3.2-
25 4-(Dimethylamino)pyridine (0.66 g, 5.41 mmol) was added to the product from Step A in dioxane (10 mL). 4-(Trifluoromethyl)benzoyl chloride (1.13 g, 5.42 mmol) was added to the mixture and the mixture was boiled for approximately 3 hours. The mixture was allowed to cool to room temperature and was poured into hydrochloric acid (100 mL, 1 N). The 30 mixture was extracted with ethyl acetate (3 x 50 mL) and the combined extracts were dried and evaporated. Chromatography on silicon gel (eluted with ethyl acetate/hexanes) gave the product as a white solid 1.56 g, (91.7%).
IR (Nujol®) 2923, 1763, 1600, 1572, 1410,1312, 1234, 1170, 1125, 1068, 1013,978,
934,851,813 cm-1. "
35 ]HNMR (CDCI3) 5.2.47 (s,3H), 7.60 (s,lH)5 7.77 (d,2H),8.45(d,2H).

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Step C: Preparation of 4-methvl^-ri-methvlethvn-3-rr4-
trifluoromethvnben2ovIlaminol-2-thiophenecarboxarnide A mixture of the product from Step B (0.2 g. 0.043 mmol) and isopropylamine (0.2 g, 3.39 mmol) in THF (5 mL) was stirred for 6 hours. The solvent was removed under reduced ■ 5 pressure to give the product, a compound of the invention, as a solid 0.21 g, (91%).
IR(Nujol®) 3294, 1664, 1625, 1573, 1524, 1409,1327, 1207, 1167 1126, 1068, 1018, 954, 885, 857 cm-1.
JHNMR(CDC13) 5 1.22 (d,6H), 2.30 (s,3H)5 4.22-4.11 (m,lH), 5.58 (d,lH), 7.03 (sslH), 7.75 (d, 2H), 8.13 (d52H), 10.63 (5,1H).
10 EXAMPLE 4
Preparation of 5-nT3-Chloro-l-(3-chIoro-2-pvridinvI)-liJr-pyrazol-5-vncarbonvllamino]-
,Af6-dimethyl-4-pyrimidinecarboxamide
Step A: Preparation of HLl-dimethylethyP) 4-ethvl-2-acetvl-3-amino-2-butenedioate
To a mixture of 17.15g (108 mmol) of ^-butyl acetoacetate and 12.8 mL (130 mmol) of 15 ethyl cyanoformate in 25 mL of dichloromethane was added 1.64g of zinc acetylacetonate hydrate. After stirring overnight the volatiles were removed with a rotary evaporator. The residue was dissolved in ethyl acetate and filtered through celite. The solvent was removed with a rotary evaporator to afford 29.9g of the title compound as a white solid as an E/Z isomer mixture. 20 . ■ *H NMR (CDC13) 6 1.33 (t,3H), 1.52 (s,9H), 2.35 (s,3H) [minor.isomer 2.40 (s,3H)], 4.33 (m,2H).
Step B: Preparation of 5-f 1.1 -dimethylethyl) hydrogen 6-methvl-4,5-
pyrimidinedicarboxylate To a solution of 11.6g (45 mmol) of the material from Step A in 55 mL of ethanol was 25 added 10.9g (135 mmol) of formamidine hydrochloride; The reaction mixture was cooled in an ice bath and 17 mL (135 mmol) of 1, 1,3,3-tetramemylguanidme was added dropwise. After the mixture was stirred overnight the solvent was removed with a rotary evaporator. The residue was partitioned between ethyl acetate and water. The aqueous layer was cooled in an ice bath, acidified with concentrated HC1 and extracted three times with ethyl acetate. 30 The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator to afford 9.12g of the title compound"as a yellow solid.
"HNMR (CDC13) 5 1. 65 (s,9H), 2.68 (s,3H), 9.19 (s,lH).
Step C: Preparation of 5-f LI-dimethyl ethyl) 4-methvl 6-methyl-4.5-
pyrimi dinedi carboxylate
>5 To a solution of 9.12g (38 mmol) of the material from Step B in 100 mL of
N,N-dimethyl formamide (DMF) was added 3.1 mL (50 mmol) of iodomethane .and 3.7g (50 mmol) of lithium carbonate. The reaction mixture was heated at 60 °C for 3 hours.

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After cooling the reaction mixture was partitioned between dichloromethane and water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary-evaporator and then a vacuum pump. The residue was purified by MPLC with a gradient of 20-30% ethyl acetate in hexanes as eluant to afford 7.58g of the title compound as an off-5 white solid.
!H NMR (CDC13)S 1.63 (s,9H), 2.67 (s,3H), 4.01 (s,3H),9.19(s,lH).
Step D: Preparation of methyl 5-ITd.l -dimemylethoxy)carbonyllammo]-6-methyl-4-
pvrimidinecarboxylate 7.55g of the material from Step C was dissolved in 40 mL of dichloromethane. 20 ml 10 of trifluoroacetic acid was added. After two days the reaction mixture was refluxed for 6
hours. After an additional day the volatiles were removed with a rotary evaporator. Toluene
was added and the solvent was removed with a rotary evaporator. This material (9.2g) was
dissolved in 100 mL of/-butanol. 9.2 mL (66 rnmol) of triethylamine and 14 mL (66 mmoi)
of diphenylphosphoryl azide were added. The reaction was refluxed 3 hours. After cooling,
15 the solvent was removed with a rotary evaporator. The residue was partitioned between
ethyl acetate and water. The organic layer was dried (sodium sulfate) and the solvent was
removed with a rotary evaporator. The residue was purified by MPLC with a gradient of
40-100% ethyl acetate in hexanes as eluant to afford 5.8 lg of the title compound as a yellow
solid.
20 *H NMR (CDC13) 5 1.52 (s,9H), 2.60 (s,3H), 4.03 (s,3H), 8.07 (br,lH),8.98 (s,lH).
Step E: Preparation of methyl 5-amino-6-methyl-4-pyrimidinecarboxvlate
5.8g of the material from Step D was dissolved in 25 mL of trifluoroacetic acid. After stirring for 90 minutes the solvent was removed with a rotary evaporator. Saturated aqueous sodium bicarbonate was added. The aqueous layer was extracted five times with 25 dichloromethane. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator to afford 3.78g of the title compound with a small amount of an impurity.
JH NMR (CDCI3) 5 2.50 (s,3H), 4.00 (s,3H), 5.76 (br,2H),8.56 (s,lH).
Step F: Preparation of 5-amino-6-methvl-4-pvrimidinecarboxylic acid monosodium
30 salt
2.0g (12"mmol) of the material from Step E was dissolved in 24 mL of methanol.
12 mL of a IN solution of sodium hydroxide was added. After 1 hour the solvent was
removed with a rotary evaporator. The residue was dried in a vacuum oven overnight to
afford 2.39 g of the title compound as a tan solid.
35 3HNMR(D20)S 2.45 (s^H), 8.37 (s,lH).
Step G: Preparation of 3-chloro-N,N-dimethvI-lH-pyrazole-l-sulfonamide
To a solution of jV-dimethylsulfemoylpyrazole (188.0 g, 1.07 mol) in dry tetrahydrofuran (1500 mL) at -78 °C was added dropwise a solution of 2.5 M"«-butyl-

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lithium (472 mLs 1.18 mol) in hexane while maintaining the temperature below
-65 °C. Upon completion of the addition the reaction mixture was maintained at -78 °C for
an additional 45 minutes, after which time a solution of hexachloroethane (279 g, 1.18 mol)
in tetrahydrofuran (120 mL) was added drop wise. The reaction mixture was maintained for
an hour at -78 °C, warmed to -20 °C and then quenched with water (1 L). The reaction
mixture was extracted with methylene chloride (4x500 mL); the organic extracts were dried
over magnesium sulfate and concentrated. The crude product was further purified by
chromatography on silica gel using methylene chloride as eluent to afford the title product
compound as a yellow oil (160 g).
}H NMR (CDC13) 5 3.07 (d, 6H), 6.33 (s, 1H), 7.61 (s, 1H).
Step H: Preparation of 3-chloropyrazole
To trifluoroacetic acid (290 mL) was added dropwise the chloropyrazole product
(160 g) from Step G, and the reaction mixture was stirred at room temperature for 1.5 hours
and then concentrated at reduced pressure. The residue was taken up in hexane, insoluble
solids were filtered off, and the hexane was concentrated to afford the crude product as an
oil. The crude product was further purified by chromatography on silica gel using
ether/hexane (40:60) as eluent to afford the title product as a yellow oil (64.44 g).
)HNMR (CDCI3) S 6.39 (s, 1H), 7,66 (s, 1H), 9.6 (br s, 1H).
Step I: Preparation of.3-chloro-2-(3-chloro-lff-pyrazol-l -yl)pyridine
To 2 mixture of 2,3-dichloropyridine (92.60 g, 0.629 mol) and 3-chloropyrazole (64.44 g, 0.629 mol) in TV.TV-dimethylformamide (400 mL) was added potassium carbonate (147.78 g, 1.06 mol), and the reaction mixture was then heated to 100 °C for 36 hours. The reaction mixture was cooled to room temperature and slowly poured into ice water. The precipitated solids were filtered and washed with water. The solid filter cake was taken up in ethyl acetate, dried over magnesium sulfate and concentrated. The crude solid was chromatographed on silica gel using 20% ethyl acetate/hexane as eluent to afford the title product as a white solid (39.75 g).
3H NMR (CDCI3) 8 6.43 (s, 1H), 7.26 (m, 1H), 7.90 (d, 1H), 8.09 (s, IE), 8.41 (d, 1H).
Step J: Preparation of 3-chloro-l-(3-chloro-2-pvridinyl)-lff-pyrazole-5-carboxylic
acid To a solution of the pyrazole product from Step I (39.75 g. 186 mmol) in dry tetrahydrofuran (400 mL) at-78 °C was added dropwise a solution of 2.0 M lithium diisopropylamide (93 mL, 186 mmol) in tetrahydrofuran. Carbon dioxide was bubbled through the amber solution for 14 minutes, after which time the solution became pale brownish-yellow. The reaction was made basic with IN aqueous sodium hydroxide solution and extracted with ether (2x500 mL). The aqueous extracts were acidified with 6N hydrochloric acid and extracted with ethyl acetate (3x500 mL). The ethyl acetate extracts were dried over magnesium sulfate and concentrated to afford the title product as an off-

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white solid (42.96 g). (Product from another run following similar procedure melted at 198— 199 °C.)
1H NMR (DMSO-d6) 6 6.99 (s, 1H), 7.45 (m, 1H); 7.93 (d, 1H), 8.51 (d, 1H).
Step K: Preparation of 2-r3-chloro-l"("3-chloro-2-pvridinvl)-lijr-pvrazol~5-vll-8-
5 methvl-4iy-pvrimidor5.4-^f][1.3]oxa2in-4-one
To a solution of 0.26 mL (3.3 mmol) of methanesulfonyl chloride in 18 mL of acetonitrile at 0°C was added 0.77g (3.0 mmol) of 3-cMoro-l-(3-chloro-2-pyridinyI)-l#-pyrazol-5-carboxylic acid from Step J. 0.42 mL (3.0 mmol) of triethylamine in 9 mL of acetonitrile was added dropwise. After 20 minutes at 0 °C, 0.525g (3.0 mmol) of material 10 from Step F was added. After 15 minutes 0.42 mL (3.0 mmol) of triethylamine was added dropwise. After 2 hours 0.26 mL (3.3 mmol) of methanesulfonyl chloride was added. After stirring overnight. The reaction mixture was poured into" water. Filtration afforded 0.27g of the title compound.
]H NMR (GDC13) § 2.20 (s,3H),-7.23 (s,lH), 7.54(dd,lH), 8.01 (dd,lH)s 8.57(dd,lH)," 15 9.20 (s,lH). .
Step L: Preparation of 5-f[["3-Chloro-l "r3-chloro-2-pvridinvl)-lff-pvra2ol-5-
y]]carbonvllamino)-A/.6-dimethv]-4"Pvrimidinecarboxamide 2 mL of a 2M solution of methylamine in tetrahydrofuran was added to 0.090g of material from Step K. After stirring overnight the solvent was removed with a rotary 20 evaporator to afford.0.071g"of the title compound, a compound of the invention, as a tan solid; m.p. 205-207 °C.
!H NMR (CDCI3) 5 2.48 (s,3H), 3.04 (d,3H), 7.06 (s,lH), 7.41(dd,lH), 7.89 (dd,lH), 8.30 (br,lH), 8.48 (dd,lH); 8.85 (s,lH), 11:57 (br,lH).
EXAMPLE 5
25 Preparation of 2.6-dichloro-3-f|"ri-(3-chloro-2-pvridinvI)-3-(trifluoromethvl)-liJ"-pyrazol-5-
vl]carbonyl1ammoTA/"-fl-methvlethvl)-4-pvridinecarboxamide
Step A; Preparation of ethyl 3-amino-4-pyridinecarboxylate
To a solution of 1 g (7.25 mmol) of 3-amino-4~pyridmecarboxylic acid in 5 mL of ethyl alcohol was added 2 mL of sulfuric acid. The mixture was warmed under reflux for 2 30 h. It was cooled and basified with cone. NH4OH solution to pH = 8. The resulting solution was extracted with ethyl acetate and the organic layer was washed with brine and water, dried (MgSCU) and concentrated in vacuo to give 1.04 g of the title compound as a white solid (87%).
]H NMR (CDCI3) 6 8.19 (s 1H), 7.93 (d 1H, J is 5.1Hz), 7.60 (d, 1H, J is 5.1Hz), 35 5.67 (brs,2H), 4.36 (q,2H), 1.40 (t, 3H).

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StepB: Preparation of ethvl 3-arnino-2,6-dichloro-4-pvridinecafboxylate
To a solution of 1.04 g (6.27 mmol) of ethyl 3-amino-4-pyridfnecarboxylate in 5 mL of DMF was added 1.67 g of JV-chlorosuccinimide (12.5 mmol) in a single portion at room temperature. The mixture was then stirred at the same temperature for 24 hours. The 5 resulting mixture was concentrated in vacuo and purified by silica gel column to give 1.40 g of the title compound as a white solid (95%).
!HNMR (CDC13) 5 7.67 (s IK), 6.18 (br s, 2H), 4.39 (q, 2H), 1.42 (t, 3H).
Step C: Preparation of 3-amino-2n6-dichloro-4-pvridinecarboxvlic monopotassium
salt
10 To a solution of 1.30 g (5.54 mmol) of ethyl 3-amino-236-dichloro-4-
pyridinecarboxylate in a mixture of 5 mL of water and 20 mL of ethyl alcohol was added
622 mg (11 .-1 mmol) of potassium hydroxide at room temperature and the reaction mixture
was warmed at 90 °C for.lhour. The mixture was then concentrated in vacuo and evaporated
with benzene three times to give 1.63 g of the title compound as a white solid. The crude
15 product was used in the next reaction without any further purification (98%).
!H NMR (DMSOd-6) 5 7.31 (s, 1H), 7.14 (br s, 2H).
Step D: Preparation of 6,8-dich]oro-2ff-pyridoF3,4-£fin,3]oxa2ine-2.4flifl-dione
To a solution of 1.64 g (5.54 mmol) of the material from Step C in 20 mL of dioxane was added 2.2 g (11.1 mmol) of diphosgene at 0 °C. The mixture was allowed to warm to 20 room temperature and stirred for 24 hours. The mixture was then concentrated in vacuo to give 1.70 g of the title compound as a white solid (quantitative).
!H NMR (DMSOd-6) 5 7.99 (s, 1H).
Step E: Preparation of 3-chloro-2-[3»ftrifluorom ethyl)-1 .ff-pyrazol-1 -vl]pyridine
To a mixture of 2,3-dichloropyridine (99.0 g, 0.67 mol) and 3-trifluoromethyl pyrazole 25 (83 g, 0.61 mol) in dry ACA"-dimethylformamide (300 mL) was added potassium carbonate (166.0 g, 1.2 mol) and the reaction was then heated to 110-125 °C over 48 hours. The reaction was cooled to 100 °C and filtered through Celite® diatomaceous filter aid to remove , solids. jVLV-Dimexhylformamide and excess dichloropyridine were removed by distillation at atmospheric pressure. Distillation of the product at reduced pressure (b.p. 139-141 °C, 30 7 mm) afforded the desired intermediate as a clear yellow oil (113.4 g).
H NMR (CDCI3) 5 6.78 (s, IK), 7.36 (t, IK), 7.93 (d, IK), 8.15 (s, IK), 8.45 (d, IK).
Step F: Preparation of 1 -f3-chloro-2-pvridinvl)-3-(trifluoromethyn-lg-pvra2ole-5-
carboxvlic acid To a solution of the pyrazole product from Step E (105.0 g5 425 mmol) in dry 35 tetrahydrofuran (700 mL) at -75 °C was added via cannula a -30 °C solution of lithium diisopropylamide (425 mmol)-in dry tetrahydrofuran (300 mL). The deep red solution was stirred for 15 minutes, after which time carbon dioxide was bubbled through at -63 °C until the solution became pale yellow and the exothermicity ceased. The reaction was stirred for

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an additional 20 minutes and then quenched with water (20 mL). The solvent was removed under reduced pressure, and the reaction mixture partitioned between ether and 0.5 N aqueous sodium hydroxide solution. The aqueous extracts were washed with ether (3x), filtered through Celite® diatomaceous filter aid to remove residual solids,- and then acidified to apH of approximately 4, at which point an orange oil formed. The aqueous mixture was stirred vigorously and additional acid was added to lower the pH to 2.5-3. The orange oil congealed into a granular solid, which was filtered, washed successively with water and IN hydrochloric acid, and dried under vacuum at 50 °C to afford the title product as an off-white solid (130 g). (Product from another run following similar procedure melted at 175-176 °C.)
!HNMR (DMSO-^y) 5 7.61 (s, 1H), 7.76 (dd, 1H), 8.31 (d, IK), 8.60 (d, 1H).
Step G: Preparation of 2.6-dichloro-3-[[[[ -(S-chloro^-pyridinvD-S-rtrifluoromethvl)-
lff-pvrazol-5-yl]carbonvIlamino1-jV-n~methylethvl")- 4-pyridinecarboxamide To a solution of 268 mg (0.92 mmol) of l-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-l.ff-pyrazole-5-carboxylic acid (from Step F) in 5 mL of dichlorom ethane was added 160 uL (1.84 mmol) of oxalyl chloride and two drops of DMF in sequence at room temperature. The mixture was then stirred at the same temperature for 1 hour. The crude mixture was then"concentrated in vacuo. The resulting mixture was dissolved with 5 mL of acetonitrile followed by additions of 280 mg (0.92 mmol) of the compound prepared in Step D and 298 u.L (3.68 mmol) of pyridine in sequence. The reaction mixture was warmed to 70 °C for 2 hours and allowed to cool to room temperature. A solution of 157 pL (1.84 mmol) of isopropylamine in 1 mL of acetonitrile was added to the mixture and it was wanned to 60 °C for J hour. The reaction was allowed to cool to room temperature and quenched with water. The aqueous layer was extracted with ethyl acetate and the organic layer was dried with MgSO"4 and concentrated in vacuo. The resulting mixture was purified with a silica gel column to give 250 mg of the title compound, a compound of the invention, as a white solid (52%). m.p. 240-242 °C.
"HNMR (CDCI3) S 9.85 (s, IK), 8.53 (dd, IK), 7.90 (dd, IK), 7.56 (s, IK), 7.42 (dd, 1H), 7.22 (s, IK), 6.08 (br d, IK), 4.13 (m, IK), 1.14 (d, 6H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 32 can be prepared. The following abbreviations are used in the Tables: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pi is isopropyl, t-Bu is tertiary butyl, Ph. is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methyltm"o, SEt is ethylthio, CN is cyano, N02 is nitro, TMS is trimethylsilyl, S(0)Me is methylsulfmyl, and S(0)2Me is methyisulfonyl. Structures of K for Tables 15,16 and 17 can be found in Exhibit 2.

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(f)m

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R4 (R5)m
R4 (R5)m
" R4 (R5)m

F 2-SCF3 F 3-SCF3 F 4-SCF3
F 2-SOCF3 F 3-SOCF3 F 4-SOCF3
F 2-S02CF3 F 3-SO7CF3 F 4-S02CF3
F 2-SCF2H F 3-SCF2H F- 4-SCF2H
F 2-SOCF2H F 3-SOCF2H F 4-SOCF2H
F 2-S02CF2H F 3-S02CF2H F 4-S02CF2H
Br 2-CF3 Br 3-CF3 Br 4-CF3
Br 2-OCF3 Br 3-OCF3 Br 4-OCF3
Br 2-OCF2H Br 3-OCF2H Br 4-OCF2H
Br 2-OCF2CF2H Br 3-OCF2CF2H Br 4-OCF2CF2H
Br 2-OCH2CF3 Br 3-OCH2CF3 Br 4-OCH2CF3
Br 2-SCF3 Br 3^SCF3 Br 4-SCF3
Br 2-SOCF3 Br" 3-SOCF3 Br 4-SOCF3
Br 2-S02CF3 Br 3-S02CF3 Br 4-S02CF3
Br . 2-SCF2H Br 3~SCF2H Br 4-SCF2H
Br 2-SOCF2H Br 3~SOCF2R Br 4-SOCF2H
Br 2-S02CF2H Br 3-S02CF2H Br 4-S02CF2H
2-CF3 3-CF3 4-CF3
2-OCF3 3-OCF3 , 4-OCF3
2-OCF2H 3-0CF2H 4-OCF2H
2-OCF2CF2H 3-OCF2CF2H 4-OCF2CF2H
2-OCH2CF3 3-OCH7CF3 4-OCH2CF3
2-SCF3 3-SCF3 4-SCF3
2-SOCF3 3-SOCF3 4-SOCF3
2-SO7CF3 3-S02CF3 4-S02CF3
2-SCF2H 3-SCF2H 4-SCF2H
2-SOCF7H 3-SOCF2H 4-SOCF2H
2-S02CF2H 3-S02CF2H 4-S02CF2H
OMe 2-CF3 OMe 3-CF3 OMe 4-CF3
OMe. 2-OCF3 OMe 3-OCF3 OMe 4-OCF3
OMe 2-OCF2H OMe 3-OCF2H OMe 4-OCF7H
OMe 2-OCF2CF2H OMe 3-OCF2CF2H OMe 4-OCF2CF2H
OMe 2-OCH2CF3 OMe 3-OCH2CF3 OMe 4-OCH7CF3
OMe 2-SCF3 OMe 3-SCF3 OMe 4-SCF3
OMe 2-SOCF3 OMe ■ 3-SOCF3 OMe - - 4-SOCF3
OMe 2-S02CF3 "OMe 3-S02CF3 OMe 4-S02CF3
OMe 2-SCF2H OMe 3-SCF2H OMe 4-SCF2H

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R4 (R5)m
R4 (R5)m

Br 2-Me-4-OCH2CF3 2-Me-4-OCH2CF3 OMe 2-Me-4-OCH2CF3
Br 2-Me-4-SCF3 2-Me-4-SCF3 ■ OMe 2-Me-4-SCF3
Br 2-Me-4-SOCF3 2-Me-4-SOCF3 OMe 2-Me-4-SOCF3
Br 2-Me-4-S02CF3 _ 2-Me-4-S02CF3 OMe 2-Me-4-S02CF3
Br 2-Me-4-SCF2H 2-Me-4-SCF2H OMe 2-Me-4-SCF2H
Br 2-Me-4-SOCF2H 2-Me-4-SOCF2H OMe 2-Me-4-SOCF2H
Br 2-Me-4-S02CF2H 2-Me-4-S02CF2H OMe 2-Me-4-S02CF2H
CF3 2-Me-4-CF3 N02 2-Me-4-CF3 SMe 2-Me-4-CF3
CF3 CFo 2-Me-4-0CF3 N02 2-Me4-0CF3 SMe 2-Me-4-0CF3

2-Me-4-OCF2H N02 2-Me4-0CF2H SMe 2-Me-4-OCF2H
3 CFn 2-Me-4-OCH2CF3 N02 2-Me-4-0CH2CF3 SMe 2-Me-4-OCH2CF3
CF3 2-Me-4-SCF3 N02 2-Me-4-SCF3 SMe 2-Me-4-SCF3
CF3 2-Me-4-SOCF3 NO7 2-Me4-S0CF3 SMe 2-Me-4-SOCF3
J
CF3 2-Me-4-S02CF3 N02 2-Me~4-S02CF3 SMe 2-Me4-S02CF3
CF3 CF3 2-Me-4-SCF2H N02 2-Me-4-SCF2H SMe 2-Me-4-SCF2H

2-Me-4-SOCF2H N02 2-Me-4-SOCF2H SMe 2-Me-4-SOCF2H
CF3 2-Me-4~S02CF2H N02 2-Me-4-S02CF2H Table 4 SMe 2-Me-4-S03CF2H


R4 (R5)m
R4 (R5)m
R4 (R5)m

Me 2-CF3 Me 3-CF3 Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-0CF3
Me 2-OCF2H Me 3-0CF2H Me 4-OCF7H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH2CF3 Me 4-OCH2CF3
Me 2-SCF3 Me 3-SCF3 Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2-S02CF3 Me 3-S02CF3 Me 4-S02CF3

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R4 (R5)m
R4 (R5)m

2-OCF3 3-OCF3 4-OCF3-
2-OCF2H 3-OCF2H 4-OCF2H
2-OCF2CF2H 3-OCF2CF2H 4-OCF2CF2H
2-OCH2CF3 3-OCH2CF3 4-OCH2CF3
2-SCF3 3-SCF3 4-SCF3
2-SOCF3 3-SOCF3 4-SOCF3
2-S02CF3 3-SO7CF3 4-S02CF3
2-SCF2H 3-SCF2H 4-SCF2H
2-SOCF2H 3-SOCF2H 4-SOCF2H
2-S02CF2H 3-S02CF2H 4-S02CF2H
OMe 2-CF3 OMe 3-CF3 ■ OMe 4-CF3
OMe 2-OCF3 OMe 3-OCF3 OMe 4-OCF3
OMe 2-OCF2H OMe 3-OCF2H OMe 4-OCF2H
OMe 2-OCF2CF2H OMe 3-OCF2CF2H OMe 4-OCF2CF2H
OMe . 2-OCH2CF3 OMe 3-OCH2CF3 OMe 4-OCH2CF3
OMe 2-SCF3 OMe 3-SCF3 OMe 4-SCF3
OMe 2.SOCF3 OMe 3-SOCF3 OMe 4-SOCF3
OMe 2-SO7CF3 OMe 3-S02CF3 OMe 4-SO7CF3
OMe 2-SCF2H OMe 3-SCF2H OMe 4-SCF2H
OMe 2-SOCF2H OMe 3-SOCF2H OMe 4-SOCF2H
OMe 2-S02CF2H OMe 3-S02CF2H OMe 4~S02CF2H
CF3 2-CF3 CF3 3-CF3 CF3 4-CF3
CF3 2-OCF3 CF3 3-OCF3 CF3 4-OCF3
CF3 2-OCF2H CF3 3-OCF2H CF3 4-0CF2H
CF3 2-OCF2CF2H CF3 3-OCF2CF2H CF3 4-0CF2CF2H
CF3 2-0"CH2CF3 CF3 3-OCH2CF3 CF3 4-OCH2CF3
CF3 . 2-SCF3 CF3 3-SCF3 CF3 4-SCF3
CF3 2-SOCF3 CF3 3-SOCF3 CF3 4-SOCF3
CF3 2-S02CF3 CT3 3-S02CF3 CF3 4-S02CF3
CF3 2-SCF2H CF3 3-SCF2H CF3 4-SCF2H
CF3 2-SOCF2H CF3 3-S0CF2H CF3 4-SOCF2H
CF3 2-S02CF2H CF3 3-S02CF2H .CF3 4-S02CF2H
OCF2H 2-CF3 OCF2H 3-CF3 OCF2H 4-CF3
OCF2H . , 2-OCF3 :OCF2H 3-OCF3 OCF2H 4-OCF3
OCF2H 2-OCF2H " OCF2H " 3-OCF2H OCF2H " 4-OCF2H
OCF2H 2-OCF2CF2H OCF2H 3-OCF2CF2H OCF2H 4-OCF2CF2H
OCF2H 2-OCH7CF3 OCF2H 3-OCH2CF3 OCF2H 4-OCH2CF3

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R4 (R5)m
R4 (R5)m
R4 (R5)m

Me ■2-CF3 Me 3-CF3 Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF2H Me 3-OCF2H Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH2CF3 Me 4-OCH2CF3
Me 2-SCF3 Me 3-SCF3 Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2S02CF3 Me 3-S02CF3 Me 4-S02CF3
Me 2-SCF2H Me 3-SCF2H Me 4-SCF2H
Me 2-SOCF2H Me 3-SOCF2H Me 4-SOCF2H
Me 2-S02CF2H Me 3-S02CF2H Me 4-S02CF2H
CF3 2-Me-4-CF3 CF2H 2-Me^-CF3 CH2CF3 2-Me^-CF3
CF3 2-Me-4-OCF3 CF2H 2-Me^-OCF3 CH2CF3 2-Me-4-OCF3
CF3 2-Me-4-OCF2H CF2H 2-Me-4-OCF2H GH2CF3 2-Me-4-OCF2H
CF3 • 2-Me4-OCH2CF3 CF2H 2-Me-4-OCH2CF3 CH2CF3 ■ 2-Me-4-OCH2CF3
CF3 2-Me-4-SCF3 CF2H 2-Me^-SCF3 CH2CF3 2-Me-4-SCF3
CF3 2-Me-4-SOCF3 CF2H 2-Me~4-SOCF3 CH2CF3 2-Me^-SOCF3
CF3 2-Me-4-S02CF3 CF2H 2-Me^-S02CF3 CH2CF3 2-Me-4-S02CF3
J
CF3 2-Me-4-SCF2H GF2H 2-Me-4-SCF2H CH2CF3 2-Me-4-SCF2H
CF3 • 2-Me-4-SOCF2H CF2H 2-Me-4-SOCF2H CH2CF3 2-Me-4-SOCF2H
CF3 2-Me-4-S02CF2H CF2H 2-Me-4-S02CF2H CH2CF3 2-Me-4-S02CF2H

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R4 (R5)m

Me 2-SCF2H
Me 2-SOCF2H
Me 2-S02CF2H
CI 2-CF3
CI 2-OCF3
CI 2-OCF2H
CI 2-OCF2CF2H
CI 2-OCH.2CF3
CI 2-SCF3
CI 2-SOCF3
CI 2-S02CF3
CI 2-SCF2H
CI 2-SOCF2H
CI 2-S02CF2H
F 2-CF3
F 2-OCF3
F 2-OCF2H
F 2-OCF2CF2H
F 2-OCH2CF3
F 2-SCF3
F 2-SOCF3
F 2-S02CF3
F 2-SCF2H
F 2-SOCF2H
F 2-S02CF2H
.Br 2-CF3
Br 2-OCF3
Br 2-OCF2H
Br. 2-OCF2CF2H
Br 2-OCB2CF3
Br 2-SCF3
Br 2-SOCF3
Br ,2-S02CF3
Br 2-SCF2H
Br 2-SOCF2H
Br 2-S02CF2H
I 2-CF3


R4 (R5)m

Me 3-SCF2H
Me 3-SOCF2H .
Me 3-S02CF2H
CI 3-CF3
CI 3-OCF3
CI 3-OCF2H
CI 3-OCF2CF2H
CI 3-OCH2CF3
CI 3-SCF3
CI 3-SOCF3
CI 3-S02CF3
CI 3-SCF2H
CI 3-SOCF2H
CI 3-S02CF2H
F 3-CF3
F 3-OCF3
F 3-OCF2H
F 3-OCF2CF2H
F 3-OCH2CF3
F 3-SCF3
F 3-SOCF3
F 3-S02CF3
F 3-SCF2H
F 3-SOCF2H
F 3-S02CF2H
Br 3-CF3
Br 3-OCF3
, Br 3-OCF2H
Br 3-OCF2CF2H
Br 3-OCH2CF3
Br 3-SCF3
Br 3-SOCF3
Br 3-S02CF3
Br 3-SCF2H
" Br " "3-SOCF2H"
Br 3-SO2CF2H
I 3-CF3


R4 (R5)m

Me 4-SCF2H
Me 4-SOCF2H
-Me 4-S02CF2H
CI 4-CF3
CI 4-OCF3
CI 4-OCF7H
CI 4-OCF2CF2H
CI 4-OCH2CF3
CI 4-SCF3
CI 4-SOCF3
CI 4-S02CF3
. CI 4-SCF2H
CI 4-SOCF2H
CI 4-S02CF2H
F "4-CF3
F 4-OCF3
F 4-OCF9H
F 4"0CF2CF2H
F 4-OCH2CF3
F 4-SCF3
F 4-SOCF3
F 4-S02CF3
F 4-SCF2H
F 4-SOCF2H
F 4-S02CF2H
Br 4-CF3
Br 4-OCF3
Br 4-OCF2H
Br 4-OCF2CF2H
Br 4-OCH2CF3
Br 4-SCF3
Br 4-SOCF3
Br 4-S02CF3
Br 4-SCF2H
Br 4-SOCF2H
Br 4-S02CF2H
■ I 4-CF3



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El OCF2H OCF2H OCF2H OCF2H OCF2H OCF2H Me Me Me Me Me Me Me Me Me Me Br Br Br Br Br Br Br Br Br Br CF3 CF3 CF3 CF3
CF3 CF3 CF3 CF3 "CF3
CF3

WO 02/070483

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R f I 6i I





El (EX El m^im El (Btm
Me 2-CF3 Me 3-CF3 Me " 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF2H Me 3-OCF2H Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH2CF3 Me 4-OCH2CF3
Me 2-SCF3 Me 3-SCF3 Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2-S02CF3 Me 3-S02CF3 Me 4-S02CF3
Me 2-SCF2H Me 3-SCF2H Me 4-SCF2H
Me 2-SOCF2H Me 3-SOCF2H Me 4-SOCF2H
.Me 2-S02CF2H Me 3-S02CF2H Me 4-S02CF2H
CI 2-CF3 CI 3-CF3 CI 4-CF3
CI 2-OCF3 CI 3-OCF3 CI 4-OCF3
CI .2-OCF2B CI 3-OCF7H CI 4-OC?2H
CI 2-OCF2CF2H CI 3-OCF2CF2H CI 4-OCF2CF2H
CI 2-OCH2CF3 CI 3-OCH2CF3 CI 4-OCH2CF3
CI 2-SCF3 CI 3-SCF3 ci 4-SCF3
CI 2-SOCF3 CI 3-SOCF3 CI 4-SOCF3
CI 2-S02CF3 CI 3-S02CF3 CI 4-S02CF3
CI 2-SCF2H CI 3-SCF2H " CI 4-SCF2H
CI 2-SOCF2H CI 3-SOCF2H CI 4-SOCF2H
CI 2-S02CF2H CI 3-S02CF2H CI 4-S02CF2H
F 2-CF3 F 3-CF3 F 4-CF3
F 2-OCF3 F 3-OCF3 F 4-OCF3
F 2-OCF2H F 3-OCF2H F 4-OCF2H
F 2-OCF2CF2H F 3-OCF2CF2H F 4-OCF2CF2H
F 2-OCH2CF3 F 3- DCH2CF3 F 4-OCH2CF3

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R4
(R5)m
R4 (R5)m
R4
(R5)m

F 2-SCF3 F 3-SCF3 F 4-SCF3
F 2-SOCF3 F 3-SOCF3 F 4-SOCF3
F 2-S02CF3 F 3-S02CF3 F 4-SO7CF3
F 2-SCF2H F 3-SCF2H F 4-SCF2H
F 2-SOCF2H F 3-SOCF2H F 4-SOCF2H
F 2-S02CF2H F 3-S02CF2H F ■ 4-S02CF2H
Br 2-CF3 Br 3-CF3 Br 4-CF3
Br 2-OCF3 Br 3-OCF3 Br 4-OCF3
Br 2-OCFoH Br 3-OCF2H Br 4-OCF2H
Br 2-OCF2CF2H Br 3~OCF2CF2H Br 4-OCF2CF2H
Br 2-OCH2CF3 Br 3-OCH2CF3 Br 4-OCH2CF3
Br 2-SCF3 Br 3-SCF3 Br 4-SCF3
Br 2-SOCF3 Br 3-SOCF3 Br 4-SOCF3
Br 2-S02CF3 Br 3-S02CF3 Br 4-S02CF3
Br . 2-SCF2H Br 3-SCF2H Br 4-SCF2H
Br 2-SOCF2H Br 3-S0CF2H Br 4-S0CF2H
Br 2-S02CF2H Br 3-S02CF2H Br 4-S02CF2H
2-CF3 3-CF3 4-CF3
2-OCF3 3-OCF3 4-OCF3
2-OCF2H 3-OCF2H 4-OCF2H
2-OCF2CF2H 3-OCF2CF2H 4-OCF2CF2H
2-OCH2CF3 3-OCH7CF3 4-OCH2CF3
2-SCF3 3-SCF3 4-SCF3
2-SOCF3 3-SOCF3 4-SOCF3
2-S02CF3 3-S02CF3 4-S02CF3
2-SCF2H 3-SCF2H 4-SCF2H
2-SOCF2H 3-SOCF2H 4-SOCF2H
2-S02CF2H 3-S02CF2H 4-S02CF2H
OMe 2-CF3 OMe 3-CF3 OMe 4-CF3
OMe 2-OCF3 OMe 3-OCF3 OMe 4-OCF3
OMe 2-OCF2H OMe 3-OCF2H OMe 4-OCF2H
OMe 2-OCF2CF2H OMe 3-OCF2CF2E OMe 4-OCF2CF2H
OMe 2-OCH2CF3 OMe 3-OCH9CF3 OMe 4-OCH2CF3
OMe 2-SCF3 ■__ OMe. 3-SCF3 OMe 4-SCF3
OMe 2-SOCF3 OMe 3-SOCF3 OMe 4-SOCF3
OMe 2-S02CF3 OMe 3-S02CF3 OMe 4-SO?CF3
OMe 2-SCF9H OMe 3-SCF2H OMe 4-SCF2H



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R4 (R5)m
R4 (R5)m
R4 (R5)m
Br 2-Me-4-OCH2CF3 2-Me-4-OCH2CF3 OMe 2-Me-4-OCH2CF3
Br 2-Me-4-SCF3 2-Me-4-SCF3 OMe 2-Me-4-SCF3
Br 2-Me-4-SOCF3 2-Me-4-SOCF3 OMe 2-Me-4-SOCF3
Br 2"Me-4-S02CF3 2-Me-4-S02CF3 OMe 2-Me-4-S02CF3
Br 2-Me-4-SCF2H 2-Me-4-SCF2H OMe 2-Me-4-SCF2H
Br 2-Me-4-SOCF2H 2-Me-4-SOCF2H OMe 2-Me-4-SOCF2H
Br 2-Me^-S02CF2H 2-Me-4-S02CF2H OMe 2-Me-4-S02CF2H
CF3 2-Me-4-CF3 N02 2-Me^-CF3 SMe 2-Me-4-CF3
CF3 2-Me-4-OCF3 N02 2-Me-4-OCF3 SMe 2-Me-4-OCF3
CF3 2-Me-4-OCF2H N02 2-Me-4-OCF2H SMe 2-Me-4-OCF2H
CF3 2-Me^-OCH2CF3 N02 2-Me-4-OCH2CF3 SMe 2-Me-4-OCH2CF3
CF3 2-Me-4-SCF3 . N02 2-Me^-SCF3 SMe 2-Me-4-SCF3
CF3 2-Me^-SOCF3 N02 2-Me4-SOCF3 SMe 2-Me-4-SOCF3
CF3 2-Me-4-S02CF3 N02 2-Me-4-S02CF3 SMe 2-Me-4-S02CF3
CF3 2-Me-4-SCF2H N02 2-Me-4-SCF2H SMe 2-Me-4-SCF2H
CF3 2-Me-4-SOCF2H N02 2-Me-4-SOCF2H SMe 2-Me-4-SOCF2H
CF3 2-Me-4-S02CF2H N02 2-Me-4-S02CF2H Table 10 SMe 2-Me-4-S02CF2H
1 H -(R5), Tl
R4°^^
I 1 H ^ ^(/-Bu)
R4 (R5)m
R4 (R5)m
R4 (R5)m

Me 2-CF3 Me 3-CF3 Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF2H Me 3-OCF2H Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH2CF3 Me 4-OCH2CF3
Me " 2-SCF3 7 Me 3-SCF3 Me 4^SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2-S02CF3 Me 3-S02C F3 Me 4-S02CF3

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R4 (R5)m
R4 (R5)m
R4 (R5)m

Me 2-SCF2H Me 3-SCF2H Me 4-SCF2H
Me 2-SOCF2H Me 3-SOCF2H Me 4-SOCF2H
Me . 2-SOjCF2H Me 3-S02CF2H Me 4-S02CF2H
CI 2-CF3 CI 3-CF3 CI 4-CF3
CI 2-OCF3 CI 3-OCF3 CI 4-OCF3
C! 2-OCF2H C) 3~OCF2H CI 4-OCF2H
CI 2-OCF2CF2H CI 3-OCF2CF2H C! 4-OCF2CF2H
CI • 2-OCH7CF3 CI 3-OCH2CF3 CI 4-OCH2CF3
CI 2-SCF3 CI 3-SCF3 C] 4-SCF3
CI 2-SOCF3 CI 3-SOCF3 CI 4-SOCF3
CI 2-SG2CF3 CI 3-S02CF3 CI 4-S02CF3
CI 2-SCF2H CI 3-SCF2H CI 4-SCF2H
CI 2-SOCF2H CI 3-SOCF2H C[ 4-SOCF2H
CI 2-S02CF2H CI 3-S02CF2H CI 4-S02CF2H
F 2-CF3 F 3-CF3 F 4-CF3
F 2-OCF3 F 3-OCF3 F 4-OCF3
F 2-OCF2H F 3-OCF2H F 4-OCF2H
F 2-OCF2CF2H F 3-OCF2CF2H F 4-OCF2CF2H
F 2-OCH2CF3 F 3-OCH2CF3 F 4-OCH2CF3
F 2-SCF3 F 3-SCF3 F 4-SCF3
F 2-SOCF3 F 3-SOCF3 F 4-SOCF3
F 2-S02CF3 F 3-SG2CF3 F 4-SO9CF3
F 2-SCF2H F 3-SCF2H F 4-SCF2H
F " 2-SOCF2H ■ F 3-SOCF2H F 4-SOCF2H "
F 2-S02CF2H F 3-S02CF2H F 4-S02CF2H
Br 2-CF3 " Br 3-CF3 Br 4-CF3
Br 2-OCF3 Br 3-OCF3 Br 4-OCF3
Br 2-OCF2H Br 3-OCF2H Br 4-OCF2H
Br 2-OCF2CF2H Br 3-OCF2CF2H Br 4-OCF2CF2H
Br 2-OCH2CF3 Br 3-OCH2CF3 Br 4-OCH2CF3
Br 2-SCF3 Br 3-SCF3 Br 4-SCF3.
Br 2-SOCF3 Br 3-SOCF3 Br 4-SOCF3
Br 2-S02CF3 Br 3-S02CF3 Br 4-S02CF3
Br 2-SCF2H ■ Br 3-SCF2H Br 4-SCF2H
Br 2-SOCF2H • Br 3-SOCF2H Br 4-SOCF2H
Br 2-SO,CF2H : Br 3-S02CF2H Br 4-S02CF2H
I 2-CF3 I 3-CF3 I 4-CF3

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73


WO 02/070483

PCT/US02/06582

74

R4 (R5)m
R4 (R5)m
R4 (R5)m

OCF2H 2-SCF3 OCF2H 3-SCF3 OCF2H 4-SCF3
OCF2H 2-SOCF3 OCF2H 3-SOCF3 OCF2H 4-SOCF3
OCF2H 2-S02CF3 OCF2H 3-S02CF3 OCF2H 4-SO?CF3
OCF2H 2-SCF2H OCF2H 3-SCF2H OCF2H 4-SCF2H
OCF2H 2-SOCF2H OCF2H 3-SOCF2H OCF2H 4-SOCF2H
OCF2H 2-S02CF2H OCF2H 3-S02CF2H OCF2H 4-SO3CF2H
Me 2-Me-4-CF3 F 2-Me-4-CF3 a 2-Me-4-CF3
Me 2-Me-4-OCF3 F 2-Me-4-OCF3 Cl 2-Me-4-OCF3
Me 2-Me-4-OCF2H F 2-Me-4-OCF2H Cl 2-Me-4-OCF2H
Me 2-Me-4-OCH2CF3 F 2-Me-4-OCH2CF3 C! 2-Me-4-OCH2CF3
Me 2-Me-4-SCF3 F 2-Me-4-SCF3 Cl 2-Me-4-SCF3
Me 2-Me-4-SOCF3 F 2-Me-4-SOCF3 Cl 2-Me-4-SOCF3
.Me 2-Me-4-S02CF3 F 2-Me-4-S02CF3 CI 2-Me-4-S02CF3
Me 2-Me-4-SCF2H F 2-Me-4-SCF2H Ci 2-Me-4-SCF2H
Me 2-Me-4-SOCF2H F 2-Me-4-SOCF2H Cl 2-Me-4-S0CF2H
Me 2-Me-4-S02CF2H F 2-Me-4-S02CF2H Cl 2-Me-4-S02CF2H
Br 2-Me-4-CF3 2-Me-4-CF3 OMe 2-Me-4-CF3
Br 2-Me-4-OCF3 2-Me-4-OCF3 OMe 2-Me-4-0CF3
Br 2-Me-4-OCF2H 2-Me-4-OCF2H OMe 2-Me-4-0CF2H
Br 2-Me^-OCH2CF3 2-Me-4-OCH2CF3 OMe 2-Me^-OCH2CF3
Br 2-Me-4-SCF3 2-Me^-SCF3 OMe 2-Me^-SCF3
Br 2-Me-4-SOCF3 2-Me^-SOCF3 OMe 2-Me-4-SOCF3
Br 2-Me-4-S02CF3 2-Me-4-S02CF3 OMe 2-Me^-S02CF3
Br 2-Me-4-SCF2H 2-Me-4-SCF2H OMe 2-Me-4-SCF2H
Br 2-Me-4-SOCF2H 2-Me-4-SOCF2H OMe 2-Me-4-SOCF2H
Br 2-Me-4-S02CF2H 2-Me-4-S02CF2H OMe 2-Me-4-SO?CF2H
CF3 2-Me-4-CF3 N02 2-Me^~CF3 SMe 2-Me-4-CF3
CF3 2-Me-4-OCF3 . N02 2-Me^-OCF3 SMe 2-Me-4-OCF3
CF3 2-Me^-OCF2H N02 2-Me-4-OCF2H SMe 2-Me-4-OCF2H
CF3 2-Me-4-OCH2CF3 N02 2-Me-4-OCH2CF3 SMe 2-Me-4-OCH2CF3
CF3 2-Me-4-SCF3 N02 2-Me-4-SCF3 SMe 2-Me-4-SCF3
CF3 2-Me-4-SOCF3 N02 2-Me-4-SOCF3 . SMe 2-Me-4-SOCF3
CF3 2-Me-4-S02CF3 N02 2-Me-4-S02CF3 SMe 2-Me-4-S02CF3
CF3 2-Me-4-SCF2H N02 2-Me-4-SCF2H SMe 2-Me-4-SCF2H
CF3 2-Me^-SOCF2H ■ -N02 2-Me-4-SOCF2H SMe 2-Me-4-SOCF2H
CF3 2-Me-4-S02CF2H N02 2-Me^-.S02CF2H." SMe 2-Me-4-S02CF2H

^ WO 02/070483

PCT/US02/06582









g4





ffi^im 7: >






mhm
Me 2-CF3 Me 3-CF3. Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF2H Me 3-OCF2H Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH2CF3 Me 4-OCH2CF3
Me 2-SCF3 Me 3-SCF3 Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2-S02CF3 Me 3-S02CF3 Me 4-S02CF3
Me 2-SCF2H Me 3-SCF2B Me 4-SCF2H
Me 2-SOCF2H Me 3-SOCF2H Me 4-SOCF2H
Me 2-S02CF2H Me 3-S02CF2H Me 4-S02CF2H
CI 2-CF3 CI 3-CF3 CI 4-CF3
CI 2-OCF3 CI 3-OCF3 CI 4-OCF3
CI 2-OCF2H CI 3-OCF2H CI 4-OCF9H
CI 2-OCF2CF2H Ci 3-OCF2CF2H CI 4-OCF2CF2H
CI 2-OCH2CF3 CI 3-OCH2CF3 CI 4-OCH2CF3
CI 2-SCF3 CI 3-SCF3 CI 4-SCF3
CI 2-SOCF3 CI 3-SOCF3 CI 4-SOCF3
ci ■ 2-S02CF3 CI 3-SO2CF3 CI 4-S02CF3
CI 2-SCF2H CI 3-SCF2H CI 4-SCF2H
CI 2-SOCF2H CI 3-SOCF2H - CI 4-SOCF2H
CI 2-S02CF2H CI 3-S02CF2H CI 4-S02CF2H
F 2-CF3 F 3-CF3 F 4-CF3
F 2-OCF3 F 3-OCF3 -F 4-OCF3
F 2-OCF2H "■ . . F 3-OCF2H F 4-OCF2H
F 2-OCF2CF2H F 3-OCF2CF2H F 4-OCF2CF2H
F 2-OCH2CF3 F 5-OCH2CF3 "F 4-OCH2CF3

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76


R4 (R5)m

F 2-SCF3
F 2-SOCF3
F 2-S02CF3
F 2-SCF2H
F 2-SOCF2H
F 2-S02CF2H
Br 2-CF3
Br 2-OCF3
Br 2-OCF2H
Br 2-OCF2CF2H
Br 2-OCH2CF3
Br 2-SCF3
Br 2-SOCF3
Br 2-S02CF3
Br . 2-SCF2H
Br 2-SOCF2H
Br 2-S02CF2H
2-CF3
2-OCF3
2-OCF2H
2-OCF2CF2H
2-OCH2CF3
2-SCF3
2-SOCF3
2-S02CF3
2-SCF2H
2-SOCF2H
2-S02CF2H
OMe 2-CF3
OMe 2-OCF3
OMe 2-OCF2H
OMe 2-OCF2CF2H
OMe 2-OCH2CF3
OMe 2^SCF3
OMe 2-SOCF3
OMe 2-S02CF3"
OMe 2-SCF7H


R4 (R5)m

F " 3-SCF3 ■
F 3-SOCF3
F 3-S02CF3
F 3-SCF2H
F 3-SOCF2H
F 3-S02CF2H
Br 3-CF3
Br 3-OCF3
Br 3-OCF2H
Br 3-OCF2CF2H
Br 3-OCH2CF3
Br 3-SCF3
Br 3-SOCF3
Br 3-SO7CF3
Br 3-SCF2H
Br 3~SOCF2H
Br 3-S02CF2H
3-CF3
3-OCF3
3-OCF2H
3-OCF2CF2H
3-OCH2CF3
3-SCF3
3-SOCF3
3-S02CF3
3-SCF2H
3-SOCF2H
3-S02CF2H
OMe 3-CF3
OMe 3-OCF3
OMe 3-OCF2H
OMe 3-OCF2CF2H
OMe 3-OCH2CF3
OMe 3-SCF3
OMe 3-SOCF3
OMe 3-S02CF3
OMe 3-SCF7H


R4 (R5)m

F 4-SCF3
F 4-SOCF3
F 4-S02CF3
F 4-SCF2H
F 4-SOCF2H
F 4-S02CF2H
Br 4-CF3
Br 4-OCF3
Br 4-OCF2H
Br 4-OCF2CF2H
Br 4-OCH2CF3
Br 4-SCF3
Br 4-SOCF3
Br 4-S02GF3
Br 4-SCF2H
Br 4-S0CF2H
Br 4-S02CF2H
4-CF3
4-OCF3
4-0CF2H
4-0CF2CF2H
4-0CH2CF3
4-SCF3
4-SOCF3
4-S02CF3
4-SCF2H
4-SOCF2H
4-S02CF2H
OMe 4-GF3
OMe 4-OCF3
OMe 4-OCF2H
OMe 4-OCF2CF2H
OMe 4-OCH7CF3
OMe 4-SCF3
OMe 4-SOCF3
OMe 4-S02CF3
OMe 4-SCF2H



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78

R4
(R5)m R4
(R5)m
R4
(R5)m

Br 2-Me-4-OCH2CF3 2-Me^-OCH2CF3 OMe 2-Me-4-OCH2CF3
Br 2-Me-4-SCF3 2-Me-4-SCF3 OMe 2-Me-4-SCF3
Br 2-Me-4-SOCF3 2-Me-4-SOCF3 OMe 2-Me-4-SOCF3
Br 2-Me-4-S02CF3 2-Me-4-S02CF3 OMe 2-Me-4-S02CF3
Br 2-Me-4-SCF2H 2-Me-4-SCF2H OMe 2-Me-4-SCF2H
Br 2-Me-4-SOCF2H 2-Me-4-SOCF2H OMe 2-Me-4-SOCF2H
Br 2-Me^-S02CF2H 2-Me-4-S02CF2H OMe 2-Me-4-S02CF2H
CF3 2-Me-4-CF3 N02 2-Me-4-CF3 SMe 2-Me-4-CF3
CF3 2-Me-4-OCF3 N02 2-Me-4-OCF3 SMe 2-Me-4-0CF3
CF3 2-Me-4-OCF2H N02 2-Me-4-OCF2H SMe 2-Me-4-OCF2H
CF3 2-Me-4-OCH2CF3 N02 2-Me-4-OCH2CF3 SMe 2-Me-4-OCH2CF3
CF3 2-Me-4-SCF3 NC"2 2-Me-4-SCF3 SMe 2-Me-4-SCF3
CF3 2-Me-4-SOCF3 N02 2-Me-4-SOCF3 SMe 2_Me-4-SOCF3
CF3 2-Me-4-S02CF3 N02 2_Me-4-S02CF3 SMe 2-Me-4-S02CF3
CF3 2-Me-4-SCF2H N02 2-Me-4-SCF2H SMe 2-Me-4-SCF2H
CF3 2-Me-4-SOCF2H N02 2-Me-4-SOCF2H SMe 2-Me-4-SOCF2H
CF3 2-Me-4-S02CF2H N02 2-Me-4~S02CF2H SMe 2-Me-4-S02CF2H
Tabl el2
-
El (Shm El ®hm - El (E^)rn
Me 2-CF3 Me 3-CF3 Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF2H Me 3-OCF2H Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me • 4-OCF2CF2H
Me 2-OCH7CF3 Me 3-OCH2CF3 Me 4-OCH7CF3
Me 2-SCF3 . Me 3-SCF3 Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3. Me 4-SOCF3
Me 2-S02CF3 Me 3-S02Cl *n Me 4-S02CF3

WO 02/070483 PCT/DS02/06582
79

R4 (R5)m
R4
(R5)m
R4
(R5)m
Mc 2^SCF2H Me 3-SCF2H Me 4-SCF2H
Me 2-SOCF2H Me 3-SOCF2H Me 4-SOCF2H
Me 2-S02CF2H Me 3-S02CF2H Me 4-S02CF2H
CI 2-CF3 CI 3-CF3 CI ■ 4-CF3
CI " 2-OCF3 CI 3-OCF3 CI 4-OCF3
CI 2-OCF2H CI 3-OCF2H CI 4-OCF2H
CI 2-OCF2CF2H CI 3-OCF2CF2H CI 4-OCF2CF2H
CI 2-OCH2CF3 Ci 3-OCH2CF3 CI 4-OCH2CF3
CI 2-SCF3 CI 3-SCF3 CI 4-SCF3
CI 2-SOCF3 C! 3-SOCF3 CI 4-SOCF3
CI 2-S02CF3 CI 3-S02CF3 CI 4-S02CF3
CI 2-SCF2H CI 3-SCF2H CI 4-SCF2H
CI 2-SOCF2H CI 3-SOCF2H CI 4-SOCF2H
CI 2-S02CF2H CI 3-S02CF2H CI 4-S02CF2H
F ■ 2-CF3 F 3-CF3 F 4-CF3
F 2-OCF3 F 3-OCF3 F 4-OCF3
F 2-OCF2H F 3-OCF2H F 40CF2H
F 2-OCF2CF2H F 3-OCF2CF2H F 4-OCF2CF2H
F 2~OCH2CF3 F 3-OCH2CF3 F 4-OCH2CF3
F 2-SCF3 F 3-SCF3 F 4-SCF3
- F 2-SOCF3 F 3-SOCF3 F 4-SOCF3
F 2-S02CF3 F 3-S02CF3 F 4-S02CF3
F 2-SCF2H F 3-SCF2H F 4-SCF2H
F 2-SOCF2H F 3>SOCF2H F 4-SOCF2H
F 2-S02CF2H F 3-S02CF2H F 4-S02CF2H
Br 2-CF3 ■ Br 3-CF3 Br 4-CF3
Br 2-OCF3 Br 3-OCF3 Br 4-OCF3
Br 2-OCF2H Br 3-OCF2H Br 4-OCF2H
Br 2-OCF2CF2H Br 3-OCF2CF2H Br 4-OCF2CF2H
Br 2-OCH2CF3 Br 3-OCH2CF3 Br 4-OCH2CF3
Br 2-SCF3 Br 3-SCF3 Br 4-SCF3
Br 2-SOCF3 Br 3-SOCF3 Br 4-SOCF3
Br 2-S02CF3 Br 3-SO0CF3 Br 4-S02CF3
■Br 2-SCF2H Br 3-SCF2H Br 4-SCF7H
Br 2-SOCF2H Br 3-SOCF2H Br 4-SOCF2H
.Br 2-S02CF2H Br 3-S02CF2H Br 4-S02CF2H
I 2-CF3 I 3-CF3 I 4-CF3

WO 02/070483


WO 02/070483 PCT/US02/06582
i

R4
(R5m)
R4
(R5m)
R4 (R5m)

OCF2H 2-SCF3 OCF2H 3-SCF3 OCF2H 4-SCF3
OCF2H 2-SOCF3 OCF2H 3-SOCF3 OCF2H 4-SOCF3
OCF2H 2-S02CF3 OCF2H 3-S02CF3 OCF2H 4-S02CF3
OCF2H 2-SCF7H OCF2H 3-SCF9H OCF2H 4-SCF2H
OCF2H 2-SOCF2H OCF2H 3-SOCF2H OCF2H 4-SOCF2H
OCF2H 2-S02CF2H OCF2H 3-S02CF2H OCF2H 4-S02CF2H
Me 2-Me-4-CF3 F 2-Me-4-CF3 CI 2-Me-4-CF3
Me 2-Me-4-OCF3 F 2-Me-4-OCF3 CI 2-Me^-OCF3
Me 2-Me-4-OCF2H F 2-Me-4-OCF2H CI 2-Me-4-OCF2H
Me 2-Me^-OCH2CF3 F 2-Me-4-OCH2CF3 CI 2-Me-4^0CH2CF3
Me 2-Me-4-SCF3 F 2-Me-4-SCF3 CI 2-Me-4-SCF3
Me 2-M&4-SOCF3 F 2-Me-4-SOCF3 CI 2-Me-4-SOCF3
Me 2-Me-4-S02CF3 F 2-Me-4-S02CF3 CI 2-Me-4-S02CF3
Me 2-Me-4-SCF2H F 2-M,e-4-SCF2H CI 2-Me-4-SCF2H
Me 2-Me-4-SOCF2H F 2-Me-4-SOCF2H CI 2-Me-4-SOCF2H
Me 2-Me-4-S02CF2H F 2-Me-4-S02CF2H CI 2-Me-4-S02CF2H
Br 2-Me-4-CF3 I 2-Me-4-CF3 OMe 2-Me-4-CF3
Br 2-Me-4-OCF3 I 2-Me-4-OCF3 OMe 2-Me-4-OCF3
Br 2-Me-4-OCF2H 2-Me-4-OCF2H OMe 2-Me^-OCF2H
Br 2-Me^t-OCH2CF3 2-Me-4-OCH2CF3 OMe 2-Me-4-OCH2CF3
Br 2-Me-4-SCF3 2-Me-4-SCF3 OMe 2-Me-4-SCF3
Br 2-Me-4-SOCF3 2-Me^-SOCF3 OMe 2-Me^-SOCF3
Br 2-Me-4-S02CF3 2-Me-4>S02CF3 OMe 2-Me-4-S02CF3
Br 2-Me-4-SCF2H 2-Me-4-SCF2H OMe 2-Me-4-SCF2H
Br 2-Me-4-SOCF2H 2-Me-4-SOCP2H OMe 2-Me^-SOCF2H
Br 2-Me-4-S02CF2H 2-Me-4-S02CF2H OMe 2-Me-4-S02CF2H
CF3 2-Me-4-CF3 N02 2-Me-4-CF3 SMe 2-Me-4-CF3
CF3 2-Me^-OCF3 N02 2-Me-4-OCF3 SMe ,2-Me-4-OCF3
CF3 2-Me-4-OCF2H N02 2-Me-4-OCF2H SMe 2-Me-4-OCF2H
CF3 2-Me-4-OCH2CF3 N02 2-Me-4-OCH2CF3 SMe 2-Me-4-OCH2CF3
CF3 2-Me-4-SCF3 NO? 2-Me-4-SCF3- SMe 2-Me-4-SCF3
CF3 2-Me-4-SOCF3 N02 2-Me-4-SOCF3 SMe 2-Me-4-SOCF3
CF3 2-Me-4-S02CF3 N02 2-Me^-S02CF3 SMe 2-Me-4-S02CF3
CF3 2-Me-4-SCF2H . ■., JMO2 2-Me-4-SCF2H SMe 2-Me-4-SCF2H
CF3 2-Me-4-SOCF2H N02 2-Me-4-SOCF2H SMe 2-Me-4-SOCF2H"
CF3 2-Me-4-S02CF2H " N02. 2-Me-4-S02CF2Hj SMe 2-Me-4-S02CF2H

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Table 13



•

N^ >
M
I \ H
y
-T ^(/-Pr)




R4 (R5m) R4 (R5m)
R4 (R5m)

Me 2-CF3 Me 3-CF3 Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF2H Me 3-OCF2H . Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH7CF3 Me 4-OCH2CF3
Me 2-SCF3 Me 3-SCF3 Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2-S02CF3 Me 3-S02CF3 Me 4-S02CF3
Me 2-SCF2H Me 3-SCF2H Me 4-SCF7H
Me 2~SOCF2H Me 3-SOCF2H Me 4-SOCF2H
Me 2-S02CF2H Me 3-S02CF2H Me 4-S02CF2H
CI 2-CF3 CI 3-CF3 CI 4-CF3
CI 2-OCF3 CI 3-OCF3 C! 4-OCF3
■CI 2-OCF2H CI 3-OCF2H ■CI 4-OCF2H
CI 2-OCF2CF2H CI 3-OCF2CF2H CI 4-OCF2CF2H
CI 2-OCH2CF3 CI 3-OCH7CF3 CI 4-OCH2CF3
CI 2-SCF3 CI 3-SCF3 CI 4-SCF3
CI 2-SOCF3 CI 3-SOCF3 CI 4-SOCF3
CI 2-S02CF3 CI 3-SQ2CF3 CI 4-S02CF3
CI 2-SCF2H CI 3^SCF2H CI . 4,SCF2H
CI 2-SOCF2H CI 3-SOCF2H CI 4-SOCF2H
CI 2-S02CF,H CI 3-S02CF2H CI 4-S02CF2H
F 2-CF3 F 3-CF3 F 4-CF3
.F 2-OCF3 F 3-OCF3 F 4-OCF3
F 2-OCF2H F. . 3-OCF2H _ F 4-OCF2H
F . 2-OCF2CF2H F 3-OCF2CF2H F 4-OCF2CF2H
F 2-OCH2CF3 F 3-OCH2CF3 F 4-OCH2CF3



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R4 (R5)n
R4 (R5)n
R4 (R5)n

OMe 2-SOCF2H OMe 3-SOCF2H OMe 4-SOCF2H
OMe 2~S02CF2H OMe 3-S02CF2H OMe 4-SO,CF2H
CF3 2-CF3 CF3 3-CF3 CF3 4-CF3
CF3 2-OCF3 CF3 3-OCF3 CF3 4-OCF3
CF3 2-OCF2H CF3 3-OCF2H CF3 4-OCF7H
CF3 2-OCF2CF2H CF3 3-OCF2CF2H CF3 4-OCF2CF2H
CF3 2-OCH2CF3 CF3 3-OCH2CF3 CF3 4-OCH2CF3
CF3 2-SCF3 CF3 3-SCF3 CF3 4-SCF3
CF3 2-SOCF3 CF3 3-SOCF3 ■ CF3 4-SOCF3
CF3 2-S02CF3 CF3 3-SO2CF3 CF3 4-S02CF3
CF3 2-SCF2H CF3 3-SCF2H CF3 4-SCF2H
CF3 2-SOCF2H CF3 3-SOCF2H CF3 4-SOCF2H
CF3 2-S02CF2H CF3 3-S02CF2H CF3 4-S02CF2H
OCF2H 2-CF3 OCF2H 3-CF3 OCF2H 4-CF3
OCF2H 2-OCF3 OCF2H 3-OCF3 OCF2H 4-OCF3
OCF2H 2-OCF2H OOF2H 3-OCF2H OCF2H 4-OCF2H
OCF2H 2-OCF2CF2H OCF2H 3-OCF2CF2Kf OCF2H 4-OCF2CF2H
OCF2H 2-OCH2CF3 OCF2H 3-OCH2CF3 OCF2H 4-OCH2CF3
OCF2H 2-SCF3 OCF2H 3-SCF3 OCF2H 4-SCF3
OCF2H 2-SOCF3 OCF2H 3-SOCF3 OCF2H 4-SOCF3
OCF2H 2~S02CF3 OCF2H 3-S02CF3 OCF2H 4-S02CF3
OCF2H 2-SCF2H OCF2H 3-SCF2R OCF2H 4-SCF2H
OCF2H 2-SOCF2H OCF2H 3-SOCF2H OCF2H 4-SOCF2H
OCF2H 2-S02GF2H OCF2H 3-S02CF2H OCF2H 4-S02CF2H
Me 2-Me-4-CF3 F 2-Me-4-CF3 CJ 2-Me^-CF3
Me 2-Me-4-OCF3 F 2-Me-4-OCF3 CI 2-Me-4-OCF3
Me 2-Me-4-OCF2H F 2-Me-4-OCF2H CI 2-Me-4-OCF2H
Me 2-Me-4-OCH2CF3 F 2-Me-4-OCH2CF3 CI 2-Me-4-OCH2CF3
Me 2-Me-4-SCF3 ■F 2-Me-4-SCF3 CI . 2-Me-4-SCF3
Me 2-Me-4-SOCF3 F 2-Me^-SOCF3 CI 2-Me-4- Ot:;F3
Me 2-Me-4-S02CF3 F 2-Me-4-S02CF3 CI 2-Me-4-S02CF3
Me 2-Me-4-SCF2H F 2-Me-4-SCF2H CI 2-Mc-4-SCF2E
Me 2-Me-4-SOCF2H F 2-Me^-SOCF2H CI 2-Me-4-SOCF2H
Me 2-Me^-SO,CF2H F 2-Me-4-S02CF2H CI 2-Me-4TS02CF2H
Br 2-Me-4-CF3" I 2-Me-4-CF3 OMe 2-Me-4-CF3
Br 2-Me-4-OCF3 I 2-Me-4-OCF3 OMe 2-Me-4-OCF3
Br 2-Me-4-OCF2H I 2-Me-4-OCF2H OMe 2-Me-4-OCF2H

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R4 (R5)n R4
(R5)n R4
(R5)n
Br 2-Me-4-OCH2CF3 2-Me-4-OCH2CF3 OMe 2-Me-4-OCH2CF3
Br 2-Me-4-SCF3 2-Me-4-SCF3 OMe 2-Me-4-SCF3
Br 2-Me-4-SOCF3 2-Me^-SOCF3 OMe 2-Me-4-SOCF3
Br 2-Me-4-S02CF3 2-Me^-S02CF3 OMe 2-Me-4-S02CF3
Br 2-Me-4-SCF2H 2-Me-4-SCF2H OMe 2-Me-4-SCF2H
Br 2-Me-4-SOCF2H 2_Me-4-SOCF2H OMe 2-Me-4-SOCF2H
Br 2-Me-4-S02CF2H 2-Me-4-S02CF2H OMe 2-Me-4-S02CF2H
CF3 2-Me-4-CF3 N02 2-Me-4-CF3 SMe 2-Me-4-CF3
CF3 2-Me-4-OCF3 N02 2-Me-4-OCF3 SMe 2-Me-4-OCF3
CF3 2-Me-4-OCF2H N02 2-Me-4-OCF2H SMe 2-Me^-OCF2H
CF3 2-Me-4-OCH2CF3 N02 2-Me-4-OCH2CF3 SMe 2-Me^-OCH2CF3
CF3 2-Me-4-SCF3 .N02 2-Me-4-SCF3 . SMe 2-Me^-SCF3
CF3~ 2-Me-4-SOCF3 N02 2-Me-4-SOCF3 SMe 2-Me-4-SOCF3
CF3 2-Me-4-S02CF3 N02 2-Me-4-S02CF3 SMe 2-Me-4-S02CF3
CF3 2-Me^-SCF2H N02 2-Me-4-SCF2H SMe 2-Me-4-SCF2H
CF3 2-Me-4-SOCF2H N02 2-Me-4-SOCF2H SMe 2-Me-4-SOCF2H
CF3
2-Me-4-S02CF2H
N02
L J 2-Me^-S02CF2H Table 14 ■ SMe
n 2-Me-4-S02CF2H



R4
(R5)n
R4
(R5)n
R4
(R5)n

Me 2-CF3 Me 3-CF3 Me 4-CF3
Me 2-OCF3 Me 3-OCF3 Me 4-OCF3
Me 2-OCF9H Me 3-OCF2H Me 4-OCF2H
Me 2-OCF2CF2H Me 3-OCF2CF2H Me 4-OCF2CF2H
Me 2-OCH2CF3 Me 3-OCH9CF3 Me 4-OCH2CF3
Me 2-SCF3 Me . 3-SCF3 . Me 4-SCF3
Me 2-SOCF3 Me 3-SOCF3 Me 4-SOCF3
Me 2-S02CF3 Me 3-S02CF3 Me 4-S02CF3

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.86

R4 (R5)n R4 (R5)n R4 (R5)n
Me 2-SCF2H Me 3-SCF2H Me 4-SCF9H
Me 2-SOCF2H Me 3-SOCF2H Me 4-SOCF2H
Me • 2-S02CF2H Me 3-S02CF2H . Me 4-S02CF2H
CI 2-CF3 CI 3-CF3 CI 4-CF3
CI 2-OCF3 CI 3-OCF3 CI 4-OCF3
CI 2-OCF2H CI 3-OCF2H CI 4-OCF2H
CI 2-OCF2CF2H CI 3-OCF2CF2H CI 4-OCF2CF2H
CI 2-OCH?CF3 CI 3-OCH2CF3 CI 4-OCH2CF3
CI 2-SCF3 CI 3-SCF3 CI 4-SCF3
CI 2-SOCF3 CI 3-SOCF3 CI 4-SOCF3 ■
CI 2-S02CF3 CI 3-S02CF3 " CI 4-S02CF3
CI 2-SCF2H CI 3-SCF2H CI 4-SCF2H
CI 2-SOCF2H CI 3-SOCF2H CI 4-SOCF2H
CI 2-S02CF2H CI 3-S02CF2H CI 4-S02CF2H
F 2-CF3 F 3-CF3 F 4-CF3
"F 2-OCF3 F 3-OCF3 F 4-OCF3
F 2-OCF2H F 3-OCF2H F 4-OCF2H
F 2-OCF2CF2H F 3-OCF2CF2H F 4-OCF2CF2H
F 2-OCH2CF3 F 3-OCH2CF3 F 4-OCH2CF3
F 2-SCF3 F 3-SCF3 F 4-SCF3
F 2-SOCF3 F 3-SOCF3 F 4-SOCF3
F 2-S02CF3 F 3-S02CF3 F 4-SO7CF3
F 2-SCF2H F 3-SCF2H F 4-SCF2H
F 2-SOCF2H F 3-SOCF2H F 4-SOCF7H
F 2~S02CF2H F 3-S02CF2H F 4-S02CF2H
Br 2-CF3 Br 3-CF3 Br 4-CF3
Br 2-OCF3 Br 3-OCF3 Br 4-OCF3
Br 2-OCF2H Br 3-OCF2H Br 4-OCF2H
Br 2-OCF2CF2H Br 3-OCF2CF2H Br 4-OCF2CF2H
Br 2-OCH2CF3 Br 3-OCH2CF3 Br 4-OCH2CF3
Br 2-SCF3 Br 3-SCF3 Br 4-SCF3
Br 2-SOCF3 Br 3^SOCF3 Br 4-SOCF3
Br 2-S02CF3 Br 3-S02CF3 Br 4-S02CF3
Br 2-SCF2H Br 3-SCF2H Br 4-SCF2H
Br 2-SOCF2H ■Br 3-SOCF2H Br 4-SOCF2H
Br 2-S02CF2H Br 3-S02CF2H Br 4-S02CF2H
I 2-CF3 I 3-CF3 I 4-CF3







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PCT/US02/06582



K R3 (R4)n R5.
K-l /-Pr 4-C1 CF3
K-18 /-Pr 4-Me CF3
K-18 /-Pr 4-C1 CF3
K-14 /-Pr 1-Me CF3
K-28 /-Pr 4-Me CF3
K-28 /-Pr 4-C1 CF3
K-30 /-Pr 5-Me CF3
K-30 /-Pr 5-C1 CF3
K-31 /-Pr 2-Me CF3
K-31 /-Pr 2-Cl CF3
K-33 /-Pr 6-Mc CF3
K-33 /-Pr 6-C1 , CF3
K-l /-Bu 4-Me CF3
K-l /-Bu 4-C1 CF3
K-18 /-Bu 4-Me CF3
K-18 /-Bu 4-CI CF3
K-14 /-Bu 1-Me CF3
K-28 /-Bu 4-Me CF3
K-28 /-Bu 4-CI CF3
K-30 /-Bu 5-Me CF3
K-30 /-Bu 5-C1 CF3
K-31 /-Bu 2-Me CF3
K-31 /-Bu 2-Cl CF3
K-33 /-Bu 6-Me CF3
K-33 f-Bu 6-C1 CF3
K-l /-Bu 4-Me CF3
K-l /-Bu 4-CI CF3
K-18 /-Bu 4-Me CF3
K-18 /-Bu 4-CI CF3
K-14 /-Bu 1-Me CF3
K-28 /-Bu 4-Me CF3
K-28 /-Bu 4-CI CF3
K-30 /-Bu 5-Me CF3
K-30 /-Bu 5-C1 CF3
K-31 /-Bu 2-Me ■ CF3
■K-31 /-Bu 2-Cl CF3
K-33 /-Bu 6-Me CF3


w X Y Z
CMe CH N CH
CMe CH N CH
CMe CH N CH
CMe CH N CH
CMe CH CH N
CMe CH CH N
CMe CH CH N
CMe CH CH N
CMe . CH CH N
CMe CH CH N
CMe CH CH N
CMe CH CH N
CMe N ■ CH CH
CMe N CH CH
CMe N CH CH
CMe N CH CH
CMe N CH CH
CMe N ■■ CH CH
CMe N CH CH
CMe N CH CH
CMe N CH CH
CMe ■ N CH CH
CMe N CH CH
CMe N CH CH
CMe N CH CH
CMe CH N CH
CMe CH N CH
■CMe CH N CH
CMe CH N CH
CMe CH N CH
CMe CH N , CH
CMe CH N CH
CMe CH N CH
CMe CH N CH
CMe CH N CH
CMe CH N CH
CMe CH N CH

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K R3 (R4)n R5 • w X 1 " 2
K-33 /-Bu 6-C1 CF3 CMe CH N CH
K-1 /-Bu 4-Me CF3 CMe CH N CH
K-1 /-Bu 4C1 CF3 CMe CH N CH
K-18 /-Bu 4-Me CF3 CMe CH N CH
K-18 r-Bu 4-C1 CF3 CMe CH N CH
K-14 /-Bu 1-Me CF3 CMe CH N CH
K-28 /-Bu 4-Me CF3 CMe CH CH N
K-28 /-Bu 4-CI CF3 CMe CH CH N
K-30 /-Bu 5-Me CF3 CMe CH CH N
K-30 /-Bu 5-C1 CF3 CMe CH CH N
K-31 /-Bu 2-Me CF3 CMe CH CH N
K-31 /-Bu 2-Cl . CF3 CMe CH CH N
K-33 /-Bu • 6-Me CF3 CMe CH CH N
K-33 /-Bu 6-C1 CP3 CMe CH CH M
K-1 /-Pr 4-Me OCF3 CMe N CH CH
K-1 /-Pr 4-CI OCF3 CMe N CH CH
K-18 /-Pr 4-Me OCF3 CMe N CH CH
K-18 /-Pr 4-CI OCF3 CMe N CH CH
K-14 /-Pr 1-Me OCF3 CMe N CH CH
K-28 i-Pr 4-Me OCF3 CMe N CH CH
K-28 i-Pr 4-CI OCF3 CMe N CH CH
K-30 /-Pr 5-Me OCF3 CMe N CH CH
K-30 /-Pr 5-C1 OCF3 CMe N CH CH
K-31 /-Pr 2-Me OCF3 CMe N CH CH
K-31 /-Pr 2-Cl OCF3 CMe N CH CH
K-33 /-Pr 6-Me OCF3 CMe N CH CH
K-33 /-Pr 6-Ci OCF3 CMe N CH CH
K-1 /-Pr 4-Me OCF3 CH N CH CH
K-1 /-Pr 4-CI OCF3 CH N CH CH
K-18 /-Pr 4-Me OCF3 CH N CH CH
K-18 /-Pr 4-CI OCF3 CH N CH CH
K-14 /-Pr 1-Me OCF3 CH N CH CH
K-28 /-Pr 4-Me OCF3 CH N CH CH
K-28 /-Pr 4-CI OCF3 CH , N CH CH
K-30 /-Pr 5-Me -" ■ OCF3 CH • N CH ■ CH
K-30 /-Pr 5-CI OCF3 CH N CH CH
K-31 /-Pr 2-Me OCF3 CH N CH CH

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K (R4)n Q R5 w X Y Z
K-31 /-Pr 2-C1 OCF3 CH N CH CH
K-33 /-Pr 6-Me OCF3 CH N CH CH
K-33 /-Pr 6-CI OCF3 CH N CH CH
K-1 /-Pr 4-Me CI CMe CH CH N
K-1 /-Pr 4-Cl CI CMe CH CH N
K-18 /-Pr 4-Me CI CMe CH CH N
K-18 /-Pr 4-Cl CI CMe CH CH N
K-14 /-Pr 1-Me CI CMe CH CH N
K-28 /-Pr 4-Me CI CMe CH CH N
K-28 /-Pr 4-Cl CI CMe CH CH N
K-30 /-Pr 5-Me CI CMe CH CH N
K-30 /-Pr 5-C1 . ■■;i CMe CH CH N
K-31 /-Pr 2-Me CI CMe CH CH N
K-31 /-Pr 2-CI Cl CMe CH CH N
K-33 /-Pr 6-Me Cl CMe CH CH N
K-33 i-Pr 6-CI Cl CMe CH CH N
Table 16
x=X

R3 is /-Pr

K (R4)n Q X Y Z
K-1 4-Me NCHF2 CMe N CH
K-1 4-Cl NCHF2 CMe N CH
K-18 4-Me NCHF2 CMe N CH
K-18 4-Cl NCHF2 CMe K CH
K-14 1-Me NCHF2 CMe N CH
K-28 4-Me NCHF2 CMe N CH
K-28 4-Cl NCHF2 CMe N CH
K-30 5-Me NCHF2 CMe N CH
K-30 5-C1 NCHF2 CMe N CH



WO 02/070483 PCT/US02/06582
94 R3 is /-Pr

K (R4) Q X Y Z
K-28 4-C1 NCH2CF3 CMe N CH
K-30 5-Me NCH2CF3 CMe N CH
K-30 5-C1 NCH2CF3 CMe N CH
K-3] 2-Me NCH2CF3 CMe N CH
K-31 2-C1 NCH2CF3 CMe N CH
K-33 6-Me NCH2CF3 CMe N CH
K-33 6-C1 NCH2CF3 CMe N CH
K-l 4-Me NCH2CF3 CH N CMe
K-l 4-C1 NCH2CF3 CH . N CMe
K-18 4-Me NCH2CF3 CH N CMe
K-18 4-C1 NCH2CF3 CH N CMe
K-14 1-Me NCH2CF3 CH N CMe
K-28 4-Me NCH2CF3 CH N CMe
K-28 . 4-C1 NCH2CF3 CH N CMe
K-30 5-Me NCH2CF3 CH N CMe
K-30 5-C1 NCH2CF3 CH N CMe
K-31 2-Me NCH2CF3 CH N CMe
K-31 2-CI NCH2CF3 CH N CMe
K-33 6-Me NCH2CF3 CH N CMe
K-33 6-CI NCH2CF3 CH N CMe
K-l 4-Me NCF2CHF2 N CH" CMe
K-l 4-C1 NCF2CHF2 N CH CMe
K-18 4-Me NCF2CHF2 N CH CMe
K-18 4-C1 NCF2CHF2 N CH CMe
K-14 1-Me NCF2CHF2 N CH CMe
K-28 4-Me NCF2CHF? N CH CMe
K-28 4-C1 NCF2CHF2 N CH CMe
K-30 5-Me NCF2CHF2 N CH CMe
K-30 5-C1 NCF2CHF2 N CH CMe
K-31 2-Me NCF2CHF2 N CH CMe
K-31 2-CI NCF2CHF2 N CH CMe
K-33 6-Me NCF2CHF2 N CH CMe
K-33 6-CI NCF2CHF2 N CH CMe

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95
R3 is f-Bu

K (R4)n 0_ X Y z
K-l 4-Me NCHF? CMe N CH
K~l 4-C1 NCHF2 CMe N CH
K-18 4-Me NCHF2 CMe N CH
K-18 4-C1 NCHF2 CMe N CH
K-14 1-Me NCHF2 CMe N CH
K-28 4-Me NCHF2 CMe N CH
K-28 4-C1 NCHF2 CMe N CH
K-30 5-Me NCHF2 CMe N CH
K-30 5-C1 NCHF2 CMe N CH
K-31 2-Me NCHF2 CMe N CH
K-31 2-C1 NCHF2 CMe N CH
K-33 6-Me NCHF2 ■CMe N CH
K-33 6-C1 NCEF2 CMe N CH
K-l . 4-Me NCHF2 CH N CMe
K-l 4-C1 NCHF2 CH N CMe
K-18 4-Me NCHF2 CH N CMe
K-18 4-C1 NCHF2 CH N CMe
K-14 1-Me NCHF2 CH N CMe
K-28 4-Me NCHF2 CH N CMe
K-28 4-C1 NCHF2 CH N CMe
K-30 5-Me NCHF2 CH N CMe
K-30 5-Cl NCHF2 CH N CMe
K-31 2-Me NCHF2 CH N CMe
K-31 2-C1 NCHF2 CH N CMe
K-33 6-Me NCHF2 CH N CMe
K-33 6-C1 NCHF2 CH N CMe
K-l 4-Me NCF2CHF2 CMe N CH
K-l 4-C1 NCF2CHF2 CMe N CH
K-18 4-Me NCF2CHF2 CMe N CH
K^18 4-C1 NCF2CHF2 CMe N CH
K-14 1-Me »CF2CHF2 CMe .N CH
K-28 4-Me NCF2CHF2 CMe N CH
K-28 4-C1 NCF2CHF2 CMe N CH
K-30 5-Me NCF2CHF2 CMe N CH
K-30 5-Cl NCF2CHF2 CMe N CH
K-31 2-Me NCF9CHF2 CMe N CH

WO 02/070483
96

PCT/US02/06582



R3 is
u



K (R4) Q
K-31 2-CI NCF2CHF2
K-3 3 6-Me NCF2CHF2
K-3 3 6-C1 NCF2CHF2
K-l 4-Me NCH2CF3
K-l 4-C1 NCH2CF3
K-18 4-Me NCH2CF3
K-18 4-C1 NCH2CF3
K-l 4 1-Me NCH2CF3
K-28 4-Me NCH2CF3
K-28 4-C1 NCH2CF3
K-30 5-Me NCH2CF3
K-30 5-C1 NCH2CF3
K-31 2-Me NCH2CF3
K-31 . 2-CI NCH2CF3
K-33 6-Me NCH2CF3
K-33 6-CI NCH2CF3
K-l 4-Me NCH2CF3
K-l 4-C1 NCH2CF3
K-18 4-Me NCH2CF3
K-18 4-C1 NCH2CF3
K-14 ]-Me NCH2CF3
K-28 4-Me NCH2CF3
K-28 4-C1 NCH2CF3
K-30 5-Me NCH7CF3
K-30 5-C1 NCH7CF3
K-31 2-Me NCH2CF3
K-31 2-CI NCH2CF3
K-33 6-Me NCH2CF3
K-33 " 6-CI NCH2CF3
K-l 4-Me NCF2CHF2
K-l 4-C1 NCF2CHF2
K-18 4-Me NCF2CHF2
K-18 4-CI NCF2CHF2
K-14 1-Me - - TsiCF2GHF2
K-28 4-Me NCF2CHF2
K-28 4-CI MCF2CHF2


X Y z
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CMe N CH
CH N CMe
CH N CMe
CH N CMe
CH N CMe
CH N CMe
CH N CMe
CH N CMe
CH N CMe
CH N . CMe
CH N CMe
CH N CMe
CH N CMe
CH. N CMe
N CH CMe
N CH CMe
N CH CMe
N " CH CMe
N CH CMe
N CH CMe
K CH CMe

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R.J is /-Bu
K (R4) Q. X Y Z
K-30 5-Me NCF2CHF2 N CH CMe
K-30 5-C1 NCF2CHF2 N CH CMe
K-31 2-Me ■ NCF2CHF2 N CH CMe
K-31 2-C1 NCF2CHF2 N CH CMe
K-33 6-Me NCF2CHF2 N CH CMe
K-33
6-C1
NCF2CHF2 Tabl \ 1 s 17 N CH
■>*> CMe









" li T°
\ A






K w X Y Z R! ffi^n E! R^
K-1 CH CH CH CH /-Pr 4-Me CF3 Me
K-1 CH CH CH CH /-Bu 4-Me CF3 Me
K-1 CH CH CH CH /-Pr 4-C1 CF3 Me
K-1 CH CH CH CH /-Bu 4-C1 ch Me
K-1 CH CH CH CH /-Pr 4-Me CF3 F
K-1 CH CH CH CH /-Bu 4-Me CF3 F
K-1 CH CH CH CH /-Pr 4-C1 CF3 F
K-1 CH CH CH CH /-Bu 4-CI CF3 F
K-1 CH CH CH CH i-Pr 4-Me CF3 CI
K-1 CH CH CH CH /-Bu 4-Me CF3 CI
K-1 CH CH CH CH /-Pr 4-CI CF3 CI
K-I CH CH CH CH /-Bu 4-C1 CF3 CI
K-1 CH - CH CH CH /-Pr 4-Me CF3 Br
K-1 CH CH CH CH /-Bu 4-Me CF3 Br
K-1 CH ■ CH CH. CH i-Vr 4-Cl CF3 Br
K-1 CH CH CH " CH /-Bu 4-CI CF3 Br
K-1 CH CH - CH CH /-Pr 4-Me CF3 CN







WO 02/070483

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K-28 CH CH CH N /-Bu 4-Cl CF3 CI
K-28 CH CH CH N /-Pr 4-Me CF3 Br
K-28 CH CH CH N /-Bu 4-Me CF3 Br
K-28 CH CH CH N /-Pr 4-Cl CF3 Br
K-28 CH CH CH N /-Bu 4-Cl CF3 Br
K-28 CH CH CH N /-Pr 4-Me CF3 CN
K-28 CH CH CH N /-Bu 4-Me CF3 CN
K-28 CH CH CH N /-Pr 4-Cl CF3 CN
K-28 CH CH CH N /-Bu 4-Cl CF3 CN
K-30 CH CH CH CH /-Pr Me CF3 Me
K-30 CH CH CH CH /-Bu Me CF3 Me
K-30 CH CH CH CH /-Pr 5-CI CF3 Me
K-30 CH CH CH CH /-Bu 5-CI CF3 Me
K-30 CH CH CH CH /-Pr Me CF3 F
K-30 CH CH CH CH /-Bu Me CF3 F
K-30 CH CH CH CH /-Pr 5-CI CF3 F
K-30 CH CH CH CH /-Bu 5-CI CF3 F
K-30 CH CH CH CH /-Pr Me CF3 CI
K-30 CH CH CH CH /-Bu Me CF3 CI
K-30 CH CH CH CH /-Pr 5-CI CF3 CI
K-30 CH CH CH CH /-Bu 5-CI CF3 CI
K-30 CH CH CH CH /-Pr Me CF3 Br
K-30 CH CH CH CH /-Bu Me CF3 Br
K-30 CH CH CH CH /-Pr 5-CI CF3 Br
K-30 CH CH CH CH /-Bu 5-CI CF3 Br
K-30 CH CH CH CH /-Pr Me CF3 CN
K-30 CH CH CH CH /-Bu Me CF3 CN
K-30 CH CH CH CH /-Pr 5-CI CF3 CN
K-30 CH CH CH CH /-Bu 5-CI CF3 CN
K-30 CH CH CH N /-Pr Me CF3 Me
K-30 CH CH CH N /-Bu Me CF3 Me
K-30 CH CH CH N /-Pr 5-CI CF3 Me
K-30 CH CH CH N /-Bu 5-CI CF3 Me
K-30 CH CH CH N /-Pr Me CF3 F
K-30 CH CH CH "N /-Bu Me CF3 F
K-30 CH CH " CH N " " /-Pr 5-CI CF3 F
K-30 CH CH CH N /-Bu 5-CI CF3 F
K-30 " CH CH CH "N /-Pr Me CF3 CI



WO 02/070483

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103

K-30 CH CH CH N /-Bu 5-C1 CF3 F
K-30 CH CH CH N /-Pr Me CF3 CI
K-30 CH CH CH N /-Bu Me CF3 CI
K-30 CH CH CH N /-Pr 5-C1 CF3 CI
K-30 CH CH CH N /-Bu 5-C1 CF3 CI
K-30 CH CH CH N /-Pr Me CF3 Br
K-30 CH CH CH N /-Bu Me CF3 Br
K-30 CH CH CH "N /-Pr 5-C1 CF3 Br
K-30 CH CH CH N /-Bu 5-C1 CF3 Br
K-30 CH CH CH "N /-Pr Me CF3 CN
K-30 CH CH CH N /-Bu Me CF3 CN
K-30 CH CH CH N /-Pr 5-C1 CF3 CN
K-30 CH CH CH "N /-Bu 5-C1 CF3 CN
K-31 CH CH CH CH /-Pr 2-Me CF3 Me
K-31 CH CH CH CH /-Bu 2-Me CF3 Me
K-31 CH CH CH CH /-Pr 2-C1 CF3 Me
K-31 CH CH CH CH /-Bu 2-C1 CF3 Me
K-31 CH CH CH CH /-Pr 2-Me CF3 F
K-31 CH CH CH CH /-Bu 2-Me CF3 F
K-31 CH CH CE CH /-Pr 2-C1 CF3 F
K-31 CH CH CH CH /-Bu 2-C1 CF3 F
K-31 CH CH CH CH /-Pr 2-Me CF3 CI
K-31 CH CH CH CH /-Bu 2-Me CF, CI
K-31 CH CH CH CH /-Pr 2-C1 CF3 CI
K-31 CH CH CH CH /-Bu 2-C1 CF3 CI
K-31 CH CH CH CH /-Pr 2-Me CF3 Br
■K-31 CH CH CH CH /-Bu 2-Me CF3 Br
K-31 CH CH CH CH /-Pr 2-C1 CF3 Br
K-31 CH CH CH CH /-Bu 2-C1 CF3 Br
K-31 CH CH CH CH /-Pr 2-Me CF3 CN
K-31 CH CH CH CH /-Bu 2-Me CF3 CN
K-31 CH CH CH CH /-Pr 2-C1 ■ CF3 CN
K-31 CH CH CH CH /-Bu 2-C1 CF3 CN
K-31 CH CH CH .N /-Pr 2-Me CF3 Me
K-31 CH CH CH N /-Bu 2-Me CF3 Me
K-31 CH CH CH " " N /-Pr 2-C1 CF3 Me
K-31 CH CH CH N /-Bu 2-C1 CF3 Me
K-31 CH CH CH N /-Pr 2-Me CF3 F

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K-31 CH CH CH N /-Bu 2-Me CF3 F
K-31 CH CH CH N /-Pr 2-Cl CF3 F
K-31 CH CH CH N /-Bu 2-Cl CF3 F
K-31 CH CH CH N /-Pr 2-Me CF3 CI
K-31 CH CH CH " N /-Bu 2-Me CF3 CI
K-31 CH CH CH N i-Pr 2-Cl CF3 CI
K-31 CH CH CH N /-Bu 2-Cl CF3 CI
K-31 CH CH CH N" /-Pr 2-Me CF3 Br
K-31 CH CH CH N /-Bu 2-Me CF3 Br
K-31 CH CH CH N /-Pr 2-Cl CF3 Br
K-31 CH CH CH N /-Bu 2-CI CF3 Br
K-31 CH CH CH N /-Pr 2-Me CF3 CN
K-31 CH CH CH N /-Bu 2-Me CF3 CN
K-31 CH CH CH N /-Pr 2-Cl CF3 CN
K-31 CH CH CH N /-Bu 2-Cl CF3 CN
K-31 CH CH CH CH /-Pr 2-Me CF3 Me
K-31 CH CH CH CH /-Bu 2-Me CF3 Me
K-31 CH CH CH CH /-Pr 2-Cl CF3 Me
K-31 CH CH CH CH /-Bu 2-Cl CF3 Me
K-31 CH CH CH CH /-Pr 2-Me CF3 F
K-31 CH CH CH CH /-Bu 2-Me CF3 F
K-31 CH CH CH CH /-Pr 2-Cl CF3 F
K-31 CH CH CH CH /-Bu 2-Cl CF3 F
K-31 CH CH CH CH /-Pr 2-Me CF3 CI
K-31 CH CH CH CH /-Bu 2-Me CF3 CI
K-33 CH CH CH CH /-Pr 2-Cl CF3 C)
K-31 CH CH CH CH /-Bu 2-Cl CF3 CI
K-31 CH CH CH CH /-Pr 2-Me CF3 Br
K-31 CH CH CH CH /-Bu 2-Me CF3 Br
K-31 CH CH CH CH /-Pr 2-Cl CF3 Br
K-31 CH CH CH CH /-Bu 2-Cl CF3 Br
K-31 CH CH CH CH /-Pr 2-Me CF3 CN
K-31 CH CH CH CH /-Bu 2-Me CF3 CN
K-31 CH CH CH CH /-Pr 2-Cl CF3 CN
K-31 CH CH CH CH /-Bu 2-CI CF3 CN
K-31 CH CH CH N /-Pr 2-Me CF3 Me
K-31 CH CH CH N /-Bu 2-Me CF3 Me
K-31 CH . CH. CH N /-Pr 2-CI CF3 Me

WO 02/070483

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105

K-31 CH CH CH N . /-Bu 2-C1 CF3 Me
K-31 CH CH CH N /-Pr 2-MB CF5 F
K-31 CH CH CH N /-Bu 2-Me CF3 F
K-31 CH CH CH N /-Pr 2-C1 CF3 F
K-31 CH CH CH N /-Bu 2-C1 CF3 F
K-31 CH CH CH N /-Pr 2-Me CF3 CI
K-31 CH CH CH N /-Bu 2-Me CF3 CI
K-31 CH CH CH N /-Pr 2-C1 CF3- CI
K-31 CH CH CH N /-Bu 2-C1 CF3 CI
K-31 CH CH CH N /-Pr 2-Me CF3 Br
K-31 CH CH CH N /-Bu . .2-Me CF3 Br
K-31 CH CH CH N j-Pr 2-C1 CF3 Br
K-31 CH CH CH N /-Bu 2-C1 CF3 Br
K-31 CH CH CH N i-Pr 2-Me CF3 CN
K-31 CH CH CH N /-Bu 2-Me CF3 CN
K-31. CH CH CH N /-Pr 2-C1 CF3 CN
K-31 CH CH CH N /-Bu 2-Ci CF3 CN
K-33 CH CH CH CH /-Pr 6-Me CF3 Me
K-33 CH CH CH CH /-Bu 6-Me CF3 Me
K-33 CH CH CH CH /-Pr 6-CI CF3 Me
K-33 CH CH CH CH /-Bu 6-C1 CF3 Me
K-33 CH CH CH CH i-Pr 6-Me CF3 F
K-33 CH CH CH CH /-Bu 6-Me CF3 F
K-33 CH CH CH CH /-Pr 6-CI CF3 F
K-33 CH CH CH CH /-Bu 6-CI CF3 F
K-33 CH CH CH CH /-Pr 6-Me CF3 CI
K-33 CH CH CH CH t-Bu 6-Me CF3 CI
K-33 CH CH .CH CH /-Pr 6-CI CF3 Cl
K-33 CH CH CH CH . /-Bu 6-CJ CF3 CI
K-33 CH CH CH CH /-Pr 6-Me CF3 Br
K-33 CH CH CH CH /-Bu 6-Me CF3 Br
K-33 CH CH CH CH /-Pr 6-CI CF3 Br
K-33 CH CH CH CH /-Bu 6-CI CF3 Br
K-33 CH CH CH CH /-Pr 6-Me CF3 CN
K-33 CH " CH CH CH /-Bu 6-Me CF3 CN
K-33 CH CH CH CH /-Pr 6-CI CF3 " CN
K-33 CH CH CH CH /-Bu 6-CI CF3 CN
K-33 CH CH CH N /-Pr 6-Me CF3 Me



WO 02/070483

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K-33 CH CH CH CH t -Bu 6-a CF3 CN
K-33 CH CH CH N i -Pr ( S-Me CF3 Me
K-33 CH CH CH N t -Bu 6-Me CF3 Me
K-33 CH CH CH N i -Pr 6-Cl CF3 Me
K-33 CH CH CH N t -Bu 6-Cl CF3 Me
K-33 CH CH CH N i -Pr 6-Me CF3 F
K-33 CH CH CH N t- Bu 6-Me CF3 F
K-33 CH CH CH N i- •Pr 6-Cl CF3 F
K-33 CH CH CH N t- Bu 5-C1 CF3 F
K-33 CH CH CH N i- Pr 6-Me CF3 CI
K-33 CH CH CH N t- Bu 6-Me CF3 a
K-33 CH CH CH N i- Pr 6-cr ■ CF3 CI
K-33 CH CH CH N t- Bu 6-Cl CF3 CI
K-33 CH CH CH N i- Pr 6-Me CF3 Br
K-33 CH CH CH N t- Bu 6-Me CF3 Br
K-33 CH CH CH N i- Pr 6-Cl CF3 Br
K-33 CH CH CH N t-Bv 6-Cl CF3 Br
K-33 CH CH CH N i- Pr 6-Me CF3 CN
K-33 CH CH CH N H3u 6-Me CF3 CN
K-33 CH CH CH N /-) ar 6-Cl CF3 CN
K-33 CH CH CH "N /-Bu 6-Cl CF3 CN






R2is H, R3 is Me R2 is H. R3 isEt R2is H. R3 is /-Pr R2is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 H CI CH3 H CI CH3 H CI CH3 H CI
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 " V " C\ CH3 1 CI CH3 i" CI
CH3 I Br CH3 I *, CH3 I Br CH3 1 Br

WO 02/070483

PCT/US02/06582

108


WO 02/070483

PCT/US02/06582

109


WO 02/070483

PCT/tTS02/06582


110 R5 is Br

WO 02/070483

PCT/US02/06582

111


WO 02/070483

PCT/DS02/06582

112


WO 02/070483

PCT/OS02/06582

113


WO 02/070483

PCT/US02/06582

114


R5 is CH3CF3

WO 02/070483 , PCT/US02/06582
115


WO 02/070483

PCT/US02/06582





WO 02/070483

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117
R5 is CI
R2 sH. R3 is Me R2 is H. R3 is Et R2 is H. R3 is /-FT R2 is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
Br I Cl Br I Cl Br I Cl Br I Cl
Br I Br Br I Br Br I Br Br I Br
Br F Cl Br F Cl Br F Cl Br F Cl
Br F Br Br F Br Br F Br Br F Br
Br CF3 Cl Br CF3 Cl Br CF3 Cl Br CF3 Ci
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br Cl Br Br CI Br Br Cl
Br Br Br Br Br Br Br Br Br Br Br Br
Br Cl Cl Br Cl Cl Br Cl Cl Br Cl Cl
Br Cl Br Br Cl Br Br Cl Br Br Cl Br
R5 is Br
R2is H.R3 is Me R2 is H, R3 isEt R2is H,R3 is /-Pr R2is Me.R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 H Cl CH3 H Cl CH3 H Cl CH3 H Cl
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I Cl CH3 r Cl CH3 1 Cl CH3 I Cl
CH3 I Br . CH3 i Br CH3 I " Br CH3 I Br
CH3 .F Cl CH3 F Cl CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 Cl CH3 -CF3 Cl CH3 CF3 Cl CH3 CF3 Cl
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br Cl CH3 Br Cl CH3 Br Cl CH3 Br Cl
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 Cl Cl CH3 Cl Cl CH3 Cl Cl CH3 Cl Cl
CH3 Cl Br CH3 CI Br CH3 Cl Br CH3 CI Br
CI H CI Cl H Cl Cl H Cl Cl H CI
CI H Br Cl H Br CI H Br Cl H Br
CI I Cl Cl I CI Cl I Cl Cl I Cl
CI I Br Cl I Br Cl 1 Br Cl J Br
CI F Cl Cl F Cl Cl F CI CI F Cl
CI ■F Br Cl F Br Cl F Br Cl F Br
Cl CF3 CI CI CF3 Cl " Cl CF3 Cl Cl CF3 Cl
CI CF3 Br CI CF3 Br Cl CF3 Br CI CF3 Br
Cl Br Cl CI Br Cl Cl Br Cl Cl Br Cl

"WO 02/070483

PCT/TJS02/06582

118


WO 02/070483

PCT/US02/06582

119


WO 02/070483

PCTYUS02/06582

120


WO 02/070483

PCT


121 Table 21

WO 02/070483

PCT/US02/06582

122


WO 02/070483

PCT/US02/06582

123
R5 is CH2CF3
R2 sH.R: " is Me R2 is H. R3 is Et R2i sH. R3 is /-Pr R2i R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CI CI CI CI CI CI CI Cl Cl Cl Cl Cl
CI CI Br CI CI Br CI Cl Br CI CI Br
Br H CI Br H CI Br H Cl Br H Cl
Br H Br Br H Br Br H Br Br H Br
Br I CI Br I CI Br I CI Br r Cl
Br I Br Br I Br Br I Br Br i Br
Br F CI Br F CI Br F Cl Br F Cl
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 CI Br CF3 Cl Br CF3 Cl
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br Cl Br Br CI
Br Br Br Br Br Br Br Br Br Br Br . Br
Br CI CI Br CI CI Br Cl CI Br Cl Cl
Br CI Br Br CI Br Br Cl Br Br Cl Br
R5 is CFoCHFi
R2is H,R3 is Me R2i5 H. R3 isEt R2is H,R3i s ;"-Pr R2is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R^
CH3 H CI CH3 H CI CH3 H Cl CH3 H Cl
CR3 H Br. CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I. CI CH3 I Cl CH3 I Cl
CH3 I Br CH3 3 Br CH3 1 Br CH3 I Br
CH3 F CI CH3 F CI CH3 F Cl CH3 F Cl
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 Cl CH3 CF3 Cl
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI CH3 Br CI CH3 Br Cl CH3 Br Cl
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 CI CI CH3 C) CI CH3 Cl Cl CH3 Cl Cl
CH3 CI Br CH3 CI Br CH3 Cl Br CH3 Cl Br"
CI H CI CI H CI CI H CI CI H CI
Ci H Br CI H . Br CI H Br Cl H Br
CI l" CI CI I CI CI I Cl Cl I Cl "
C3 I Br Cl I Br CI I Br CI r Br
CI F CI CI F CI Cl F Cl Cl F Cl

WO 02/070483

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124"


WO 02/070483

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125
R5 is CI
R2 is H. R- is Me R2 s H. R3 is Et R2 is H. R3 is /-Pr R2is Me.R J is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 I Br CH3 I Br CH3 I Br CH3 I Br
CH3 F Cl CH3 F CI CH3 F CI CH3 F Cl
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 Cl CH3 CF3 Cl CH3 CF3 C! CH3 CF3 Cl
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br Cl CH3 Br Cl CH3 Br Cl CH3 Br Cl
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 CI Cl CH3 CI CI CH3* Cl CI CH3 CI Cl
CH3 Cl Br CH3 CI Br CH3 CI Br CH3 Cl Br
CI H Cl ci H Cl Cl H Cl Cl H CI
CI H Br CI H Br CI H Br CI H Br
CI I Cl Cl I Cl Cl I CI Cl I Cl
ci I Br Cl I Br Cl I Br Cl T Br
CI F Cl Cl F C) Cl F Cl Cl F Cl
■CI F Br Cl F Br Cl F Br Cl F Br
CI CF3 Cl Cl CF3 CI CI CF3 Cl Cl CF3 Cl
Cl CF3 Br Cl CF3 Br CI CF3 Br CI CF3 Br
CI Br Cl Cl Br Cl C! Br Cl Cl Br Cl
Cl Br Br . Cl Br Br Cl Br Br Cl Br Br
Cl C) Cl Cl Cl Cl Cl Cl Cl CI Cl Cl
CI Cl Br Cl Cl Br Cl Cl Br Cl Cl Br
Br H Cl Br H Cl Br H Cl Br H Cl
Br H Br Br H Br Br H Br Br H Br
Br I Cl Br I Cl Br I Cl Br I CI
Br I Br Br I Br Br I Br Br I Br
Br F CI Br F Cl Br F Cl Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 Cl Br CF3 Cl Br CF3 Cl Br CF3 Cl
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br Cl Br Br CI Br Br Cl Br Br Cl
Br Br Br Br Br Br Br Br Br Br Br Br
Br Cl Cl Br Cl Cl Br Cl Cl Br Cl Cl
Br Cl Br Br Cl Br BT Cl Br Br CI Br

WO 02/070483

PCT/TJS02/O6582

126


WO 02/070483

PCT7US02/06582

127


WO 02/070483

PCT/US02/06582

128


WO 02/070483

PCT/OS02/06582

129


_ WO 02/070483

PCT/US02/06582

130


WO 02/070483

PCTYUS02/06582

131


WO 02/070483

PCT/US02/06582

132


WO 02/070483

PCT/US02/06582

133
Table 24
RP


WO 02/070483

PCT/US02/06S82

134


^WO 02/070483

PCT/US02/O6582

135


WO 02/070483

PCT7tJS02/0
136


WO 02/070483

PCT/US02/06582

137"


WO 02/070483

PCT7US02/06582





,W0 02/070483

PCT/US02/06582

139


WO 02/070483

PCT/US02/06582

140
VisN
R2 is H, R3 is Me ■ R2 is H. R3 is Et B 2 is H. R3 is i-Pr R- - is Me. R3 is Me
R4 R5 R6 R4 R5 R6 R4 R5 R6 R4 R5 R6
CI OCH2CF3 CI CI OCH2CF3 CI CI "OCH2CF3 CI CI OCH2CF3 C!
CI OCH7CF3 Br CI OCH2CF3 Br CI OCH2CF3 Br CI OCH2CF3 Br
CI OCH2CF3 CN CI OCH2CF3 CN CI OCH2CF3 CN CI OCH2CF3 CN
Br Br CI Br Br CI Br Br CI Br Br CI
Br Br Br Br Br Br Br Br Br Br Br Br
Br Br CN Br Br CN Br Br CN Br Br CN
Br CI CI Br CI CI Br CI CI Br CI CI
Br CI Br Br CI Br Br CI Br Br CI Br
Br CI CN Br CI CN Br CI CN Br CI CN
Br CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br CF3 CN Br CF3 CN Br CF3 CN Br CF3 CN
Br OCH2CF3. CI Br OCH7CF3 CI Br OCH2CF3 CI Br OCH2CF3 CI
Br OCH2CF3 Br Br OCH2CF3 Br Br OCH2CF3 Br Br OCH2CF3 Br
Br OCH9CF3 CN Br OCH2CF3 CN Br OCH9CF3 CN Br OCH7CF3 CN
CH3 Br CI CH3 Br CI CH3 Br CI CH3 Br CI
CH3 Br Br CH3 Br . Br CH3 Br Br CH3 Br Br
CH3 Br CN CH3 Br CN CH3 Br CN CH3 Br CN
CH3 CI CI CH3 CI CI CH3 CI CI CH3 CI CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CH3 CI CN CH3 CI CN CH3 CI CN CH3 CI CN
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3" CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 CF3 CN CH3 CF3 CN CH3 CF3 CN CH3 CF3 CN
CH3 OCH2CF3 CI CH3 OCH2CF3 CI CH3 OCH2CF3 CI CH3 OCH2CF3 CI
CH3 OCB2CF3 Br CB3 OCB2CF3 Br CKi3 OCH2CF3 BT CH3 ocn2c^3 Br
CH3 OCH2CF3 CN CH3 OCH2CF3 CN CH3 OCH2CF3 CN CH3 OCH2CF3 CN
CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br CI
CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br Br
CF3 Br CN CF3 Br CN CF3 Br CN CF3 Br CN
CF3 CI CI CF3 CI CI CF3 CI CI CF3 CI CI
CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI Br
CF3 CI CN CF3 . -CI CN CF3 C) CN CF3 • CI CN
CF3 CF3 CI -, CF3 CF3 CI CF3 CF3 CI CF3 CF3 CI
CF3 CF3 Br ." :F3 CF3 Br CF3 CF3 Br CF3 CF3 Br

► WO 02/070483

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" Cl OCH2CF3 Br CN Cl OCH2CF3 Br CN Cl OCH2CF3 Br CN Cl
Br Br Br Br Br Br Br Br
Br CN Br CN Br CN Br CN
CI Cl Cl Cl Cl Cl Cl Cl
CI Br Cl Br Cl Br Cl Br
CI CN Cl CN Cl CN .Cl • CN
CF3 Cl CF3 Cl CF3 Cl CF3 Cl
CF3 Br CF3 Br CF3 Br CF3 Br

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R4 is CHi
R2 IS n_ R3 is M& R2 is H. R3 isEt R2 is H. R3 is z"-Pr R2 is Me. R3 is Me
R5 R6 R5 R6 R5 R6 R5 R6
CF3 CN CF3 CN CF3 CN CF3 CN
OCH2CF3 CI OCH2CF3 Cl OCH2CF3 Cl OCH2CF3 Cl
OCH2CF3 Br OCH2CF3 Br OCH9CF3 Br OCH2CF3 Br
OCH2CF3 CN OCH2CF3 CN OCH2CF3 CN OCH2CF3 CN
R4 is CF3
R2 is H. R3 is K4c R2 is H, R3 isEt R2 is H. R3 is /-Pr R2 is Me, R3 is Me

R6 R5 R6 R5 R6 R5 R6
Br Cl Br Cl Br ci. Br Cl
Br Br Br Br Br Br Br Br
Br CN Br CN Br CN Br CN
C! C! Cl Cl CI Cl Cl Cl
ci Br Cl Br Cl Br Cl Br
Cl CN Cl CN Cl CN CI CN
CF3 Cl CF3 Cl CF3 Cl CF3 CI
CF3 Br CF3 Br CF3 Br CF3 Br
CF3 CN CF3 CN CF3 CN CF3 CN
OCH2CF3 Cl OCH2CF3 Cl OCH2CF3 Cl OCH2CF3 Cl
OCH9CF3 Br OCH9CF3 Br OCH2CF3 Br OCH2CF3 Br
OCH2CF3 CN OCH2CF3 CN OCH2CF3 CN OCH2CF3 CN
Br Cl Br Cl Br Cl Br Cl
Br Br Br Br Br Br Br Br
Br CN Br CN Br CN Br CN
CI Cl Cl Cl Cl Cl Cl Cl
ci Br Cl Br Cl Br Cl Br
CI CN Cl CN Cl CN CI CN
CF3 Cl CF3 CI CF3 Cl CF3 Cl
CF3 Br CF3 Br CF3 Br CF3 Br
CF3 CN CF3 CN CF3 CN CF3 CN
OCH2CF3 CI OCH2CF3 Cl OCH2CF3 Cl OCH2CF3 CI
OCH2CF3 Br OCH7CF3 Br OCH2CF3 Br OCH2CF3 Br
OCH2CF3 CN OCH7CF3 CN OCH2CF3 CN OCH2CF3 CN
Br Cl Br Cl Br Cl Br Cl
Br Br Br Br Br Br Br Br
Br CN Br CN Br CN Br CN

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CI Br CN CI Br CN CI Br CN CI Br CN CI Br CN CI Br CN CI Br CN
R2 is H-. R3 is Me
R5 CI Cl
Cl CF3 CF3 CF3 OCH2CF3 OCH2CF3 OCH2CF3 Br Br Br CI CI CI CF3 CF3 CF3 OCH2CF3 OCH2CF3 OCH2CF3

RiisiLRi

CI
CI
CI
CF3
CF3
CF3
OCH2CF3
OCH2CF3
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Br
Br
Br
CI
CI
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CF3
CF3
CF3 OCH2CF3 OCH2CF3 OCH2CF3

R4 is CF?
is Et
R6
Cl Br CN Cl Br CN Cl Br CN Cl Br CN Cl Br CN Cl Br CN Cl Br CN


R2isH,R3 is i-Pr R^jsJvjOli sMe
R5 R6 R5 R6
Cl Cl Cl Cl
ci Br Cl Br
Cl CN Cl CN
CF3 Cl CF3 Cl
CF3 Br CF3 Br
CF3 CN . CF3 CN
OCH2CF3 Cl OCH2CF3 Cl
OCH2CF3 Br OCH2CF3 Br
OCH2CF3 CN OCH2CF3 CN
Br Cl Br Cl
Br Br Br Br
Br CN Br CN
Cl Cl Cl Cl
Cl Br Cl Br
Cl CN Cl CN
CF3 Cl CF3 Cl
CF3 Br CF3 Br
CF3" CN CF3 CN
OCH2CF3 Cl OCH2CF3 Cl
OCH2CF3 Br OCH2CF3 Br
OCH2CF3 CN OCH2CF3 CN




CI
Br
CN
CI
Br
CN
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T?2 is H. R3 is Me
Br
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R2 is H. R3 is /-Pr
R6
Cl Br CN Cl Br CN Cl Br CN Cl
RiisJlRdisEt
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Br
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Cl Br CN Cl Br CN Cl Br CN Cl
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Br Br Br Cl Cl Cl CF3 CF
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Cl Br CN Cl Br CN Cl Br CN Cl
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CF3
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OCH2CF3

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R4is


R2 is H. R3 is Me
R5 R6
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
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OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
OCH2CF3 CI
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN


R2 is H. R3 isEt
R5 R6
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
OCH2CF3 CI
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
OCH2CF3 CI
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN


R2 is H. R3 isf-Pr
R5 R6
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
cl- CI
CI Br
CI CN
CF3 CI
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CF3 CN
OCH2CF3 CI
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
OCH2CF3 CI
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
• Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN

R2 is Me. R3 is Me

R5 R6
OCH2CF3 Br
OCH2CF3 CN
Br. CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
OCH2CF3 CI
OCH2CF3 Br
OCH2CF3 CN
Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN
OCH2CF3 C!
OCH2CF3 Br
OCH2CF3 CN

Br CI
Br Br
Br CN
CI CI
CI Br
CI CN
CF3 CI
CF3 Br
CF3 CN

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R4 is CHnCF;

R2 is H. R3 is Me R2 is H. R
R! 3isEt R2 is H. R3 is /-Pr
R! R^ R2 is Me. R3 is Me
R!

R6

ll R^
OCH2CF3 Cl. OCH2CF3 Cl OCH2CF3 Cl OCH2CF3 Cl
OCH2CF3 Br OCH2CF3 Br . OCH2CF3 Br OCH2CF3 .Br
OCH2CF3 CN OCH2CF3 CN OCH2CF3 CN OCH2CF3 CN



R2is H, R3 is Me R2 is H. R3 isEt R2isRR3is/-Pr R2is Me, R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 H Cl CH3 H Cl CH3 H Cl CH3 H Cl
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I Cl CH3 I Cl CH3 I Cl CH3 I Cl
CH3 1 Br CH3 I Br CH3 I Br CH3 1 Br
CH3 F Cl CH3 F Cl CH3 F Cl CH3 F Cl
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 Cl CH3 CF3 Cl CH3 CF3 Cl CH3 CF3 Cl
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br Cl CH3 Br Cl CH3 Br Cl CH3 Br Cl
CH3 Br Br" CH3 Br Br CH3 Br Br CH3 Br Br
CH3 Cl Cl CH3 Cl Cl CH3 Cl Cl CH3 Cl Cl
CH3 CI Br CH3 Cl Br CH3 Ci Br CH3 Cl Br
CI H Cl Cl H CI Cl H Cl Cl H Cl
CI H Br Cl H Br Cl H Br
1 Cl H Br
CI 1 Cl Cl I ci j ci r ci Cl I Cl
CI I Br Cl I Br Cl J Br Cl I Br
CI F Cl ■ -XI F Cl Cl F Cl Cl F Cl
CI F .Br Cl F Br Cl F Br Cl F Br
CI CF3 Cl Cl CF 3 Cl Cl CF 3 C1 Cl CF3 Cl

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R5b is CI
R2 s H.R3 is Me R2 isH.R 3 isEt R2 is H. R3 is ;"-Pr R2 is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R^
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br CI CI Br CI CI Br CI CI Br CI
CI Br Br CI Br Br CI ■ Br Br CI Br Br
CI CI. CI CI CI CI CI CI CI CI CI CI
CI CI Br CI CI Br CI CI Br CI CI Br
Br H CI Br H CI Br H CI Br H CI
Br H Br Br H Br Br H Br Br H Br
Br I CI Br I CI Br I CI Br I CI
Br I Br Br I Br Br I Br Br I Br
Br F CI Br F CI Br F CI Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI
Br. CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br Ci Br Br CI Br Br CI
Br Br Br Br Br Br Br Br Br Br Br Br
Br CI CI Br CI CI Br CI CI Br CI CI
Br CI Br Br CI Br Br CI Br Br CI Br
R5 is OCF3
R2is H. R3i s Me R2is H. R3 isEt R2is H, R3 is /-Pr R2is] Vie. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 H CI CH3 H CI CH3 H CI CH3 H CI
CH3 H Br C% H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I CI CH3 I C! CH3 I CI
CH3 I Br CH3 I Br CH3 I Br CH3 I Br
CH3 F CI CH3 F CI CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI CH3 Br CI CH3 Br CI CH3 Br CI
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 CI CI CH3 CI CI CH3 CI ci. CH3 CI CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H . CI CI H CI CI H CI CI H CI
CI H Br CI H Br CI H Br CI H Br

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R5 is OCF-
R2iH.R3 is Me R2 sH.R3 isEt —■ "» ^
R2is H.R3 is i-Pr R2 is Me. R3 is Me
R4S R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CI I CI CI I CI CI I CI ci I CI
CI I Br CI I Br CI I Br CI I Br
CI F CI CI F CI CI F CI CI F CI
CI F Br CI ? BT a F BT C\ F Br
CI CF3 CI CI CF3 CI CI CF3 CI Cl CF3 CI
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br CI CI Br CI Ci Br CI CI Br CI
CI Br Br CI Br Br CI Br Br CI Br Br
CI CI CI CI CI CI CI CI CI CI CI CI
CI CI Br ci CI Br CI a Br CI CI Br
Br H CI Br H CI Br H CI Br H CI
Br H Br Br H Br Br n Br Br H Br
Br. I CI Br I CI Br I CI Br I CI
Br I Br Br I Br Br I Br Br I Br
Br F CI Br F ■CI Br F CI Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br CI . Br Br CI
Br Br Br Br Br Br Br Br Br Br Br Br
Br CI CJ Br CI CI Br CI CI Br CI CI
Br CI Br Br CI Br Br CI Br Br CI Br
R5 is CF3

R2 is Ft. R3 is Me R2i sH.R3 is Et R2is H,R3 is ?-Pr R2is Me, R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 H CI CH3 H Cl CH3 H Cl CH3 H Cl
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I Cl CH3 I CI CH3 I Cl
CH3 I Br CH3 1 Br CH3 1 Br CH3 I Br
CH3 F CI CH3 F Cl CH3 F Cl CH3 F Cl
CH3 .F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 a CH3 CF3 CI CH3 CF3 Cl CH3 CF3 Cl
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI CH3 Br Cl CH3 Br. Cl CH3 Br Cl

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R5 is CF3
R2 is H. R3 is Me R2 is H. R3 is Et ->
R2is H. R3 is /-Pr R2is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 CI CI CH3 CI CI CH3 CI CI CH3 CI CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H CI CI H CI CI H CI CI H CI
CI H Br CI H Br CI H Br CI H Br
CI I CI CI I CI CI I CI CI I CI
CI I Br CI I Br CI I Br. CI I Br
CI F CI CI F CI CI F CI CI F CI
CI F Br CI F Br CI F Br CI F Br
CI CF3 CI CI CF3 CI CI CF3 CI CI CF3 CI
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br CI CI Br CI CI Br CI CI Br Cl
CI . Br Br C! Br Br CI Br Br CI Br Br
CI CI CI CI CI CI CI cI CI CI CI CI
CI CI Br CI CI Br CI CI Br CI CI Br
Br H CI Br H CI Br H CI Br H CI
Br H Br Br H Br Br H Br Br H Br
Br 1 CI Br I CI Br I CI Br I CI
Br I Br Br I Br Br I Br Br 1 Br
Br F CI Br F CI Br F CI Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br CI Br Br CI
Br Br Br Br Br Br Br Br Br Br Br Br
Br Cl Cl Br CI CI Br CI CI Br CI Cl
Br CI Br Br Ci Br Br CI Br Br CI Br
R5b is CFfCFi"h
R2 is H. R3 is Me R2is HL R3 is Et R2isF I. R3 is /-Pr R2 is Me. R3 i s Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 H CI CH3 H CI CH3 H CI CH3 H CI
CH3 H Br CH3 H Br CH3 . H Br CH3" H Br
CH3 r ci CH3 I CI CH3 I CI CH3 I CI
CH3 I Br" ^£13 I Br CH3 I Br CH3 ] Br

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I l5b is ( :Ffc?3 >2
R2 is H. R3 is Me R2i sH. R3 is Et R2is H.R3 is i-Pr R2is Me. R: is Me
R4a R4b R6 R4a R4b R6 R4a R4b. R6 R4a R4b R6
CH3 F CI CH3 F ci CH3 F ci CH3 F Cl
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 Cl
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI CH3 Br CI CH3 Br CI CH3 Br CI
CH3 Br Br CH3 -Br Br CH3 Br Br CH3 Br Br
CH3 CI CI CH3 CI CI CH3 CI CI CH3 C! CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H CI CI H CI CI H CI CI H Cl
CI H Br Ci H Br CI H Br CI H Br
CI I CI CI I CI CI I CI CI I Cl
CI I Br CI I Br CI 1 Br CI I Br
cI. F C! CI F CI CI F CI CI F Cl
CI F Br CI F Br CI F Br CI F Br
CI CF3 C! CI CF3 CI CI CF3 CI CI CF3 Cl
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br Ci Ci Br Ci Cl Br CI CI Br Cl
CI Br Br CI Br Br CI Br Br CI Br Br
CI CI CI CI CI CI CI CI CI CI CI Cl
CI C1 Br C) CI Br CI CI Br CI CI Br
Br H CI Br H CI Br H CI Br H Cl
Br H Br Br H Br Br H Br Br H Br
Br I cI Br I CI Br I CI Br I CI
Br I Br Br I Br Br I Br Br r Br
Br F CI " Br F CI BT F CI Br F Cl
Br F Br Br F Br Br F Br Br F .Br
Br CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br CI Br Br Cl
Br Br Br Br Br Br Br Br Br Br Br Br
Br CI cI Br CI CI Br CI CI Br CI Cl
Br CI Br ..Br CI Br Br CI Br Br CI Br

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R4b

[62
CH3
N R5b

















R2i >H.R3 is Me R2 is H. R2 is Et R2is H.R3 is /-Pr R2is Me.R: " is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R*
CH3 H CI CH3 •H CI CH3 H ci" CH3 H CI
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I CI CH3 I C! CH3 I CI
CH3 I Br CH3 I Br CH3 r Br CH3 I Br
CH3 F CI CH3 F CI CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 &3 Br CH3 CF3 Br
CH3 Br CI CH3 Br CI CH3 Br CI CH3 Br CI
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 CI CI CH3 CI CI CH3 CI CI CH3 CI CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H CI CI H CI CI H CI CI H CI
CI H Br CI H Br CI H Br CI H Br
CI I CI CI I CI CI I CI CI I CI
CI I Br CI I Br CI I Br CI I Br
CI F CI CI F CI CI F CI CI F CI
CI F Br CI F Br CI F Br CI F Br
cI CF3 CI CI CF3 CI CI CF3 CI CI CF5 CI
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br CI CI Br CI CI Br CI CI Br CI
CI Br Br CI Br Br CI Br Br CI ■Br Br
CI CI CI CI CI CI CI CI CI CI CI CI
CI -CI Br CI CI Br CI CI Br CI CI Br
Br H CI Br H CI Br H CI Br H CI
Br H Br Br H Br Br H Br Br H Br

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R5b is CHF2
R2 is H, R: is Me R2 is H. R3 is Et R4a R4b R6 R2 is H. R3 R4a R4b is /-Pr R6 R2iE R4a Me. R R4b 3 is Me
R4a R4b R«




R*
Br I Cl Br 1 Cl Br r Cl Br I CI
Br I Br Br I Br Br i Br Br I Br
Br F Cl Br F Cl Br F Cl Br F Cl
Br F Br Br F Br Br F Br Br F Br
Br CF3 Cl Br CF3 Cl Br CF3 Cl Br, CF3 Cl
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br Cl Br Br Cl Br Br Cl Br Br Cl
Br Br Br Br Br Br Br Br Br Br Br Br
Br Cl Cl Br Cl Cl Br Cl CI Br Cl Cl
Br Cl Br Br CI Br Br CI Br Br Cl Br
] \5b is CH2CF 3
R2is H. R3 R4b is Me R6 R2 is H. R3 is Et R2is R4a H. R3 R4b s /-Pr R6 R2is R4a Me. R3
R4b is Me
R4a

R|a R4b R6




R6
CH3 H Cl Cffi3 _ H Cl CH3 H Cl CH3 H Cl
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I Cl CH3 I CI CH3 I CI CH3 I Cl
CH3 I Br CH3 I Br CH3 J Br CH3 I Br
CH3 F Cl CH3 F CI CH3 F Cl CH3 F Cl
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 Cl CH3 CF3 Cl CH3 CF3 Cl CH3 CF3 Cl
CH3 CF3 Br CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br Cl CH3 Br Cl CH3 Br Cl CH3 Br Cl
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 Cl CI CH3 Cl Br ( CH3 Br CH3 C) Br CH3 Cl Br
CI H Cl Cl H ci Cl H Cl Cl H Cl
CI H Br CI H Br Cl H Br Cl H Br
CI I Cl Cl I a Cl J a CI J Cl
CI I Br Cl I Br Cl I Br Cl I Br •
CI F CI CI F Cl Cl F CI CI F Cl
CI F Br ■ Cl F Br Cl F Br Cl F Br
CI CF3 Cl Cl CF3 Cl Cl " CF3 Cl Cl CF3 Cl
CI CF3 Br Cl CF3 Br Cl CF3 Br Cl CF3 Br
Cl Br Cl CI Br Cl Cl Br Cl Cl Br Cl

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R5b is CHoCFs
R2 is H. R3 is Et 1 R2 is H. R3 is i-Pr R4a R4b R6 R4a R4b R6
R2 is H. R3 is Me
R4a R4b R6 R4a R4b R6
Cl Br Br Cl Br Br
Ci Cl Cl Cl Cl CI
Cl Cl Br Cl Cl Br
Br H Cl Br H Cl
Br H Br Br H Br
Br 1 Cl Br I Cl
Br I Br Br I Br
Br F Cl Br F Cl
Br F Br Br F" Br
Br CF3 Cl . Br CF3 Cl
Br CF3 Br Br CF3 Br
Br Br Cl Br Br Cl
Br. Br Br Br Br Br
Br Cl Cl Br CI CI
Br Cl Br Br Cl Br

Cl
Cl
Cl
Br
Br
Br
Br
Br
Br
Br
Br
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Br
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6
R4a
Bfb
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IT
CI
Br
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Cl
Cl
Cl
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Br
H
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Br
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Cl
r
Br
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Br
F
Cl
r
Br
F
Br
1
Br
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Cl
r
Br
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Br
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r
Br
Br
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Br
Cl
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Br
Cl
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R2 is Me. R3 is Me

R4b R6 R4a R4b R6
Br Br CI Br Br
Cl Cl Cl Cl Cl
Cl Br Cl Cl Br
H Cl Br H Cl
H Br Br H Br
I Cl Br I. Cl
I Br Br I Br
F Cl Br F Cl
F Br Br F Br
^3 Cl Br CF3 Cl
^3 Br Br CF3 Br
Br CI Br Br Cl
Br Br Br Br Br
CI Cl Br Cl CI
Cl Br Br Cl Br

R5b is CF3


R2 is Me. R3 is Me R4a R4b R6
R2 is H. R3 is Me R2 is E. R3 is Et
R4a R4b R6

CH3 H Cl
CH3 H Br
CH3 i Cl
CH3 I Br
CH3 F Cl
CH3 F Br
CH3 CF3 Cl
CH3 CF3 Br
CH3 Br Cl
CH3 Br Br
CH3 Cl CI
CH3 Cl Br
Cl H Cl
Cl H Br
Cl I Cl
Cl I Br


R4a R4b R6

CH3 H Cl
CH3 H Br
CH3 I CI
CH3 I Br
CH3 F Cl
CH3 F Br
CH3 CF3 CI
CH3 CF3 Br
CH3 Br Cl
CH3 Br" Br
CH3 CI CI
CH3 Cl Br
Cl H Cl
Cl H Br
Cl I Cl
Cl I Br


r
R2 is H. R3_is /-Pr R4a R4b R6

CH3 H Cl
CH3 H Br
CH3 I Cl
CH3 I Br
CH3 F Cl
CH3 F Br
CH3 CF3 Cl
CH3 CF3 Br
CH3 Br Cl
CH3 Br Br
CH3 Cl CI
CH3 CI Br
Cl H Cl
Cl ■H Br
CI I CI
Cl I \Br


R2is Me. R3 is Me
R4a R4b R6
CH3 H Cl
CH3 H Br
CH3 I Cl
CH3 I Br
CH3 F Cl
CH3 F Br
CH3 CF3 .CI
CH3 CF3 Br
CH3 Br Cl
CH3 Br Br
CH3 Cl Cl
CH3 Cl Br
Cl H CI
CI H Br
Cl I Cl
CI I Br

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R5b isCF3
R2 is H. R; is Me R2 is H. R3 is Et R2 is H. R3 is /-Pr R2i >Me. R 3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
a F Cl Cl F Cl Cl F Cl Cl F Cl
Cl F Br Cl F Br Cl F Br CI F " Br
Ci CF3 Cl Ci CF3 Cl Cl CF3 Cl Cl CF3 Cl
CI CF3 Br CI CF3 Br Cl CF3 Br Cl CF3 Br
Cl Br Cl Cl Br CI Cl Br Cl Cl Br Cl
Cl Br Br Cl Br Br Cl Br Br Cl Br Br
Cl Cl CI Cl Cl Cl Cl Cl Cl Cl Cl Cl
Cl Cl Br Cl Cl Br Cl Cl Br Cl Cl Br
Br Ft Cl Br H c1 Br H Cl Br H Cl
Br H Br Br H Br Br H Br Br H Br
Br I Cl Br 1 Cl Br I Cl Br I Cl
Br I Br Br I Br Br I Br Br I Br
Br. F Cl Br F Cl Br F Cl Br F Cl
Br F Br Br F Br Br F Br Br F Br
Br CF3 Cl Br CF3 Cl Br CF3 Cl Br CF3 Cl
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br Cl Br Br Cl Br Br CI Br Br Cl
Br Br Br Br Br Br Br Br Br Br Br Br
Br Cl Cl ■ Br Cl Cl Br CI Cl Br Cl Cl
Br Cl Br J Br Cl Br | Br Cl Br Br Cl Br
R- 5b is CFoCHFo
R2is H. R3 is"Me R2is H,R3 sEt R2is H. R3 is /-Pr R2 is 3 Vie. R3 is Me
R4a R4b R CH3 H Cl CH3 H Cl CH3 H Cl CH3 H Cl
CH3 H Br CH3 H Br CH3 H Br- CH3 H Br
CH3 I. Cl CH3 I ■CI CH3 I Cl CH3 I Cl
CH3 I Br CH3 I Br CH3 I Br CH3 T Br
CH3 F Cl CH3 F Cl CH3 F Cl CH3 F Cl
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 Cl CH3 CF3 CI CH3 CF3 Cl CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br Cl CH3 Br Cl CH3 Br Cl CH3 Br CI
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 Cl Cl CH3 Cl Cl CH3 Cl Cl CH3 Cl Cl

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R5b is CFoCHF-,
R2i sH,R3 R4b is Me R6 R2 R4a sH.R3 R4b is Et R6 R2is R4a H. R3 R4b is ;"-Pr R6 R2 is Me.R3 is Me
R4a







R4a R4b R6
CH3 Cl Br CH3 Cl Br CH3 Cl Br CH3 Cl Br
CI H CI Cl H Cl CI -H CI CI H Cl
CI H Br Cl H Br Cl H Br Cl H Br
Cl I Cl Cl I Cl Cl I Cl Cl 1 Cl
Cl 1 Br Cl I Br Cl I Br Cl I Br
CI F Cl Cl F Cl Cl F Cl Cl F Cl
Cl F Br Cl F Br Cl F Br Cl F Br
CI CF3 Cl Cl CF3 Cl CI CF3 Cl Cl CF3 Cl
Cl CF3 Br Cl CF3 Br Cl CF3 Br "Cl CF3 Br
CI Br Cl Cl Br CI Cl Br Cl Cl Br Cl
Cl Br Br Cl Br Br CI Br Br Cl Br Br
Cl Cl Cl Cl Cl Cl Cl CI Cl Cl Cl Cl
CI Cl Br Cl Cl Br CI Cl Br Cl Cl Br
Br H Cl Br H CI Br H CI Br H Cl
Br H Br Br H Br Br H Br Br H Br
Br I Cl Br I Cl Br I Cl Br I Cl
Br I Br Br I Br Br I Br Br I Br
Br F Cl Br F Cl Br F Cl Br F Cl
Br F Br Br F Br Br F Br Br F Br
Br CF3 Cl Br CF3 a Br CF3 Cl Br CF3 Cl
Br CF3 Br Br CF3 Br Br CF3 .Br Br CF3 Br
Br Br Cl Br Br CI Br Br Cl Br Br Cl
Br Br Br Br- Br Br Br Br Br Br Br Br
Br CI Cl Br Cl Cl Br Cl Cl Br ci Cl
Br Cl Br Br Cl Br Br Cl Br Br Cl Br

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sH, R R2"" ^R3
R5b is CHF-7
3 is Et R2 is

H.R3


R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b E^
CH3 H C1 CH3 H CI CH3 H CI CH3 H CI
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I CI CH3 I CI CH3 I CI
CH3 I Br CH3 I Br CH3 I Br CH3 r Br
CH3 F CI CH3 F CI CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI CH3 Br CI CH3 Br. Ci CH3 Br CI
CH3 Br Br CH3 Br Br CH3 Br Br CR3 Br Br
CH3 C! CI CH3 CI CI CH3 CI CI CH3 Ci CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H CI CI H CI CI H CI CI H CI
CI H Br CI H Br CI H Br ci H Br
CI 1 CI CI I CI CI I CI CI I CI
CI J Br CI I Br CI I Br CI I Br
CI F CI CI F CI CI F CI CI F CI
CI F Br CI F Br CI F Br CI F Br
CI CF3 CI CI CF3 CI CI CF3 CI CI CF3 CI
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br CI CI Br CI CI Br CI CI Br CI
CI Br Br CI Br Br CI Br Br CI Br Br
CI CI CI CI CI CI CI CI CI CI CI CI
CI CI Br CI CI Br CI. CI Br CI CI Br
Br H CI Br H CI Br H CI . Br H CI
Br H Br Br H Br Br H Br" Br H Br

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R5b is CHFo
R2 sH.R- is Me R2 is H. R3 is Et R2 is H, R3 is /-Pr R2i R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R^
Br I CI Br I CI Br I CI Br I CI
Br I Br Br I Br Br I Br Br I Br
Br F CI Br F CI Br F CI Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 CI Br CF3 CI Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br CI Br Br CI
Br Br Br Br Br Br Br Br Br Br Br Br
Br CI CI Br .CI CI Br CI . CI Br CI CI
Br CI Br Br CI Br "Br CI Br Br CI Br
R5b is CH2CF 3 ■
R2is ^R3 is Me R2 is H. R3 isEt R2is H. R3 is i-Pr R2 is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R^
CH3 H CI CH3 H CI CH3 H CI CH3 H CI
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I CI CH3 I CI CH3 I CI
CH3 I Br CH3 I Br CH3 I Br CH3 I Br
CH3 F CI CH3 F CI CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br , CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI CH3 Br CI CH3 Br CI ■CH3 Br CI
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 C! CI CH3 CI CI CH3 C! CI CH3 CI CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H CI CI H CI CI H CI CI H CI
CI H Br CI H Br CI H Br CI H Br
CI I CI" CI I CI CI I CI C) I CI
CI I Br CI I Br CI I Br CI I Br
CI F CI CI F CI CI F CI CI F CI
CI F Br CI F Br CI F Br CI F Br
CI CF3 CI CI CF3 CI CI CF3 CI CI CF3 CI
CI CF3 Br CI CF3 Br CI CF3 Br CI CF3 Br
CI Br CI CI •Br CI CI Br CI CI Br CI

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R5b is CH2CF3
, = 3-
R2 is H. R: " is Me R^ is H, R3 is Bt R2, sH.R3 is /-Pr R2 IE Me. R^ is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R^
CI Br Br CI Br Br CI Br Br CI Br Br
CI CI CI CI CI CI CI CI CI CI CI CI
CI CI Br CI CI Br CI CI Br CI CI Br
Br H CI Br H CI Br H CI Br H CI
Br H Br Br H Br Br H Br Br H Br
Br I CI Br I CI Br I CI Br I CI
Br f Br Br I Br Br I Br Br I Br
Br F CI Br F CI Br F CI Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 C! Br CF3 CI Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br CI Br Br CI
Br , Br Br Br Br Br Br Br Br Br Br Br
Br CI CI Br CI CI Br CI CI Br CI C!
Br CI Br Br CI Br Br CI Br Br CI Br
R5b is CF3
R2is H.R3 is Me R2is H.R3 isEt R2 is H. R3 is /-Pr R2 is! Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4t> R6
CH3 H C! CH3 H CI CH3 H CI CH3 H CI
CH3 H Br CH3 H Br CH3 H Br CH3 H Br
CH3 I CI CH3 I CI CH3 I CI CH3 I CI
CH3 I Br CH3 I Br CH3 I Br CH3 I Br
CH3 F CI CH3 F CI CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br C! CH3 Br CI CH3 Br CI CH3 Br CI
CH3 Br Br CH3 Br Br CH3 Br Br CH3 Br Br
CH3 CI CI CH3 CI CI CH3 CI CI CH3 CI CI
CH3 CI Br CH3 CI Br CH3 CI Br CH3 CI Br
CI H CI CI H CI CI H CI CI H CI
CI H Br CI H Br CI H Br Cf H Br
CI I CI CI I CI CI I CI CI I- C!
CI I Br CI I Br CI I Br CI I Br

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R5b isCF3
R2 is H. R: * is Me R2 is H. R3 is Et R2~, s H. R3 is /-FT R2 is Me. R 3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R CI F CI CI F CI CI F CI CI F CI
CI F Br CI F Br CI F Br CI F Br
CI CF3 CI CI CF3 CI CI CF3 CI CI CF3 CI
CI CF3 Br CI CF3 Br CI CF3 Br C! CF3 Br
CI Br CI CI Br CI CI Br CI CI Br CI
CI Br Br CI Br Br CI Br Br CI Br Br
CI CI C! CI CI CI CI CI CI CI CI CI
CI CI Br CI CI Br CI CI Br CI CI Br
Br H CI Br H CI Br ■H CI Br H CI
Br H Br Br H Br Br H Br Br H Br
Br I CI Br I CI Br I CI Br I CI
Br I Br Br I Br Br I Br Br I Br
Br. F CI Br F CI Br F CI Br F CI
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 CI Br CF3 C! Br CF3 CI
Br CF3 Br Br CF3 Br Br CF3 Br Br CF3 Br
Br Br CI Br Br CI Br Br CI Br Br CI
Br Br Br Br Br Br Br Br Br Br Br Br
Br CI CI Br CI CI Br CI CI Br CI CI
Br CI Br Br CI Br Br C! Br Br CI Br
R5b is CF2CHF 2
R2is H. R3 is Me R2is H.R3 is Et R2is H, R3is/-Pr ]R2isMe..R3 is Me
R4a R4b R6 R4a R4b R6 R4a R«b R6 R4a R4b R6
CH3 H CI CH3 H CI CH3 H CI CH3 H CI
CH3 H Br CH3 H Br CU3 H Br CH3 H Br
CH3 I CI CH3 I CI CH3 I CI CH3 I CI
CH3 I Br CH3 I Br CH3 I Br CH3 I Br
CH3 F CI CH3 F CI CH3 F CI CH3 F CI
CH3 F Br CH3 F Br CH3 F Br CH3 F Br
CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI CH3 CF3 CI
CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br CH3 CF3 Br
CH3 Br CI ( CH3 Br CI CH3 Br CI CH3 Br CI
CH3 Br Br ( =H3" Br Br ( :H3 Br Br CH3 Br Br
CH3 CI CI ( "H3 CI CI ( 3H3 CI CI 2E3 CI ■ CI

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I R3is CFoCHF-)
R2 is H. R3 is Me R2 sH.R3 is Et R2iH.R3 is f"-Pr R2is Me. R3 is Me
R4a R4b R6 R4a R4b R6 R4a R4b R6 R4a R4b R6
CH3 CI Br CH3 C) Br CH3 Cl Br CH3 Cl Br
CI H CI CI H Cl Cl H Cl Cl H Cl
CI H Br C! H Br Cl H Br CI H Br
CI I CI C! I Cl Cl I Cl Cl I Cl
CI I Br CI I Br Cl 1 Br Cl I Br
CI F CI CI F Cl Cl F Cl CI F Cl
CI F Br CI F Br Cl F Br CI F Br
CI CF3 CI CI CF3 CI Cl CF3 Cl Cl CF3 CI
CI CF3 Br CI CF3 Br CI CF3 Br Cl CF3 Br
CI Br CI Q Br Cl CI Br CI Cl Br Cl
CI Br Br CI Br Br CI Br Br Cl Br Br
CI CI CI a CI CI Cl CI CI Cl Cl CI
ci. CI Br Cl CI Br CI CI Br CI Cl Br
Br H CI Br fi CI Br H Cl Br H CI
Br H Br Br H Br Br H Br Br H Br
Br I CI Br I Cl Br I Cl Br I Cl
Br I Br Br I Br Br I Br Br I Br
Br F . CI Br F "Cl Br F Cl Br F Cl
Br F Br Br F Br Br F Br Br F Br
Br CF3 CI Br CF3 Cl Br CF3 Cl Br CF3 Cl
Br CF3 Br Br CF3 BT Br CF3 Br Br CF3 Br
Br Br CI Br Br Cl Br Br Cl .Br Br Cl
Br Br Br Br Br Br Br Br Br Br Br Br
Br CI CI Br Cl Cl Br Cl Cl Br Cl Cl
Br CI Br Br Cl Br Br Cl Br Br C! Br
Formulation/Utility
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions-(including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts,

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powders, granules, pellets, tablets, films, and the like which can be water-dispersible
("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further
formed into a suspension or solid formulation; alternatively the entire formulation of active
ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release
of the active ingredient. Sprayable formulations can be extended in suitable media and used
at spray volumes from about one to several hundred liters per hectare. High-strength
compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent
and surfactant within the following approximate ranges that add up to 100 percent by weight.
Weight Percent
Active
Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15
Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15
(including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0—15
High Strength Compositions 90-99 0-10 "0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon "s Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide,N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as

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cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone: and alcohols such as methanol, cyclohexanol. decanol and tetrahydroforfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the
ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a
5 hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for
example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active
material upon preformed granular carriers or by agglomeration techniques. See Browning,
"Agglomeration""", Chemical Engineering, December 4, 1967, pp 147^8, Perry"s Chemical
Engineer"s Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following,
10 and PCT Publication WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714.
Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050,
U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S.
5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S.
3,299,566.
15 For further information regarding the art of formulation, see T. S. Woods, "The
Formulator"s Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and
Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds.,
Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of
Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through
20 Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62
and Examples 8, 12, 15, 39,41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed
Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance
et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
25 In the following Examples, all percentages are by weight and all formulations are
prepared in conventional ways. Compound numbers refer to compounds in Index Table A.
Example A Wettable Powder
Compound 1 65.0%
30 dodecylphenol polyethylene glycol ether 2.0%
sodium, ligninsulfonate 4.0%
sodium silicoaluminate 6.0%
. montmorillonite (calcined) 23.0%.

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Example B Granule
Compound 1 10.0%
attapulgite granules (low volatile matter,
5 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example C Extruded Pellet
Compound 1 25.0%
anhydrous sodium sulfate 10.0%
10 crude calcium ligninsulfonate 5.0%
sodium alkylnaphthalenesulfonate 1.0%
calcium/magnesium bentonite 59.0%.
Example D
Emulsifiable Concentrate
15 Compound 1 20.0%
blend of oil soluble sulfonates
and polyoxyethylene ethers 10.0%
isophorone 70.0%.
Example E 20 Granule
Compound! 0.5%
cellulose 2.5%
lactose 4.0%
commeal 93.0%o.
25 Compounds of this invention are characterized by favorable metabolic and/or soil
residual patterns and exhibit activity controlling a spectrum of agronomic and non-agronomic invertebrate pests. (In the context of this disclosure "invertebrate pest control" means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest; related
30 expressions are defined analogously.) As referred "to in this disclosure, the term
"invertebrate pesi" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other Stylommatophora. The term "nematode" includes all of the helminths, such as: 35 roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. Compounds of this invention display

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activity against economically important agronomic and nonagronomic pests. The term "agronomic" refers to the production of field crops such as for food and fiber and includes the growth of cereal crops (e.g., wheat, oats, barley, rye, rice, maize), soybeans, vegetable crops (e.g., lettuce, cabbage, tomatoes, beans), potatoes, sweet potatoes, grapes, cotton, and 5 tree fruits (e.g., pome fruits, stone fruits and citrus fruits). The term "nonagronomic1" refers to other horticultural (e.g., forest, greenhouse, nursery or ornamental plants not grown in a field), public (human) and animal health, domestic and commercial structure, household, and stored product applications or pests. For reason of invertebrate pest control spectrum and economic importance, protection (from damage or injury caused by invertebrate pests) of 10 agronomic crops of cotton, maize, soybeans, rice, vegetable crops, potato, sweet potato, grapes and tree fruit by controlling invertebrate pests are preferred embodiments of the invention. Agronomic or nonagronomic pests include larvae of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua 15 Hiibner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni
Hubner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European com borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), com root webworm (Crambus caliginosellus Clemens), sod webworm (Herpetogramma 20 licarsisalis Walker)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydiapomonella Linnaeus), grape berry moth (Endopiza viteano Clemens), oriental fruit moth {Grapholita molesta Busck)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar 25 Linnaeus)); nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach {Periplaneta brunnea Burmeister), 30 Madeira cockroach (Leucophaea maderae Fabricius)); foliar feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)); flea beetles, cucumber beetles, rootworms, leaf 35 beetles, potato beetles, and leafminers in the family Chrysomeiidae (e.g., Colorado potato beetle (Leptinotarsa decemllneata Say), western com roorworm (Diabrotica virgifera virgifera LeConte)); chafers andother beetles from the family Scaribaeidae (e.g., Japanese beetle (Popilliajaponica Newman) and European chafer (Rhizotrogus majalis

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Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition agronomic and nonagronomic pests include: adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig 5 (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)): adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies 10 from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g., Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family 15 Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also included are adults and larvae of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)), flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)), rust and 20 bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae, ticks in the order Ixodidae (e.g., deer tick {Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma 25 americanum Linnaeus) and scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), 30 house cricket (Acheta domesticus Linnaeus), mole crickets (Gryllotalpa spp.)); adults and immatures of the order Diptera including leafminers, midges, fruit flies (Tephritidae), frit flies (e.g., Oscinellafrit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis"Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya 35 spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bat flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g.. Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium

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spp.), biting midges, sand flies, sciarids, and other Nematocera; adults and immatures of the order Thysanoptera including onion thxips {Thrips tabaci Lindeman) and other foliar feeding thrips; insect pests of the order Hymenoptera including ants (e.g., red carpenter ant {Camponotus ferrugineus Fabricius), black carpenter ant {Camponotus pennsylvanicus De 5 Geer), Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant {Solenopsis invicta Buren), Argentine ant (Iridomyrmex kumilis Mayr), crazy ant {Paratrechina longicornis Latreille), pavement ant {Tetramorium caespitum Linnaeus), cornfield ant {Lasius alienus Forster), odorous house ant {Tapinoma sessile Say)), bees 10 (including carpenter bees), hornets, yellow jackets and wasps; insect pests of the order
Isoptera including the eastern subterranean termite {Reticulitermes flavipes Kollar), western subterranean termite {Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite {Incisitermes immigrans Snyder) and other termites of economic importance; insect pests of the order Thysanura such 15 as silverfish (Lepisma saccharina Linnaeus) and firebrat {Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse {Pediculus humanus humanus Linnaeus), chicken body louse {Menacanthus stramineus Nitszch), dog biting louse {Trichodectes canis De Geer), fluff louse {Goniocotes gallinae De Geer), sheep body louse {Bovicola ovis Schrank), short-nosed 20 cattle louse {Haematopinus eurysternus Nitzsch), long-nosed cattle louse {Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea {Xenopsylla cheopis Rothschild), cat flea {Ctenocephalides felisBouche), dog flea {Ctenocephalides canis Curtis), hen flea {Ceratophyllus gallinae Schrank), sticktight flea {Echidnophaga gallinacea 25 Westwood), human flea {Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider {Loxosceles reclusa Gertsch & Mulaik) and the black widow spider {Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede {Scutigera coleoptrata Linnaeus). Compounds of the present invention also 30 have activity on members of the Classes Nematoda, Cestoda, Trematoda, and
Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the 35 genus Trickodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, -Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

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Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g.. Alabama argillacea Hiibner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Ar chips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice 5 leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny"bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hiibner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod 10 webworm), Lobesia botrana Denis & Schiffermuller (grape berry moth), Pectinophora gossypiellaSaunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafininer), Pieris brassicae Linnaeus (large white butterfly), Pier is rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hiibner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), 15 Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hiibner (cabbage
looper) and Tuta absoluta Meyrick (tomato leafininer)). Compounds of the invention also have commercially significant activity on members from the order Homoptera including: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi 20 De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaeto siphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopteruspruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip 25 aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosipum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribism"gri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (com leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English 30 grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii
Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and 35 Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris
(potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper),Nilaparvata lugens Stal (brownplanthopper),

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Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper). Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythrone.ov.ra spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Iceryapurchasi Maskell (cottony cushion scale), Ouadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster ■ (pear psylla), Trioza diospyri Ashmead (persimmon psylla). These compounds also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthothrips citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemlimata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural utility. Thus compositions of the present invention can further comprise a biologically effective amount of at least one additional biologically active compound or agent. Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid, avermectin, azadirachtin, azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chJorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfiuthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenotbicarb, fenoxycarb, fenpropathrin, fenprbximate, fenvalerate, fipronil, flonicamid, flucythrinate, tau-fluvalinate, flufenoxuron, fonophos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos,

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lufenuron, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, mefhoxychlor. monocrotophos, methoxyfenozide, nithiazin, novaluron, oxamyl parathion. parathion-methyL permethrin, phorate, phosalone, phosmet, phosphamidon. pirimicarb. profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, sulprofos, 5 tebufenozide, teflubenzuron. tefluthrin, terbufos, tetrachlorvinphos, thiacloprid,
thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, carpropamid, captafoL captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cyflufenamid, cymoxanii, 10 cyproconazole, cyprodinil, (5)-3,5-dichloro-A/-(3-chloro-l-ethyl-1 -methyl-2-oxopropyl)-4-methylbenzamide (RH 7281), diclocymet (S-2900), diclomezine, dicloran, difenoconazole, (iS)-3,5-dihydro-5-memyl-2-(memyltMo)-5-phenyl-3-(phenylainino)-4H"-imidazol-4-one (RP 407213), dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid 15 (SZX0722), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide,
fiuazinam, fludioxonil, flumetover (RPA 403397), fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metomino-20 strobin/fenominostrobin (SSF-126), myclobutanil, neo-asozin (ferric methanearsonate),
oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propamocarb, propiconazole,
pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen. spiroxamine, sulfur,
tebuconazole, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram,
tiadinil, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and
25 vinclozolin; nematocides such as aldicarb, oxamyl and fenamiphos; bactericides such as
streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin,
dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate,
hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus
thuringiensis including ssp. aizawai and kurstaki, Bacillus thuringiensis delta endotoxin,
30 baculovirus, and entomopathogenic bacteria, virus and fungi. Compounds of this invention
and compositions thereof may be applied to plants genetically transformed to express
proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin). The effect of the
exogenous invertebrate pest control compounds and compositions may be synergistic with
the expressed toxin proteins.
35 A general reference for these agricultural protectants is The Pesticide Manual, 12th
Edition, C. D. S. Tomlin. Ed., British Crop Protection Council, Famham, Surrey, U.K., 2000.

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Preferred insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as cypermethrin, cyhalothrin, cyfluthrin, beta-cyfiuthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; 5 neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avermectin and emamectin; y-aminobutyric acid (GABA) antagonists such as endosulfan, ethiprole and fipronil; insecticidal ureas such as fhifenoxuron and triflumuron; juvenile hormone mimics such as diofenolan and pyriproxyfen; pymetrozine; and amitraz. Preferred biological agents for mixing with 10 compounds of this invention include Bacillus thuringiensis and Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi.
Most preferred mixtures include a mixture of a compound of this invention with cyhalothrin; a mixture of a compound of this invention with beta-cyfluthrin; a mixture of a 15 compound of this invention with esfenvalerate; a mixture of a compound of this invention with methomyl; a mixture of a compound of this invention with imidacloprid; a mixture of a compound of this invention with thiacloprid; a mixture of a compound of this invention with indoxacarb; a mixture of a compound of this invention with abamectin; a mixture of a compound of this invention with endosulfan; a mixture of a compound of this invention with 20 ethiprole; a mixture of a compound of this invention with fipronil; a mixture of a compound of this invention with flufenoxuron; a mixture of a compound of this invention with pyriproxyfen; a mixture of a compound of this invention with pymetrozine; a mixture of a compound of this invention with amitraz; a mixture of a compound of this invention with Bacillus thuringiensis and a mixture of a compound of this invention with Bacillus 25 thuringiensis delta endotoxin.
In certain instances, combinations with other invertebrate pest control compounds or
agents having a similar spectrum of control but a different mode of action will be
particularly advantageous for resistance management. Thus, compositions of the present
invention can further comprise a biologically effective amount of at least one additional
30 invertebrate pest control compound or agent having a similar spectrum of control but a
different mode of action. Contacting a plant genetically modified to express a plant
protection compound (e.g., protein) or the locus of the plant with a biologically effective
amount of a compound of invention can also provide a broader spectrum of plant protection
and be advantageous for resistance management.
35 Invertebrate pests are controlled in agronomic and nonagronomic applications by
applying one-or more of the compounds of this invention in an effective amount to the environment of the pests including the agronomic and/or nonagronomic locus of infestation to the area to be protected, or directly on the pests to be controlled. Thus, the present

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invention further comprises a method for the control of invertebrates in agronomic and/or nonagronomic applications, comprising contacting the invertebrates or their environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and an effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional biologically active compound is present on the same granule as the compound of the invention or on granules separate from those of the compound of this invention.
A preferred method of contact is by spraying. Alternatively, a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil. Compounds of this invention are also effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Compounds are also effective by topical application of a composition comprising a compound of this invention to the locus of infestation. Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds of this invention may also be impregnated into materials for fabricating invertebrate control devices (e.g. insect netting).
The compounds of this invention can be incorporated into baits that are consumed by the invertebrates or within devices such as traps and the like. Granules or baits comprising between 0.01-5% active ingredient, 0.05-10% moisture retaining agent(s) and 40-99% vegetable flour are effective in controlling soil insects at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact.
The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the pest"s life cycle, life stage, its size, location, time of year, host crop or animal, feeding

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behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, 5 effective use rates will range from about 1.0 to 50 mg/square meter but as little as
0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control.
The following TESTS demonstrates the control efficacy of compounds of this
10 invention on specific pests. "Control efficacy" represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A through K and L for compound descriptions. The following abbreviations are used in the Index Tables which follow: t is tertiary, n is normal, i is iso, c is cyclo, s is
15 secondary, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyi, c-Pr is cyclopropyl, Bu is butyl, s-Bu is secondary butyl, Pent is pentyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is efhylthio, CN is cyano, and N02 is nitro. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.

20

INDEX TABLE A






Compound R2 R3
l(Ex. 3) H /-Pr
2 H /-Bu
H /-Pr
4 H /-Pr
5 H r-Bu
6 H /-Bu
1 H /-Pr
8 H /-Pr

{R4}2
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me

4-CF3-Ph
4-CF3-Ph
4-OCF3~Ph
2-Me,4-SCHF2-Ph
2-Me,4-SCHF2-Pii
4-OCF3-Ph
2-Me;4-S02CHF2-Ph
2-Me,4-SOCF3-Ph

m.p. °C.

184


Compound R2 R3 (R4)n
9 H f-Bu 4-Me
10 H f-Bu 4-Me
11 H i-Pr 4-Me :
12/ H r-Bii 4-Me
" 13." . H "->**.■" 4-Me
14 H i-Pr 4-Me.
15 H >Bu 4-Me
16 H f-Bu 4-Me
17 H i-Pr 4-Me
.18 H f-Bu 4-Me
"..19 H i-Pr 4-Me
20 H r-Bu 4-Me
21 H i-Pr 4-Me
22 H r-Bu 4-Me
. 23/ H i-Pr 4-Me
. 24 H f-Bu 4-Me
,25
26
27
28
29 H H 4-r-Bu-Ph
30 H Me 4-Me
31 H i-Pr 4-Me
32 H i-Pr 4-Me
33 H Me 4-Me
34 H i-Pr 4-Me
35 H Me 4-Me
36 H Me 4,5-Cl2
37 H i-Pr 4,5-Cl2
.: 38 H i-Pr 4,5-Cl2
39 H Me " 4,5-Cl2
: 40 H i-Pr 4-Me-5-Cl
; 41 H Me 4-Me-5-Cl
42 H i-Pr 4-Me-5-Cl
43 H Me 4-Me-5-Cl

2-Me,4-S02CHF2-Ph
2-Me,4-SOCHF2"ph
4-SCHF2-Ph ■.".:■ 4-SCHF^Pt 2-Me,4-GF3-Ph 2-Me,4>OCEyPh
2-Me,4-Cl-Ph
2-Me,4-Cl-Ph
2-Me-6-GF3-3-pyridiQyl
2-MeT6-GF3-3-pyridihyl
l-Ph-3rMe-5-pyrazolyl
l-Ph-3-Me^pyrazdyl
2-Me-6-Cl-3-pyridinyl
2-Me-6-Cl-3-pyridinyi
3,5-Cl2-Ph l-(2-a-3-pyridinyl)-3-Br-5-pyrazolyl l-(2-Cl-3-pyridinyl)-3-Br-r5-pyrazolyl
l-(2-Cl-Ph)-3-CF3-5-pyrazolyl l-(2-Cl-3-pyridinyI)-3-CF3-5-pyrazolyl l-(2-Ci-3-pyridinyl)-3-CF3-5-pyrazolyl l-(2-Cl-Ph)-3-CF3-5-pyrazolyl l-(2-Cl-Ph)-3^CF3-5.pyrazolyl l-(2-Cl-Th)-3-CF3-5-pyrazolyl l-(2-Cl-3-pyridinyl>3-Br-5-pyrazolyl l-(2-Cl-3-pyridiriyl)-3-Br-5-pyrazolyl l-(2-Ci-3-pyridinyi)-3-CF3-5-pyrazolyl l-(2-Cl-3-pyridinyi)-3-Br-5-pyrazolyl l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl l-(2-Cl-3-pyridihyl)-3-CF3-5-pyrazolyl

mp:?C.
■■.*."-"■■
.■*■■;.. * .■
*:"
*
*.
222.5-225 214-215
*
* *
. *
*■■ 214-215 159-161 198-202 188-190 170-174 201-203 238-240
240 208-210
208 234-236 229-231 222-223 226-228

* See Index Table L for !H NMR data.

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185 INDEX TABLE B





Compound R3
Bl /i-Pr
B2 /-Pr
B3 /-Pr
B4 /-Pr
B5 i-?T
B6 /-Pr
B7 r-Bu
B8 r-Bu
B9 /-Pr
BIO Me
Bll /-Pr
B12 Me
B13 /-Pr
B14 Me
B15 /-Pr
* See Index Table L for l H NMR data.

J m.p. "C.
2-Me,4-SCHF2-Ph 178.5-180.5
2-Me,4-S02CHF2-Ph 207-210
2-Me,4-SOCF3-Ph 175-180
2-Me,4-CF3-Ph . 201-203
2-Me-6-CF3-3-pyridinyl 221-5-222.5
l-Ph-3-Me-5-pyrazolyl *
l-Pb-3-Me-5-pyrazo!y) *
2-Me-6-CF3-3-pyridinyl *
2-Me-5-Cl-3-thienyl *
1 -C2-Cl-Ph)-3-CF3-5-pyTazolyl 266-270
1 -(2-Cl-Ph)-3-CF3-5-pyrazo)yl 232-236
1 -C2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl 233-236
l-(2-Cl-3-pyridinyI)-3-CF3-5-pyrazolyl 220-222
1 -(2-Cl~3-pyridinyl)-3-Br-5-pyrazolyl 235-238
l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 198-200
INDEX TABLE C







Compound
E2
R! R4

R3

J
CJ H /-Pr Me 4-F-Ph
C2 H /-Pr Me 4-Br-Ph

m.p. °C.
*

186


(Inmpound R2. R3
C3 H i-Pr
C4 H i-Pr
.C5 H i-Pr
C6 H i-Pr
C7 H i-Pr
C8 H i-Pr
C9 Ex.2) H i-Pr
C10 H I-PR
C12
C14 C15
-(CH2)5-
H H
i-Pr c-hexyl

R4 Me Me Me Me Me : Me Me Me
Ph
Me Ph

" 4-Cl-Ph 2-N02-Ph 3-Cl-Ph 4-CN-Fh i-G%Ph 2-Me-4-SOCF3Ph ■ 4-pCT3-Ph 2-Me-4-Br-Ph
2-rthienyl
3-pyridinyI 2-thienyl"


m ;p;6c;
■ *:■.■
, *: ■■■
■: ■*"■■".-
■ .*,„-■ "■
*"■"■"!■"
68-75-




C23 H Et Me
C24 H i-Pr Me
C25 . H Me Me
C26 H Me Me
C27 H i-Pr Me
C28 H i-Pr Me
C30 H Et CH2CF3
C31 H i-Pr CH2CF3
C32 H Me Et
C33 H Et Et
C34 H i-Pr Et
C35 H Me CH2CF3
C36 H Me CH2CF3
C37 H Et CH2CF3
C38 H i-Pr CH2CF3
C39 H Me . - Et

l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-a-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl
l-(2-Cl-Ph)-3-CF3-5-pyrazolyl
l-(2-Cl-Ph)-3-Br-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl>3-GF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
l-(2-Gl-3-pyridmyl)-3-Br-5-pyrazolyl
l-(2-Cl3-pyridinyl)-3-Br-5-pyrazolyl
l-(2-CI-3-pyridmyD-3-Br-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl

253-255 -.-;
214-216
230-232 ::
234-236
218-220
170-173
236-238
216-218
238-240
216-218
198-201
260-262
253-256
220-223
188-190
221-223

187


Compound R2 R3 R4.
C40 H Et Et
C41 H i-Pr Et

l-(2-Cl-3-pyricliiiyl)-3-Br-5-pyrazolyl l-2-Cl-3-pyridinyi)-3-Br-5-pyrazoIyl

m.p. °C 182-184 172-175

INDEX TABLED
* See Index Table L for JH NMR data.


Compound R2 R3 R4 J m.p. °C.
Dl H i-Pr 2-Me 4-CF3-Ph 223-225
D2 H f-Bu 2-Me 4-CF3-PI1 260-261
D3 (Ex. 1) H i-Pr 2-Me 4-OCF3-ph 202-204
D4 H i-Pr 2-Me 2-.Me,4-CF3-Ph 235-236
D5 H z-Pr 2-Me 2-Me,4-OCF3-Ph 198-200
D6 H i-Pr 2-Me 2-Me-€-CF3-3-pyridinyl 240-243
D7 H i-Pr 2-Me l-Ph-3-CF3-5-pyrazblyI 215-220 (dec.)
D8 H i-Pr 2-Me l-(2-Cl-Ph)-3-CF3-5-pyrazolyl 140-144
D9 H i-Pr 2-Me 2-Me-3-Cl-Ph 260-261
D10 H i-Pr 2-Me l-(2-Cl-3-pyridiijyl)-3-CF3-5-pyrazolyl 207-209*
Dll Me Me 2-Me l-(2-CI-Ph)-3-CF3-5-pyrazoryl 172-175
D12 H Me 2-Me l-(2-a-Ph)-3-CF3-5-pyrazolyl 193-195
D13 H i-Pr 2-C1 l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl 175-179
D14 H i-Pr 2-Me l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazoIyl 156-158
D15 H i-Pr 2-C1 l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 160-165

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Compound R2 R3 R4
D16 H Me 2-C1
D17 H Me 2-C1
D18 H Me 2-Me
D19 H Me 2-Me
D20 H ally! Me
D21 H all.yl Me
See Index Table L for lE NMR data.

J m.B. °C.
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl 178-180
1 -(2-Cl-3-pyridmy])-3-Br-5-pyrazolyl 118-125
1 -(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl 207-209
1 -(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 216-218
1 -(2-Cl-3-pyridinyI)-3-CF3-5-pyra2olyl 187
l-f2-C!-3-pyridinyl)-3-Br-5-pyrazolyl 199-201
INDEX TABLE E






Compound R2 R3 {R4
El H /-Pr H
E2 H /-Pr H
E3 H /-Pr 2-C1
E4 H /-Pr H
E5 H /-Pr 2-Me
E6 H /-Pr 2-Me
E7 H /-FT 2-Me
E8 H /-Pr 2-Me
E9 H /-Pr 2-Me
E10 H ■ Et 2,6-Cl2
EH H Me 2,6-Ci2
E12 H /-Pr 2,6-Ch
E13 H Me 2,6-Ch
EI4 H Et 2,6-Ch
EI5(Ex. 5) H /-Pr 2,6-Ch
E16 Me Me 2,6-Ch
E17 Me Me 2:6-C12
E18 Me Me . 2,6-Br2
E19 H Et 2,6-Br2

J
4-CF3-Ph 4-OCF3-Ph 4-CFrPh 2-Me,3-Cl-Ph l-(2-CI-3-pyridinyl)-3-CF3-5-pyrazolyl 1 -(2-Cl-Ph)-3-CF3-5-pyra2olyl 1 -(2-C]-Ph)-3-Br-5-pyrazolyl l-(2-Cl-3-pyridinyl)-3-CN-5-pyrazolyl K2-Cl-3-pyridinyI)-3-Br-5-pyrazolyl l-C2-Cl-3-pyridinyl)-3-Br-5-pyra2olyl 1 -(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl ]-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl ■ 1 -(2-Cl-3-pyridinyl)-3-CF3-5-pyra2olyl l-(2-CI-3-pyridinyI)-3-CF3-5-pyrazoly[ l-(2-"Cl-3-pyridmy])-3-CF3-5-pyrazolyl l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl I-(2-Cl-3-pyridinyI)-3-Cl-5-pyrazoIyI 2,6-Br2-3-NH2-4-pyridinyl l-(2-Cl-3-pyridmyl)-3-CF3-5-pyrazolyl

m.p. °C.
*
138-140
170-173
*
112-115
147-150
223-224
142-145
238-240
207-209
240-242
153-155
224-226
208-210
223-225

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Compound R2
E20
E2I
E22
E23
E24
E25
E26
E27
E28
E29
E30
E31
E32
E33
E34
E35
E36
H Et H H H H Me H H H H H H H H H Et
R3 /-Pr Et /-Pr
NMe2 H
NMe2 Me Me Et Me Et Me /-Pr
NMe2 /-Pr
NMe2 Et
* See Index Table L for *H NMR

2,6-Br2 2:6-Cl2 2-Cl-6-Br 2,6-Br2 2,6-C!2 2,6-C\2 2-Cl-6-NMe2 2,6-Br2 2,6-BF2 236-Br2 2,6-Br2 2,6~Br2 2,6-Br2 2,6-Cl2 2,6-Br2 2,6-Cl2 2,6-Cl2 data.

J
l-(2-Clo-pyridinyI>3-CF3"5-pyrazolyl
]-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyi
l-(2-Cl-3-pyridinyI)-3-Cl-5-pyrazolyl
]-(2-Cl-3-pyridinyI)-3-Br-5-pyrazolyl
U(2-C\-3-pyridmyl)-3-BT-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl
1 -(2~CI-Ph)-3-CF3-5-pyrazoiyi
1 -(2-Cl-Ph)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
I-(2-Cl-3-pyridirryI)-3-Cl-5-pyrazoiyl
1 -(2-C1-3 -pyridinyl)-3-Cl-5-pyrazolyl
l-(2-Cl-3-pyridiriyl)-3-Cl-5-pyrazolyl
H2-Cl-3-pyridinyI)-3-CF3-5-pyrazoIyI
1 -(2-Cl-Ph)-3-CF3-5-pyrazoly!
2,6-Cl2-3-NH2-4-pyridiiryI
2,6-ci2-3-NH2-4-pyTidiny1


m.D. °C.
>240
231-233
224-226

INDEX TABLE F


Compound R3 (R4 J m.p. °C.
Fl /-Pr H 4-CF3-Ph
F2 t-Bu H 4-CF3-Ph 199-200
F3 /-Pr 6-Me 4-CF3-Ph 218-220
F4 ;-Pr 4,6-Me-2 4-CF3-Ph 235-237
F5 /-Pr 6-Me 2-Me-4-Cl-Ph 172-174
F6 t-Bu H 2-Me-3-CJ-Ph 2IS-220
F7 " /-Pr H 2-Me-3-Cl-Ph
* See Index Table L for lH NMR data

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190 INDEX TABLE G
Compound R2. R3 (R4)n J m.p. °C.
Gl H /-Pr 4-Me 4-CF3~Ph 121-123*
G2 H /-Pr 4-Me . l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl 183-184
G3 H S-CH(Ph)Me H 3-pyridinyl
G4 H /-Pr 4--Me l-(2-C]-3-pyridinyl)-3-Br-5-pyrazo!yl 172-175
G5 H /-Pr 4-Me l-(2-Cl-3-Ph)-3-Br-5-pymzolyl
G6 H /-Pr 4-Me-6-Cl l-(2-Cl-3-pyridinyl)-3-Br~5-pyrazoIyi 175-177
G7 H Me 4-Me-6-Cl l-(2-C]-3-pyridiayl)-3-Br-5-pyrazolyl 230-235
G8 Me Me 4,6-Cl? l-C2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 225-227
G9 H NMe2 4,6-Ci2 l-(2-Cl-3-pyridinyl>3-Br-5-pyrazolyl 125-130
G10 H H 4,6-Cl2 K2-C]-3-pyridiny])-3-Br-5-pyrazoly] 130-135
Gil H Me 4,6-Cl2 l-(2-Cl-3-pyridinyI)-3-Br-5-pyrazolyl 214-216
G12 H - Et 4,6-Cl2 l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 210-212
G13 H /-Pr 4,6-Cl2 l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyI 208-210
G14 . H NMe2 4,6-Cl2 4,6-C]2-3-NH2-2-pyridinyl 192-194
G15 Me Me 4,6-C!2 4,6-Cl2-3-NH2-2-pyridmy] 171-172
G16 H H 4,6-Br2 l-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl >240
G17 H Me 4,6-Cl2 l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
G18 H Et 4,6-Cl2 l-(2-Cl-3-pyridinyI)-3-CF3-5-pyrazolyl
G19 H /-Pr 4,6-Cl2 . l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
G20 H H 4,6-Cl2 l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl
G21 Et Et 4,6-CI2 l-(2-CI-3-pyridinyl)-3-CF3-5-pyrazolyI
G22 H Me . 4,6-Cb l-(2-CI-3-pyridinyl>3-Cl-5-pyrazolyl
G23 H Et 4,6-Cl2 l-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G24 H /-Pr 4,6-Cb l-(2-Cl-3-pyridinyI)-3-Cl-5-pyrazoJyI
G25 H NMe2 4,6-Cl2 l-(2-CI-3-pyridinyl)-3-CF3-5-pyra2;oly]
G26 Me Me. . 4,6-Cl2 l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazo]yl
G27 Me Me 4,6-Cl2 l-(2-Cl-3-pyridinyI)-3-C]-5-pyrazoly]
G28 H H 4..6-Cl2 l-(2-Cl-3-pyridinyl)-3-a-5-pyrazolyl

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ComDOund R2 R3 (R4)n
G29 H NMe2 4,6-012
G30 Et Et 4:6-Cl2
G31 H Me 4,5,6-Cl3
G32 H -Et 4,5,6-CS3
G33 H CH2CH2SMe 4,6-Cl2

l-(2-Cl-3-pyridinyI)-3-Cl-5-pyrazoryI
l-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
l-(2-Cl-3-pyridinyI)-3-CF3-5-pyrazolyl
l-(2-CI-3-pyridmyI}-3-CF3"5-pyra2olyl
l-(2-Cl-3-pyridiDyl)-3-CI-5-pyrazolyl

m.p. °C.

* See Index Table L for * H NMR data.
INDEX TABLE H

HNi-Pr

Compound HI * See Index Table J for l H NMR data.

2~Me-4-Br-Ph

m.p. °C.
*

INDEX TABLE I




Compound
U 12 13 14 15 16 (Ex. 4) 17 18 .19

Ed
Me H H Me H Me H H H

R3 Me
/-Pr
Me
Me,
Me
Me
/-Pr
/-Pr
Me

(R4) J m.p. °C.
4,6-Me2 ]-(2-CJ-3-pyridinyI)-3-CF3-5-pyrazoIyl 244-245*
4,6-Me2 l-(2-Cl-3-pyridinyl)-3-CF3-5-pyra20lyl
4,6-Me2 l"(2-Cl-3-pyridinyl)-3-CF3-5-pyrazolyl 195-197
4,6-Me2 l-(2-C]-3-pyridinyJ}-3-Br-5-pyrazolyl 243-244
4;6-Me2 l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 202-204
4-Me l-(2-Cl-3~pyridinyI)-3-Cl-5-pyrazolyl 232-236
4-Me 2-(2-a-3-pyridmyI>3-Cl-5-pyrazo]yl 87-90
4,6-Me2 l-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl 81-83
4-Me l-(2-C]-3-pyridinyl)-3-Cl-5-pyrazolyl 205-207

* See Index Table L for ] H NMR data.

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Compound R2 R3
J1 H i-Pr
J2 H /-Pr
J3 H Me
J4 H Me
J5 H Me
J8 H /-Pr

El Me
Me Me Me Me Me

] -(2-C1-Ph)-3-CF3-5-pyrazoIyI 1 -(2-C1-3 -pyridinyI)-3 -CF3 -5 -pyrazolyl
1 -(2-Cl-Ph)-3-CF3-5-pyrazolyl
1-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazoly]
l-(2-CI-3-pyridinyl)-3-Br-5-pyrazolyl
1 -(2-C1-3 -pyridinyI)-3-Br-5-pyrazo)yl

m.p. °C.
174-176*
206-208
166-168
176-178
227-229
172-174

See Index Table L for 1HNMR data.
INDEX TABLE K




m.p. °C. 224-226* 168-172 185-190 160-162 176-179

Compound R2 R3
Kl H Me
K2 H /-Pr
K3 H Me
K4 H /-Pr
■K5 H Me
K6 H /-Pr

EZ Me Me Me Me Me Me

l-(2-Cl-3-pyridinyI)-3-Br-5-pyrazolyl
1 -(2-C1-3 -pyridinyI)-3-Br-5-pyrazo]yl
■1 -(2-CI-Ph)-3-CF3-5-pyrazoIyI
1 -(2-C!-Ph)-3-CF3-5-pyrazolyl
l-(2-Cl-3-pyridinyl)-3-CF3-5-pyrazo]yl
] -(2-a-3-pyri&myd-3-CF3-5-pyrazo)yl 180-182

* See Index Table L for ] H NMR data.

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INDEX TABLE L
Compd. No. 1HNMR Partial Spectrum Data (CDCI3 solution unless indicated otherwise)5
1 10.63 (s,lH), 5.58 (d,1lH)"
2 10.55 (s,lH), 5.60 (s.lH)
3 " 10.55 (S.1H), 5.58 (d,lH)
4 9.80 (s,lH), 5.60 (d,lH)
5 9.68 (s,lH), 5.60 (s,lH)
6 10.45 (s/IH), 5.60 (d,lH)
7 9.93 (s,!H), 5.60 (d,lH)
8 9.90 (s,lH), 5.59 (d,lH)
9 9.83 (s,lH), 5.60 (s,lH)
10 9.78 (s,lH), 5.60 (s,lH)
11 10.57 (s,lH), 5.58 (d,lH)
12 10.46 (s1H), 5.60 (s1H)
13 9.85 (s,lH), 5.60 (d,lH)
14 9.82 (s,lH), 5.58 (d,lH)
15 9.76{s,lH), 5.62(s,IH)
16 9.68 (s,lH), 5.60 (s,lH)
. CI 10.19 (s,lH), 5.72 (d;IH)
C2 10.23 (s, IH), 5.71 (d,IH)
C3 10.23 (s,!H), 5.66 (s,lH)
C4 9.50 (s,lH), 5.62 (d,IH)
C5 10.18 (s,lH), 5.67 (s,lH)
C6 10.41 (s,lH), 5.62 (s,IH)
C7 10.36 (s,lH), 5.66 (sslH)
C8 9.56 (s.lH).. 5.54 (d,lH)
C10 9.56 (s,lH), 5.53 (d,lH)
D10 12.2 (brs,lH), 6.0 (s,IH)
El 10:10 (s,lH), 6.24 (s,lH)
E2 10.08 (s,lH),6.30 (s,lH)
E3 8.36 (mJH), 7.94 (d,lH), 7.79 (d,2H), 4.36 (m,lH), 1.32 (d,6H)
E4 10.05;IH),6.16(d,IH)
E7 7.75 (d,lH), 7.67 (sTlH)
ES 8.23 (s,lH),7.77 (d,IHy
E23 (DMSO-d6) 10.8 Cm, 1H), 9.5 (s, 1H)
E24 (DMSO-d6))10.5(s,lH)
E25 (DMSOd6)) 10.9 (s,lH)
E26 (DUSO-d6) 13.4(brS;lH)

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E27 9.0(s,lED,6.2(m,lH)
E28 9.25 (s5lH), 6.18 (rn5lH)
E29 (DMSO-d6) 10.9 (s,]H), 8.55 (m,lH)
E30 9.3(s,lH), 625(t,lH)
E31 (DMSO-d6) 10.75 (s,lH), 8.55 (m,lH)
E32 (DMSOd6)13.5(brs,lH)
E33 (DMSO-d6) 10.9 (m,lH), 9.6 (s,lH)
E34 9.5 (brs,lH), 6.05 (d,lH)
E35 (DMSO-d6) 10.9 (s,lH), 6.66 (m,lH)
E36 10.3 (s,lH)
Fl 11.56 felH), 8.4] (d,lH)
Gl 11.97 (s,lH)
HI 5.56 (d,lH)
a 1H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singiet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-rrraltiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.
. BIOLOGICAL EXAMPLES OF THE INVENTION
.TESTA For evaluating control of diamondback moth (Plutella xylostella) the test unit consisted of a small open container with a 12-14-day-old radish plant inside. This was pre-infested with 10-15 neonate larvae on a piece of insect diet by use of a core sampler to remove a plug from a sheet of hardened insect diet having many larvae growing on it and transfer the plug containing larvae and diet to the test unit. The larvae moved onto the test plant as the diet plug dried out.
Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc.), unless otherwise indicated. The formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co.) positioned 1.27 cm (0.5 inches) above the top of each test unit. AH experimental compounds in these tests were sprayed at 250 ppm and replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed.
Of the compounds tested the following provided very good to excellent levels of plant protection (ratings of 0-1,10% or less feeding damage): 1, 2, 3, 4, 5, 6, 7, 8,9, 12, 13,15,

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16,19, 20, 21, 22, 23, 24, 30, 31, 32, 33, 34, 36, 37, 38, Bl, B3, B5, Bl 1, B12, B15, CI, C2, C3, C7, C9, C24, Dl, D3, D4, D5, D6, D7, D8, D10, Dl 1, D12, D13, D14, D18, D19, D20, D21, E5, E6, E7, E8, E9, E10, El 1, E12, E13, E14, E15, E16, E17, E19, E20, E21, E22, Gl, G2, G4, G5, G6, G7, G8 G9: G10, G1l, G12, G13, J6, Kl and K2.
5 TEST B
For evaluating control of fall armyworm (Spodoptera frugiperda) the test unit consisted of a small open container with a 4—5-day-old com (maize) plant inside. This was pre-infested (using a core sampler) with 10-15 1-day-old larvae on a piece of insect diet. Test compounds were formulated and sprayed at 250 ppm as described for Test A. 10 The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A.
Of the compounds tested, the following provided excellent levels of plant protection (10% or less feeding damage): 30, 31, 32, 33, 34, 35, 36, B10, Bll, B12, B13, B14, Dl, D3, D7,D8, D10,D11, D14, D15, E5, E6, E7, E9, ElO, El 1, E12, E13, E22, G2, G4, G5, G6, G7, 15 G9, G10, Gll,G12,G13,J6 and K2.
TEST C
For evaluating control of tobacco budworm (Heliothis virescens) the test unit
consisted of a small open container with a 6-7 day old cotton plant inside. This was pre-
infested (using a core sampler) with 8 2-day-old larvae on a piece of insect diet.
20 Test compounds were formulated and sprayed at 250 ppm as described for Test A.
The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A.
Of the compounds tested, the following provided very good to excellent levels of plant protection (20% or less feeding damage): 31,32,33,34,35,36,37,312313,614, ; 25 B15, Dl, D4, D5, D6, D8, D10, Dl 1, D12, D13, D14, D15, D18, D19, D20, D21, E5, E6, E7,E9, E10,E12, E15,E20,E21, E22, G2, G5t G6, G7, G8, G9, G10, Gil, G12, and G13.
TEST D For evaluating control of beet armyworm (Spodoptera exigua) the test unit consisted of a small open container with a 4—5-day-old corn plant inside. This was pre-infested (using 30 a core sampler) with 10-15 1-day-old larvae on a piece of insect diet.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A.
Of the compounds tested, the following provided very good to excellent levels of 35 plant protection (20% or less feeding damage): 31, 32, 34, B13, B15, Dl, D3, D4, D7, D8, D10, Dll, D14, D19, E5, E6, E7, E9, ElO, E15, E22, Gl, G2, G4, G5, G6, G7, G9, G10, Gl 1, G12, G13, D20, J6 and K2.

WO 02/070483

PCT/US02/06582

196
TEST E For evaluating control of green peach aphid {Myzus persicae) through contact and/or systemic means, the test unit consisted of a small open container with a 12-15-day-old radish plant inside. This was pre-infested (using the cut leaf method) with 30-40 insects on 5 each piece of leaf, and the soil was covered with a layer of sand.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were repUcated three times. After spraying, the test units were maintained in a growth chamber and then visually assessed for insect mortality.
Of the compounds tested, the following resulted in at least 80% mortality: C48, El 3, 10 E14,E16, G4, G9,G1Q,G11 and G13.
TEST F For evaluating control of cotton melon aphid (Aphis gossypii) through contact and/or systemic means, the test unit consisted of a small open container with a 6-7-day-old cotton plant inside. This was pre-infested (using the cut leaf method) with 30-40 insects on each 15 piece of leaf, and the soil was covered with a layer of sand.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test E.
Of the compounds tested, the following resulted in at least 80% mortality: E9.

We Claim
1. A compound of Formula I, an //-oxide thereof or suitable salt thereof


" .N. ■"."■.
I
wherein
A and B are independently O or S;
each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4 R5;
K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered heteroaromatic ring optionally substituted with 1 to 3 R4;
nis 1 to 3;
R1 is H; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, N02, hydroxy, C1-C4 alkoxyC1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylammo, C2-C6 dialkylammo and C3-C6 cycloalkylamino; or
R1 is C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl,C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl or C(=A)J;
R2 is H, CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylammo, C2-C6 dialkylammo, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl or C2-Cg alkylcarbonyl;
R3 is H; G; or CrC6 alkylC2-C6 alkenyl,C2-C6 alkynyl, C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of G, halogen, CN, N02, hydroxy,C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthioC1-C4alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl and a phenyl,

phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6; or
R2 and R3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring may be optionally substituted with one to four substituents selected from R12; and G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=0), SO and S(0)2, and optionally substituted with one to four substituents selected from R12;
each R4 is independently H,C1C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1C6 haloalkyl, C2-C6 haloalkenyl, C2-C6g haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, NO2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, Cj-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylammo, C2-C6 dialkylamuio, C3-C6 cycloalkylamino, C1-C4 alkoxyalkyl, C1-C4hydroxyalkyl, C(O)RW, C02R10, C(O)NRlOR11, NR10Rn, N(R11)C02R10; or each R4 is independently a phenyl, benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R6;
each R5 is independently H, C^-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C3-Cg cycloalkyl, Cj-Cg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, C02H, CONH2, N02, hydroxy, CrC4 alkoxy, C1-C4 haloalkoxy, C!-C4 alkylthio, CJ-C4 alkylsulfinyl, CJ-C4 alkylsulfonyl, C1-C4 haloalkylthio, C \ -C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-Cg trialkylsilyl; or
each R5 is independently a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted with one to three substituents independently selected from R6; or
(R5)2 when attached to adjacent Carbon atoms can be taken together as -OCF2Q-," -CF2CF20-, or-OCF2CF20-; and

each R6 is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6
cycloalkylC1-C4 haloalkyl/C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkylthio, C1-C4 alkylsulfinylC1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C4 dialkylamino, C3-C6 cycloalkylamino, C4-C6 (alkyl)cydoalkylamino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl or, C3-C6trialkylsilyl;
each R10 is independently H, C1-C4 alkyl or C4-C6 haloalkyl;
each R11 is independently H or C1-C4 alkyl; and
each R12 is independently C1-C2 alkyl, halogen, CN, N02 or C1-C2 alkoxy; provided that
(1) when J is a phenyl ring optionally substituted with 1 to 4 R5, then
A and B are both O;
R1sH;
R2 is H or CH3;
R3 is C1-C4 4 alkyl optionally substituted with one or more substituents independently selected from halogen, CN, OCH3 or S(0)pCH3;
each R4 is independently CH3, CF3, CN or halogen, and one R4 group is attached to the K ring at the atom adjacent to the NR^C(=A)J moiety;
each R5 is independently H, halogen, methyl, CF3, OCF3, OCHF2, S(0)pCF3,
S(0)pCHF2, OCH2CF3, OCF2CHF2, S(0)pCH2CF3 or S(0)pCF2CHF2; or a phenyl, pyrazole, imidazole, triazole, pyridine or pyrimidine ring, each ring optionally substituted with one to three substituents independently selected from C1-C4 alkyl, C1-C4 haloalkyl, halogen or CN;
p is 0,1 or 2;
(2) the compound of Formula I is other than 5-(benzoylamino)-iV-methyl- \H-
imidazole-4-carboxamide; and
(3) the compound of Formula I is other than l-(4-fluorobenzyl)-4-(3-
pyridylcarbonylamino)-5-irnidazolecarboxamide, l-(3-chlorobenzyl)-4-(3-pyridylcarbonylammo)-5-imidazolecarboxarnide, l-(4-t-butylbenzyi)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-(3-methoxybenzyl)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-(4-methylbenzyl)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-(2-fiuorobenzyl)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-benzyl-4-(2-pyridylcarbonylamino)-5-imidazolecarboxamide, 1 -benzyl-4-(4-pyridylcarbonylammo)-5-imidazolecarboxamide, l-(4-t-butylbenzyl)-4-(4-

pyridylcarbonylanimo)-5-imidazolecarboxarmde/l-(4-fluorobenzyl)-4-(4-pyridylcarbonylamino)-5-imidazolecarboxamide, and l-benzyl-4-(2-mienylcarbonylammo)-5-imidazolecarboxamide.
2. The compound as claimed in claim 1 wherein J is a phenyl ring optionally substituted with 1 to 4 R5.
3. The compound as claimed in claim 2 wherein R3 is C1-C4 alkyl.
4. The compound as claimed in claim 1 wherein
A and B are both O;
J is a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-1.J-2.J-3, J-4 and J-5,





Q is O, S or NR5; and
W, X, Y and Z are independently N or CR5, provided that in J-4 and J-5 at least one ofW,X,Y or Z is N.
5. The compound of Claim 4 wherein
each R4 is independently C1C4 alkyl C1C4haloalkyl, halogen, CN, N02 or
C1C4 alkoxy, and one R4 group is attached to the K ring at the atom adjacent to either the NR1C(=A)J moiety or the C(=B)NR2R3 moiety; and
each R5 is independently H, C1C4alkyl, C1C4 haloalkyl, halogen, CN, N02, C1-C4 haloalkoxy C1C4alkylthio, C1C4alkylsulfinyl, C1C4 alkylsulfonyl, C1C4 haloalkylthio, C1C4haloalkylsulfinyl, C1C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; or a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with R6.
6. The compound as claimed in claim 5 wherein
J is selected from the group consisting of J-6, J-7, J-8, J-9, J-10, J-11, J-12 and J-13









and

R5 is H, C1C4 alkyl, C1-C4 haloalkyl, or
V is N, CH, CF, CC1, CBr or CI;
each R6 and R7 is independently H, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6
haloalkyl, halogen, CN, C1-C4 alkoxy, C1-C4 haloalkoxy or C1-C4
haloalkylthio; and R9 is H, CrC6 alkyl, CrC6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6
alkynyl or C1-C6 haloalkynyl; provided R7 and R9 are not both H.
7. The compound of Claim 6 wherein V is N.
8. The compound of Claim 6 wherein V is CH, CF, CC1 or CBr.
9. The compound of Claim 7 or Claim 8 wherein R1is H;
R2is H or CH3;
R3 is C1-C4 alkyl optionally substituted with one Or more substituents
independently selected from halogen, CN, OCH3 or S(0)pCH3; each R4 is independently CH3, CF3, CN or halogen, and one R4 group is attached
to the K ring at the atom adjacent to the NR1C(=A)J moiety;

R6 is CrC4 alkyl, CrC4 haloalkyl, halogen or CN; R7 is H, CH3, CF3, OCH2CF3, OCHF2 or halogen; and p is 0,1 or 2.
10. The compound as claimed in claim 9 wherein R3 is C1-C4 alkyl; one R4 group is independently CH3, C1, Br or I and is attached to the K ring at the atom adjacent to the NR!C(=A)J moiety; and a second optional R4 is H, F, CI, Br, I or CF3.
11. The compound as claimed in claim 10 wherein J is J-6; R6 is Cl or Br; and R7 is halogen, OCH2CF3 or CF3.
12. The compound as claimed in claim 11 wherein V is N; R3 is methyl, ethyl, isopropyl or tertiary butyl; and R7 is Br, Cl, OCH2CF3, or CF3.
13. The compound as claimed in claim 10 wherein J is J-7; R6 is Cl or Br; and R9 is CF3, CHF2, CH2CF3 or CF2CHF2.
14. The compound as claimed in claim 10 wherein J is J-8; R6 is Cl or Br; and R7 is halogen, OCH2CF3 or CF3.
15. The compound as claimed in claim 10 wherein J is J-9; R6 is Cl or Br; and R7 is OCH2CF3 or CF3.
16. The compound as claimed in claim 10 wherein J is J-10;R6 is Cl or Br; and R9 is CF3, CHF2, CH2CF3 or CF2CHF2.
17. The compound as claimed in claim 10 wherein J is J-ll; R6 is Cl or Br; and R7 is halogen, OCH2CF3 or CF3.
18. The compound as claimed in claim 10 wherein J is J-12; R6 is Cl or Br; R7 is H, halogen or CF3, and R9 is H, CF3, CHF2, CH2CF3, or CF2CHF2.
19. The compound as claimed in claim 10 wherein J is J-13; R6 is Cl or Br; R7 is H, halogen or CF3, and R9 is H, CF3, CHF2, CH2CF3 or CF2CHF2-
20. The compound as claimed in claim 1 selected from the group consisting of:
4- [[[ 1 -(2-Chlorophenyl)-3 -(trifluoromethyl)- l#-pyrazol-5-yl] carbonyl] amino] -
5-memyl-iV-l-memylethyl)-3-pyridincarboxamide,
4-Memyl-N(l-methylethmyl)-3-[[2-memyl-4-(trifluoromemyl)benzoyl]amino]-2-thiophencarboxamide,
1 -Methyl-N-( 1 -methylethyl)-5- [ [4-(trifluoromethyl)benzoyl] amino] - \H-
pyrazole-4-carboxamide;
4-[[[3-Bromo-l-(3-chloro-2-pyridmyl)-l/f-pyrazol-5-yl]carbonyl]amino]-5-
chloro-iV-methyl-3-pyridinecarboxamide;
3-[[[3-Bromo-l-(3-chloro-2-pyridmyl)-l//-pyrazol-5-yl]carbonyl]amino]-2,6-
dichloro-iV-methyl-4-pyridinecarboxamide;

2,6-dichlord-3-f[[l-(3-chloro-2-pyridinyl)-3-(truf1uoromethyl)-li/-pyrazol-5-
yl] carbonyl] amino] -N-( 1 -methylethyl)- 4-pyridinecarboxamide;
3-[[[3-Bromo-l-(3-chloro-2-pyridinyl)-lH-pyrazol-5-yl]carbonyl]amino]-6-
chloro-A^,4-dimethyl-2-pyridinecarboxamide;
3-[[[3-Bromo-l-(3-chloro--2-pyridmyl)-l//-pyrazol-5-yl]carbonyl]amino]-4,6-
dichloro-A^methyl-2-pyridinecarboxamide;
5- [[ [3 -Chloro-1 -(3 -ehloro-2-pyridjnyl)- l#-pyrazol-5-yl] carbonyl] amino] -N,6-
dimethyl-4-pyrimidinecarboxami(|e; and
5- [[ [3-Bromo-l -(3 -chloro-2-pyridinyl)- l/7-pyrazol-5-yl] carbonyl] amino] -
Af,A^2,6tetramemyl-4-pyridmecarboxamide.
21. A method for controlling an invertebrate pest comprising contacting the
invertebrate pest or its environment with a biologically effective amount of a compound
of Claim 1 or a compound selected from the group consisting of 5-(benzoylamino)-iV-
methyl- l/H-midazole-4-carboxamide, 1 -(4-fluorobenzyl)-4-(3 -pyridylcarbonylamino)-5-
imidazolecarboxamide, l-(3-cmorobenzyl)-4-(3-pyridylearbonylamino)-5-
imidazolecarboxamide, l-(4-t-butylbenzyl)-4-(3-pyridylcarbonylamino)-5-
imidazolecarboxamide, l-(3-memoxybenzyl)-4-(3-pyridylcarbonylamino)-5-
imidazolecarboxamide, l-(4-memylberizyl)-4-(3-pyridylcarbonylamino)-5-
imidazolecarboxamide, l-(2-fluoroberizyl)-4K3-pyridylcarbonylamino)-5-
imidazolecarboxamide, 1 -benzyl-4-(2-pyridylcarbonylamino)-5-imidazolecarboxamide,
1 -benzyl-4-(4-pyridylcarbonylamino)-5-imidazolecarboxamide, 1 -(4-t-butylbenzyl)-4-(4-pyridylcarbonylamino)-5-imidazolecarboxamide) l-(4-fluorobenzyI)-4-(4-pyridylcarbonylamino)-5-imidazolecarboxamide, and 1-benzyl-4-(2-thienylcarbonylamino)-5-imidazolecarboxamide, or an agriculturally suitable salt thereof.
22. The method as claimed in claim 21 comprising a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
23. A composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Claim 1, or a compound Selected from the group consisting of 5-(benzoylamino)-iV-methyl-l//-imidazole-4-carboxamide, l-(4-fluorobenzyl)-4-(3-pyridylcarbonylammo)-5-imidazolecarboxamide, l-(3-chlorobenzyl)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-(4-t-butylbenzyl)-4-(3-pyridylcarbonylanTino)-5-imidazolecarboxamide, l-(3-methoxybenzyl)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-(4-methylbenzyl)-4-(3-pyridylcarbonylammo)-5-imidazolecarboxamide, l-(2-fluorobenzyl)-4-(3-pyridylcarbonylamino)-5-imidazolecarboxamide, l-benzyl-4-(2-pyridylcarbonylamino)-5-imidazolecarboxamide, l-benzyl-4-(4-pyridylcarbonylamino)-5-

imidazolecarboxamide, l-(4-t-butylbenzyl)-4-(4-pyridylcarbonylamino)-5-imidazolecarboxamide, 1 -(4-fluorobenzyl)-4-(4-pyridylcarbonylamino)~5-imidazolecarboxamide, and l-benzyl-4-(2-thienylcarbonylamino)-5-irnidazolecarboxamide, or an agriculturally suitable salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
24. The composition as claimed in claim 23 further comprising a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
Dated this 22nd day of July 2003
Archana Shanker
Anand and Anand Advocates
Attorneys for the applications
Anand and Anand, Advocates Attorneys for the applicants

Documents:

720-mumnp-2003-abstract(08-02-2008).doc

720-mumnp-2003-abstract(08-02-2008).pdf

720-mumnp-2003-cancelled pages(08-02-2008).pdf

720-mumnp-2003-claims(granted)-(08-02-2008).doc

720-mumnp-2003-claims(granted)-(08-02-2008).pdf

720-mumnp-2003-correspondence 1(08-08-2003).pdf

720-mumnp-2003-correspondence 2(08-02-2008).pdf

720-MUMNP-2003-CORRESPONDENCE(18-4-2011).pdf

720-mumnp-2003-correspondence(ipo)-(19-02-2007).pdf

720-mumnp-2003-form 1(08-02-2008).pdf

720-MUMNP-2003-FORM 1(18-4-2011).pdf

720-mumnp-2003-form 13(08-02-2008).pdf

720-mumnp-2003-form 13(18-4-2011).pdf

720-mumnp-2003-form 13(22-07-2003).pdf

720-mumnp-2003-form 13(22-11-2005).pdf

720-mumnp-2003-form 18(27-02-2006).pdf

720-mumnp-2003-form 1a(22-07-2003).pdf

720-mumnp-2003-form 2(granted)-(08-02-2008).doc

720-mumnp-2003-form 2(granted)-(08-02-2008).pdf

720-MUMNP-2003-FORM 2(TITLE PAGE)-(18-4-2011).pdf

720-mumnp-2003-form 5(08-02-2008).pdf

720-mumnp-2003-form 5(22-07-2003).pdf

720-mumnp-2003-form-pct-ipea-409(22-07-2003).pdf

720-mumnp-2003-form-pct-isa-210(22-07-2003).pdf

720-mumnp-2003-power of attorney(08-02-2008).pdf

720-mumnp-2003-power of attorney(22-07-2003).pdf


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Patent Number 216029
Indian Patent Application Number 720/MUMNP/2003
PG Journal Number 13/2008
Publication Date 28-Mar-2008
Grant Date 05-Mar-2008
Date of Filing 22-Jul-2003
Name of Patentee E.I. DU PONT DE NEMOURS AND COMPANY
Applicant Address 1007 MARKET STREET, WILMINGTON, DELAWARE 19898
Inventors:
# Inventor's Name Inventor's Address
1 GARY DAVID ANNIS 13 FRANKLIN ROAD,LANDENBERG, PA 19350, USA
2 BRUCE LAWRENCE FINKELSTEIN 204 VALLEY STREAM DRIVE, NEWARK, DE 19702
PCT International Classification Number C07D213/82
PCT International Application Number PCT/US02/06582
PCT International Filing date 2002-02-28
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/273,474 2001-03-05 U.S.A.