AU2015201987A1 - Pesticidal compositions and processes related thereto - Google Patents
Pesticidal compositions and processes related thereto Download PDFInfo
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Abstract
5 This document discloses molecules having the following formula (I): and processes related thereto. (I)
Description
P/00/011 Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Invention Title: Pesticidal compositions and processes related thereto The following statement is a full description of this invention, including the best method of performing it known to us: 01064210_1.docx PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority from U.S. provisional application serial number 5 61/409,702 that was filed on 03 November 2010 the entire contents of this U.S. provisional application is hereby incorporated by reference. FIELD OF THE DISCLOSURE This disclosure is related to the field of processes to produce molecules that are useful 0 as pesticides (e.g., acaricides, insecticides, molluscicides, and nematicides), such molecules, and processes of using such molecules to control pests. BACKGROUND Pests cause millions of human deaths around the world each year. Furthermore, there 5 are more than ten thousand species of pests that cause losses in agriculture. The world-wide agricultural losses amount to billions of U.S. dollars each year. Termites cause damage to all kinds of private and public structures. The world-wide termite damage losses amount to billions of U.S. dollars each year. Stored food pests eat and adulterate stored food. The world-wide stored food losses .0 amount to billions of U.S. dollars each year, but more importantly, deprive people of needed food. There is an acute need for new pesticides. Certain pests are developing resistance to pesticides in current use. Hundreds of pest species are resistant to one or more pesticides. The development of resistance to some of the older pesticides, such as DDT, the carbamates, and 25 the organophosphates, is well known. But resistance has even developed to some of the newer pesticides. Therefore, for many reasons, including the above reasons, a need exists for new pesticides. 30 SUMMARY OF INVENTION In one aspect of the invention, there is provided a composition comprising a molecule according to: 1 A 01064210_1.docx "Formula One" R7 A ,N R8 R6 wherein (a) Ais R4 R2 1Nx attachment bond R5
R
1 N R 3 5 Al (b) RI is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, 0 substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
20 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O) 1 OR9, S(O)nN(R9) 2 , or R9S(O) 1 R9, wherein each said RI, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 15 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O) 1 OR9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); 20 (c) R2 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted CI-C 6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 o heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, 25 C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)aOR9, or R9S(O) 1 R9, 10 01064210_1.docx wherein each said R2, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)aOR9, C 6
-C
2 0 aryl, 5 or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); (d) R3 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted CI-C 6 alkoxy, 0 substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O), 1 R9, wherein each said R3, which is substituted, has one or more substituents 5 selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)nOR9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); 0 (e) Al is either (1) All R4 N-N attachment bond attachment bond to carbon R5 to nitrogen All where R4 is H, NO 2 , substituted or unsubstituted C 1
-C
6 25 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, S(O)nOR9, or R9S(O), 1 R9, 10C 01064210_1.docx wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, CI-C 6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)aOR9, C 6
-C
2 0 aryl, 5 or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9), or (2) A12 R 4 N attachment bond attachment bond-- ontoe to carbon R5 A12 where R4 is a C 1
-C
6 alkyl, 0 (f) R5 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted CI-C 6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted CI-C 6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, 5 OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O), 1 R9, wherein each said R5, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio 20 cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)nOR9, or C6-C20 aryl, (each of which that can be substituted, may optionally be substituted with R9); (g) R6 is substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2 C 6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 25 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 CIO cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, R9S(O), 1 R9, C 1
-C
6 alkyl C 6
-C
20 aryl (wherein the alkyl and aryl can 1 D 01064210_1.docx independently be substituted or unsubstituted), C(=X2)R9, C(=X1)X2R9, R9X2C(=X1)R9, R9X2R9, C(=O)(C 1
-C
6 alkyl)S(O)n(CI-C 6 alkyl), C(=O)(C 1
-C
6 alkyl)C(=O)O(CI-C 6 alkyl),
(C
1
-C
6 alkyl)OC(=0)(C 6
-C
2 O aryl), (C 1
-C
6 alkyl)OC(=O)(C 1
-C
6 alkyl), C 1
-C
6 alkyl-(C 3 -Cio cyclohaloalkyl), or (CI-C 6 alkenyl)C(=O)O(CI-C 6 alkyl), or R9X2C(=X1)X2R9, 5 wherein each said R6, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O) 1 OR9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, R9aryl, (each of which that can be substituted, may optionally be 0 substituted with R9), optionally R6 and R8 can be connected in a cyclic arrangement, where optionally such arrangement can have one or more heteroatoms selected from 0, S, or, N, in the cyclic structure connecting R6 and R8; 5 (h) R7 is 0, S, NR9, or NOR9; (i) R8 is substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2 C 6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 0 CIO cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl OR9, OR9S(O), 1 R9, C(=X1)R9, C(=X1)OR9, R9C(=X1)OR9, R9X2C(=X1)R9X2R9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)(R9S(O), 1 R9), N(R9)C(=X1)R9, SR9,
S(O)
1 OR9, R9S(O), 1 R9, or R9S(O)n(NZ)R9, wherein each said R8, which is substituted, has one or more 25 substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, N(R9)S(O)R9, oxo, OR9,
S(O)
1 OR9, R9S(O), 1 R9, S(O), 1 R9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); 30 (j) R9 is (each independently) H, CN, substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, 1 E 01064210_1.docx substituted or unsubstituted C 1
-C
2 0 heterocyclyl, S(O)CI-C 6 alkyl, N(CI-C 6 alkyl) 2 , wherein each said R9, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio 5 cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OC 1
-C
6 alkyl, OC 1
-C
6 haloalkyl, S(O)nC 1 -Csalkyl, S(O)aOC 1
-C
6 alkyl, C 6
-C
2 o aryl, or CI-C 2 o heterocyclyl; (k) n is 0, 1, or 2; 0 (1) X is N or CRai 1 where Rai, is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6
-C
20 aryl, substituted or unsubstituted C 1
-C
20 heterocyclyl, OR9, 5 C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O), 1 R9, S(O)aOR9, or R9S(O), 1 R9, wherein each said Rai which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio 0 cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)aOR9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); (m) Xl is (each independently) 0 or S; 25 (n) X2 is (each independently) 0, S, =NR9, or =NOR9; and (o) Z is CN, NO 2 , C 1
-C
6 alkyl(R9), C(=X1)N(R9) 2 ; and 30 (p) with the following provisos (1) that R6 and R8 cannot both be C(=O)CH 3 , (2) that when Al is Al 1 then R6 and R8 together do not form fused ring systems, (3) that R6 and R8 are not linked in a cyclic arrangement with only -CH 2 -. 1- 01064210_1.docx DEFINITIONS The examples given in the definitions are generally non-exhaustive and must not be construed as limiting the invention disclosed in this document. It is understood that a 5 substituent should comply with chemical bonding rules and steric compatibility constraints in 1G relation to the particular molecule to which it is attached. "Alkenyl" means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl. 5 "Alkenyloxy" means an alkenyl further consisting of a carbon-oxygen single bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy. "Alkoxy" means an alkyl further consisting of a carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy. "Alkyl" means an acyclic, saturated, branched or unbranched, substituent consisting 10 of carbon and hydrogen, for example, methyl, ethyl, (C 3 )alkyl which represents n-propyl and isopropyl), (C4)alkyl which represents n-butyl, sec-butyl, isobutyl, and tert-butyl. "Alkynyl" means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl. 15 "Alkynyloxy" means an alkynyl further consisting of a carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy. "Aryl" means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl. "(Cr-Cy)" where the subscripts "x" and "y" are integers such as 1, 2, or 3, means the 20 range of carbon atoms for a substituent - for example, (CI-C4)alkyl means methyl, ethyl, n propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, each individually. "Cycloalkenyl" means a monocyclic or polycyclic, unsaturated (at least one carbon carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl, 25 tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl. "Cycloalkenyloxy" means a cycloalkenyl further consisting of a carbon-oxygen single bond, for example, cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy. "Cycloalkyl" means a monocyclic or polycyclic, saturated substituent consisting of 30 carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl. "Cycloalkoxy" means a cycloalkyl further consisting of a carbon-oxygen single bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and 2 bicyclo[2.2.2]octyloxy. "Halo" means fluoro, chloro, bromo, and iodo. "Haloalkoxy" means an alkoxy further consisting of, from one to the maximum possible number of identical or different, halos, for example, fluoromethoxy, 5 trifluoromethoxy, 2,2-difluoropropoxy, chloromethoxy, trichloromethoxy, 1,1,2,2 tetrafluoroethoxy, and pentafluoroethoxy. "Haloalkyl" means an alkyl further consisting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, trifluoromethyl, 2,2 difluoropropyl, chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl. 10 "Heterocyclyl" means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, that atom can be in other oxidation states such as a sulfoxide and sulfone. Examples of aromatic heterocyclyls include, but are not limited to, benzofuranyl, benzoisothiazolyl, 15 benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl, cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and triazolyl. Examples of fully saturated heterocyclyls include, but are not limited 20 to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl and tetrahydropyranyl. Examples of partially unsaturated heterocyclyls include, but are not limited to, 1,2,3,4-tetrahydroquinolinyl, 4,5-dihydro-oxazolyl, 4,5 dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and 2,3-dihydro-[1,3,4]-oxadiazolyl. Additional examples include the following 25 S thietanyl thietanyl-dioxide. 3 DETAILED DESCRIPTION This document discloses molecules having the following formula ("Formula One"): R7 AsN R8 R6 5 wherein (a) A is either R4 R2 NN x '' attachment bond R5 R1 N R3 Al or R4 R2 N x N / attachment bond R5 R1 N R3 A2 10 (b) R1 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 0 cycloalkyl, substituted or unsubstituted C 3
-C
1 0 cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, 15 substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=Xl)R9, C(=X1)OR9, C(=Xl)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, S(O)nN(R9) 2 , or R9S(O),R9, wherein each said R1, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 4 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3 -CIO cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)nOR9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); 5 (c) R2 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, 10 substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O),R9, wherein each said R2, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
10 cycloalkyl, C 3
-C
10 15 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)"OR9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); (d) R3 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, 20 substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O),R9, 25 wherein each said R3, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
1 O cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)"OR9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted 30 with R9); (e) when A is (1) Al then Al is either 5 (a) All 7R4 N-N attachment bond attachment bond to carbon R5 to nitrogen All where R4 is H, NO 2 , substituted or unsubstituted C 1
-C
6 5 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 3
-C
10 cycloalkyl, substituted or unsubstituted C 3
-C
10 cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, S(O)nOR9, or R9S(O),R9, 10 wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
1 O cycloalkyl, C 3
-C
1 O cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)"OR9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted 15 with R9), or (b) A12 R4 attachment bond attachment bond to carbon R5 to mtrogen A12 20 where R4 is a C 1
-C
6 alkyl, (2) A2 then R4 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or 6 unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, or 5 R9S(O),R9, wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
1 O cycloalkyl, C 3
-C
1 O cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)"OR9, C 6
-C
20 aryl, 10 or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); (f) R5 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, 15 substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O),R9, wherein each said R5, which is substituted, has one or more substituents 20 selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
1 O cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)"OR9, or C6-C20 aryl, (each of which that can be substituted, may optionally be substituted with R9); 25 (g) (1) when A is Al then R6 is substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, 30 substituted or unsubstituted CI-C 2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, R9S(O),R9, C 1
-C
6 alkyl C 6
-C
2 0 aryl (wherein the alkyl and aryl can independently be substituted or unsubstituted), C(=X2)R9, C(=X1)X2R9, R9X2C(=X1)R9, R9X2R9, C(=O)(C 1
-C
6 alkyl)S(O),(C 1
-C
6 alkyl), 7
C(=O)(C
1
-C
6 alkyl)C(=O)O(CI-C 6 alkyl), (C 1
-C
6 alkyl)OC(=O)(C-C 2 0 aryl), (C 1
-C
6 alkyl)OC(=O)(CI-C 6 alkyl), C 1
-C
6 alkyl-(C 3 -CIO cyclohaloalkyl), or (C 1
-C
6 alkenyl)C(=O)O(CI-C 6 alkyl), or R9X2C(=X1)X2R9, wherein each said R6, which is substituted, has one or more 5 substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
10 cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OR9, S(O)"OR9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, R9aryl, (each of which that can be substituted, may optionally be substituted with R9), 10 optionally R6 and R8 can be connected in a cyclic arrangement, where optionally such arrangement can have one or more heteroatoms selected from 0, S, or, N, in the cyclic structure connecting R6 and R8, and (2) when A is A2 then R6 is H, substituted or unsubstituted C 1
-C
6 alkyl, 15 substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted CI-C 2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)nOR9, R9S(O),R9, C 1
-C
6 alkyl C 6
-C
2 0 20 aryl (wherein the alkyl and aryl can independently be substituted or unsubstituted), C(=X2)R9, C(=X1)X2R9, R9X2C(=X1)R9, R9X2R9, C(=O)(C 1
-C
6 alkyl)S(O),(C 1
-C
6 alkyl),
C(=O)(C
1
-C
6 alkyl)C(=O)O(CI-C 6 alkyl), (C 1
-C
6 alkyl)OC(=O)(C-C 2 0 aryl), (C 1
-C
6 alkyl)OC(=O)(C 1
-C
6 alkyl), C 1
-C
6 alkyl-(C 3
-C
1 O cyclohaloalkyl), or (C 1
-C
6 alkenyl)C(=O)O(CI-C 6 alkyl), or R9X2C(=X1)X2R9, 25 wherein each said R6, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
10 cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3 -CIO halocycloalkenyl, OR9, S(O)"OR9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, R9aryl, (each of which that can be substituted, may optionally be 30 substituted with R9), optionally R6 and R8 can be connected in a cyclic arrangement, where optionally such arrangement can have one or more heteroatoms selected from 0, S, or N, in the cyclic structure connecting R6 and R8; 8 (h) R7 is 0, S, NR9, or NOR9; (i) R8 is substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2 5 C 6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3 C 10 cycloalkenyl, substituted or unsubstituted C 6
-C
2 O aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl OR9, OR9S(O),R9, C(=X1)R9, C(=X1)OR9, R9C(=X1)OR9, R9X2C(=X1)R9X2R9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)(R9S(O),R9), N(R9)C(=X1)R9, SR9, 10 S(O)nOR9, R9S(O),R9, or R9S(O),(NZ)R9, wherein each said R8, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl,
C
2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
10 cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, N(R9)S(O)"R9, oxo, OR9, 15 S(O)nOR9, R9S(O),R9, S(O),R9, C 6
-C
20 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); (j) R9 is (each independently) H, CN, substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 1
-C
6 alkoxy, 20 substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 O aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, S(O)"C 1
-C
6 alkyl, N(CI-C 6 alkyl) 2 , wherein each said R9, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 25 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
10 cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
1 O halocycloalkenyl, OC 1
-C
6 alkyl, OC 1
-C
6 haloalkyl, S(O)CI-Calkyl, S(O),OC 1
-C
6 alkyl, C 6
-C
20 aryl, or CI-C 2 0 heterocyclyl; (k) n is 0, 1, or 2; 30 (1) X is N or CRei where Ri is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted CI-C 6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted CI-C 6 alkoxy, substituted or unsubstituted C 2
-C
6 alkenyloxy, substituted or 9 unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 3
-C
1 O cycloalkenyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted C 1
-C
2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O),R9, S(O)nOR9, or R9S(O),R9, 5 wherein each said Ri which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 1
-C
6 haloalkyl, C 2
-C
6 haloalkenyl, C 1
-C
6 haloalkyloxy, C 2
-C
6 haloalkenyloxy, C 3
-C
10 cycloalkyl, C 3
-C
10 cycloalkenyl, C 3
-C
10 halocycloalkyl, C 3
-C
10 halocycloalkenyl, OR9, S(O)nOR9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted 10 with R9); (m) Xl is (each independently) 0 or S; (n) X2 is (each independently) 0, S, =NR9, or =NOR9; and 15 (o) Z is CN, NO 2 , C 1
-C
6 alkyl(R9), C(=X1)N(R9) 2 ; and (p) with the following provisos (1) that R6 and R8 cannot both be C(=O)CH 3 , 20 (2) that when Al is All then R6 and R8 together do not form fused ring systems, (3) that R6 and R8 are not linked in a cyclic arrangement with only -CH 2 -, (4) that when A is A2 then R5 is not C(=O)OH, (5) that when A is A2 and R6 is H then R8 is not a -(C 1
-C
6 alkyl)-O 25 (substituted aryl), and (6) that when A is A2 then R6 is not -(Cialkyl)(substituted aryl). In another embodiment of this invention A is Al. In another embodiment of this invention A is A2. 30 In another embodiment of this invention R1 is H. In another embodiment of this invention R2 is H. In another embodiment of this invention R3 is selected from H, or substituted or unsubstituted C 1
-C
6 alkyl. 10 In another embodiment of this invention R3 is selected from H or CH 3 . In another embodiment of the invention when A is Al then Al is A11. In another embodiment of the invention when A is A1, and Al is A11, then R4 is selected from H, or substituted or unsubstituted C 1
-C
6 alkyl, or substituted or unsubstituted 5 C 6
-C
2 0 aryl. In another embodiment of the invention when A is A1, and Al is All then R4 is selected from CH 3 , CH(CH 3
)
2 , or phenyl. In another embodiment of the invention when A is Al, and Al is A12, then R4 is CH4 3 . 10 In another embodiment of this invention when A is A2 then R4 is selected from H, or substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 3
-C
1 O cycloalkyl, substituted or unsubstituted C 6
-C
2 0 aryl, wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, or I. 15 In another embodiment of this invention when A is A2 then R4 is H or C 1
-C
6 alkyl. In another embodiment of this invention when A is A2 then R4 is H, CH 3 , CH 2
CH
3 ,
CH=CH
2 , cyclopropyl, CH 2 Cl, CF 3 , or phenyl. In another embodiment of this invention when A is A2 then R4 is Cl. In another embodiment of this invention R5 is H, F, Cl, Br, I, or substituted or 20 unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 1
-C
6 alkoxy. In another embodiment of this invention R5 is H, OCH 2
CH
3 , F, Cl, Br, or CH 3 . In another embodiment of this invention, when A is Al then R6 is substituted or unsubstituted C 1
-C
6 alkyl. In another embodiment of this invention when A is A2 then R6 is selected from is 25 substituted or unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 3
-C
10 cycloalkyl, C(=X1)R9, C(=X1)X2R9, R9X2R9,
C(=O)(C
1
-C
6 alkyl)S(O),(C 1
-C
6 alkyl), (C 1
-C
6 alkyl)OC(=O)(C-C 2 0 aryl), (C 1
-C
6 alkyl)OC(=O)(C 1
-C
6 alkyl), or R9X2C(=X1)X2R9. In another embodiment of this invention when A is A2 then R6 and R8 are connected 30 in a cyclic arrangement, where optionally such arrangement can have one or more heteroatoms selected from 0, S, or, N, in the cyclic structure connecting R6 and R8. In another embodiment of this invention R6 is C 1
-C
6 alkyl, or C 1
-C
6 alkyl-phenyl. In another embodiment of this invention R6 is H, CH 3 , CH 2
CH
3 , CH 2
CH
2
CH
3 , 11
CH(CH
3
)
2 , CH 2 phenyl, CH 2
CH(CH
3
)
2 , CH 2 cyclopropyl, C(=O)CH 2
CH
2
SCH
3 ,
C(=O)OC(CH
3
)
3 , CH 2
CH=CH
2 , C(=O)OCH 2
CH
3 , C(=O)CH(CH 3
)CH
2
SCH
3 , cyclopropyl,
CD
3 , CH 2 0C(=O)phenyl, C(=O)CH 3 , C(=O)CH(CH 3
)
2 , CH 2 0C(=O)CH(CH 3
)
2 ,
CH
2 0C(=O)CH 3 , C(=O)phenyl, CH 2 0CH 3 , CH 2 0C(=O)CH 2 0CH 2
CH
3 , CH 2
CH
2 0CH 3 , 5 CH 2 0C(=O)OCH(CH 3
)
2 , CH 2
CH
2 0CH 2 0CH 3 , CH 2
CH
2 0CH 3 , CH 2
CH
2 0C(=O)CH 3 ,
CH
2 CN. In another embodiment of this invention R6 is methyl or ethyl. In another embodiment of this invention R7 is 0 or S. In another embodiment of this invention R8 is selected from substituted or 10 unsubstituted C 1
-C
6 alkyl, substituted or unsubstituted C 2
-C
6 alkenyl, substituted or unsubstituted C 3
-C
10 cycloalkyl, substituted or unsubstituted C 6
-C
2 0 aryl, substituted or unsubstituted CI-C 2 0 heterocyclyl, R9C(=X1)OR9, SR9, S(O)nOR9, R9S(O),R9, or R9S(O),(NZ)R9. In another embodiment of this invention R8 is CH(CH 3
)CH
2
SCH
3 , CH(CH 3
)
2 , 15 C(CH 3
)
2
CH
2
SCH
3 , CH 2
CH
2
SCH
3 , CH 2
CF
3 , CH 2
CH
2 C(=0)OCH 3 , N(H)(CH 2
CH
2
SCH
3 ),
OCH
2
CH
2
SCH
3 , CH(CH 2
SCH
3
)(CH
2 phenyl), thiazolyl, oxazolyl, isothiazolyl, substituted furanyl, CH 3 , C(CH 3
)
3 , phenyl, CH 2
CH
2 0CH 3 , pyridyl, CH 2
CH(CH
3
)SCH
3 , OC(CH 3
)
3 ,
C(CH
3
)
2
CH
2
SCH
3 , CH(CH 3
)CH(CH
3
)SCH
3 , CH(CH 3
)CF
3 , CH 2
CH
2 -thienyl,
CH(CH
3
)SCF
3
,CH
2
CH
2 Cl, CH 2
CH
2
CH
2
CF
3 , CH 2
CH
2 S(=0)CH 3 , CH(CH 3
)CH
2 S(=0)CH 3 , 20 CH 2
CH
2 S(=0) 2
CH
3 , CH(CH 3
)CH
2 S(=0) 2
CH
3 , NCH 2
CH
3 , N(H)(CH 2
CH
2
CH
3 ),
C(CH
3
)=C(H)(CH
3 ), N(H)(CH 2
CH=CH
2 ), CH 2
CH(CF
3
)SCH
3 , CH(CF 3
)CH
2
SCH
3 , thietanyl,
CH
2
CH(CF
3
)
2 , CH 2
CH
2
CF(OCF
3
)CF
3 , CH 2
CH
2
CF(CF
3
)CF
3 , CF(CH 3
)
2 , CH(CH 3 )phenyl-Cl,
CH(CH
3 )phenyl-F, CH(CH 3 )phenyl-OCF 3 , CH 2
N(CH
3 )(S(=0) 2
N(CH
3
)
2 ,
CH(CH
3
)OCH
2
CH
2
SCH
3 , CH(CH 3
)OCH
2
CH
2 0CH 3 , OCH 3 , CH(CH 3
)SCH
3 , CH 2
SCH
3 , 25 N(H)CH 3 , CH(Br)CH 2 Br, or CH(CH 3
)CH
2
SCD
3 . In another embodiment of this invention R8 is selected from (substituted or unsubstituted C1-C 6 alkyl)-S (0),-(substituted or unsubstituted C1-C 6 alkyl) wherein said substituents on said substituted alkyls are selected from F, Cl, Br, I, CN, NO 2 , N(R9)S(O)oR9, OR9, S(O)nOR9, R9S(O),R9, S(O),R9, C 6
-C
2 0 aryl, or C 1
-C
2 0 heterocyclyl, (each of which 30 that can be substituted, may optionally be substituted with R9). In another embodiment of this invention X is CRei where Ri is H or halo. In another embodiment of this invention X is CRei where Ri is H or F. In another embodiment of this invention X1 is 0. 12 In another embodiment of this invention X2 is 0. While these embodiments have been expressed, combinations of these embodiments are envisioned. Furthermore, other embodiments, and combinations of these expressed embodiments and other embodiments are possible. 5 The molecules of Formula One will generally have a molecular mass of about 100 Daltons to about 1200 Daltons. However, it is generally preferred if the molecular mass is from about 120 Daltons to about 900 Daltons, and it is even more generally preferred if the molecular mass is from about 140 Daltons to about 600 Daltons. 10 The following schemes illustrate approaches to generating aminopyrazoles. In step a of Scheme I, treatment of a 3-acetopyridine or a 5-acetopyrimidine of Formula II, wherein RI, R2, R3 and X are as previously defined, with carbon disulfide and iodomethane in the presence of a base such as sodium hydride and in a solvent such as dimethyl sulfoxide provides the compound of Formula III. In step b of Scheme I, the compound of Formula III 15 can be treated with an amine or amine hydrochloride, in the presence of a base, such as triethylamine, in a solvent such as ethyl alcohol to afford the compound of Formula IV, wherein R1, R2, R3, R6 and X are as previously defined. The compound of Formula IV can be transformed into the aminopyrazole of Formula Va where R5 = H as in step c of Scheme I and as in Peruncheralathan, S. et al. J. Org. Chem. 2005, 70, 9644-9647, by reaction with a 20 hydrazine, such as methylhydrazine, in a polar protic solvent such as ethyl alcohol. Scheme I 13 R2 0 R2 O S R 2 0 S X a X S X NH R NRR N R 3 R5 6
R
1 N R 3
R
1 N R3 ~1 R4 R2 N X , N R, N R5 R6 R3 5 Va Another approach to aminopyrazoles is illustrated in Scheme II. In step a, the nitrile of Formula VI wherein X, RI, R2 and R3 are as previously defined and R5 is hydrogen, is 5 condensed as in Dhananjay, B. Kendre et al. J Het Chem 2008, 45, (5), 1281-86 with hydrazine of Formula VII, such as methylhydrazine to give a mixture of aminopyrazoles of Formula Vb, wherein R5 and R6 = H, both of whose components were isolated. Scheme II R2 O R2 R4 N N-|-N /N R 4 X a X \ <- N R5 H 2 N H R -
R
1 N R 3 N R3 R5 6 10 VI VII Vb Preparation of aminopyrazoles such as those of Formula XIIa is demonstrated in Scheme III. The compound of Formula X in step a and as in Cristau, Henri-Jean et al. Eur. J Org. Chem. 2004, 695-709 can be prepared through the N-arylation of a pyrazole of Formula 15 IX with an appropriate aryl halide of Formula VIIIa where Q is bromo in the presence of a 14 base such as cesium carbonate, a copper catalyst such as copper (II) oxide and a ligand such as salicylaldoxime in a polar aprotic solvent such as acetonitrile. Compounds of Formula IX, as shown in Scheme III, wherein R4 = Cl and R5 = H, can be prepared as in Pelcman, B. et al WO 2007/045868 Al. Nitration of the pyridylpyrazole of Formula X as in step b of Scheme 5 III and as in Khan, Misbanul Ain et al. J. Heterocyclic Chem. 1981, 18, 9-14 by reaction with nitric acid and sulfuric acid gave compounds of Formula Xla. Reduction of the nitro functionality of compounds of Formula XIa in the presence of hydrogen with a catalyst such as 5% Pd/C in a polar aprotic solvent such as tetrahydrofuran gave the amine of Formula XlIa, as shown in step c in Scheme III. Reduction of the nitro functionality of compounds of 10 Formula Xla, wherein RI, R2, R3, R4 and X are as previously defined and R5 = H, in the presence of hydrogen with a catalyst such as 10% Pd/C in a polar protic solvent such as ethanol gave the amine of Formula XlIa, wherein R5 = H, as well as the amine of Formula XlIa, wherein R5 = OEt, as shown in step d of Scheme III. Compounds of Formula Xla, wherein RI, R2, R3, R5 and X are as previously defined and R4 = Cl, can be reduced in the 15 presence of a reducing agent such as iron in a mixture of polar protic solvents such as acetic acid, water, and ethanol to give amines of Formula XIIa, wherein RI, R2, R3, R5 and X are as previously defined R4 = Cl, as shown in step e of Scheme III. Compounds of Formula Xla, wherein RI, R2, R3, R5 and X are as previously defined and R4 = Cl, can be allowed to react under Suzuki coupling conditions with a boronic acid such as phenylboronic acid in the 20 presence of a catalyst such as palladium tetrakis, a base such as 2M aqueous potassium carbonate, and in a mixed solvent system such as ethanol and toluene to provide cross coupled pyrazoles of Formula XIb, as shown in stepf of Scheme III. Scheme III 15 R4 R2R5 R, Nx + Na N
R
4 N Ri N R 3 H R5 Ri N R3 VIIIa IX X R4 R4
R
2 N- R 2 N- H N / NO 2 c,dore N N x x H R5 R5H Ri N R 3 Ri N R 3 XIa XIIa R4
R
2
N
N /NO R5 R N
R
3 XIb In step a of Scheme IV, the compounds of Formula XIlb can be treated with triethylorthoformate and an acid such as trifluoroacetic acid. Subsequent addition of a 5 reducing agent such as sodium borohydride in a polar protic solvent such as ethanol gave a compound of Formula XIIIa, wherein R6 = methyl. In step b of Scheme IV, the compound of Formula XIlb can be treated with acetone in a solvent such as isopropyl acetate, an acid such as trifluoroacetic acid and sodium triacetoxyborohydride to give compounds of Formula XIIIa, wherein R6 = isopropyl. 10 In step c of Scheme IV, the compounds of Formula XIlb can be acylated with an acid chloride such as acetyl chloride in a polar aprotic solvent such as dichloromethane using the conditions described in Scheme V. Reduction of the amide with a reducing agent such as lithium aluminum hydride in a polar aprotic solvent such tetrahydrofuran gives compounds of 16 Formula Xll1a, wherein R6 = ethyl. Alternatively, in step d of Scheme IV, the compounds of Formula XIlb can be treated with benzotriazole and an aldehyde in ethanol followed by reduction using, for example, sodium borohydride, to afford compounds of Formula XIIIa. In step e of Scheme IV, the 5 compounds of Formula XIlb can be treated with an aldehyde such as propionaldehyde and sodium triacetoxyborohydride in a polar aprotic solvent such as dichloromethane to give compounds of Formula XIIIa, wherein R6 = propyl. As in stepf, acylation of compounds of Formula XlIIa in Scheme IV using the conditions described in Scheme IX affords compounds of Formula Ia, wherein RI, R2, R3, R4, R5, R6, R8 and X are as previously defined. 10 Scheme IV R4 R4
R
2 N- H 2 / aorborcordore N N / N - X R5
R
1 N R 3 Ri N
R
3 XIIIa XIIb R4 0
R
2 N- R8 f N N N /N X R6 I , R5 6 1 3% Ri N R 3 Ia In step a of Scheme V, the compounds of Formula Vc, wherein RI, R2, R3, R4, R5 15 and R6 and X are as previously defined, can be treated with an acid chloride of Formula XIV, in the presence of a base such as triethylamine or NN-dimethylaminopyridine in a polar aprotic solvent such as dichloroethane (DCE) to yield compounds of Formula Ib, wherein R8 is as previously defined. Additionally, when R6 = H the 2' amide may be subsequently alkylated in step b of Scheme V with an alkyl halide such as iodoethane, in the presence of a 20 base such as sodium hydride and a polar aprotic solvent such as NN-dimethylformamide 17 (DMF) to yield the desired compounds of Formula lb. The acid chlorides used in the acylation reactions herein are either commercially available or can be synthesized by those skilled in the art. 5 Scheme V R2 R4R - R2 R4 O SI H Cl R 8 bN-|-N X \ , 'K- N 8 aora,b -|- ) - N R8 N + ~ 'Y N R0 R R3 5N R -- N R5 R6 R 3 Ve XIV lb In step a of Scheme VI and as in Sammelson et al. Bioorg. Med. Chem. 2004, 12, 3345-3355, the aminopyrazoles of Formula Vd, wherein RI, R2, R3, R4, R6 and X are as 10 previously defined and R5 = H, can be halogenated with a halogen source such as N chlorosuccinimide or N-bromosuccinimide in a polar aprotic solvent such as acetonitrile to provide the R5-substituted pyrazole. In step b, acylation of this compound using the conditions described in Scheme V affords the compound of Formula Ic, wherein RI, R2, R3, R4, R5, R6, R8 and X are as previously defined. 15 Scheme VI R2 R4 R 2 R4 O l - N,- N X' /,,) NH a, b y. N)- R 8
N
1 N R 'N Rs R6 R 5 R6 R3 R 3 R5 Vd Ic In step a of Scheme VII, ureas and carbamates are made from the aminopyrazoles of 20 Formula Ve. Compounds of Formula Ve, wherein X, RI, R2, R3, R4, R5 and R6 are as previously defined are allowed to react with phosgene to provide the intermediate carbamoyl chloride which is subsequently treated with an amine, as shown in step b, or alcohol, as shown in step c, respectively, to generate a urea of Formula Id or a carbamate of Formula Ie, 18 respectively, wherein R9 is as previously defined. Scheme VII R2 R4 / H X \ , H N R1 NAR R6 N R3 5 Ve
R
2 R4 O X N ' C1 R1 NR5 R6 N 3R 3 5 xvj b c R 0 0 2 NN R9 R2 R4 0 X \ )s N \9 N N, H N RR/ \ N N 1 3R IN R5 R R36 Id le 5 In step a of Scheme VIII, compounds of Formula XIlc, wherein X, RI, R2, R3, R4 and R5 are as previously defined, can be treated with di-tert-butyl dicarbonate (Boc 2 0) and a base such as triethylamine in a polar aprotic solvent such as dichloromethane (DCM) to yield compounds of Formula XVIa. Treatment of the carbamate functionality with an alkyl halide 10 such as iodomethane or Boc-anhydride in the presence of a base such as sodium hydride and in a polar aprotic solvent such as DMF yields carbamates of Formula XVII, as shown in step b of Scheme VIII, wherein R6 is as previously defined, except where R6 is hydrogen. The Boc-group can be removed under conditions that are well-known in the art, such as under 19 acidic conditions such as trifluoroacetic acid (TFA) in a polar aprotic solvent like dichloromethane to give compounds of Formula XIIIb as in step c. Scheme VIII R4 R4 O
R
2 N- H
R
2
N
I N a /N b \N N / H H R5 R5
R
1 N R 3
R
1 N R 3 XTIC XVIa R4 O R4
R
2 N- R 2 N- H I N - C 2 I
-
/ N / N /N x X * 6xR R5 6R5 6
R
1 N R 3 R 1 N R 3 5 XVII Xlllb In steps a, b and c of Scheme IX, compounds of Formula XIIIc, wherein X, RI, R2, R3, R4, R5 and R6 are as previously defined, can be treated with a compound of Formula XVIII, wherein R8 is as previously defined and RIO is either OH, OR9 or O(C=O)OR9, to 10 yield compounds of Formula Id. When RIO = OH, compounds of Formula XIIIc can be converted to compounds of Formula Id in the presence of a coupling reagent such as 1-(3 dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC. HCl) and a base such as N,N-dimethylaminopyridine (DMAP) in a polar aprotic solvent such as dichloroethane (DCE), as shown in step a. When RIO = OR9, compounds of Formula XIIIc can be 15 converted to compounds of Formula Id in the presence of 2,3,4,6,7,8-hexahydro-iH pyrimido[1,2-a]pyrimidine in a polar aprotic solvent such as 1,4-dioxane under elevated temperature, as shown in step b. When RIO = O(C=O)OR9, compounds of Formula XIIIc can be converted to compounds of Formula Id in a polar aprotic solvent such as dichloromethane (DCM), as shown in step c. Acylation of amides of Formula Id, when R6 = H, with an acid 20 chloride in the presence of a base such as diisopropyl ethylamine in a polar aprotic solvent such as dichloroethane (DCE) yields imides of Formula le, as shown in step d. Furthermore, 20 alkylation of amides of Formula Id, when R6 = H, with an alkyl halide in the presence of a base such as sodium hydride in a polar aprotic solvent such as NN-dimethylformamide (DMF) yields alkylated amides of Formula Je, as shown in step e. Halogenation of compounds of Formula Id, wherein RI, R2, R3, R4, R6, R8 and X are as previously defined 5 and R5 = H, with a halogen source such as N-bromosuccinimide in a polar aprotic solvent such as DCE or a halogen source such as N-chlorosuccinimide in a polar aprotic solvent such as DCE or acetonitrile or a halogen source such as Selectfluor@ in a mixture of polar aprotic solvents such as acetonitrile and DMF give halogenated pyrazoles of Formula Je, wherein R5 = halogen, as shown in stepf of Scheme IX. Amides of Formula Id can be converted to 10 thioamides of Formula If in the presence of a thionating agent such as Lawesson's reagent in a polar aprotic solvent such as dichloroethane (DCE), as shown in step g. Scheme IX R4 R4 0 R2 NH R R R8 a orb orc R2 N-- R8 x N N -|- NN R5 R6 O R5 6 RL N R53 R N R3 XIIIc XVIII Id d or e orf g R4 0 R4 S R2 N- jR8 R2 N- N N X N \ R5 Ri N R(3 R1L N R3 le If 15 In step a of Scheme X, compounds of Formula XIIId, wherein X, RI, R2, R3, R4, R5 and R6 are as previously defined, can be treated with compounds of Formula XIX, wherein R8 is as previously defined, in a polar aprotic solvent such as dichloroethane (DCE) to yield 21 compounds of Formula XX. Additionally, when R6 = H and R8 contains a halogen, compounds of Formula XX can be treated with a base, such as sodium hydride, in a polar aprotic solvent, such as THF, to yield compounds of Formula XXI, where m is an integer selected from 1, 2, 3, 4, 5, or 6, as shown in step b of Scheme X. 5 Scheme X R4[0, S]
R
4 [0,S] R
R
2 N- H a R 2 N- N N / + II X X Rs 68 Rs5 R
R
1 N R 3 Rk N R 3 XIIId XIX XX
R
4 0 b R 2 N- NH NN N Rs
R
1 N R 3 XXI Oxidation of the sulfide to the sulfoxide or sulfone is accomplished as in Scheme XI 10 where (-S-) can be any sulfide previously defined within the scope of R8 of this invention. The sulfide of Formula XXIIa, wherein X, RI, R2, R3, R4, R5 and R6 are as previously defined, is treated with an oxidant such as sodium perborate tetrahydrate in a polar protic solvent such as glacial acetic acid to give the sulfoxide of Formula XXIII as in step a of Scheme XI. Alternatively, the sulfide of Formula XXIIa can be oxidized with an oxidant such 15 as hydrogen peroxide in a polar protic solvent such as hexafluoroisopropanol to give the sulfoxide of Formula XXIII as in step d of Scheme XI. The sulfoxide of Formula XXIII can be further oxidized to the sulfone of Formula XXIV by sodium perborate tetrahydrate in a polar protic solvent such as glacial acetic acid as in step c of Scheme XI. Alternatively, the sulfone of Formula XXIV can be generated in a one-step procedure from the sulfide of 20 Formula XXIIa by using the aforementioned conditions with >2 equivalents of sodium 22 perborate tetrahydrate, as in step b of Scheme XI. Scheme XI
R
4 0 R4 0
R
2 N- ~S a or d R 2
N
N/N N/N X R X-' R / R5 6R5 6 RI N R 3 Ri N R 3 XXIIa XXIII b c R4 0
R
2 N- ~S(O)2~ N/N X R6 Ri N R 3 XXIV 5 Oxidation of the sulfide to the sulfoximine is accomplished as in Scheme XII where (-S-) can be any sulfide previously defined within the scope of R8 of this invention. The sulfide of Formula XXIIb, wherein X, RI, R2, R3, R4, R5 and R6 are as previously defined, is oxidized as in step a with iodobenzene diacetate in the presence of cyanamide in a polar aprotic solvent 10 such as methylene chloride (DCM) to give the sulfilimine of the Formula XXV. The sulfilimine of Formula XXV may be further oxidized to the sulfoximine of Formula XXVI with an oxidant such as meta-Chloroperoxybenzoic acid ("mCPBA") in the presence of a base such as potassium carbonate in a protic polar solvent system such as ethanol and water as in step b of Scheme XII. 15 Scheme XII 23
R
4 o R4 O R, N- ~S~ a R, N- ~S~ / ' // N N / \NCN X RX R R5 6 R56
R
1 N R 3 R1 N R 3 XXIIb XXV R4 O0O b R2 N N / NCN X R6 RI N R 3 XXVI Iodination of the pyrazole of Formula Xb as in step a of Scheme XIII and as in Potapov, A. et al. Russ. J. Org. Chem. 2006, 42, 1368-1373 was accomplished by reaction 5 with an iodinating agent such as iodine in the presence of acids such as iodic acid and sulfuric acid in a polar protic solvent such as acetic acid gives compounds of Formula XXVII. In step b of Scheme XIII and as in Wang, D. et al. Adv. Synth. Catal. 2009, 351, 1722-1726, aminopyrazoles of Formula XIIIe can be prepared from iodopyrazoles of Formula XXVII through cross coupling reactions with an appropriate amine in the presence of a base such as 10 cesium carbonate, a copper catalyst such as copper (I) bromide, and a ligand such as 1 (5,6,7,8-tetrahydroquinolin-8-yl)ethanone in a polar aprotic solvent such as DMSO. Scheme XIII 24 R4 R4
R
2 N- R 2
N
N a X -Z 1- XN R5 lo R5 R N R 3 R1 N R 3 Xb XXVII R4
R
2 N- H b N / N X R Rs5
R
1 N
R
3 XIIle In step a of the Scheme XIV, compounds of the formula XXIX, wherein R4 is Cl, R5 is H and X- represents Cl-, can be prepared according to the methods described in Acta. 5 Pharm. Suec. 22, 147-156 (1985) by Tolf, Bo-Ragnar and Dahlbom, R. In a similar manner, compounds of the Formula XXIX, wherein R4 is Br, X- represents Br- and R5 is as defined previously, can be prepared by treating compounds of the Formula XXVIII with hydrogen gas in the presence of a metal catalyst such as 5% Pd on alumina and a solution of 50% aqueous HBr in a solvent such as ethanol. Alternatively, in step a of Scheme XIV, compounds of the 10 Formula XXIX, wherein R4 is Cl or Br, X- represents Cl- or Br- and R5 is as defined previously, can be prepared by treating compounds of the Formula XXVIII, wherein R5 is as defined previously, with a hydrosilane such as triethyl silane in the presence of a metal catalyst such as 5% Pd on alumina and an acid such as HCl or HBr, respectively, in a solvent such as ethanol. 15 In step b of the Scheme XIV, compounds of the Formula XXX, wherein R4 is Cl or Br and R5 is as defined previously, can be prepared by treating the compounds of the Formula XXIX, wherein R4 is Cl or Br, X- represents Cl- or Br- and R5 is as defined previously, with di-tert-butyl dicarbonate (Boc 2 0) in the presence of a mixture of solvents such as THF and water and a base such as sodium bicarbonate. 20 In step c of the Scheme XIV, compounds of the Formula XVIa, wherein X, RI, R2, R3 and R5 are as defined previously and R4 is Cl or Br can be obtained by treating 25 compounds of the Formula XXX, wherein R4 is Cl or Br and R5 is as defined previously, with compounds of the Formula VIIb, wherein X, RI, R2 and R3 are as defined previously and Q is bromo or iodo, in the presence of a catalytic amount of copper salt such as CuCl 2 , an ethane-1,2-diamine derivative such as N ,N 2-dimethylethane- 1,2-diamine and a base such as 5 K3PO 4 in a polar aprotic solvent such as acetonitrile at a suitable temperature. The Boc-group of compounds of Formula XVIa can be removed under conditions that are well-known in the art such as under acidic conditions such as TFA in a polar aprotic solvent such as dichloromethane to give compounds of Formula XJld, as shown in step d of Scheme XIV. 10 Scheme XIV 26 R4 N a N | I NI- NH3X HN \ HN / 0 R5 R5 XXVIII XXIX Ib R4 0 Y
R
2 N R OO
R
4 0 1 NH cN O X | NH NR2 HN RI N R3 X Q R5 XR N R 3 d VIIIb R4 R, N/ X N / NH R5 RI N R3 Bromopyrazoles of Formula XXXI, wherein RI, R2, R3, R5, R8 and X are as previously defined, can be allowed to react under Suzuki coupling conditions with a boronic 5 ester such as vinylboronic acid pinacol ester or cyclopropylboronic acid pinacol ester in the presence of a catalyst such as palladium tetrakis, a base such as 2 M aqueous potassium carbonate, and in a mixed solvent system such as ethanol and toluene to provide compounds of Formula XXXII, as shown in step a of Scheme XV. 10 Scheme XV 27 Br 0 R4 O
R
2 N- -R 8 a R 2 N- R8 N N / N H X H R1 N R 3 RI N R 3 XXXI XXXII The vinyl group of compounds of Formula XXXIII, wherein RI, R2, R3, R5, R6, R8 and X are as previously defined, can be reduced in the presence of hydrogen with a catalyst 5 such as 10% Pd/C in a polar protic solvent such methanol to give compounds of Formula XXXIV, as shown in step a of Scheme XVI. Oxidation of the vinyl group of compounds of Formula XXXIII using an oxidant such as osmium tetroxide in the presence of sodium periodate in mixture of a polar protic solvent such as water and a polar aprotic solvent such as THF gave compounds of Formula XXXV, as shown in step b of Scheme XVI. Reduction of 10 the aldehyde of compounds of Formula XXXV, as shown in step c of Scheme XVI, with a reducing agent such as sodium borohydride in a polar protic solvent such as methanol gave the corresponding alcohol of Formula XXXVI. Treatment of compounds of Formula XXXVI with a chlorinating agent such as thionyl chloride in a polar aprotic solvent such as dichloromethane gave compounds of Formula XXXVII, as shown in step d of Scheme XVI. 15 28 Scheme XVI O 0
R
2 N' R8 R 2 N' R8 N (1 N RR3 5 R6 R5 R6 Ri" R3 R I N R 3 xxXIII xxxIV b HO 0 0 R NR
R
2 N' R8
R
2 N-R N NN CN / R6 R13 R6 8RR3 5 R R5 R)--N
R
3
R
1 _N R 3 XXXV XXXVI d Cl 0 R2 N' R8 N N XR N R 3 XXX VII In step a of Scheme XVII, an ax, -unsaturated acid XXXVIII can be treated with a 5 nucleophile such as sodium thiomethoxide in a polar protic solvent such as methanol to give acid XXXIX. Scheme XVII 29 0 0 SMe a H O
CF
3 HO
CF
3 XXXVIII XXXIX EXAMPLES The examples are for illustration purposes and are not to be construed as limiting the 5 invention disclosed in this document to only the embodiments disclosed in these examples. Starting materials, reagents, and solvents that were obtained from commercial sources were used without further purification. Anhydrous solvents were purchased as Sure/SealTM from Aldrich and were used as received. Melting points were obtained on a Thomas Hoover Unimelt capillary melting point apparatus or an OptiMelt Automated Melting Point System 10 from Stanford Research Systems and are uncorrected. Molecules are given their known names, named according to naming programs within ISIS Draw, ChemDraw or ACD Name Pro. If such programs are unable to name a molecule, the molecule is named using conventional naming rules. All NMR shifts are in ppm (6) and were recorded at 300, 400 or 600 MHz unless otherwise stated. 15 Example 1, Step 1: Preparation of 3,3-bis-methylsulfanyl-1-pyridin-3-yl-propenone O S " S N 20 To a room-temperature suspension of sodium hydride (NaH, 60% suspension in mineral oil; 4.13 g, 86 mmol) in dry dimethyl sulfoxide (DMSO, 60 mL) under an atmosphere of nitrogen
(N
2 ) was added 3-acetylpyridine (5.00 g, 41.3 mmol) dropwise over 30 minutes (min). The mixture was stirred for an additional 30 minutes at the same temperature. Carbon disulfide
(CS
2 ; 3.27 g, 43 mmol) was added dropwise with vigorous stirring followed by iodomethane 25 (12.21 g, 86 mmol) dropwise over a period of 45 min. Stirring was continued for an additional 18 hours (h) under N 2 . The reaction was quenched with cold water (H 2 0, 50 mL). The dark solid was filtered and washed with ice-cold ethyl alcohol (EtOH) until the washings 30 were colorless. The off-white solid product was dried under vacuum at 60 'C to provide 3,3 bis-methylsulfanyl-1-pyridin-3-yl-propenone as a brown solid (4.8 g, 5 1%): 'H NMR (300 MHz, CDCl 3 ) 8 9.13 (d, J= 1.8 Hz, 1H), 8.72 (dd, J= 4.8, 1.6 Hz, 1H), 8.23 (ddd, J= 7.9, 2, 2 Hz, 1H), 7.40 (dd, J = 7.9, 4.8 Hz, 1H), 6.73 (s, 1H), 2.58 (d, J = 9.4 Hz, 6H); MS m/z 5 226.2 (M+1). 1-(5-fluoropyridin-3-yl)-3,3-bis(methylthio)prop-2-en- 1-one was prepared as described in Example 1, Step 1: mp 150-152 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.93 (t, J= 1.6 Hz, 1H), 8.58(d, J = 2.8 Hz, 1H),7.94 (ddd, J = 8.9, 2.8, 1.7 Hz, 1H),, 6.69 (s, 1H), 2.60 (s, 3H), 2.57 10 (s, 3H). Example 1, Step 2: Preparation of (Z)-3-methylamino-3-methylsulfanyl-1-pyridin-3-yl propenone O S NH 15 N A solution of 3,3-bis-methylsulfanyl-1-pyridin-3-yl-propenone (18.6 g, 82.5 mmol) in absolute alcohol (400 mL) under N 2 was treated with methylamine hydrochloride (27.86 g, 412 mmol) followed by triethylamine (Et 3 N; 58.5 mL, 412 mmol). The mixture was heated to 20 reflux for 3 h, cooled to room temperature and concentrated under reduced pressure. The solid residue was dissolved in ethyl acetate (EtOAc; 150 mL). The solution was washed with
H
2 0 (2 x 50 mL) and brine (50 mL), dried over Na 2
SO
4 , concentrated under reduced pressure and purified by silica gel chromatography eluting with 10% EtOAc in petroleum ether to yield (Z)-3-methylamino-3-methylsulfanyl-1-pyridin-3-yl-propenone as a pale yellow 25 solid (8.6 g, 50%): 'H NMR (300 MHz, CDCl 3 ) 8 11.8 (br s, 1H), 9.06 (s, 1H); 8.67 (d, J= 3.9 Hz, 1H), 8.26 (d, J= 8.0 Hz 1H), 7.46 (dd, J= 7.6, 4.9 Hz 1H), 5.62 (s, 1H), 3.10 (d, J= 5.2 Hz, 3H), 2.52 (s, 3H); MS (m/z) 209.2 [M+1]. (Z)-3-(ethylamino)-3(methylthio)- 1-(pyridin-3-yl)prop-2-en- 1-one was prepared as described 30 in Example 1, Step 2: 'H NMR (400 MHz, CDCl 3 ) 6 11.81 (bs, 1H), 9.04 (dd, J= 2.2, 0.7 31 Hz, 1H), 8.64 (dd, J= 4.8, 1.7 Hz, 1H), 8.29 - 7.98 (m, 1H), 7.35 (ddd, J= 7.9, 4.8, 0.9 Hz, 1H), 3.45 (q, J= 7.2, 5.6 Hz, 2H), 2.50 (s, 3H), 1.35 (t, J= 7.2 Hz, 3H). (Z)-3-(cyclopropylmethyl)amino-3 (methylthio)- 1 -(pyridin-3 -yl)prop-2-en- 1-one was prepared 5 as described in Example 1, Step 2: 'H NMR (400 MHz, CDCl 3 ) 6 9.00 (s, 1H), 9.05 (dd, J= 2.2, 0.7 Hz, 1H), 8.64 (dd, J= 4.8, 1.7 Hz, 1H), 8.16 (dt, J= 7.9, 2.0 Hz, 1H), 7.35 (ddd, J= 7.9, 4.8, 0.8 Hz, 1H), 5.62 (s, 1H), 3.27 (dd, J= 7.0, 5.5 Hz, 2H), 2.50 (s, 3H), 1.20 - 1.07 (m, 1H), 0.73 - 0.49 (m, 2H), 0.41 - 0.17 (m, 2H). 10 Example 1, Step 3: Preparation of methyl-(2-methyl-5-pyridin-3-pyrazol-3-yl)-amine N-N N H N A solution of (Z)-3-methylamino-3-methylsulfanyl-1-pyridin-3-yl-propenone (3.00 g, 14 15 mmol) and methylhydrazine (729 mg, 15.4 mmol) in absolute EtOH (64 mL) was stirred at reflux for 18 h under N 2 , cooled to room temperature and evaporated under reduced pressure. The residue was dissolved in EtOAc (50 mL), and the organic layer was washed with H 2 0 (2 x 30 mL) and brine (30 mL), dried over Na 2
SO
4 , concentrated under reduced pressure and purified using silica gel chromatography eluting with a gradient of 0-1% EtOH in EtOAc to 20 yield two regioisomers in a 1:2 ratio, with the major regioisomer as a brown solid (1.0 g, 27%): 'H NMR (300 MHz, CDCl 3 ) 8 8.97 (d, J= 1.3 Hz, 1H), 8.51 (dd, J= 3.6, 1.0 Hz, 1H), 8.07 (ddd, J= 5.9, 1.4, 1.4 Hz, 1H), 7.30 (dd, J= 5.9, 3.6 Hz, 1H), 5.82 (s, 1H), 3.69 (s, 3H), 2.93 (s, 3H); MS (m/z) 188.6 [M+1]. 25 1-Ethyl-N-methyl-3-(pyridin-3-yl)-1H-pyrazol-5-amine was prepared as described in Example 1, Step 3: ESIMS m/z 204 ([M+2H]). N-ethyl-1-methyl-3-(pyridin-3-yl)-1H-pyrazol-5-amine was prepared as described in Example 1, Step 3: ESIMS m/z 203 ([M+H]). 30 32 N-methyl-1-phenyl-3-(pyridin-3-yl)-1H-pyrazol-5-amine was prepared as described in Example 1, Step 3: ESIMS m/z 252 ([M+2H]). N-(cyclopropylmethyl)-1-methyl-3-(pyridin-3-yl)-1H-pyrazol-5-amine was prepared as 5 described in Example 1, Step 3: ESIMS m/z 230 ([M+2H]). 1-Isopropyl-N-methyl-3-pyridin-3-yl)-1H-pyrazol-5-amine was prepared as described in Example 1, Step 3: 'H NMR (300 MHz, CDCl 3 ) 6 8.53 (s, 1H), 8.06 - 7.90 (m, J= 7.2 Hz, 2H), 7.13 (dd, J= 7.9, 5.6 Hz, 1H), 5.33 (s, 1H), 3.70 (bs, 1H), 3.65 (dt, J= 13.2, 6.6 Hz, 10 1H), 2.31 (s, 3H), 0.88 (d, J= 6.6 Hz, 6H); ESIMS m/z 217 ([M+H]). 3-(5-Fluoropyridin-3-yl)-N, 1-dimethyl-1H-pyrazol-5-amine was prepared as described in Example 1, Step 3: 'H NMR (300 MHz, CDCl 3 ) 6 8.28 (s, 1H), 7.87 (t, J= 1.3 Hz, 1H), 7.60 (m, 1H), 6.66 (s, 1H), 5.28 (bs, 2H), 3.12 (s, 3H), 2.34 (s, 3H); ESIMS m/z 206 ([M+H]) 15 Example 2: Preparation of (4-chloro-2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-methyl amine N-N N H N CI 20 A mixture of methyl-(2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-amine (0.35 g, 1.8 mmol) and N-chlorosuccinimide (0.273 g, 2 mmol) was combined in acetonitrile (3 mL), stirred at room temperature for 30 minutes, concentrated under reduced pressure and purified using silica gel chromatography eluting with a gradient of EtOAc in hexanes to yield the title 25 compound as a yellow oil (0.096 g, 23%): IR (thin film) 1581.6 cm-1; 'H NMR (400 MHz, CDCl 3 ) 8 9.12 (d, J= 1.5 Hz, 1H), 8.57 (dd, J= 4.8, 1.3 Hz, 1H), 8.15 (ddd, J= 7.8, 2.0, 2.0 Hz, 1H), 7.33 (dd, J= 8.1, 5.1 Hz, 1H), 3.80 (s, 3H), 2.91 (d, J= 5.8 Hz, 3H); ESIMS (m/z) 225.6 [M+2]. 30 The reaction also gave 4-chloro-2-methyl-5-pyridin-3-yl-2H-pyrazol-3-ylamine as a green 33 gum (0.046 g, 13%): IR (thin film) 1720.5 cm-.; 1H NMR (CDCl 3 , 400 MHz) 6 9.13 (br s, 1H), 8.57 (br s, 1H), 8.16 (dt, J= 8.0, 2.0 Hz, 1H), 7.33 (dd, J= 7.8, 4.8 Hz, 1H), 3.76 (s, 3H); ESIMS (m/z) 207.0 [M-1]. 5 Example 3: Preparation of 2,N-dimethyl-N-(2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-3 methylsulfanyl-propionamide (Compound 1) N-N O S N 10 To a solution of methyl-(2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-amine (150 mg, 0.8 mmol) under N 2 in ice-cold dichloroethane (DCE; 2 mL) was added dropwise via pipette a solution of 2-methyl-3-methylsulfanyl-propionylchloride (146 mg, 0.9 mmol) in DCE (1.5 mL). After stirring for 10 minutes (min), a solution of 4-NN-dimethylaminopyridine (DMAP; 107 mg, 0.9 mmol) in DCE (2 mL) was added dropwise. The ice bath was removed 15 after 30 min, and the mixture was stirred at room temperature for 90 min and then at reflux for 14 h. The mixture was concentrated under reduced pressure and was purified by silica gel chromatography eluting with a gradient of EtOAc in hexane. The product, 2,N-dimethyl-N (2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-3-methylsulfanyl-propionamide, was isolated as a yellow semi-solid (44 mg, 24%): 'H NMR (400 MHz, CDCl 3 ) 8 9.00 (s, 1H), 8.58 (s, 1H), 20 8.08 (br d, J = 7.0 Hz, 1H), 7.35 (br dd, J = 7.3, 4.8 Hz, 1H), 6.58 (br s, 0.5 H), 6.49 (br s, 0.5 H), 3.89-3.79 (m, 3H), 3.25 (s, 3H), 2.96-2.80 (m, 1H), 2.42-2.40 (m, 1H), 2.02-1.99 (m, 3H), 2.62 (m, 1H), 1.15 (d, J= 6.0 Hz, 3H); MS (m/z) 305.0 [M+1]. Compounds 2 - 6, 9-10, 12, 18 - 21, 24 - 33, 477, 487, 509, 520, 556-557, 562-568 25 were made from the appropriate amines in accordance with the procedures disclosed in Example 3. Example 4: Preparation of 1-methyl-l-(2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-3-(2 methylsulfanyl-ethyl)-urea (Compound 7) 30 34 N-N p SN N To a solution of methyl-(2-methyl-5-pyridin-3-yl-2H-pyrazol-3-yl)-amine (150 mg, 0.8 mmol) in ice-cold DCE (2 mL) under N 2 was added a solution of phosgene in toluene (20%, 5 0.43 mL, 0.88 mmol). The ice bath was removed after 30 min, and the mixture was stirred at room temperature for 1 h and at reflux for 2 h. The mixture was cooled to room temperature and then more phosgene (0.86 mL, 1.76 mmol) was added. The mixture was stirred at reflux for 90 min and then cooled in an ice bath. To this was added a solution of 2 methylthioethylamine (80 mg, 0.88 mmol) in DCE (2 mL). The ice bath was removed after 10 10 min, and the reaction mixture was stirred at reflux for 14 h, cooled, and diluted with DCE (30 mL). The diluted reaction mixture was washed with saturated NaHCO 3 (20 mL), dried over MgSO 4 , adsorbed onto silica gel and purified using silica gel chromatography eluting with a gradient of methanol in dichloromethane to afford 1-methyl-1-(2-methyl-5-pyridin-3 yl-2H-pyrazol-3-yl)-3-(2-methylsulfanyl-ethyl)-urea as a yellow gum (14 mg, 6%): 'H NMR 15 (400 MHz, CDCl 3 ) 8 8.99 (d, J= 1.5 Hz, 1H), 8.57 (dd, J= 4.8, 1.5 Hz, 1H), 8.08 (ddd, J= 8.1, 2.1, 2.1 Hz, 1H), 7.34 (dd, J= 7.9, 4.8 Hz, 1H), 6.52 (s, 1H), 4.88 (br t, J= 5.5 Hz, 1H), 3.80 (s, 3H), 3.41 (q, J = 6.3 Hz, 2H), 3.24 (s, 3H), 2.61 (t, J = 6.3, 2H), 2.06 (s, 3H); ESIMS (m/z) 292.2 [M+2]. 20 Compound 8 was made in accordance with the procedures disclosed in Example 4 using 2-(methylthio)ethanol in place of 2-methylthioethylamine. Example 5: Preparation of 1-methyl-5-(pyridin-3-yl)-1H-pyrazol-3-amine and 1-methyl 3-(pyridin-3-yl)-1H-pyrazol-5-amine 25 2 2 1 N-N 3 N-N N N To ethanol (8.53 ml) was added 3-oxo-3-(pyridin-3-yl)propanenitrile (0.82 g, 5.61 mmol) and 35 methylhydrazine (0.25 g, 5.61 mmol) and stirred at reflux for 2 hours. The reaction was cooled to room temperature and concentrated to dryness. The crude material was purified by silica gel chromatography by eluting with 0-20% MeOH/dichloromethane to yield two products - 1-methyl-5-(pyridin-3-yl)-1H-pyrazol-3-amine (0.060 g; 6.14%): 'H NMR (300 5 MHz, CDCl 3 ) 8 8.72 (s, 1H), 8.53 (d, 1H), 7.76-7.63 (m, 1H), 7.43-7.33 (m, 1H), 5.75 (s, 1H), 3.76-3.57 (m, 5H) and 1-methyl-3-(pyridin-3-yl)-1H-pyrazol-5-amine (0.150 g, 15.35%): 'H NMR (300 MHz, CDCl 3 ) 6 8.88 (s, 1H), 8.48 (d, 1H), 7.99 (d, 1H), 7.38-7.07 (m, 1H), 585 (s, 1H), 3.80-3.59 (m, 5H). 10 Example 6, Step 1: Preparation of 3-pyrazol-1-yl-pyridine N To a solution of 3-bromopyridine (5 g, 0.031 mol) in 50 ml of acetonitrile were added 15 pyrazole (2.6 g, 0.038 mol), Cs 2
CO
3 (16.5 g, 0.050 mol), Cu 2 0 (0.226 g, 0.0016 mol), and salicylaldoxime (0.867 g, 0.006 mol) under N 2 atmosphere. The reaction mass was refluxed for 24 hrs at 80 C. The reaction mass was concentrated and the crude was purified by column chromatography using ethyl acetate and hexane (1:1) to afford the pyrazolyl pyridine as a dark brown liquid (2 g, 43 %): 'H NMR (400 MHz, CDCl 3 ) 8 8.99 (d, J = 2.8 Hz, 1H), 8.48 (dd, J 20 = 4.8, 1.2 Hz, 1H), 8.11 - 8.08 (m, 1H), 7.99 (d, J= 1.2 Hz, 1H), 7.78 (d, J= 1.2 Hz, 1H), 7.38 - 7.35 (m, 1H), 6.53 (t, J = 1.2 Hz, 1H); MS (m/z) 146 [M+1]. 3-(3-chloro-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 1: mp 98-106 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.93 (d, J= 2.6 Hz, 1H), 8.57 (dd, J= 4.8, 1.4 Hz, 1H), 8.03 25 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.90 (d, J= 2.5 Hz, 1H), 7.42 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 6.46 (d, J = 2.5 Hz, 1H); 3C (DMSO-d) 148, 142, 140, 136, 131, 126, 125, 108. 2-methyl-3-(3-methyl-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 1: 'H NMR (400 MHz, CDCl 3 ) 6 8.53 (d, J = 4.7 Hz, 1H), 7.67 (d, J = 7.9 Hz, 1H), 7.54 (t, J = 8.0 30 Hz, 1H), 7.27 - 7.19 (m, 1H), 6.27 (d, J= 1.4 Hz, 1H), 2.53 (s, 3H), 2.38 (s, 3H). 36 3-(3-(Trifluoromethyl)-1H-pyrazol-1-yl)pyridine was prepared from the appropriate starting materials as described in Example 6, Step 1.: mp 59.0-61.0 'C; I H NMR (400 MHz, CDCl3) 6 9.00 (s, 1H), 8.70 - 8.59 (m, 1H), 8.11 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 8.05 - 7.98 (m, 1H), 5 7.46 (dd, J= 8.3, 4.8 Hz, 1H), 6.79 (d, J= 2.4 Hz, 1H); EIMS m/z 213. 3-Fluoro-5-(3-methyl-1H-pyrazol-1-yl)pyridine was prepared from the appropriate starting materials as described in Example 6, Step 1: mp 70.0-72.0 'C; 'H NMR (400 MHz, CDCl3) 6 8.76 - 8.73 (m, 1H), 8.37 - 8.33 (m, 1H), 7.88 - 7.85 (m, 1H), 7.84 - 7.79 (m, 1H), 6.34 - 6.29 10 (m, 1H), 2.37 (s, 3H); EIMS m/z 177. 3-(3-Chloro-1H-pyrazol-1-yl)-5-fluoropyridine was prepared from the appropriate starting materials as described in Example 6, Step 1: mp 77.0-82.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.75 (d, J= 1.8 Hz, 1H), 8.43 (d, J= 2.3 Hz, 1H), 7.92 (d, J= 2.6 Hz, 1H), 7.84 (dt, J= 9.3, 15 2.4 Hz, 1H), 6.48 (d, J= 2.6 Hz, 1H); EIMS m/z 198. 3-(3-methyl-1H-pyrazol-1-yl)pyridine was prepared as described in Example 6, Step 1: IH NMR (400 MHz, CDCl 3 ) 6 8.94 (bs, 1H), 8.51 (d, J= 3.9 Hz, 1H), 8.02 (ddd, J= 8.3, 2.6, 1.5 Hz, 1H), 7.90 - 7.79 (m, 1H), 7.39 (dd, J= 8.2, 5.1 Hz, 1H), 6.30 (d, J= 2.4 Hz, 1H), 20 2.39 (s, 3H). 3-(5-methyl-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 1: 'H NMR (400 MHz, CDCl 3 ) 6 8.77 (d, J= 2.5 Hz, 1H), 8.65 (dd, J= 4.8, 1.5 Hz, 1H), 7.84 (ddd, J= 8.2, 2.5, 1.5 Hz, 1H), 7.63 (d, J= 1.6 Hz, 1H), 7.44 (ddd, J= 8.2, 4.8, 0.7 Hz, 1H), 6.225 (dd, J= 25 1.6, 0.7 Hz, 1H), 2.40 (s, 3H). Example 6, Step 2: Preparation of 3-(4-nitro-pyrazol-1-yl)-pyridine S/
NO
2 N 30 37 3-Pyrazol-1-yl-pyridine (2 g, 0.032 mol) was dissolved in concentrated H 2
SO
4 (32 mL 0.598 mmol.) and cooled to -5 C using an ice bath. To the reaction mass, a 1:1 mixture of concentrated HNO 3 (30 mL, 0.673 mmol) and concentrated H 2
SO
4 (30ml, 15 Vol.) was added dropwise over a period of 30 min. Cooling was discontinued and the reaction mixture was 5 stirred at room temperature overnight. After the reaction was complete, the mixture was poured over crushed ice and neutralized with saturated NaHCO 3 , filtered, washed with water and dried to furnish the nitro pyrazole as pale yellow solid (1.8 g, 68%): 'H NMR (400 MHz, DMSO-d 6 ) 8 9.03 (d, J= 2.8 Hz, 1H); 8.70 (dd, J= 4.8, 1.6 Hz, 1H), 8.69 (s, 1H), 8.33 (s, 1H), 8.11 - 8.08 (m, 1H), 7.51 (dd, J= 8.4, 4.8 Hz, 1H); MS (m/z) 191 [M+1]. 10 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 2: mp 139 142 -C, 'H NMR (400 MHz, CDCl 3 ) 6 9.01 (d, J= 2.0 Hz, 1H), 8.73 (d, J= 4.9 Hz, 2H), 8.08 (ddd, J= 8.3, 2.5, 1.3 Hz, 1H), 7.52 (dd, J= 8.3, 4.8 Hz, 1H), EIMS m/z 224. 15 3-(5-methyl-4-nitro-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 2: 'H NMR (400 MHz, CDCl 3 ) 6 8.81 - 8.71 (m, 2H), 8.32 (s, 1H), 7.83 (ddd, J= 8.2, 2.5, 1.6 Hz, 1H), 7.54 (dd, J= 8.2, 4.8 Hz, 1H), 2.72(s, 3H). 2-methyl-3-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 2: 20 'H NMR (400 MHz, d 6 -DMSO) 6 14.01 (s, 1H), 9.37 (d, J = 4.0 Hz, 1H), 8.69 (t, J = 17.3 Hz, 1H), 8.21 (dd, J= 7.7, 4.8 Hz, 1H), 2.29 (s, 3H), 2.20 (s, 3H); .1C 154, 150, 146, 135, 134.9, 134.8, 134.3, 122, 21, 14; EIMS m/z 218. 3-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyridine was prepared as in Example 6, Step 2: mp 122 25 - 124 'C; ' H NMR (400 MHz, CDCl 3 ) 6 9.01 (d, J = 2.5 Hz, 1H), 8.77 - 8.56 (m, 2H), 8.07 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.56 - 7.37 (m, 1H), 2.66 (s, 3H); EIMS m/z 208. 3-Fluoro-5-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyridine was prepared from the appropriate starting material as described in Example 6, Step 2: mp 90.0-92.0 0 C; 'H NMR (400 MHz, 30 CDCl3) 6 8.82 (d, J = 2.0 Hz, 1H), 8.69 (s, 1H), 8.54 (d, J = 2.5 Hz, 1H), 7.89 (dt, J = 8.9, 2.4 Hz, 1H), 2.66 (s, 3H); EIMS m/z 222. 3-(4-Nitro-3-(trifluoromethyl)-1H-pyrazol-1-yl)pyridine was prepared from the appropriate 38 starting material as described in Example 6, Step 2: mp 121.0-123.0 'C; 'H NMR (400 MHz, CDCl3) 6 9.04 (d, J= 2.5 Hz, 1H), 8.79 (s, 1H), 8.77 (d, J= 0.9 Hz, 1H), 8.13 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.55 (dt, J = 10.8, 5.4 Hz, 1H); EIMS m/z 258. 5 3-(3-Chloro-4-nitro-1H-pyrazol-1-yl)-5-fluoropyridine was prepared from the appropriate starting material as described in Example 6, Step 2: mp 109.5-111.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.83 (d, J= 2.1 Hz, 1H), 8.75 (s, 1H), 8.60 (d, J= 2.4 Hz, 1H), 7.89 (dt, J= 8.6, 2.4 Hz, 1H); EIMS m/z 242. 10 3-(3-Bromo-4-nitro-1H-pyrazol-1-yl)pyridine was prepared from the appropriate starting material as described in Example 6, Step 2: mp 139.0-141.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 9.01 (d, J= 2.5 Hz, 1H), 8.73 (dd, J= 4.7, 1.1 Hz, 1H), 8.71 (s, 1H), 8.15 - 8.00 (m, 1H), 7.52 (dd, J= 8.3, 4.8 Hz, 1H); ESIMS m/z 271 ([M+2]+). 15 Example 6, Step 3: Preparation of 1-pyridin-3-yl-1H-pyrazol-4-ylamine N- H H N To a solution of 3-(4-nitro-pyrazol-1-yl)-pyridine (1.8 g, 0.009 mol) in dry THF (18 ml) was 20 added 5% Pd/C (180 mg) under nitrogen atmosphere. The mixture was then stirred under hydrogen atmosphere until the reaction was complete. The reaction mixture was filtered through a pad of celite, and concentrated to dryness to give an impure dark brown solid (1.76 g): 'H NMR (400 MHz, DMSO-d 6 ) 8 8.89 (dd, J= 2.8. 0.4 Hz, 1H); 8.48 (dd, J= 4.8, 1.2 Hz, 1H), 7.99 - 7.96 (m, 1H), 7.54 (d, J = 1.2 Hz, 1H), 7.45 (d, J = 0.4 Hz, 1H), 7.38 - 7.35 (m, 25 1H), 4.81 (bs 1H); ESIMS (m/z) 161 [M+1]. 5-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as in Example 6, Step 3: 'H NMR (400 MHz, CDCl 3 ) 6 8.74 (d, J= 2.3 Hz, 1H), 8.63 - 8.50 (m, 1H), 7.81 (ddd, J= 8.2, 2.5, 1.5 Hz, 1H), 7.46 - 7.33 (m, 2H), 2.64 (bs, 1H), , 2.29 (s, 3H); 1 3 C (DMSO-d 6 ) 147, 144, 30 137, 133, 130, 129, 124, 123, 10; EIMS m/z 174 39 3-methyl-1-(pyrimidin-5-yl)-1H-pyrazol-4-amine was prepared as in Example 6, Step 3: mp 211-215 0 C; I H NMR (400 MHz, CDCl 3 ) 6 9.10 - 8.87 (m, 3H), 7.51 (s, 1H), 3.24 (bs, 2H), 2.29 (s, 3H); ESIMS m/z 176 ([M+H]). 5 3-chloro-1-(pyrimidin-5-yl)-1H-pyrazol-4-amine was prepared as in Example 6, Step 3: mp 146-148 0 C; I H NMR (400 MHz, CDCl 3 ) 6 9.07 (s, 1H), 9.02 (s, 2H), 7.52 (s, 1H), 3.45 (s, 2H); ESIMS m/z 196 ([M+H]). 10 Example 7: Preparation of methyl-(1-pyridin-3-yl-1H-pyrazol-4-yl)-amine N H
I
N Method A: 15 To a 25 ml round bottom flask containing 1-pyridin-3-yl-1H-pyrazol-4-ylamine (1.76 g, 0.011 mol) in ethanol (26.4 ml) was added benzotriazole (1.31 g, 0.011 mol). The reaction was cooled to 0 0 C - 100 C and formaldehyde (0.36 mL, 0.0121 mol) was added slowly and kept for 30 min at this temperature. The reaction was filtered and concentrated to dryness. The crude material (2.56 g, 0.009 mol) was dissolved in dry tetrahydrofuran (25.6 mL), cooled to 20 00 C and sodium borohydride (0.326 g, 0.00882 mol.) was added over 15 min. The reaction was warmed to room temperature and stirred for 2 hours. The reaction was poured into water and extracted using dichloromethane, the organic layer was dried over anhydrous Na 2
SO
4 and concentrated to dryness. Purified the crude material by silica gel chromatography eluting with 20% methanol/chloroform to afford the desired product as a brown solid (0.610 g, 32 %): 'H 25 NMR (400 MHz, d 6 -DMSO) 8 8.92 (d, J= 2.4 Hz, 1H), 8.47 (dd, J= 4.8, 1.6 Hz, 1H), 8.01 7.98 (m, 1H), 7.45 (s, 1H), 7.30 (s, 1H), 7.37 (dd, J= 8.0, 4.4 Hz, 1H), 2.84 (s, 3H); ESIMS m/z 175 ([M+1]). Method B: 30 1-pyridin-3-yl-1H-pyrazol-4-ylamine (1.0 g, 6.2 mmol) was dissolved in triethyl orthoformate 40 (5 ml, 30 mmol) and to that was added trifluoroacetic acid (3-4 drops). The reaction mixture was refluxed at 120'C for 3 hours and was then concentrated. The crude was dissolved in ethanol (5 ml), cooled to 0 0 C and treated with sodium borohydride (0.6 g, 15.7 mmol). After warming to room temperature, the mixture was refluxed for 3 hours. The mixture was 5 concentrated and the residue was suspended between water and diethyl ether. The diethyl ether layer was separated and concentrated to dryness. The crude material was purified by silica gel chromatography, eluting with 5% methanol/chloroform to afford the desired product as a pale yellow solid (0.3 g, 27%): mp 65 - 67 0 C; 'H NMR (300 MHz, CDCl 3 ) 6 8.91 (bs, 1H), 8.46 (d, J= 4.5 Hz, 1H), 7.99 (d, J= 8.3 Hz, 1H), 7.43 (s, 1H), 7.41 (s, 1H), 7.36 (dd, J 10 = 8.3, 4.7 Hz, 1H), 2.86 (d, J= 12.4 Hz, 3H); ESIMS m/z 175 ([M+1]). Example 8: Preparation of ethyl-(1-pyridin-3-yl-1H-pyrazol-4-yl)-amine N- H N N 15 Method A: To 1-pyridin-3-yl-1H-pyrazol-4-ylamine (0.5 g, 3.12 mmol) in dichloromethane (5 ml) was added acetyl chloride (0.28 g, 3.75 mmol) followed by DMAP (0.57 g, 4.68 mmol) and stirred at room temperature for 3 hours. The reaction mixture was concentrated and purified 20 by silica gel column chromatography. The recovered material was dissolved in tetrahydrofuran (5ml) and lithium aluminum hydride (0.23 g, 6.25 mmol) was added and stirred at room temperature for 12 hours. The reaction was quenched with saturated Na 2
SO
4 and filtered through celite. The filtrate was collected and concentrated to dryness. The crude material was purified by silica gel column chromatography eluting with 0-5% 25 methanol/chloroform and resubjected to silica gel chromatography, eluting with 0-100% ethyl acetate/hexanes) to give the desired product (0.080 g, 14%): 'H NMR (400 MHz, CDCl 3 ) 6 8.90 (d, J= 2.7 Hz, 1H), 8.46 (dd, J= 4.7, 1.3 Hz, 1H), 7.98 (ddd, J= 8.3, 2.6, 1.5 Hz, 1H), 7.41 (dt, J= 13.3, 6.6 Hz, 2H), 7.36 (ddd, J= 8.3, 4.7, 0.7 Hz, 1H), 3.10 (q, J= 7.1 Hz, 2H), 1.27 (t, 3H). 30 Method B: 41 To a solution of tert-butyl ethyl(1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (3.4 g, 11.79 mmol) in dichloromethane (4.54 ml) was added trifluoroacetic acid (9 ml), and the reaction mixture was stirred for 1 hour at room temperature. Toluene was added and the reaction was concentrated to near dryness. The reaction was poured into a separatory funnel and carefully 5 quenched with saturated aqueous NaHCO 3 and extracted with dichloroethane. The organic layer was dried (MgSO4), filtered and concentrated to dryness. The crude product was purified by silica gel chromatography (0-10% MeOH/dichloromethane) to give the desired product as a pale yellow oil (2.10 g, 95%): 'H NMR (400 MHz, CDCl 3 ) 6 8.90 (dd, J= 1.8, 0.8 Hz, 1H), 8.51 - 8.39 (m, 1H), 7.97 (ddt, J= 8.3, 2.7, 1.3 Hz, 1H), 7.41 (d, J= 0.8 Hz, 2H), 10 7.38 - 7.30 (m, 1H), 3.21 - 2.93 (m, 2H), 1.34 - 1.19 (m, 3H). 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as described in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 8.87 (d, J= 2.5 Hz, 1H), 8.47 (dd, J= 4.7, 1.2 Hz, 1H), 7.96 (ddd, J= 8.4, 2.6, 1.4 Hz, 1H), 7.38 - 7.32 (m, 2H), 3.11 (q, J = 7.1 Hz, 2H), 15 2.97 (bs, 1H), 1.31 (t, J= 7.1 Hz, 3H). 3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as in Example 8, Method B: mp 108-118 C; 'H NMR (400 MHz, CDCl 3 ) 6 8.88 (d, J= 2.4 Hz, 1H), 8.48 (dd, J= 4.7, 1.4 Hz, 1H), 7.96 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.41 - 7.29 (m, 2H), 2.87 (s, 3H); 20 EIMS m/z 208. N,3-dimethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 9.03 - 8.73 (m, 1H), 8.41 (dd, J= 4.7, 1.4 Hz, 1H), 7.95 (ddd, J= 8.4, 2.7, 1.4 Hz, 1H), 7.42 - 7.27 (m, 2H), 2.85 (s, 4H), 2.25 (s, 3H); EIMS m/z 189 25 3-chloro-N-(cylopropylmethyl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 8.86 (d, J= 2.5 Hz, 1H), 8.47 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 - 7.89 (m, 1H), 7.40 - 7.29 (m, 2H), 3.21 (s, 1H), 2.91 (d, J= 4.4 Hz, 2H), 1.18 - 1.02 (m, 1H), 0.65 - 0.45 (m, 2H), 0.41 - 0.12 (m, 2H). 30 3-chloro-N-propyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 8.86 (d, J= 2.6 Hz, 1H), 8.47 (dd, J= 4.7, 1.4 Hz, 1H), 8.01 - 7.89 (m, 1H), 7.42 - 7.27 (m, 2H), 3.23 - 2.84 (m, 3H), 1.77 - 1.59 (m, 2H), 1.03 42 (t, J= 7.4 Hz, 3H). 1-(5-Fluoropyridin-3-yl)-N,3-dimethyl-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 142.0-143.5 'C; 1H NMR 5 (400 MHz, CDCl 3 ) 6 8.67 (s, IH), 8.26 (d, J= 2.3 Hz, IH), 7.73 (dt, J= 10.0, 2.4 Hz, IH), 7.27 (s, IH), 2.92 - 2.81 (m, 4H), 2.24 (s, 3H); ESIMS m/z 207 ([M+H]*). N-ethyl-1-(5-fluoropyridin-3-yl)-3-methyl-iH-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 85.0-86.0 'C; 'H NMR 10 (400 MHz, CDCl 3 ) 6 8.66 (s, iH), 8.25 (d, J= 2.5 Hz, iH), 7.72 (dt, J= 10.0, 2.3 Hz, iH), 7.27 (s, iH), 3.07 (q, J= 7.1 Hz, 2H), 2.71 (s, iH), 2.25 (s, 3H), 1.30 (t, J= 7.1 Hz, 3H); ESIMS m/z 221 ([M+H]*). 3-Methyl-N-propyl-1-(pyridin-3-yl)-iH-pyrazol-4-amine was prepared from the appropriate 15 Boc-amine as described in Example 8, Method B: mp 65.0-67.0 'C; 'H NMR (400 MHz, CDCl3) 6 8.86 (d, J= 2.4 Hz, IH), 8.40 (dd, J= 4.7, 1.4 Hz, IH), 7.94 (ddd, J= 8.3, 2.7, 1.5 Hz, IH), 7.35 - 7.28 (m, 2H), 3.00 (t, J= 7.1 Hz, 2H), 2.26 (s, 3H), 1.76 - 1.58 (m, 2H), 1.03 (t, J= 7.4 Hz, 3H); ESIMS m/z 217 ([M+H]*). 20 N-(cyclopropylmethyl)-3-methyl-1-(pyridin-3-yl)-iH-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 73.0-75.0 'C; 'H NMR (400 MHz, CDCl3) 6 8.86 (d, J= 2.4 Hz, IH), 8.40 (dd, J= 4.7, 1.3 Hz, IH), 7.94 (ddd, J= 8.3, 2.6, 1.5 Hz, IH), 7.35 - 7.28 (m, 2H), 2.87 (d, J= 6.9 Hz, 2H), 2.75 (s, IH), 2.28 (s, 3H), 1.22 - 1.05 (m, IH), 0.63 - 0.56 (m, 2H), 0.26 (q, J= 4.7 Hz, 2H); ESIMS m/z 229 ([M+H]*). 25 N-isopropyl-3-methyl-1-(pyridin-3-yl)-iH-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: IR (thin film) 3303 cm-1; 'H NMR (400 MHz, CDCl3) 6 8.86 (d, J = 2.3 Hz, IH), 8.41 (dd, J= 4.7, 1.4 Hz, IH), 7.94 (ddd, J= 8.3, 2.7, 1.5 Hz, IH), 7.36 - 7.28 (m, 2H), 3.30 (hept, J= 6.3 Hz, IH), 2.25 (s, 3H), 30 1.24 (d, J = 6.3 Hz, 6H); EIMS m/z 216. 5-Ethoxy-1-(5-fluoropyridin-3-yl)-N,3-dimethyl-iH-pyrazol-4-amine was prepared from the 43 appropriate Boc-amine as described in Example 8, Method B: IR (thin film) 3340 cm-1; 'H NMR (400 MHz, CDCl 3 ) 6 8.91 (s, 1H), 8.31 (d, J= 2.5 Hz, 1H), 7.88 - 7.80 (m, 1H), 4.24 (q, J= 7.1 Hz, 2H), 2.79 (s, 3H), 2.24 (s, 3H), 1.36 (t, J= 7.1 Hz, 3H); EIMS m/z 250. 5 5-Bromo-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 77.0-79.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.90 (d, J= 2.0 Hz, 1H), 8.63 (d, J= 3.9 Hz, 1H), 7.93 (ddd, J= 8.2, 2.4, 1.5 Hz, 1H), 7.51 (s, 1H), 7.43 (dd, J = 8.2, 4.8 Hz, 1H), 4.49 (s, 1H), 2.91 (s, 3H); ESIMS m/z 255 ([M+2]*). 10 5-Fluoro-N,3-dimethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 8.91 (t, J= 2.1 Hz, 1H), 8.50 (dd, J= 4.8, 1.5 Hz, 1H), 7.93 (ddt, J= 8.3, 2.8, 1.5 Hz, 1H), 7.37 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 2.86 (d, J= 1.6 Hz, 3H), 2.43 (s, 2H), 2.24 (s, 3H); EIMS 15 m/z 206. 5-Bromo-N,3-dimethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 8.86 (dd, J= 2.5, 0.5 Hz, 1H), 8.59 (dd, J= 4.8, 1.5 Hz, 1H), 7.88 (ddd, J= 8.2, 2.6, 1.5 Hz, 20 1H), 7.40 (ddd, J= 8.2, 4.8, 0.7 Hz, 1H), 2.85 (s, 3H), 2.69 (s, 1H), 2.35 (s, 3H); ESIMS m/z 268 ([M+H]*). 5-Chloro-N,3-dimethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 25 8.87 (d, J= 2.3 Hz, 1H), 8.59 (dd, J= 4.8, 1.3 Hz, 1H), 7.90 (ddd, J= 8.2, 2.6, 1.5 Hz, 1H), 7.40 (ddd, J= 8.2, 4.8, 0.6 Hz, 1H), 2.87 (s, 3H), 2.45 - 2.19 (m, 4H); EIMS m/z 223. 3-Chloro-1-(5-fluoropyridin-3-yl)-N-methyl-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 117.5-119.0 'C; 'H NMR 30 (400 MHz, CDCl 3 ) 6 8.68 (d, J= 1.1 Hz, 1H), 8.33 (d, J= 2.5 Hz, 1H), 7.75 (dt, J= 9.6, 2.4 Hz, 1H), 7.31 (s, 1H), 3.14 (s, 1H), 2.87 (s, 3H); ESIMS m/z 227 ([M]+). 3-Chloro-N-ethyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine amine was prepared from the 44 appropriate Boc-amine as described in Example 8, Method B: 'H NMR (400 MHz, CDCl 3 ) 6 8.70 - 8.63 (m, 1H), 8.32 (d, J = 2.4 Hz, 1H), 7.74 (dt, J = 9.7, 2.4 Hz, 1H), 7.31 (s, 1H), 3.11 (q, J= 7.2 Hz, 2H), 1.31 (t, J= 7.1 Hz, 3H). 5 1-(5 -Fluoropyridin-3-yl)-N-methyl-3 -vinyl-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: 105.0-107.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.72 (s, 1H), 8.31 (d, J= 2.5 Hz, 1H), 7.81 (dt, J= 9.8, 2.4 Hz, 1H), 7.33 (s, 1H), 6.75 (dd, J= 18.0, 11.6 Hz, 1H), 5.83 (dd, J= 18.0, 1.1 Hz, 1H), 5.46 (dd, J= 11.6, 1.1 Hz, 1H), 2.86 (s, 3H); ESIMS m/z 219 ([M+H]*). 10 3-Cyclopropyl- 1-(5-fluoropyridin-3-yl)-N-methyl- 1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 118.0-119.5 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.66 - 8.58 (m, 1H), 8.23 (d, J= 2.5 Hz, 1H), 7.75 - 7.68 (m, 1H), 7.25 (s, 1H), 3.09 (s, 1H), 2.86 (s, 3H), 1.78 - 1.63 (m, 1H), 0.99 - 0.90 (m, 4H); ESIMS m/z 233 15 ([M+H]*). 3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate Boc-amine as described in Example 8, Method B: mp 137.9-139.9; 'H NMR (400 MHz, CDCl 3 ) 6 8.84 (d, J= 2.4 Hz, 1H), 8.50 (dd, J= 4.7, 1.4 Hz, 1H), 7.95 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.52 20 (s, 1H), 7.37 (ddd, J= 8.4, 4.7, 0.7 Hz, 1H), 3.18 (s, 2H); ESIMS m/z 196 ([M+H]*). 2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)amino)acetonitrile was prepared from tert butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(cyanomethyl)carbamate as in Example 8, Method B: mp 141-143 'C; 'H NMR (300 MHz, CDCl 3 ) 6 8.91 (d, J= 2.7 Hz, 1H), 8.54 (dd, 25 J= 5.1, 1.8 Hz, 1H), 7.97 (m, 1H), 7.62 (s, 1H), 7.38 (dd, J= 12.0, 7.5 Hz, 1H), 4.97 (d, J = 6.9 Hz, 2H), 3.52 (m, 1H); EIMS m/z 235 ([M+1]*). N-3-dimethyl-1-(pyrimidin-5-yl)-1H-pyrazol-4-amine was prepared as in Example 8, Method B: mp 139-143 'C; 'H NMR (400 MHz, CDCl 3 ) 6 9.02 (s, 2H), 9.00 (s, 1H), 7.30 (s, 1H), 30 2.87 (d, J= 11.5 Hz, 3H), 2.27 (s, 3H); ESIMS m/z 190 ([M+H]). 3-chloro-N-methyl-1-(pyrimidin-5-yl)1-1H-pyrazol-4-amine was prepared as in Example 8, Method B: mp 111-114 'C; 'H NMR (400 MHz, CDCl 3 ) 6 9.09 - 9.04 (m, 1H), 9.02 (s, 2H), 45 7.30 (s, 1H), 3.14 (bs, 1H), 2.88 (s, 3H); ESIMS m/z 196 ([M+H]). 1-(5-Fluoro-3-pyridyl)-3-methyl-N-(trideuteriomethyl)pyrazol-4-amine was prepared from compound 380 using the procedure as described in Example 8, method B: mp 146-148 'C; 1H 5 NMR (400 MHz, CDCl 3 ) 6 8.67 (s, 1H), 8.25 (d, J= 2.5 Hz, 1H), 7.73 (dt, J= 10.0, 2.3 Hz, 1H), 7.27 (s, 1H), 2.87 (s, 1H), 2.24 (s, 3H); ESIMS m/z 210 ([M+H]*); IR (Thin film) 1599 cm 3-Chloro-1-(3-pyridyl)-N-(trideuteriomethyl)pyrazol-4-amine was prepared from compound 10 381 using the procedure as described in Example 8, method B: mp 104-106 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.87 (d, J= 1.9 Hz, 1H), 8.47 (d, J= 4.7 Hz, 1H), 8.00 - 7.90 (m, 1H), 7.40 7.30 (m, 2H), 3.10 (s, 1H); ESIMS m/z 212 ([M+H]*); IR (Thin film) 1579 cm-1. 3-Chloro-N-(cyclopropylmethyl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from 15 compound 361 using the procedure as described in Example 8, method B: mp 82-83 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.86 (d, J= 2.5 Hz, 1H), 8.47 (dd, J= 4.7, 1.3 Hz, 1H), 7.95 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 7.38 - 7.32 (m, 2H), 3.22 (s, 1H), 2.90 (d, J = 6.9 Hz, 2H), 1.23 1.06 (m, 1H), 0.65 - 0.53 (m, 2H), 0.31 - 0.19 (m, 2H).; ESIMS m/z 249 ([M+H]*); 20 3-Chloro-N-propyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from compound 360 using the procedure as described in Example 8, method B: mp 92-94 0 C; 'H NMR (400 MHz, CDCl 3 ) 6 8.86 (d, J= 2.6 Hz, 1H), 8.47 (dd, J= 4.7, 1.4 Hz, 1H), 7.95 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.35 (ddd, J= 8.4, 4.7, 0.6 Hz, 1H), 7.33 (s, 1H), 3.22 - 2.94 (m, 3H), 1.75 - 1.52 (m, 2H), 1.02 (t, J = 7.4 Hz, 3H); ESIMS m/z 237 ([M+H]*). 25 Example 9: Preparation of isopropyl-(1-pyridin-3-yl-1H-pyrazol-4-yl)-amine N- H
N
N 30 1-pyridin-3-yl-1H-pyrazol-4-ylamine (0.6 g, 3.7 mmol) was dissolved in isopropyl acetate (8.5 ml). To the mixture, acetone (0.261 g, 4.5 mmol), trifluoroacetic acid (0.855 g, 7.5 46 mmol) and sodium triacetoxyborohydride (0.945 g, 4.5 mmol) were added. The reaction was stirred under nitrogen at room temperature for 4.5 hours and then quenched with 10% sodium hydroxide solution until the pH reached - 9. The layers were separated, and the aqueous phase was extracted with ethyl acetate. The organic extracts were combined, dried 5 over sodium sulfate and concentrated to dryness. The crude material was purified by silica gel chromatography (gradient elution of 5% methanol/dichloromethane) to give the title compound as an off white solid (0.35 g, 46%): mp 105 - 107 'C; IH NMR (300 MHz, CDCl 3 ) 6 8.82 (d, J= 2.2 Hz, 1H), 8.63 (dd, J= 4.8, 1.5 Hz, 1H), 8.13 (d, J= 1.8 Hz, 1H), 8.03 (d, J= 2.7 Hz, 1H), 7.94 - 7.77 (m, 1H), 7.38 (dt, J= 15.2, 7.6 Hz, 1H), 6.99 (t, 1H), 10 3.72 (m, 1H), 1.30 (t, J= 10.0 Hz,6H). ESIMS 214 m/z (M+1). Example 10: Preparation of propyl-(1-pyridin-3-yl-1H-pyrazol-4-yl-amine NH IIN N 15 To 1-pyridin-3-yl-1H-pyrazol-4-ylamine (0.5 g, 3.12 mmol) in dichloromethane (5 ml) was added propionaldehyde (0.18 g, 3.12 mmol) and sodium triacetoxy borohydride (0.99 g, 4.68 mmol) and stirred at room temperature for 16 hours. The reaction was taken up in dichloromethane and was washed with water and brine. The organic layer was dried 20 (MgS04), filtered and concentrated to dryness. The crude material was purified by silica gel chromatography eluting with 0-5% MeOH/Dichloromethane and resubjected in 0-100% ethylacetate/hexanes) to give the title compound as a dark oil (0.05 g, 7%): 'H NMR (300 MHz, CDCl 3 ) 6 8.92 (d, J= 2.6 Hz, 1H), 8.48 (dd, J= 4.7, 1.4 Hz, 1H), 8.00 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.47 - 7.40 (m, 2H), 7.37 (dd, J= 8.3, 4.7 Hz, 1H), 3.04 (t, J= 7.1 Hz, 25 3H), 1.92 - 1.46 (m, 2H), 1.03 (t, J = 7.4 Hz, 3H). Example 11: Preparation of N-methyl-N-(1-pyridin-3-yl-1H-pyrazol-4-yl) isobutyramide (Compound 42) 47 0 N/N N A solution of isobutyryl chloride (0.138 g, 1.3 mmol) in dichloroethane (1 mL) was pipetted at a dropwise rate into an ice-cold suspension of methyl-(1-pyridin-3-yl-1H-pyrazol-4-yl) 5 amine (0.15 g, 0.86 mmol) in dichloroethane (5 mL), stirred for 10 minutes and then treated at a dropwise rate with a solution of 4-NN-dimethylaminopyridine (0.11 g, 0.9 mmol) in dichloroethane (1.5 mL). The cooling bath was removed after 30 minutes, stirred under nitrogen at room temperature for 14 hours, diluted with dichloroethane (40 mL), washed with water (30 mL), brine (10 mL), dried over MgSO 4 and purified by reversed phase column 10 chromatography to give a yellowish gum (0.114 g, 54%) 'H NMR (300 MHz, CDCl 3 ) 6 9.01 8.93(m, 1H), 8.67 (s, 0.4H), 8.61 (d, J = 4.2 Hz, 0.6H), 8.54 (d, 0.4H), 8.08-8.02 (m, 1H), 7.96 (s, 0.6H), 7.80 (s, 0.4H), 7.70 (s, 0.6H), 7.47-7.37 (m, 1H), 3.49 (s, 1.2H), 3.26 (s, 2.8H), 3.06-2.98 (m, 0.4H), 2.86 - 2.70 (m, 0.6H), 1.25 (d, J= 6.1 Hz, 2.4H), 1.09 (d, J= 6.6 Hz, 3.6H). ESIMS m/z 245 ([M+1]). 15 Compounds 32 - 41, 43 - 52, 54 - 56, 59-61, 66, 73 - 75, 77 - 79, 82 - 85, 93 100, 113, 117 - 129, 131 - 134, 139-140, 142 - 144, 148, 160, 163, 173 - 175, 184 - 186, 197-198, 202, 208, 215-217, 252-253, 277, 282 - 285, 287 - 290, 314 - 316, 347, 350-351, 353 - 355, 365 - 367, 370, 388, 395, 399 - 403, 407, 409, 415 - 418, 444-449, 452 - 454, 20 462 - 463, 465, 467 - 469, 496 - 498, 506 - 507, 512, 525 - 527, 569, 577, 581, 591 and 592 were made from the appropriate amines in accordance with the procedures disclosed in Example 11. Example 12: Preparation of 4,4,4-trifluoro-2-methyl-N-(1-(pyridin-3-yl)-1H-pyrazol-4 25 yl)butanamide (Compound 65) 0 FF N N F H 48 To a solution of 1-(pyridin-3-yl)-1H-pyrazol-4-amine (0.150 g, 0.93 mmol) in dichloroethane (1.8 ml) was added 4,4,4-trifluoro-2-methylbutanoic acid (0.14 g, 0.93 mmol) and 4-NN dimethylaminopyridine (0.23 g, 1.87 mmol) followed by 1-(3-dimethylaminopropyl)-3 5 ethylcarbodiimide hydrochloride (0.36 g, 1.87 mmol). The reaction stirred at room temperature overnight. The reaction mixture was concentrated and the crude product was purified by silica gel chromatography eluting with 0-5% MeOH/dichloromethane to give a white solid (0.15 g, 55%); mp 140-145'C; 1H NMR (400 MHz, CDCl 3 ) 6 9.00 (d, J= 2.4 Hz, 1H), 8.62 - 8.47 (m, 2H), 8.01 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.68 (s, 1H), 7.53 (bs, 1H), 10 7.40 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 2.92 - 2.61 (m, 2H), 2.32 - 2.05 (m, 1H), 1.38 (d, J= 6.6 Hz, 3H); ESIMS m/z 300 ([M+2]). Compounds 53, 58, 62-63, 72, 76, 80 - 81, 107 - 108, 136 - 138, 147, 151 - 159, 164 - 168, 176 - 179, 187 -196, 201, 203 - 207, 209 - 214, 220, 224 - 249, 251, 259 - 275, 15 286, 292 - 296, 303 - 313, 323 - 326, 341 - 344, 356 - 359, 371, 378 - 379, 382, 384, 419 426, 439 -443, 455, 458 - 461, 464, 466, 476, 486, 490 - 493, 505, 508, 517, 528 - 529, 536 - 537, 539- 541, 544 - 545, 549 - 554, 572 - 577, 578, 579 and 580 were prepared from the appropriate amines in accordance with the procedures disclosed in Example 12. 20 Example 13: Preparation of tert-butyl 1-(pyridin-3-yl)-1H-pyrazol-4-ylcarbamate (Compound 57) 0 N/ N \H N 25 Method A: To a solution of 1-(pyridin-3-yl)-1H-pyrazol-4-amine (3 g, 18.73 mmol) in dichloromethane (33.4 ml) was added triethylamine (3.13 ml, 7.68 mmol) and BOC-anhydride (4.5 g, 20.60 mmol). The resulting solution was stirred at room temperature overnight. The reaction mixture was partitioned between ethyl acetate and water. The organic portion was dried 30 (MgS04), filtered and concentrated to dryness. The crude product was purified by silica gel 49 chromatography eluting with 0-100% ethyl acetate/hexanes to yield a white solid (2.0 g, 41%); mp 108 - 112 'C; 1H NMR (400 MHz, CDCl 3 ) 6 9.02 (d, J= 2.2 Hz, 1H), 8.51 (t, J= 8.7 Hz, 1H), 8.37 (s, 1H), 8.30 (s, 1H), 7.98 (ddd, J= 8.3, 2.4, 1.3 Hz, 1H), 7.68 (s, 1H), 7.36 (dd, J = 8.2, 4.8 Hz, 1H), 1.52 (s, 9H); ESIMS m/z 261 ([M+1]). 5 Compounds 64 and 130 were prepared in accordance with the procedures disclosed in Example 13, Method A. Method B: 10 To a solution of 1-(pyridin-3-yl)-1H-pyrazol-4-amine (0.1 g, 0.624 mmol) and di-tert-butyl dicarbonate (0.161 ml, 0.693 mmol) in tetrahydrofuran (1.890 ml) and water (0.568 ml) was added dropwise saturated aqueous sodium bicarbonate (0.572 ml, 0.687 mmol). The reaction was stirred at room temperature overnight. The reaction was diluted with water and extracted with ethyl acetate. The combined organic phases were concentrate to give tert-butyl 1 15 (pyridin-3-yl)-1H-pyrazol-4-ylcarbamate (135 mg, 0.519 mmol, 83 %), for which the analytical data was consistent with that reported in Example 13, Method A. Compounds 150, 172, 223, and 317 were prepared in accordance with the procedures disclosed in Example 13, Method B. Compound 172 and 317 was also prepared in 20 accordance with the procedures disclosed in Example 17. These compounds, as well as, certain other compounds, were made by alternative methods further illustrating certain embodiments. Example 14: Preparation of tert-butyl methyl(1-(pyridin-3-yl)-1H-pyrazol-4 25 yl)carbamate (Compound 67) 0 N O N To a solution of tert-butyl 1-(pyridin-3-yl)-1H-pyrazol-4-ylcarbamate (1.6 g, 6.15 mmol) in 30 DMF (30.7 ml) at 0 0 C was added sodium hydride (0.34 g, 8.61 mmol, 60% dispersion in 50 mineral oil) in one portion and the suspension was stirred for 30 minutes. The ice bath was removed and stirred for an additional 30 minutes. Iodomethane (0.46 ml, 7.38 mmol) was added in one portion and stirred overnight at room temperature. Water and ethyl acetate were added and the resulting biphasic mixture was separated. The aqueous layer was extracted one 5 time with ethyl acetate. The combined organic extracts were washed with brine, dried (MgS04), filtered and concentrated to dryness. The crude product was purified by silica gel chromatography eluting with 0-35% ethyl acetate/hexanes to yield a light yellow semi-solid (0.85 g, 50%): IR (KBr) 1703 cm-1; 1H NMR(400 MHz, CDCl 3 ) 6 8.98 (s, 1H), 8.52 (d, J= 3.8 Hz, 1H), 8.32 (s, 0.5H), 8.13 - 7.97 (m, 1H), 7.84 (s, 0.5H), 7.74 (s, 1H), 7.39 (dd, J= 8.0, 10 4.8 Hz, 1H), 3.30 (s, 3H), 1.56 (s, 9H); ESIMS m/z 275 ([M+H]). Compounds 68, 86 - 92, 105 - 106, 114 - 116, 141, 149, 161 - 162, 199 - 200, 254, 258, 291, 332, 352, 360 - 361, 380 - 381, 414, 430 - 431, 450, 457, 474 - 475, 485, 488, 510 511, 515, 523, and 590 were prepared from the appropriate amides in accordance with the 15 procedures disclosed in Example 14. Tert-butyl methyl(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate was prepared as in Example 14: 'H NMR (400 MHz, CDCl 3 ) 6 8.91 (d, J= 2.5 Hz, 1H), 8.51 (dd, J= 4.7, 1.3 Hz, 1H), 8.00 (ddd, J= 8.3, 2.4, 1.4 Hz, 1H), 7.83 (s, 1H), 7.38 (dd, J= 8.3, 4.7 Hz, 1H), 3.20 20 (s, 3H), 2.22 (s, 3H), 1.60 - 1.30 (m, 9H). Example 15: Preparation of N-ethyl-N-(1-methyl-3-(pyridin-3-yl)-1H-pyrazol-5 yl)isobutyramide (Compound 23) N-N 25 To a solution of N-(1-methyl-3-(pyridine-3-yl)-1H-pyrazol-5-yl)isobutyramide (0.08 g, 0.33 mmol) in DMF (0.66 ml) at 0 0 C was added sodium hydride (0.016 g, 0.39 mmol, 60% dispersion in mineral oil) in one portion and the suspension was stirred for 30 minutes. The 30 ice bath was removed and stirred for an additional 30 minutes. Iodoethane (0.06 g, 0.39 51 mmol) was added in one portion and stirred overnight at room temperature. Water and ethyl acetate were added and the resulting biphasic mixture was separated. The aqueous layer was extracted one time with ethyl acetate. The combined organic extracts were washed with brine, dried (MgSO4), filtered and concentrated to dryness. The crude product was purified by silica 5 gel chromatography to give the title compound as a clear oil (27.5 mg, 30%): 'H NMR (300 MHz, CDCl 3 ) 6 9.00 (bs, 1H), 8.57 (s, 1H), 8.09 (dd, J= 7.9 Hz, 1H), 7.34 (dd, 1H), 6.48 (s, 1H), 4.00 (m, 1H), 3.76 (s, 3H), 3.36 (m, 1H), 2.33 (m, 1H), 1.17 (t, J= 7.1 Hz, 3H), 1.08 (t, J = 6.7 Hz, 6H); ESIMS m/z 273 (M+H). 10 Compound 22 was prepared in accordance with the procedures disclosed in Example 15. Example 16: Preparation of 5-bromo-1H-pyrazol-4-amine, HBr Br H \ NH 2 .HBr 15 N A mixture of 4-nitro-1H-pyrazole (10 g, 88 mmol) and 5% palladium on A1 2 0 3 (1 g) in a mixture of ethanol (150 mL) and 50% aqueous HBr (50 mL) was shaken in a Par apparatus under hydrogen (10 psi) for 36 h. The mixture was filtered and the catalyst washed with 20 ethanol. The filtrate was concentrated in vacuo to give a white solid. This solid was suspended in 10 mL of ethanol. After swirling the flask for 5 min, ether was added to complete the crystallization. The solid was filtered, was washed with ether and dried under high vacuum to afford 5-bromo-1H-pyrazol-4-amine, HBr (18.1 g, 84 % yield) as a white solid: mp 248 'C dec; 'H NMR (400 MHz, DMSO-d 6 ) 6 11.47 (s, 1H), 10.00 (s, 1H), 7.79 (s, 25 1H). Example 17: Preparation of tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4 yl)carbamate (Compound 172) 30 Example 17, Step 1: Preparation of 3-chloro-1H-pyrazol-4-amine hydrochloride 52 CI N NH HCI
H
2 N Into a 2 L three-necked round bottom flask affixed with an overhead stirrer, a temperature probe, an addition funnel, and a nitrogen inlet were added ethanol (600 mL) and 4-nitro-1H 5 pyrazole (50.6 g, 447 mmol). To this solution was added, in one portion, conc. HCl (368 mL) (note: rapid exotherm from 15 OC to 39 OC) and the resulting mixture was purged with nitrogen for 5 minutes. Palladium on alumina (5%w/w) (2,6 g, Alfa, black solid) was added to the mixture and stirred at room temperature while triethylsilane (208 g, 1789 mmol) was added drop-wise over 4 h. The reaction, which started to slowly exotherm from 35 OC to 55 10 OC over 2.0 h, was stirred for a total of 16 h and vacuum filtered through a plug of Celite* to give a biphasic mixture. The mixture was transferred to a separatory funnel, the bottom aqueous layer was collected and rotary evaporated (60 OC, 50 mmHg) to dryness with the aid of acetonitrile (3 x 350 mL). The resulting yellow solid was suspended in acetonitrile (150 mL) and allowed to stand for 2 h at room temperature followed by 1 h at 0 OC in the 15 refrigerator. The solids were filtered and washed with acetonitrile (100 mL) to afford the titled compound 3-chloro-1H-pyrazol-4-amine hydrochloride (84 g, 97% yield, 80% purity) as a white solid: mp 190-193 0 C; 'H NMR (400 MHz, DMSO-d 6 ) 6 10.46 -10.24 (bs, 211), 8.03 (s, 0.54H), 7.75 (s, 0.46H), 5.95 (bs, 1H)); 1 3 C-NMR (101 MHz, DMSO) 6 128.24, 125.97, 116.71. 20 Example 17, Step 2: Preparation of tert-butyl (3-chloro-1H-pyrazol-4-yl)carbamate CI NH HN -to Into a 2 L round bottom flask was added 3-chloro-1H-pyrazol-4-amine hydrochloride (100 g, 25 649 mmol) and THF (500 mL). To this mixture were added di-tert-butyldicarbonate (156 g, 714 mmol) followed by sodium bicarbonate (120 g, 1429 mmol) and water (50.0 ml). The 53 mixture was stirred for 16 h, diluted with water (500 mL) and ethyl acetate (500 mL) and transferred to a separatory funnel. This gave three layers; bottom- a white gelatinous precipitate, middle- light yellow aqueous, top- auburn organic. The phases were separated collecting the white gelatinous precipitate and the aqueous layer together. The aqueous was 5 extracted with ethyl acetate (2 x 200 mL) and the ethyl acetate extracts were combined, washed with brine (200 mL), dried over anhydrous sodium sulfate, filtered and rotary evaporated to give an auburn thick oil (160 g.). The thick oil was suspended in hexane (1000 mL) and stirred at 55 OC for 2 h. This gave a light brown suspension. The mixture was cooled to 0 OC and the solid collected by vacuum filtration and rinsed with hexane (2 x 10 mL). The 10 sample was air dried to constant mass to afford (3-chloro-1H-pyrazol-4-yl)carbamate (102.97 g, 72% yield, 80% purity) as a light brown solid: mp 137-138 'C; 'H NMR (400 MHz, CDCl 3 ) 6 10.69 (s, 1H), 7.91 (s, 1H), 1.52 (s, 9H). Example 17, Step 3: Preparation of tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4 15 yl)carbamate (Compound 172) CI 0
N
N NH N To a dry 2 L round bottom flask equipped with mechanical stirrer, nitrogen inlet, 20 thermometer, and reflux condenser was charged the 3-iodopyridine (113.0 g, 551 mmol), (3 chloro-1H-pyrazol-4-yl)carbamate (100 g, 459 mmol), potassium phosphate (powdered in a mortar and pestle) (195g, 919 mmol), and copper chloride (3.09, 22.97 mmol). Acetonitrile (1 L) followed by N',N 2 -dimethylethane- 1,2-diamine were added and the mixture was heated to 81 'C for 4 hours. The mixture was cooled to room temperature and filtered through a bed of 25 Celite*. The filtrate was transferred to a 4 L Erlenmeyer flask equipped with mechanical stirrer and diluted with water until the total volume was about 4 L. The mixture was stirred for 30 minutes at room temperature and the resulting solid was collected by vacuum filtration. The solid was washed with water and washed with water and oven dried for several days in vacuo at 40 'C to a constant weight to give tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol 30 4-yl)carbamate (117.8 g, 87% yield, 80% purity) as a tan solid: mp 140-143 C; 'H NMR 54 (400 MHz, CDCl 3 ) 6 8.96 (s, 1H), 8.53 (dd, J= 4.7, 1.2 Hz, 1H), 8.36 (s, 1H), 7.98 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.38 (dd, J = 8.3, 4.8 Hz, 1H), 6.37 (s, 1H), 1.54 (s, 9H); ESIMS (m/z) 338 ([M-t-Bu]*), 220 ([M-0-t-Bu]-). 5 Compound 172 was also prepared in accordance with the procedures disclosed in Example 13. Compound 317 was prepared in accordance with the procedures disclosed in Example 17 from tert-butyl (3-bromo-1H-pyrazol-4-yl)carbamate and also in accordance with the procedures disclosed in Example 13. 10 Example 18: Preparation of 3-(3-methyl-1H-pyrazol-1-yl)pyridine and 3-(5-methyl-1H pyrazol-1-yl)pyridine N- N N N 15 To a solution of 3-methyl-1H-pyrazole (10.99 g, 134 mmol) in NN-dimethylformamide (100 ml) at 0 'C was added sodium hydride (3.71 g, 154 mmol, 60% dispersion). The reaction was stirred at 0 'C for 2 hours. 3-Fluoropyridine (10.0 g, 103 mmol) was added, and the reaction was stirred at 100 'C overnight. The reaction was cooled to room temperature and water was added slowly. The mixture was extracted with dichloromethane and the combined organic 20 phases were washed with brine, concentrated and chromatographed (0-100% ethyl acetate/hexanes) to afford 3-(3-methyl-1H-pyrazol-1-yl)pyridine (8.4g, 52.77 mmol, 51.2 %) and 3-(5-methyl-1H-pyrazol-1-yl)pyridine (1.0 g, 6%). Analytical data of both products is consistent with that reported under Example 6, Step 1. 25 3-(3-Bromo-1H-pyrazol-1-yl)pyridine was prepared from 3-fluoropyridine and 3 bromopyrazole, which was made as in W02008130021, as described Example 18: mp 89.5 92.5 'C; IH NMR (400 MHz, CDCl3) 6 8.94 (d, J = 2.4 Hz, 1H), 8.62 - 8.49 (m, 1H), 8.03 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.87 (d, J= 2.5 Hz, 1H), 7.42 (dd, J= 8.2, 4.7 Hz, 1H), 6.54 (d, J= 2.5 Hz, 1H); ESIMS m/z 224 ([M]+). 30 55 Example 19, Preparation of 3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine CI
NH
2 F N 5 To a stirred solution of 5-chloro-1H-pyrazol-4-amine, HCl (2 g, 12.99 mmol) and cesium carbonate (8.89 g, 27.3 mmol) in DMF (13 mL) was added 3,5-difluoropyridine (1.794 g, 15.58 mmol) and the mixture heated at 70 'C for 12 h. The mixture was cooled to room temperature and filtered. The solids were washed with copious amount of ethyl acetate. The filtrates was washed with brine, dried over anhydrous MgSO 4 and concentrated in vacuo to 10 give a brown solid. This solid was dissolved in ethyl acetate and the resulting solution was saturated with hexanes to precipitate 3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine (2.31g, 10.32 mmol, 79 % yield) as a brown solid: 'H NMR (400 MHz, DMSO-d 6 ) 6 8.89 8.82 (m, 1H), 8.45 (d, J= 2.5 Hz, 1H), 8.07 (d, J= 10.4 Hz, 1H), 7.94 (s, 1H), 4.51 (s, 2H); EIMS (m/z) 213 ([M+1]+). 15 3-Bromo-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine was prepared from the corresponding pyrazole as described in Example 19: mp 164-165 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.65 (d, J= 1.7 Hz, 1H), 8.36 (d, J= 2.5 Hz, 1H), 7.76 (dd, J= 5.9, 3.6 Hz, 1H), 7.48 (s, 1H), 3.22 (s, 2H). 1 C NMR (101 MHz, CDCl 3 ) 6 160.87, 158.30, 135.36, 135.13, 134.39, 134.35, 131.16, 20 123.31, 114.02, 112.77, 112.54; EIMS (m/z) 258 ([M+1]+). Example 20: Preparation of 1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-amine
N
F N/ NH 2 N 25 To a solution of 3-fluoro-5-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyridine (3.133 g, 14.10 mmol) in ethanol (28.2 ml) was added ethyl acetate until all of the starting material went into 56 solution. The solution was degassed and 10% palladium on carbon (0.750 g, 0.705 mmol) was added and the reaction was stirred in a parr hydrogenator at 40 psi for 3 hours. The solution was filtered through celite with ethyl acetate and concentrated to give 1-(5 fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-amine (2.000 g, 10.41 mmol, 73.8 %) as a brown 5 solid: mp 136.0-138.0 0 C; 'H NMR (400 MHz, CDCl3) 6 8.67 - 8.59 (m, 1H), 8.27 (d, J= 2.5 Hz, 1H), 7.73 (dt, J= 9.9, 2.3 Hz, 1H), 7.45 (s, 1H), 3.01 (s, 2H), 2.28 (s, 3H); EIMS m/z 192. 1-(Pyridin-3-yl)-3-(trifluoromethyl)-1H-pyrazol-4-amine was prepared from the appropriate 10 nitropyrazole as described in Example 20: mp 112.5-115.0 0 C; 'H NMR (400 MHz, CDCl3) 6 8.89 (d, J= 2.4 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.56 (d, J= 0.7 Hz, 1H), 7.41 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 3.47 - 3.31 (m, 2H); EIMS m/z 228. 15 Example 21: Preparation of 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine CI
N
/ NH 2 N To 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (0.95 g, 4,23 mmol) in acetic acid (8.46 mL), 20 ethanol (8.46 mL) and water (4.23 mL) was added iron powder (1.18 g, 21.15 mmol) and the reaction was stirred at room temperature for 30 minutes. To this was added carefully 2 M KOH and extracted with ethyl acetate. The ethyl acetate layers were combined, dried (MgS04), filtered and concentrated to dryness. The crude material was purified by silica gel chromatography (0-10% methanol/dichloromethane) to give the desired product as a white 25 solid (0.66 g, 80%): 'H NMR (400 MHz, CDCl 3 ) 6 8.84 (d, J = 2.6 Hz, 1H), 8.49 (dd, J = 4.7, 1.4 Hz, 1H), 7.95 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.53 (s, 1H), 7.37 (ddd, J= 8.4, 4.7, 0.6 Hz, 1H), 3.17 (bs, 2H). 3-methyl-1-(2-methylpyridin-3-yl)-1H-pyrazol-4-amine was prepared as described in 30 Example 21: 'H NMR (400 MHz, CDCl 3 ) 6 8.48 (dd, J= 4.8, 1.6 Hz, 1H), 7.62 (dd, J= 8.0, 57 1.6 Hz, 1H), 7.23 - 7.18 (m, 2H), 2.91 (bs, 2H), 2.55 (s, 3H), 2.28 (s, 3H); EIMS m/z 188. 3-Phenyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate nitropyrazole as described in Example 21: IR (thin film) 3324 cm-1; 1H NMR (400 MHz, 5 CDCl3) 6 8.94 (d, J= 2.2 Hz, 1H), 8.47 (dd, J= 4.7, 1.4 Hz, 1H), 8.07 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.87 - 7.80 (m, 2H), 7.60 (s, 1H), 7.50 - 7.44 (m, 2H), 7.40 - 7.34 (m, 2H), 3.86 (s, 2H); EIMS m/z 236. 3-Chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate 10 nitropyrazole as described in Example 21: mp 149.0-151.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.65 (d, J= 1.6 Hz, 1H), 8.35 (d, J= 2.4 Hz, 1H), 7.75 (dt, J= 9.5, 2.4 Hz, 1H), 7.51 (s, 1H), 3.21 (s, 2H); ESIMS m/z 213 ([M]+). 3-Bromo-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared from the appropriate 15 nitropyrazole as described in Example 21: mp 143.0-146.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.85 (d, J= 2.4 Hz, 1H), 8.50 (dd, J= 4.7, 1.4 Hz, 1H), 7.96 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.49 (s, 1H), 7.37 (ddd, J = 8.4, 4.7, 0.7 Hz, 1H), 3.21 (s, 2H); ESIMS m/z 241 ([M+2]+). Example 22: Preparation of tert-butyl (5-methyl-1-(pyridin-3-yl)-1H-pyrazol-4 20 yl)carbamate (Compound 281) O N YO NH / NH N To a solution of (E)-tert-butyl 1-(dimethylamino)-3-oxobut-1-en-2-ylcarbamate (0.59 g, 2.58 mmol) in ethanol (2.5 mL) was added 3-hydrazinylpyridine, 2HCl (0.470 g, 2.58 mmol). The 25 reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was concentrated and purified using silica gel chromatography (0-100 % ethyl acetate/hexanes) to yield the title compound as an orange foam (0.235 g, 30%): IR (thin film) 3268, 2978 and 1698 cm-1; 'H NMR (400 MHz, CDCl 3 ) 6 8.75 (dd, J= 2.5, 0.5 Hz, 1H), 8.62 (dd, J= 4.8, 1.5 Hz, 1H), 7.82 (ddd, J= 8.2, 2.6, 1.5 Hz, 1H), 7.78 (s, 1H), 7.43 (ddd, J= 8.1, 4.8, 0.6 Hz, 30 1H), 6.04 (s, 1H), 2.29 (s, 3H), 1.52 (s, 9H); ESIMS m/z 275 ([M+H]*), 273 ([M-H]-). 58 Example 23: Preparation of tert-butyl 1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4 ylcarbamate (Compound 111) and tert-butyl 5-ethoxy-1-(5-fluoropyridin-3-yl)-3-methyl 1H-pyrazol-4-ylcarbamate (Compound 112) 5 N- N- N F N F N H 0 H IN~~ N To a solution of 3-fluoro-5-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyridine (3.133 g, 14.10 mmol) in ethanol (28.2 ml) was added ethyl acetate until all of the starting material went into 10 solution. The solution was degassed and 10% palladium on carbon (0.750 g, 0.705 mmol) was added and the reaction was stirred in a parr hydrogenator at 40 psi for 3 hours. The solution was filtered through celite with ethyl acetate and the solvent was removed under reduced pressure. The residue was dissolved in tetrahydrofuran (32.0 ml) and water (9.61 ml). Di-tert-butyl dicarbonate (2.52 g, 11.55 mmol) was added followed by saturated aqueous 15 sodium bicarbonate (9.54 ml, 11.45 mmol). The reaction was stirred at room temperature overnight, diluted with water and extracted with ethyl acetate. The combined organic phases were concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give tert-butyl 1 (5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-ylcarbamate (1.673 g, 5.72 mmol, 41.0 %) as a yellow solid and the tert-butyl 5-ethoxy-1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4 20 ylcarbamate (0.250 g, 0.74 mmol, 5.2 %) as a brown oil: Tert-butyl 1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-ylcarbamate (Compound 111): mp 131.5-133.0 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.75 (s, 1H), 8.32 (d, J= 2.5 Hz, 1H), 8.28 (s, 1H), 7.77 (dt, J= 9.7, 2.4 Hz, 1H), 6.15 (s, 1H), 2.29 (s, 3H), 1.54 (s, 9H); ESIMS m/z 293 25 ([M+H]*). Tert-butyl 5-ethoxy-1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-ylcarbamate (Compound 112): IR (thin film) 1698 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.88 (s, 1H), 8.34 (d, J= 2.5 Hz, 1H), 7.83 (d, J= 9.9 Hz, 1H), 5.99 (s, 1H), 4.37 (q, J= 7.0 Hz, 2H), 2.17 (s, 3H), 1.50 (s, 30 9H), 1.37 (t, J= 7.1 Hz, 3H); ESIMS m/z 337 ([M+H]*). 59 Example 24: Preparation of Bis tert-t-butyl (1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (Compound 595) N O ~N/N 5 N To a solution of tert-butyl (1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (2.00 g, 7.68 mmol) in dry THF (21.95 mL) at 0 'C was added 60% sodium hydride (0.33 g, 8.45 mmol) in one portion and stirred at that temperature for 30 minutes. To this was then added Boc-Anhydride 10 (1.84 g, 8.45 mmol) in one portion and stirred for 5 minutes at 0 'C. The water bath was removed and the reaction was warmed to room temperature and stirred at additional 30 minutes. The reaction was quenched with water and extracted with ethyl acetate. The ethyl acetate layers were combined, dried (MgS04), filtered and concentrated to dryness. The crude material was purified by silica gel chromatography (0-100% ethyl acetate/hexanes) to give the 15 desired product as a white solid (2.0 g, 72%): 'H NMR (400 MHz, CDCl 3 ) 6 9.12 - 8.86 (m, 1H), 8.55 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 8.01 (d, J= 0.5 Hz, 1H), 7.84 - 7.65 (m, 1H), 7.41 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 1.51 (s, 18H). Example 25: Preparation of 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (Compound 20 516) CI
N
N NH 2 N To tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (2 g, 6.79 mmol) in 25 dichloromethane (6.79 ml) was added trifluoroacetic acid (6.79 ml) and the mixture was left stirring at room temperature for 2 hours. Toluene (12 mL) was added and the reaction was concentrated to near dryness. The mixture was poured into a separatory funnel containing 60 saturated aqueous sodium bicarbonated and was extracted with dichloromethane. The combined organic layers were concentrated to give 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4 amine (0.954g, 4.90 mmol, 72.2 %) as a white solid: mp 137.9-139.9 'C; IH NMR (400 MHz, CDCl 3 ) 6 8.84 (d, J= 2.4 Hz, 1H), 8.50 (dd, J= 4.7, 1.4 Hz, 1H), 7.95 (ddd, J= 8.3, 5 2.7, 1.5 Hz, 1H), 7.52 (s, 1H), 7.37 (ddd, J= 8.4, 4.7, 0.7 Hz, 1H), 3.18 (s, 2H); ESIMS m/z 196 ([M+H]*). Example 26: Preparation of N-allyl-1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4 amine hydrochloride 10 N F N / NH.HCI N To a solution of tert-butyl allyl(1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-yl)carbamate (908 mg, 2.73 mmol) in dioxane (5 mL) was added HCl (IM in ether) (13.65 mL, 13.65 15 mmol) and the mixture stirred at room temperature for 48 h. The resulting white solid was filtered, washed with ether and dried under vacuum to give N-allyl-1-(5-fluoropyridin-3-yl)-3 methyl-1H-pyrazol-4-amine, HCl (688 mg, 94 % yield) as a white solid: mp 189-190 'C; 1H NMR (400 MHz, CDCl 3 ) 6 8.79 - 8.68 (m, 1H), 8.32 - 8.26 (m, 1H), 8.23 (s, 1H), 7.98 7.86 (m, 1H), 5.86 - 5.68 (m, 1H), 5.28 - 5.17 (m, 1H), 5.17 - 5.03 (m, 1H), 3.59 (d, J= 6.2 20 Hz, 2H), 2.11 (s, 3H); EIMS (m/z) 233 ([M+1]+). N-Allyl-3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl was prepared as described in Example 26 from tert-butyl allyl(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate: mp 172-174 'C; 'H NMR (400 MHz, CDCl 3 ) 6 9.20 (d, J= 2.5 Hz, 1H), 8.65 (dd, J= 5.3, 1.1 25 Hz, 1H), 8.61 (ddd, J= 8.6, 2.5, 1.1 Hz, 1H), 8.24 (s, 1H), 7.93 (dd, J= 8.6, 5.3 Hz, 1H), 3.66 (dt, J = 5.5, 1.3 Hz, 2H); EIMS (m/z) 235 ([M+1]+). N-Allyl-3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl was prepared as described in Example 26 from tert-butyl allyl(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl): mp 195-197 'C; 30 'H NMR (400 MHz, DMSO-d) 6 9.12 (d, J= 2.4 Hz, 1H), 8.58 (dd, J= 5.0, 1.2 Hz, 1H), 61 8.48 (s, 1H), 8.43 (d, J= 9.7 Hz, 1H), 7.77 (dd, J= 8.4, 5.0 Hz, 1H), 6.04 - 5.92 (m, 1H), 5.44 (dd, J= 17.2, 1.4 Hz, 1H), 5.32 (d, J= 9.4 Hz, 1H), 3.81 (d, J= 6.2 Hz, 2H); EIMS (m/z) 249 ([M-1]+). 5 3-Bromo-1-(5-fluoropyridin-3-yl)-N-methyl-1H-pyrazol-4-amine, HCl was prepared as described in Example 26 from tert-butyl 3-bromo-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4 yl(methyl)carbamate: mp 167-168 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.93 (s, 1H), 8.50 (d, J = 2.5 Hz, 1H), 8.23 (s, 1H), 8.14 (dt, J= 10.4, 2.3 Hz, 1H), 2.73 (s, 3H). 10 3-Bromo-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl was prepared as described in Example 26 from tert-butyl (3-bromo-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate (160 mg, 0.45 mmol) in dioxane (1 mL) was added 4M HCl: mp. 226-228 'C; 'H NMR (400 MHz, DMSO-d 6 ) 6 9.26 - 9.06 (d, J= 2.6 Hz, 1H), 8.69 - 8.54 (m, 1H), 8.54 - 8.39 (d, J= 8.0 Hz, 1H), 8.33 - 8.14 (s, 1H), 7.90 - 7.72 (m, 1H), 2.82 - 2.67 (s, 3H); EIMS (m/z) 253 15 ([M+1]+), 255 ([M+2H]+). 3-Bromo-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl was prepared as described in Example 26 from 3-bromo-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl: mp 216-217 OC; 'H NMR (400 MHz, DMSO-d 6 ) 6 10.66 - 10.05 (s, 3H), 9.28 - 9.20 (d, J = 2.5 Hz, 1H), 20 8.74 - 8.67 (m, 1H), 8.67 - 8.56 (m, 3H), 7.96 - 7.84 (m, 1H), 3.21 - 3.14 (m, 2H), 1.29 - 1.22 (m, 3H); EIMS (m/z) 267 ([M+1]+). 3-Chloro-N-(2-methoxyethyl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl was prepared as described in Example 26 from tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(2 25 methoxyethyl)carbamate, HCl: mp 157-158 GC;1H NMR (400 MHz, DMSO) 6 9.22 - 9.14 (d, J= 2.5 Hz, 1H), 8.70 - 8.65 (s, 1H), 8.65 - 8.59 (m, 1H), 8.38 - 8.33 (m, 1H), 8.00 - 7.89 (m, 1H), 3.59 - 3.50 (t, J = 5.8 Hz, 2H), 3.32 - 3.27 (s, 3H), 3.22 - 3.14 (m, 2H); EIMS (m/z) 253 ([M+1]+). 30 Example 27: Preparation of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine hydrochloride 62 CI N /NH 2HCI N, N Into a 500 mL three-necked round bottom flask equipped with a magnetic stir bar was added a solution of tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)carbamate (21 g, 65.1 5 mmol) in 1.4-dioxane (35 mL). This pale yellow solution was placed into an ice bath and cooled to 1 oC. A solution of 4M HCl/dioxane (65 mL, 260 mmol) was added in one portion. After stirring for 20 minutes, the ice bath was removed and the suspension was stirred further at ambient temperature for 16 hours. The reaction was diluted with 200 mL of ethyl ether and the solid was filtered and washed with ether and placed in a vacuum oven at 40 OC for 18 10 hours. The title compound was isolated as a pale yellow solid (18.2 g, 95%): 'H NMR (400 MHz, MeOD) 6 9.52 (d, J= 2.5 Hz, 1H), 9.17 (s, 1H), 9.14 (ddd, J= 8.7, 2.5, 1.1 Hz, 1H), 8.93 (ddd, J= 5.7, 1.1, 0.6 Hz, 1H), 8.31 (ddd, J= 8.7, 5.7, 0.5 Hz, 1H), 3.58 (q, J= 7.3 Hz, 2H), 1.48 (t, J = 7.3 Hz, 3H); ESIMS m/z 223 ([M+H]*). 15 3-Chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazole-4-amine, 2HCl was prepared as described in Example 27: 'H NMR (400 MHz, MeOD) 6 9.28 (d, J= 2.5 Hz, 1H), 8.86 (ddd, J= 8.7, 2.5, 1.2 Hz, 1H), 8.79 - 8.75 (m, 1H), 8.62 (s, 1H), 8.19 (ddd, J= 8.7, 5.6, 0.5 Hz, 1H), 3.06 (s, 3H); 1C NMR (101 MHz, MeOD) 6 141.42, 139.58, 137.76, 134.58, 134.11, 129.33, 127.55, 122.14, 35.62); ESIMS m/z 209 ([M+H]*). 20 Example 28: Preparation of 3-(4-nitro-3-phenyl-1H-pyrazol-1-yl)pyridine
N
/ NO 2 N 25 To a suspension of phenylboronic acid (0.546 g, 4.47 mmol) in toluene (6.63 ml) was added 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (0.335 g, 1.492 mmol) followed by ethanol 63 (3.31 ml) and 2 M aqueous potassium carbonate (1.492 ml, 2.98 mmol). The solution was degassed by applying vacuum and then purging with nitrogen (3 times). To the reaction mixture was added palladium tetrakis (0.086 g, 0.075 mmol) and the flask was heated at 110 'C under nitrogen for 16 hours. The aqueous layer was removed and the organic layer was 5 concentrated. The crude product was purified via silica gel chromatography (0-100% ethyl acetate/hexanes) to give 3-(4-nitro-3-phenyl-1H-pyrazol-1-yl)pyridine (499 mg, 1.874 mmol, 80 %) as a yellow solid: mp 144.0-146.0 'C; IH NMR (400 MHz, CDCl3) 6 9.09 (d, J = 2.3 Hz, 1H), 8.82 (s, 1H), 8.71 (dd, J= 4.8, 1.4 Hz, 1H), 8.16 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.82 - 7.74 (m, 2H), 7.55 - 7.48 (m, 4H); EIMS m/z 266. 10 Example 29: Preparation of 5-bromo-1-(pyridin-3-yl)-1H-pyrazol-4 yl(methyl)carbamate (Compound 110) 0>6 N/N IBr N 15 To tert-butyl methyl(1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (0.200 g, 0.729 mmol) in dichloroethane (3.65 ml) was added 1-bromopyrrolidine-2,5-dione (0.260 g, 1.458 mmol) and the reaction was stirred overnight at 50'C. The reaction was concentrated, diluted with dichloromethane, and washed with water and saturated aqueous sodium thiosulfate. The 20 organic phase was concentrated to give tert-butyl 5-bromo-1-(pyridin-3-yl)-1H-pyrazol-4 yl(methyl)carbamate (256 mg, 0.725 mmol, 99 %) as a brown oil: IR (thin film) 1697 cm-1; IH NMR (400 MHz, CDCl 3 ) 6 8.89 (s, 1H), 8.68 (d, J= 4.1 Hz, 1H), 7.93 (ddd, J= 8.2, 2.5, 1.5 Hz, 1H), 7.69 (s, 1H), 7.46 (dd, J= 8.1, 4.8 Hz, 1H), 3.22 (s, 3H), 1.44 (s, 9H); ESIMS m/z 352 ([M-H]-). 25 Example 30: Preparation of Bis tert-t-butyl (5-chloro-1-(pyridin-3-yl)-1H-pyrazol-4 yl)carbamate (Compound 109) 64 N0 O SN / -N 0 N To Bis tert-t-butyl (1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (1.30 g, 3.61 mmol) in acetonitrile (21.22 mL) was added N-chlorosuccinimide (0.96 g, 7.21 mmol) and the reaction 5 was stirred at 45 'C for 48 hours. The reaction was cooled to room temperature and poured into water and extracted with dichloromethane. The dichloromethane layers were combined, poured through a phase separator to remove water and concentrated to dryness. The crude material was purified by silica gel chromatography (0-60% ethyl acetate/hexanes) to give the desired product as a yellow solid (0.90 g, 63%): mp 109-115 'C; 1H NMR (400 MHz, CDCl 3 ) 10 6 8.90 (d, J= 2.3 Hz, 1H), 8.68 (dd, J= 4.8, 1.5 Hz, 1H), 7.94 (ddd, J= 8.2, 2.5, 1.5 Hz, 1H), 7.70 (s, 1H), 7.47 (dtd, J= 11.0, 5.6, 5.5, 4.8 Hz, 1H), 1.49 (s, 18H); ESIMS m/z 395 ([M+H]*). Tert-butyl (5-chloro-3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate was 15 prepared from the appropriate pyrazole in dichloroethane as the solvent as described in Example 30: ESIMS m/z 324 ([M+H]*). Compounds 110 (see also procedure in Example 29) and 146 were prepared from the appropriate pyrazoles using N-bromosuccinimide in accordance with the procedures 20 disclosed in Example 30. Tert-butyl 5-bromo-3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl(methyl)carbamate was prepared from the appropriate pyrazole in dichloroethane as described in Example 30: 'H NMR (400 MHz, CDCl 3 ) 6 8.88 (d, J = 2.3 Hz, 1H), 8.69 - 8.60 (m, 1H), 7.96 - 7.86 (m, 1H), 25 7.48 - 7.39 (m, 1H), 3.18 (s, 3H), 2.26 (s, 3H), 1.60 - 1.36 (m, 9H); ESIMS m/z 368 ([M+H]*). Example 31: Preparation of bis tert-butyl (5-fluoro-1-(pyridin-3-yl)-1H-pyrazol-4 yl)carbamate (Compound 135) 30 65 N N N To a solution of bis tert-t-butyl (1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (0.075 g, 0.208 mmol) in DMF (0.416 ml) and acetonitrile (0.416 ml) was added Selecfluor@ (0.184 g, 0.520 5 mmol). The reaction was stirred at room temperature for one week. The reaction was concentrated, saturated aqueous ammonium chloride was added and the mixture was extracted with ethyl acetate. The combined organic phases were concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give bis tert-butyl (5-fluoro-1-(pyridin-3 yl)-1H-pyrazol-4-yl)carbamate (16 mg, 0.042 mmol, 20.32 %) as an off-white solid: 'H NMR 10 (400 MHz, CDCl 3 ) 6 8.97 (t, J= 2.0 Hz, 1H), 8.61 (dd, J= 4.8, 1.4 Hz, 1H), 7.99 (ddt, J= 8.3, 2.6, 1.3 Hz, 1H), 7.57 (d, J= 2.5 Hz, 1H), 7.44 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 1.50 (s, 18H); ESIMS m/z 379 ([M+H]*). Tert-butyl (5-fluoro-3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate was 15 prepared as described in Example 31: 'H NMR (400 MHz, CDCl 3 ) 6 8.94 (s, 1H), 8.57 (d, J= 4.2 Hz, 1H), 7.96 (d, J= 7.7 Hz, 1H), 7.41 (dd, J= 7.9, 4.7 Hz, 1H), 3.17 (s, 3H), 2.23 (s, 3H), 1.58 - 1.40 (m, 9H); ESIMS m/z 307 ([M+H]*). Example 32: Preparation of N-cyclopropyl-3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4 20 amine Example 32, Step 1: Preparation of 3-(4-iodo-3-methyl-1H-pyrazol-1-yl)pyridine N N 25 To a mixture of 3-(3-methyl-1H-pyrazol-1-yl)pyridine (6.7 g, 42.1 mmol), iodic acid (2.96 g, 16.84 mmol), and diiodine (8.55 g, 33.7 mmol) in acetic acid (60.1 ml) was added 66 concentrated sulfur acid (3.74 ml, 21.04 mmol). The reaction mixture heated to 70 'C for 30 minutes. The reaction mixture was poured onto ice with sodium thiosulfate and was extracted with diethyl ether. The combined organic phases were washed with saturated aqueous sodium bicarbonate. The organic phases were then dried with magnesium sulfate, filtered and 5 concentrated in vacuo. The solid residue was dissolved in dichloromethane , applied to a 80g silica gel column, and eluted with 0-80% acetone in hexanes to afford 3-(4-iodo-3-methyl 1H-pyrazol-1-yl)pyridine (11.3 g, 35.7 mmol, 85 %) as a white solid: mp 131 'C; IH NMR (400 MHz, CDCl 3 ) 6 8.95 - 8.85 (m, 1H), 8.52 (dd, J = 4.8, 1.4 Hz, 1H), 8.00 - 7.94 (m, 1H), 7.91 (s, 1H), 7.38 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 2.34 (s, 3H); EIMS m/z 285. 10 Example 32, Step 2: Preparation of N-cyclopropyl-3-methyl-1-(pyridin-3-yl)-1H pyrazol-4-amine N I :/ NH N N 15 To a solution of 3-(4-iodo-3-methyl-1H-pyrazol-1-yl)pyridine (2.0 g, 7.02 mmol) in dimethylsulfoxide (7.02 ml) was added 1-(5,6,7,8-tetrahydroquinolin-8-yl)ethanone (0.246 g, 1.403 mmol), cyclopropanamine (0.486 ml, 7.02 mmol), cesium carbonate (6.86 g, 21.05 mmol) and copper(I) bromide (0.101 g, 0.702 mmol). The reaction mixture was stirred at 35 20 'C for 2 days. The reaction mixture was diluted with water and extracted with dichloromethane. The combined organics were washed with brine, concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give N-cyclopropyl-3-methyl-1-(pyridin 3-yl)-1H-pyrazol-4-amine (269 mg, 1.255 mmol, 17.90 %) as a yellow solid: mp 104.0-107.0 OC; 'H NMR (400 MHz, CDCl 3 ) 6 8.89 (dd, J= 2.7, 0.5 Hz, 1H), 8.41 (dd, J= 4.7, 1.4 Hz, 25 1H), 7.96 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.51 (s, 1H), 7.33 (ddd, J= 8.3, 4.7, 0.7 Hz, 1H), 3.42 (s, 1H), 2.53 - 2.42 (m, 1H), 2.22 (s, 3H), 0.72 - 0.65 (m, 2H), 0.60 - 0.53 (m, 2H); ESIMS m/z 215 ([M+H]*). 3-Methyl-N-(3-(methylthio)propyl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as 30 described in Example 32: IR (thin film) 3298 cm-1; 'H NMR (400 MHz, CDCl 3 ) 6 8.87 (d, J 67 = 2.3 Hz, 1H), 8.40 (dd, J= 4.7, 1.4 Hz, 1H), 7.93 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.35 (s, 1H), 7.34 - 7.29 (m, 1H), 3.16 (t, J = 6.8 Hz, 2H), 2.89 (s, 1H), 2.64 (t, J = 7.0 Hz, 2H), 2.25 (s, 3H), 2.13 (s, 3H), 1.95 (p, J= 6.9 Hz, 2H); ESIMS m/z 263 ([M+H]*). 5 3-Methyl-N-(2-methyl-3-(methylthio)propyl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine was prepared as described in Example 32: IR (thin film) 3325 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.86 (d, J= 2.5 Hz, 1H), 8.40 (dd, J= 4.7, 1.2 Hz, 1H), 7.93 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.35 (s, 1H), 7.32 (ddd, J= 8.3, 4.7, 0.5 Hz, 1H), 3.12 (dd, J= 11.5, 6.1 Hz, 1H), 2.94 (dd, J = 11.9, 6.6 Hz, 1H), 2.62 (dd, J= 12.9, 6.9 Hz, 1H), 2.52 (dd, J= 12.9, 6.2 Hz, 1H), 2.26 (s, 10 3H), 2.14 (s, 3H), 2.12 - 2.02 (m, 1H), 1.11 (d, J= 6.8 Hz, 3H); EIMS m/z 276. Example 33: Preparation of tert-butyl (3-cyclopropyl-1-(5-fluoropyridin-3-yl)-1H pyrazol-4-yl)carbamate (Compound 434) and tert-butyl (1-(5-fluoropyridin-3-yl)-1H pyrazol-4-yl)carbamate (Compound 489) 15 N- N F NH F N NN To a suspension of 2-cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.087 g, 6.47 mmol) in toluene (13.69 ml) was added tert-butyl (3-bromo-1-(5-fluoropyridin-3-yl)-1H 20 pyrazol-4-yl)carbamate (1.1 g, 3.08 mmol) followed by ethanol (6.84 ml) and 2 M aqueous potassium carbonate (3.08 mL, 6.16 mmol). The solution was degassed by applying vacuum and then purging with nitrogen (3 times). To the reaction mixture was added palladium tetrakis (0.178 g, 0.154 mmol) and the flask was heated at 100 'C under nitrogen for 36 hours. Water (5 mL) was added and the mixture was extracted with ethyl acetate. The 25 combined organics were concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give tert-butyl (3-cyclopropyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)carbamate (705 mg, 2.215 mmol, 71.9 % yield) as a yellow solid and tert-butyl (1-(5-fluoropyridin-3-yl)-1H pyrazol-4-yl)carbamate (242 mg, 0.870 mmol, 28.2 % yield) as a yellow solid. tert-Butyl (3-cyclopropyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)carbamate: mp 156.5 30 158.0; 1 H NMR (400 MHz, CDCl3) 6 8.73 (s, 1H), 8.30 (d, J = 2.5 Hz, 1H), 8.27 (s, 1H), 68 7.76 (dt, J= 9.8, 2.4 Hz, 1H), 6.43 (s, 1H), 1.55 (s, 9H), 1.01 - 0.91 (m, 4H); ESIMS m/z 319 ([M+H]*). (1-(5-Fluoropyridin-3-yl)-1H-pyrazol-4-yl)carbamate: mp 121.0-123.0 'C; I H NMR (300 MHz, CDCl3) 6 8.78 (s, 1H), 8.37 (s, 1H), 8.28 (s, 1H), 7.81 (d, J = 9.6 Hz, 1H), 7.59 (s, 5 1H), 6.44 (s, 1H), 1.53 (s, 9H). ESIMS m/z 278 ([M]+). Compounds 340 and 404 were prepared as described in Example 33. Example 34: Preparation of tert-butyl (3-ethyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4 10 yl)(methyl)carbamate (Compound 408)
N
F N/N N To a N 2 -purged solution of tert-butyl (1-(5-fluoropyridin-3-yl)-3-vinyl-1H-pyrazol-4 15 yl)(methyl)carbamate (0.730 g, 2.293 mmol) in methanol (15.29 ml) was added 10% palladium on carbon (0.036 g, 0.339 mmol). The reaction was purged with hydrogen and run under 80 psi of hydrogen at room temperature for 60 hours. The reaction gave less than 20% conversion. The reaction mixture was filtered through celite, concentrated, and redissolved in ethyl acetate (4 mL) and transferred to a bomb. The reaction was heated at 50 'C at 600 psi of 20 hydrogen for 20 hours. The reaction was only 50% complete. Methanol (1 mL) and 10% palladium on carbon (36 mg) were added, and the reaction was heated at 80 'C at 650 psi of hydrogen for 20 hours. The reaction was filtered through celite and concentrated to give tert butyl (3-ethyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate (616 mg, 1.923 mmol, 84 % yield) as yellow oil: IR (thin film) 1692 cm-1; 'H NMR (300 MHz, CDCl 3 ) 6 25 8.71 (t, J= 1.4 Hz, 1H), 8.35 (d, J= 2.6 Hz, 1H), 7.83 (dt, J= 9.5, 2.3 Hz, 2H), 3.18 (s, 3H), 2.65 (q, J= 7.5 Hz, 2H), 1.44 (s, 9H), 1.25 (t, J= 7.1 Hz, 3H); EIMS m/z 320. Example 35: Preparation of N-(1-(5-fluoropyridin-3-yl)-3-formyl-1H-pyrazol-4 yl)isobutyramide (Compound 560) 30 69 0 0
N
F N N H N To a solution of N-(1 -(5 -fluoropyridin-3 -yl)-3-vinyl- 1H-pyrazol-4-yl)isobutyramide (0.706 g, 2.57 mmol) in tetrahydrofuran (12.87 ml) and water (12.87 ml) was added osmium tetroxide 5 (0.164 ml, 0.026 mmol). After 10 minutes at room temperature, sodium periodate (1.101 g, 5.15 mmol) was added in portions over 3 minutes and the resulting solution was stirred at room temperature. After 18 hours, the solution was poured into 10 mL water and was extracted with 3 x 10 mL dichloromethane. The combined organic layers were dried, concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give N-(1-(5 10 fluoropyridin-3-yl)-3-formyl-1H-pyrazol-4-yl)isobutyramide (626 mg, 2.266 mmol, 88 % yield) as a yellow solid: mp 140.0-142.0 0 C; 'H NMR (300 MHz, CDCl 3 ) 6 10.12 (s, 1H), 9.14 (s, 1H), 8.90 (d, J= 2.0 Hz, 1H), 8.82 (s, 1H), 8.51 (d, J= 2.5 Hz, 1H), 7.92 (dt, J= 9.2, 2.4 Hz, 1H), 2.65 (dt, J= 13.8, 6.9 Hz, 1H), 1.31 (d, J= 6.9 Hz, 6H); ESIMS m/z 277 ([M+H]*). 15 Compound 369 was prepared in accordance with the procedures disclosed in Example 35. Example 36: Preparation of N-(1-(5-fluoropyridin-3-yl)-3-(hydroxymethyl)-1H-pyrazol 20 4-yl)isobutyramide (Compound 435) and N-(1-(5-fluoropyridin-3-yl)-1H-pyrazol-4 yl)isobutyramide (Compound 436) HO 0 7N0 N- F N/NHI HN N 25 To a solution of N-( 1-(5 -fluoropyridin-3 -yl)-3-formyl- 1H-pyrazol-4-yl)isobutyramide (0.315 g, 1. 140 mmol) in methanol (5.70 mil) at 0 0 C was added sodium borohydride (0.086 g, 2.280 70 mmol). The reaction was stirred at 0 'C for 2 hours, and room temperature for 20 hours. 0.5 M HCl was added, the reaction was neutralized with saturated aqueous sodium bicarbonate, and the mixture was extracted with dichloromethane. The organic phases were concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give N-(1-(5-fluoropyridin-3-yl)-3 5 (hydroxymethyl)-1H-pyrazol-4-yl)isobutyramide (180 mg, 0.647 mmol, 56.7 %) as a white solid and N-(1-(5-fluoropyridin-3-yl)- 1H-pyrazol-4-yl)isobutyramide (9 mg, 0.036 mmol, 3.18 %) as a white solid. N-(1-(5-fluoropyridin-3-yl)-3-(hydroxymethyl)-1H-pyrazol-4-yl)isobutyramide: mp 144.0 10 146.0 'C; I H NMR (400 MHz, CDCl 3 ) 6 8.74 (d, J = 1.1 Hz, 1H), 8.64 (s, 1H), 8.37 - 8.29 (m, 2H), 7.74 (dt, J = 9.5, 2.3 Hz, 1H), 4.95 (d, J = 3.0 Hz, 2H), 3.21 - 3.06 (m, 1H), 2.63 2.48 (m, 1H), 1.26 (d, J = 6.9 Hz, 6H); ESIMS m/z 279 ([M+H]*). N-(1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)isobutyramide: IR (thin film) 1659 cm-1; 'H 15 NMR (400 MHz, CDCl 3 ) 6 8.79 (d, J= 1.2 Hz, 1H), 8.60 (s, 1H), 8.38 (d, J= 2.5 Hz, 1H), 7.81 (dt, J= 9.5, 2.3 Hz, 1H), 7.68 (s, 1H), 7.54 (s, 1H), 2.63 - 2.51 (m, 1H), 1.28 (d, J= 6.9 Hz, 6H); ESIMS m/z 249 ([M+H]*). Example 37: Preparation of N-(3-(chloromethyl)-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4 20 yl)isobutyramide (Compound 561) CI 0 N F N/ N H N To a solution of N-(1-(5-fluoropyridin-3-yl)-3-(hydroxymethyl)-1H-pyrazol-4 25 yl)isobutyramide (0.100 g, 0.359 mmol) in dichloromethane ( 3.59 ml) was added thionyl chloride (0.157 ml, 2.15 1 mmol). The reaction was stirred at room temperature for 2 hours. Saturated aqueous sodium bicarbonate was added, and the mixture was extracted with dichloromethane. The combined organic phases were washed with brine and concentrated to give N-(3-(chloromethyl)- 1-(5-fluoropyridin-3-yl)- 1H-pyrazol-4-yl)isobutyramide (100 mg, 71 0.337 mmol, 94 % yield) as a white solid: mp 172.0-177.0 'C; IH NMR (400 MHz, CDCl 3 ) 6 8.79 (s, 1H), 8.67 (s, 1H), 8.40 (s, 1H), 7.80 (dt, J= 9.4, 2.3 Hz, 1H), 7.42 (s, 1H), 4.77 (s, 2H), 2.63 (hept, J = 6.9 Hz, 1H), 1.30 (d, J = 6.9 Hz, 6H); ESIMS m/z 298 ([M+H]*). 5 Example 38: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2 methoxyacetamide (Compound 512) (see also Example 11) CI O O N- N N 10 To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, 2HCl (0.130 g, 0.502 mmol) and in DCM (2.508 ml) was added N-ethyl-N-isopropylpropan-2-amine (0.257 ml, 1.505 mmol) followed by 2-methoxyacetyl chloride (0.109 g, 1.003 mmol) and the reaction mixture was stirred at ambient temperature for 16 hours. The reaction was quenched by the addition of saturated sodium bicarbonate. The organic layer was extracted with DCM. The 15 organic layer was dried over sodium sulfate, filtered, concentrated and purified using silica gel chromatography (0-100% ethyl acetate/hexanes) to yield the title compound as a pale yellow oil (0.12 g, 77%): IR (thin film) 3514, 3091, 2978, 1676 cm-1; 'H NMR (400 MHz, CDCl 3 ) 6 8.96 (d, J = 2.4 Hz, 1H), 8.63 (d, J = 3.8 Hz, 1H), 8.09 - 8.03 (m, 1H), 7.99 (s, 1H), 7.47 (dd, J= 8.3, 4.8 Hz, 1H), 3.88 (s, 2H), 3.77 - 3.65 (m, 2H), 3.40 (s, 3H), 1.18 (t, J= 7.2 20 Hz, 3H); ESIMS m/z 295 ([M+H]*). Compounds 71, 478, 481, 483 - 484, and 543 were prepared in accordance with the procedures disclosed in Example 38. 25 Example 39: Preparation of N-(3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N ethyl-2-methyl-3-(methylthio)butanamide (Compound 182) and (Z)-N-(3-chloro-1-(5 fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methylbut-2-enamide (Compound 183) 72 010~C 0 /H F N F N N /_ N F NN To a solution 2-methyl-3-(methylthio)butanoic acid (0.154 g, 1.039 mmol) in dichloromethane (1 mL) at room temperature was added 1 drop of dimethylformamide. 5 Oxalyl dichloride (0.178 ml, 2.078 mmol) was added dropwise and the reaction was stirred at room temperature overnight. The solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (1 mL) and the solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (0.5 mL) and the solution was added to a solution of 3-chloro-N-ethyl-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-amine (0.100 10 g, 0.416 mmol) and 4-dimethylaminopyridine (0.254 g, 2.078 mmol) in dichloromethane (1.5 mL) and stirred at room temperature overnight. The solvent was removed under reduced pressure and the residue was purify by chromatography (0-100% ethyl acetate/hexanes) to give N-(3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methyl-3 (methylthio)butanamide (34 mg, 0.092 mmol, 22.06 %) as a faint yellow oil and (Z)-N-(3 15 chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methylbut-2-enamide (38 mg, 0.118 mmol, 28.3 % yield) as a yellow oil. N-(3-chloro- 1 -(5-fluoropyridin-3-yl)- 1H-pyrazol-4-yl)-N-ethyl-2-methyl-3 (methylthio)butanamide: IR (thin film) 1633 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.79 (d, J= 20 2.0 Hz, 0.66H), 8.77 (d, J= 2.0 Hz, 0.33H), 8.50 (d, J= 2.6 Hz, 0.33H), 8.49 (d, J= 2.5 Hz, 0.66H), 8.08 (s, 0.66H), 7.95 (s, 0.33H), 7.92 - 7.81 (m, 1H), 4.03 - 3.46 (m, 2H), 3.03 - 2.78 (m, 1H), 2.59 - 2.33 (m, 1H), 2.04 (s, 2H), 2.02 (s, 1H), 1.32 (d, J= 6.7 Hz, 1H), 1.27 (d, J= 6.2 Hz, 1H), 1.23 (d, J= 6.9 Hz, 2H), 1.18 - 1.12 (m, 5H); ESIMS m/z 371 ([M]+). 25 (Z)-N-(3-chloro-1-(5-fluoropyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methylbut-2-enamide: IH NMR (400 MHz, CDCl 3 ) 6 8.73 (d, J = 2.0 Hz, 1H), 8.46 (d, J = 2.4 Hz, 1H), 7.87 (d, J = 4.9 Hz, 1H), 7.84 (dt, J= 9.2, 2.4 Hz, 1H), 5.93 - 5.76 (m, 1H), 3.73 (q, J= 7.1 Hz, 2H), 1.72 (s, 3H), 1.58 (dd, J= 6.9, 0.9 Hz, 3H), 1.17 (t, J= 7.1 Hz, 3H); ESIMS m/z 323 ([M]+). 30 Compounds 70, 180 - 181, 389 - 392, 397 - 398, 405 - 406, 427 - 429, 432, 456, 482, 521 73 522, 532 - 534, 555, and 589 were prepared from the corresponding intermediates and starting materials in accordance with the procedures disclosed in Example 39. Example 40: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2 5 (methylthio)acetamide (Compound 337) CI O S
N
N To an ice cold solution of 2-(methylthio)acetic acid (0.092 g, 0.863 mmol) in DCM (2 mL) 10 was added N-ethyl-N-isopropylpropan-2-amine (0.111 g, 0.863 mmol) followed by isobutyl chloroformate (0.099 ml, 0.767 mmol). Stirring was continued for 10 minutes. Next, the mixed anhydride was added to a solution of 3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol 4-amine (0.08 g, 0.383 mmol) in DCM (0.66 mL) and the reaction mixture was stirred at ambient temperature for 2 hours. The reaction mixture was concentrated and purified using 15 reverse phase C-18 column chromatography (0-100% CH3CN/H20) to yield the title compound as a pale yellow oil (0.075 g, 66%): 'H NMR (400 MHz, CDCl 3 ) 6 8.95 (d, J = 2.5 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 8.13 (s, 1H), 8.04 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.50 - 7.43 (m, 1H), 3.26 (s, 3H), 3.12 (s, 2H), 2.24 (s, 3H); 1C NMR (101 MHz, CDCl 3 ) 6 170.00, 148.61, 140.15, 140.03, 135.68, 126.56, 126.42, 125.33, 124.15, 37.16, 34.94, 16.22; 20 ESIMS m/z 297 ([M+H]*). Compounds 335, 336, and 542 were prepared in accordance with the procedures disclosed in Example 40. 25 Example 41, Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2 methyl-3-oxobutanamide (Compound 499) 74 ci0 0 N N To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, HCl (259 mg, 1 mmol) and ethyl 2-methyl-3-oxobutanoate (144 mg, 1.000 mmol) in dioxane (1 mL) was 5 added 2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine (181 mg, 1.30 mmol) and the mixture was heated in a microwave (CEM Discover) at 150 'C for 1.5 h, with external IR sensor temperature monitoring from the bottom of the vessel. LCMS (ELSD) indicated a 40% conversion to the desired product. The mixture was diluted with ethyl acetate (50 ML) and saturated aqueous NH 4 Cl (15 mL) , and the organic phase was separated. The aqueous phase 10 was extracted with ethyl acetate (20 mL) and the combined organic phase was washed with brine, dried over MgSO 4 and concentrated in vacuo to give an oily residue. This residue was purified on silica gel eluting with mixtures of ethyl acetate and hexanes to give N-(3-chloro- 1 (pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methyl-3-oxobutanamide (37 mg, 11 % yield, 96% purity) as a colorless oil: 'H NMR (400 MHz, CDCl 3 ) 6 9.02 - 8.92 (dd, J = 2.6, 0.8 Hz, 1H), 15 8.68 - 8.60 (dd, J = 4.8, 1.5 Hz, 1H), 8.09 - 7.98 (m, 1H), 7.96 - 7.87 (s, 1H), 3.87 - 3.58 (d, J = 3.0 Hz, 2H), 3.49 - 3.38 (m, 1H), 2.16 - 2.08 (s, 3H), 1.39 - 1.32 (d, J = 7.0 Hz, 3H), 1.22 1.13 (m, 3H); EIMS (m/z) 321 ([M+1]*), 319 ([M-i]-). Example 42: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N 20 ethylcyclopropanecarboxamide (Compound 538) CI O N N N To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine monohydrochloride 25 (0.10 g, 0.0.38 mmol) in dichloroethane (0.75 ml) was added cyclopropanecarboxylic acid (0.03 g, 0.38 mmol) and 4-NN-dimethylaminopyridine (0.14 g, 1.15 mmol) followed by 1-(3 dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.14 g, 0.77 mmol). The reaction 75 was stirred at room temperature overnight. The reaction mixture was concentrated to dryness and the crude product was purified by reverse phase silica gel chromatography eluting with 0 50% acetonitrile/water to give a white solid (0.03 g, 25%); mp 111-119 'C; 'H NMR (400 MHz, CDCl 3 ) 6 8.96 (d, J= 2.5 Hz, 1H), 8.63 - 8.59 (m, 1H), 8.06 (ddd, J= 8.3, 2.6, 1.4 Hz, 5 1H), 8.01 (s, 1H), 7.46 (dd, J= 8.3, 4.7 Hz, 1H), 3.73 (q, J= 7.2 Hz, 2H), 1.46 (ddd, J= 12.6, 8.1, 4.7 Hz, 1H), 1.16 (t, J= 7.2 Hz, 3H), 1.04 (t, J= 3.7 Hz, 2H), 0.71 (dd, J= 7.7, 3.0 Hz, 2H); ESIMS m/z 291 ([M+H]). Compounds 69, 516, 524, 546, 558 - 559, 582-588, 593, and 594 were prepared 10 from the appropriate acids in accordance with the procedures disclosed in Example 42. Example 43: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl-3 (methylthio)-N-(3-(methylthio)propanoyl)propanamide (Compound 407) 01 0 /
N
N N O S 15 To a solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(methylthio)propanamide (0.216 g, 0.728 mmol) in DCE (2.91 ml) in a 10 mL vial was added 2-methyl-3 (methylthio)propanoyl chloride (0.244 g, 1.601 mmol). The vial was capped and placed in a 20 Biotage Initiator microwave reactor for 3 hours at 100 'C, with external IR-sensor temperature monitoring from the side of the vessel. The crude mixture was concentrated and purified using reverse phase C-18 column chromatography (0-100% acetonitrile/water) to yield the title compound as a pale yellow oil (67 mg, 22%): IR (thin film) 2916 and 1714 cm ; H NMR (300 MHz, CDCl 3 ) 6 8.96 - 8.92 (d, J= 2.7 Hz, 1H), 8.64 - 8.59 (dd, J= 4.9, 1.4 25 Hz, 1H), 8.07 - 7.99 (m, 2H), 7.50 - 7.40 (dd, J= 8.4, 4.8 Hz, 1H), 3.39 - 3.28 (m, 1H), 3.10 2.99 (td, J = 7.2, 3.9 Hz, 2H), 2.96 - 2.86 (dd, J = 13.2, 8.7 Hz, 1H), 2.86 - 2.79 (t, J = 7.3 Hz, 2H), 2.58 - 2.48 (dd, J= 13.1, 5.8 Hz, 1H), 2.14 - 2.12 (s, 3H), 2.09 - 2.06 (s, 3H), 1.30 - 1.26 (d, J= 6.9 Hz, 3H); ESIMS m/z 413 ([M+H]*). 76 Compounds 383, 410, 433, 437, 451, 470, 530 and 531 were prepared in accordance with the procedures disclosed in Example 43. Example 44: Preparation of N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-2,2-dideuterio-N 5 ethyl-3-methylsulfanyl-propanamide (Compound 393) Cl o / N- 4 N / D N To a 7 mL vial was added 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (111 mg, 10 0.5 mmol), 2,2-dideuterio-3-methylsulfanyl-propanoic acid (58.0 mg, 0.475 mmol) and followed by DCM (Volume: 2 mL) . The solution was stirred at 0 'C. Then the solution of DCC (0.500 mL, 0.500 mmol, 1.OM in DCM) was added. The solution was allowed to warm up to 25 C slowly and stirred at 25 C overnight. White precipitate formed during the reaction. The crude reaction mixture was filtered through a cotton plug and purified by silica 15 gel chromatography (0-100% EtOAc/hexane) to giveN-[3-chloro-1-(3-pyridyl)pyrazol-4-yl] 2,2-dideuterio-N-ethyl-3-methylsulfanyl-propanamide (97 mg, 0.297 mmol, 59.4 % yield) as a colorless oil: 'H NMR (400 MHz, CDCl 3 ) 6 8.96 (d, J = 2.4 Hz, 1H), 8.63 (dd, J = 4.6, 0.9 Hz, 1H), 8.06 (ddd, J= 8.4, 2.7, 1.4 Hz, 1H), 7.98 (s, 1H), 7.52 - 7.40 (m, 1H), 3.72 (q, J= 7.2 Hz, 2H), 2.78 (s, 2H), 2.06 (s, 3H), 1.17 (t, J= 7.2 Hz, 3H); ESIMS m/z 327 ([M+H]*); IR 20 (Thin film) 1652 cm-1. Compounds 394, 396, and 471 - 473 were prepared from the corresponding intermediates and starting materials in accordance with the procedures disclosed in Example 44. 25 Example 45: Preparation of 1-ethyl-3-(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)urea (Compound 145) 77 0 N >-NH / NH N N To a solution of 3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (0.1 g, 0.574 mmol) in DCM (5.74 ml) was added ethyl isocyanate (0.041 g, 0.574 mmol) and the reaction mixture was 5 stirred at ambient temperature for 40 minutes. The reaction mixture had turned from a clear solution to a suspension with white solid material. The reaction mixture was concentrated and purified using silica gel chromatography (0-20% MeOH/DCM) to yield the title compound as a white solid (0.135 g, 95%): mp 197-200 'C; 1 H NMR (400 MHz, CDCl 3 ) 6 8.94 (d, J = 2.3 Hz, 1H), 8.48 - 8.37 (m, 1H), 8.32 (s, 1H), 7.94 (d, J = 8.3 Hz, 1H), 7.52 (br 10 s, 1H), 7.41 - 7.25 (m, 1H), 5.79 (br s, 1H), 3.33 - 3.23 (m, 2H), 2.29 (d, J= 2.9 Hz, 3H), 1.16 (dd, J= 8.7, 5.7 Hz, 3H); ESIMS m/z 246 ([M+H]*), 244 ([M-H]-). Compounds 169 - 171, 221 - 222, 255 - 257, 278 - 280, 297 - 302, 318 - 322, 334, 345, 348, 375 - 377, 385 - 387, and 411 - 413 were prepared in accordance with the 15 procedures disclosed in Example 45. Example 46: Preparation of 3-butyl-1-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-1 ethylurea (Compound 500) CI 0 N- 7-NH -NNH 20 N To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, 2HCl (0.130 g, 0.502 mmol) in DCE (1.25 ml) was added N-ethyl-N-isopropylpropane-2-amine (0.21 mL, 1.255 mmol) followed by 1-isocyanatobutane (0.109 g, 1.104 mmol) and the reaction mixture was 25 stirred at ambient temperature for 16 hours. The reaction mixture was concentrated and purified using silica gel chromatography (0-20% MeOH/DCM) to yield the title compound as a beige solid (0.131 g, 77%): IR (thin film) 3326, 2959, 2931, 1648 cm-1; 1H NMR (400 78 MHz, CDCl 3 ) 6 8.95 (s, 1H), 8.62 (d, J = 4.0 Hz, 1H), 8.08 - 8.01 (m, 1H), 7.97 (s, 1H), 7.46 (dd, J= 8.3, 4.7 Hz, 1H), 4.42 - 4.32 (m, 1H), 3.74 - 3.61 (m, 2H), 3.27 - 3.15 (m, 2H), 1.49 1.37 (m, 2H), 1.37 - 1.22 (m, 2H), 1.19 - 1.12 (m, 3H), 0.94 - 0.84 (m, 3H); ESIMS m/z 322 ([M+H]*). 5 Compounds 479 - 480, 501 - 504, 513, 518 and 519 were prepared according to Example 46. Example 47: Preparation of 1-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)imidazolidin 10 2-one (Compound 374) CI 0 N- NH N / N j N To a solution of 1-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(2-chloroethyl)urea (0.1 g, 15 0.333 mmol) in THF (6.66 ml) was added sodium hydride (8.00 mg, 0.333 mmol) and the reaction mixture was stirred at ambient temperature for 30 minutes. The reaction was quenched by the addition of a solution of saturated ammonium chloride and the product was extracted with ethyl acetate (2x). The combined organic layers were dried over sodium sulfate, filtered and concentrated. The product was a beige solid which was pure and did not 20 need any further purification (63 mg, 72%): mp 167-170 'C; 1H NMR (400 MHz, CDCl 3 ) 6 8.96 (d, J= 2.2 Hz, 1H), 8.56 (dd, J= 4.7, 1.4 Hz, 1H), 8.33 (s, 1H), 7.99 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.40 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 5.00 (s, 1H), 4.14 - 4.07 (m, 2H), 3.68 - 3.58 (m, 2H); ESIMS m/z 264 ([M+H]*). 25 Compound 349 was prepared in accordance with the procedures disclosed in Example 47. Example 48: Preparation of S-tert-butyl (3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4 yl)(ethyl)carbamothioate (Compound 514) 30 79 N1 0 N To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine, 2HCl (0.13 g, 0.502 mmol) in DCM (2.508 ml) was added N-ethyl-N-isopropylpropan-2-amine (0.257 ml, 1.505 5 mmol) followed by S-tert-butyl carbonochloridothioate (0.153 g, 1.003 mmol). The reaction mixture was stirred at ambient temperature for 16 hours. The reaction was quenched by the addition of saturated sodium bicarbonate. The organic layer was extracted with DCM. The organic layer was dried over sodium sulfate, filtered, concentrated and purified using silica gel column chromatography (0-100% ethyl acetate/hexanes) to yield the title compound as a 10 white solid (132 mg, 78%): mp 91-93 'C; 1H NMR (400 MHz, CDCl 3 ) 6 8.96 (d, J = 2.5 Hz, 1H), 8.60 (dd, J = 4.7, 1.4 Hz, 1H), 8.08 - 8.03 (m, 1H), 7.97 (s, 1H), 7.47 - 7.41 (m, 1H), 3.69 (q, J = 7.2 Hz, 2H), 1.47 (s, 9H), 1.21 - 1.13 (m, 3H); ESIMS m/z 339 ([M+H]*). Compounds 333, 338, 339, 346, 368 and 373 were prepared in accordance with the 15 procedures disclosed in Example 48. Example 49: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2 methyl-3-(methio)propanethioamide (Compound 364) CI g / N- S N -N 20 N To a microwave reaction vessel was added N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N ethyl-2-methyl-3-(methio)propanamide (0.07 g, 0.22 mmol) in dichloroethane (1.87 mL) and Lawesson's reagent (0.05 g, 0.12 mmol). The vessel was capped and heated in a Biotage 25 Initiator microwave reactor for 15 minutes at 130 'C, with external IR-sensor temperature monitoring from the side of the vessel. The reaction was concentrated to dryness and the crude material was purified by silica gel chromatography (0-80% acetonitrile/water) to give 80 the desired product as a yellow oil (0.33 g, 44%): IR (thin film) 1436 cm-1; IH NMR (400 MHz, CDCl 3 ) 6 8.97 (d, J= 2.5 Hz, 1H), 8.77 - 8.52 (m, 1H), 8.11 - 7.89 (m, 2H), 7.60 - 7.38 (m, 1H), 4.62 (bs, 1H), 4.02 (bs, 1H), 3.21 - 2.46 (m, 3H), 2.01 (s, 3H), 1.35 - 1.15 (m, 6H); ESIMS m/z 355 ([M+H]*). 5 Compounds 372, 438 and 548 were prepared in accordance with the procedures disclosed in Example 49. Example 50: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4,4,4 10 trifluoro-3-(methylsulfinyl)butanamide (Compound 570) C' oF 3 C N N To a 20 mL vial was added N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4,4,4 15 trifluoro-3-(methylthio)butanamide (82 mg, 0.209 mmol) and hexafluoroisopropanol (1.5 mL). Hydrogen peroxide (0.054 mL, 0.626 mmol, 35% solution in water) was added in one portion and the solution was stirred at room temperature. After 3 hours the reaction was quenched with saturated sodium sulfite solution and extracted with EtOAc (3 x 20 mL). The combined organic layers were dried over sodium sulfate, concentrated and purified by 20 chromatography (0-10% MeOH/DCM) to give N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl) N-ethyl-4,4,4-trifluoro-3-(methylsulfinyl) butanamide (76 mg, 0.186 mmol, 89 % yield) as white semi-solid: 'H NMR (400 MHz, CDCl 3 ) 6 8.98 (d, J = 2.3 Hz, 1H), 8.63 (td, J = 4.8, 2.4 Hz, 1H), 8.14 - 8.01 (m, 2H), 7.46 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 4.26 (dd, J= 17.2, 8.4 Hz, 1H), 3.89 - 3.61 (m, 2H), 3.01 (dd, J= 17.6, 8.2 Hz, 1H), 2.77 (s, 2H), 2.48 (dd, J= 17.7, 25 3.3 Hz, 1H), 1.19 (t, J= 7.2 Hz, 3H) (only one isomer shown); ESIMS m/z 409 ([M+H]*); IR (Thin film) 1652 cm-1. Compound 571 was prepared from the corresponding intermediates and starting materials in accordance with the procedures disclosed in Example 50. 30 81 Example 51: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3 (methylsulfinyl)propanamide (Compound 362) CIO /
N
N N N 5 To N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylthio)propanamide (0.08 g, 0.24 mmol) in glacial acetic acid (0.82 mL) was added sodium perborate tetrahydrate (0.05 g, , 0.25 mmol), and the mixture was heated at 60 'C for 1 hour. The reaction mixture was carefully poured into a separatory funnel containing saturated aqueous NaHCO 3 resulting in 10 gas evolution. When the gas evolution had ceased, ethyl acetate was added and the layers were separated. The aqueous layer was extracted twice with ethyl acetate, and all the organic layers were combined, dried over MgS04, filtered and concentrated under reduced pressure. The crude material was purified by silica gel chromatography (0-10% methanol/ dichloromethane) to give the desired product as a clear oil (0.03 g, 40%): IR (thin film) 1655 15 cm-1; 1H NMR (400 MHz, CDC 13 ) 6 8.95 (t, J= 9.2 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.20 - 7.86 (m, 2H), 7.59 - 7.33 (m, 1H), 3.73 (ddt, J= 20.5, 13.4, 6.8 Hz, 2H), 3.23 - 3.06 (m, 1H), 2.94 - 2.81 (m, 1H), 2.74 - 2.62 (m, 2H), 2.59 (s, 3H), 1.25 - 1.07 (m, 3H); ESIMS m/z 341 ([M+H]*). 20 Compounds 101 - 102, 218, 328, 330, and 494 were prepared from the appropriate sulfides in accordance with the procedures disclosed in Example 51. Example 52: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3 (methylsulfonyl)propanamide (Compound 363) 25 CI O 0/ N-N QN 82 To N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylthio)propanamide (0.08 g, 0.25 mmol) in glacial acetic acid (0.85 mL) was added sodium perborate tetrahydrate (0.11 g, 0.52 mmol), and the mixture was heated at 60 'C for 1 hour. The reaction mixture was carefully poured into a separatory funnel containing saturated aqueous NaHCO 3 resulting in 5 gas evolution. When the gas evolution had ceased, ethyl acetate was added and the layers were separated. The aqueous layer was extracted twice with ethyl acetate, and all the organic layers were combined, dried over MgS04, filtered and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (0 to 10% methanol/dichloromethane) to give the desired product as a clear oil (0.04, 47%): (thin film) 10 1661 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.95 (t, J= 11.5 Hz, 1H), 8.64 (dd, J= 4.8, 1.4 Hz, 1H), 8.17 - 7.96 (m, 2H), 7.59 - 7.39 (m, 1H), 3.73 (d, J= 7.0 Hz, 2H), 3.44 (dd, J= 22.5, 15.7 Hz, 2H), 2.96 (s, 3H), 2.71 (t, J= 6.9 Hz, 2H), 1.18 (dd, J= 8.8, 5.5 Hz, 3H); ESIMS m/z 357 ([M+H]*). 15 Compounds 103, 104, 219, 329, 331 and 495 were prepared from the appropriate sulfides in accordance with the procedures disclosed in Example 52. Example 53: Preparation of N-(3-methyl-1-(3-fluoropyridin-5-yl)-1H-pyrazol-4-yl)N ethyl-2-methyl-(3-oxido-X 4 -sulfanylidenecyanamide)(methyl)propanamide (Compound 20 250) 0 0N NN F N NN N To a solution of N-ethyl-N-(1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-yl)-2-methyl-3 25 (methylthio)propanamide (0.30 g, 0.89 mmol) in dichloromethane (3.57 mL) at 0 'C was added cyanamide (0.07 g, 1.78 mmol) and iodobenzenediacetate (0.31 g, 0.98 mmol) and subsequently stirred at room temperature for 1 hour. The reaction was concentrated to dryness and the crude material was purified by silica gel column chromatography (10% methanol/ethyl acetate) to give the desired sulfilamine as a light yellow solid (0.28 g, 85%). 30 To a solution of 70% mCPBA (0.25 g, 1.13 mmol) in ethanol (4.19 mL) at 0 'C was added a 83 solution of potassium carbonate (0.31 g, 2.26 mmol) in water (4.19 mL) and stirred for 20 minutes after which a solution of sulfilamine (0.28 g, 0.75 mmol) in ethanol (4.19 mL) was added in one portion. The reaction was stirred for 1 hour at 0 'C. The excess mCPBA was quenched with 10% sodium thiosulfite and the reaction was concentrated to dryness. The 5 residue was purified by silica gel chromatography (0-10% methanol/dichloromethane) to give the desired product as a clear oil (0.16 g, 56%): IR (thin film) 1649 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.80 (dd, J= 43.8, 10.1 Hz, 1H), 8.51 - 8.36 (m, 1H), 8.11 (d, J= 38.7 Hz, 1H), 7.96 - 7.77 (m, 1H), 4.32 - 3.92 (m, 2H), 3.49 - 3.11 (m, 6H), 2.32 (s, 3H), 1.27 - 1.05 (m, 6H); ESIMS m/z 393 ([M+H]*). 10 Example 54: Preparation of N-ethyl-4,4,4-trifluoro-3-methoxy-N-(3-methyl-1-(pyridin 3-yl)-1H-pyrazol-4-yl)-3-(trifluoromethyl)butanamide (Compound 276) N 0 N - OMe
CF
3 N 15 To a solution of N-ethyl-4,4,4-trifluoro-3-hydroxy-N-(3-methyl-1-(pyridin-3-yl)-1H-pyrazol 4-yl)-3-(trifluoromethyl)butanamide (184 mg, 0.448 mmol) in DMF (3 mL) stirring at 0 'C was added sodium hydride (26.9 mg, 0.673 mmol). The solution was stirred at 0 'C for 0.5 hour. Then iodomethane (0.034 mL, 0.538 mmol) was added and ice bath was removed and 20 the mixture was stirred at 25 'C overnight. Reaction was worked up by slow addition of water and further diluted with 20 mL of water, then extracted with 4x20 mL of EtOAc. The combined organic layers were washed with water, dried over Na 2
SO
4 and concentrated. Silica Gel chromatography (0-100% EtOAc/hexane) gave N-ethyl-4,4,4-trifluoro-3-methoxy-N-(3 methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(trifluoromethyl)butanamide (52 mg, 0.123 25 mmol, 27.3 % yield) as a white solid: mp = 83-86 C; 'H NMR (400 MHz, CDCl 3 ) 6 8.94 (d, J= 2.5 Hz, 1H), 8.59 (dd, J= 4.7, 1.3 Hz, 1H), 8.01 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.85 (s, 1H), 7.44 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 4.00 (brs, 1H), 3.73 (s, 3H), 3.39 (brs, 1H), 2.86 (s, 2H), 2.26 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H); ESIMS m/z 425 ([M+H]*); IR (Thin film) 1664 cm 30 84 Compound 327 was prepared from the corresponding intermediates and starting materials in accordance with the procedures disclosed in Example 54. Example 55, Step 1: Preparation of N-(2-((tert-butyldimethylsilyl)oxy)ethyl)-N-(3 5 chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl-3-(methylthio)propanamide CI 0
N
N N0 Si / ( A solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl-3 10 (methylthio)propanamide (0.150 g, 0.483 mmol) in NN-dimethylformamide (2.413 ml) was cooled to 0 'C. Sodium hydride (0.039 g, 0.965 mmol, 60% dispersion) was added at and the reaction was stirred at 0 'C for 30 minutes. (2-Bromoethoxy)(tert-butyl)dimethylsilane (0.231 g, 0.965 mmol) was added, the ice bath was removed, and the reaction was stirred at room temperature for 2 hours. The reaction was heated at 65 'C for 1.5 hours and then cooled to 15 room temperature. Brine was added and the mixture was extracted with dichloromethane. The combined organic phases were concentrated and chromatographed (0-100% ethyl acetate/hexanes) to give N-(2-((tert-butyldimethylsilyl)oxy)ethyl)-N-(3-chloro-1-(pyridin-3 yl)-1H-pyrazol-4-yl)-2-methyl-3-(methylthio)propanamide (0.120g, 0.243 mmol, 50.4 %) as an orange oil: IR (thin film) 1669 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.88 (d, J= 2.5 Hz, 20 1H), 8.55 (dd, J = 4.7, 1.4 Hz, 1H), 8.05 (s, 1H), 7.98 (ddd, J = 8.3, 2.6, 1.4 Hz, 1H), 7.41 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 4.35 - 3.06 (m, 4H), 2.86 - 2.73 (m, 1H), 2.73 - 2.59 (m, 1H), 2.41 (dd, J= 12.8, 5.7 Hz, 1H), 1.94 (s, 3H), 1.11 (d, J= 6.7 Hz, 3H), 0.80 (s, 9H), 0.00 (s, 3H), -0.01 (s, 3H); ESIMS m/z 470 ([M+H]*). 25 Example 55, Step 2: Preparation of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(2 hydroxyethyl)-2-methyl-3-(methylthio)propanamide (Compound 535) 85 CI 0
N
N S N OH To a solution of N-(2-((tert-butyldimethylsilyl)oxy)ethyl)-N-(3-chloro-1-(pyridin-3-yl)-1H pyrazol-4-yl)-2-methyl-3-(methylthio)propanamide (0.180 g, 0.384 mmol) in tetrahydrofuran 5 (1.54 ml) was added tetrabutylammonium fluoride (0.201 g, 0.767 mmol) and the reaction was stirred at room temperature for 2 hours. Brine was added and the mixture was extracted with ethyl acetate. The combined organic phases were concentrated and chromatographed (0 100% water/acetonitrile) to give N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(2 hydroxyethyl)-2-methyl-3-(methylthio)propanamide as a white oil (0.081g, 0.217 mmol, 56.5 10 %): IR (thin film) 3423, 1654 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 9.00 (d, J = 2.5 Hz, 1H), 8.62 (dd, J= 4.7, 1.2 Hz, 1H), 8.25 (s, 1H), 8.07 (ddd, J= 8.3, 2.4, 1.3 Hz, 1H), 7.47 (dd, J= 8.3, 4.7 Hz, 1H), 4.47 - 3.70 (m, 3H), 3.65 - 3.09 (m, 2H), 2.91 - 2.68 (m, 2H), 2.48 (dd, J= 12.4, 5.0 Hz, 1H), 2.01 (s, 3H), 1.18 (d, J= 6.5 Hz, 3H); ESIMS m/z 356 ([M+H]*). 15 Example 56: Preparation of 2-(N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl 3-(methylthio)propanamido)ethyl acetate (Compound 547) CI 0
N
NS N o 0 20 To a solution of N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(2-hydroxyethyl)-2-methyl 3-(methylthio)propanamide (0.045 g, 0.127 mmol) in dichloromethane (1.27 ml) was added N,N-dimethylpyridin-4-amine (0.023 g, 0.190 mmol) and triethylamine (0.019 g, 0.190 mmol) followed by acetyl chloride (0.015 g, 0.190 mmol). The reaction was stirred at room temperature overnight. Water was added and the mixture was extracted with 25 dichloromethane. The combined organic phases were concentrated and chromatographed (0 100% ethyl acetate/hexanes) to give 2-(N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2 86 methyl-3-(methylthio)propanamido)ethyl acetate as a yellow oil (0.015 g, 0.034 mmol, 26.8 %): IR (thin film) 1739, 1669 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 8.97 (d, J= 2.3 Hz, 1H), 8.64 (dd, J= 4.7, 1.4 Hz, 1H), 8.15 (s, 1H), 8.04 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.47 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 4.50 - 3.40 (m, 4H), 2.84 (dd, J= 12.7, 8.9 Hz, 1H), 2.78 - 2.63 (m, 5 1H), 2.46 (dd, J= 12.7, 5.4 Hz, 1H), 2.03 (s, 3H), 2.01 (s, 3H), 1.16 (d, J= 6.6 Hz, 3H); ESIMS m/z 398 ([M+H]*). Example 57: Preparation of 2,2-dideuterio-3-methylsulfanyl-propanoic acid 0 HO SMe 10 D D To a 100 mL round bottom flask was added 3-(methylthio)propanoic acid (3 g, 24.96 mmol), followed by D 2 0 (23 mL) and KOD (8.53 mL, 100 mmol) (40% wt solution in D 2 0) , the solution was heated to reflux overnight. NMR showed ca. 95% D at alpha-position. The 15 reaction was cooled down and quenched with concentrated HCl until pH<2. White precipitate appeared in aqueous layer upon acidifying. Reaction mixture was extracted with 3 x 50 mL EtOAc, the combined organic layers were dried over Na 2
SO
4 , concentrated in vacuo to almost dryness. 100 mL hexane was added and the solution was concentrated again to give 2,2 dideuterio-3-methylsulfanyl-propanoic acid as a colorless oil (2.539 g, 20.78 mmol, 83%): IR 20 (Thin film) 3430, 1704 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 2.76 (s, 2H), 2.14 (s, 3H); 1C NMR (101 MHz, CDCl 3 ) 6 178.28, 38.14-28.55(m), 28.55, 15.51; EIMS m/z 122.. 2-Deuterio-2-methyl-3-methylsulfanyl-propanoic acid was prepared as described in Example 57 to afford a colorless oil (3.62 g, 26.8 mmol, 60.9 %): IR (Thin film) 2975, 1701 cm-1; 'H 25 NMR (400 MHz, CDCl 3 ) 6 11.39 - 10.41 (brs, 1H), 2.88 - 2.79 (d, J = 13.3 Hz, 1H), 2.61 2.53 (d, J = 13.3 Hz, 1H), 2.16 - 2.09 (s, 3H), 1.32 - 1.25 (s, 3H); 1C NMR (101 MHz, CDCl 3 ) 6 181.74, 39.74 - 39.02 (m), 37.16, 16.50, 16.03; EIMS m/z 135. Example 58: Preparation of 2-methyl-3-(trideuteriomethylsulfanyl)propanoic acid 30 87 0 D HO S D To a 50 mL round bottom flask was added 3-mercapto-2-methylpropanoic acid (5 g, 41.6 mmol), followed by MeOH (15 mL), the solution was stirred at 25 'C. Potassium hydroxide 5 (5.14 g, 92 mmol) was added slowly as the reaction is exothermic. Iodomethane-d 3 (6.63 g, 45.8 mmol) was added slowly and then the reaction mixture was heated at 65 'C overnight. The reaction was worked up by addition of 2 N HCl until the mixture was acidic. It was then extracted with EtOAc (4x50 mL) and the combined organic layers were dried over Na 2
SO
4 , concentrated and purified with flash chromatography, eluted with 0-80% EtOAc/hexane to 10 give 2-methyl-3-(trideuteriomethylsulfanyl)propanoic acid (4.534 g, 33.0 mmol, 79 %) as colorless oil: IR (Thin film) 3446, 1704 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 2.84 (dd, J= 13.0, 7.1 Hz, 1H), 2.80 - 2.66 (m, 1H), 2.57 (dd, J= 13.0, 6.6 Hz, 1H), 1.30 (d, J= 7.0 Hz, 3H); EIMS m/z 137. 15 Example 59: Preparation of 2-hydroxy-3-(methylthio)propanoic acid 0 HO SMe OH Sodium methanethiolate (4.50 g, 64.2 mmol) was added at 25 'C to a solution of 3-chloro-2 20 hydroxypropanoic acid (2 g, 16.06 mmol) in MeOH (120 mL). The reaction mixture was heated at reflux for 8 hours, then cooled to 25 C. The precipitate was removed by filtration and the filtrate was evaporated. The residue was acidified to pH 2 with 2 N HCl, extracted with EtOAc (3 x 30 mL), combined organic layers were dried with Na 2
SO
4 , concentrated to give 2-hydroxy-3-(methylthio)propanoic acid as a white solid, (1.898 g, 13.94 mmol, 87 % 25 yield): mp 55-59 'C; IR (Thin film) 2927, 1698 cm-1; 'H NMR (400 MHz, CDCl 3 ) 6 6.33 (s, 3H), 4.48 (dd, J = 6.3, 4.2 Hz, 1H), 3.02 (dd, J = 14.2, 4.2 Hz, 1H), 2.90 (dd, J = 14.2, 6.3 Hz, 1H), 2.20 (s, 3H); EIMS m/z 136. Example 60: Preparation of 2-methoxy-3-(methylthio)propanoic acid 30 88 0 HO SMe OMe To a stirred solution of sodium hydride (0.176 g, 4.41 mmol) in DMF (5 mL) was added a solution of 2-hydroxy-3-(methylthio)propanoic acid (0.25 g, 1.836 mmol) in 1 mL DMF at 25 5 C and stirred for 10 min. Vigorous bubbling was observed upon addition of NaH. Then iodomethane (0.126 mL, 2.020 mmol) was added and the solution was stirred at 25 C overnight. The reaction was quenched by addition of 2 N HCl, extracted with 3 x 10 mL of EtOAc, the combined organic layers were washed with water (2 x 20 mL), concentrated and purified by column chromatography, eluted with 0-100% EtOAc/hexane, gave 2-methoxy-3 10 (methylthio)propanoic acid (126 mg, 0.839 mmol, 45.7 % yield) as colorless oil: 'H NMR (400 MHz, CDCl 3 ) 6 9.10 (s, 1H), 4.03 (dd, J = 6.9, 4.4 Hz, 1H), 3.51 (s, 3H), 2.98 - 2.93 (m, 1H), 2.86 (dd, J = 14.1, 6.9 Hz, 1H), 2.21 (s, 3H); EIMS m/z 150. Example 61: Preparation of 2-(acetylthiomethyl)-3,3,3-trifluoropropanoic acid 15 o 0 HO S'K
CF
3 To a 50 mL round bottom flask was added 2-(trifluoromethyl)acrylic acid (6 g, 42.8 mmol), followed by thioacetic acid (4.59 ml, 64.3 mmol). The reaction was slightly exothermic. The 20 mixture was then stirred at 25 C overnight. NMR showed some starting material (-30%). One more equiv of thioacetic acid was added and the mixture was heated at 95 C for 1 hour, then allowed to cool to room temperature. Mixture was purified by vacuum distillation at 2.1 2.5 mm Hg, fraction distilled at 80-85 C was mostly thioacetic acid, fraction distilled at 100 110 C was almost pure product, contaminated by a nonpolar impurity (by TLC). It was again 25 purified by flash chromatography (0-20% MeOH/ DCM), to give 2-(acetylthiomethyl)-3,3,3 trifluoropropanoic acid (7.78 g, 36.0 mmol, 84 % yield) as colorless oil, which solidified under high vacuum to give a white solid: mp 28-30 'C; 1H NMR (400 MHz, CDCl 3 ) 6 7.52 (brs, 1H), 3.44 (dt, J = 7.5, 3.5 Hz, 2H), 3.20 (dd, J = 14.9, 11.1 Hz, 1H), 2.38 (s, 3H); 1 3 C NMR (101 MHz, CDCl 3 ) 6 194.79, 171.14, 123.44 (q, J = 281.6 Hz), 50.47 (q, J = 27.9 Hz), 30 30.44, 24.69 (q, J = 2.6 Hz); 19F NMR (376 MHz, CDCl 3 ) 6 -67.82. 89 Example 62: Preparation of 3,3,3-trifluoro-2-(methylthiomethyl)propanoic acid 0 HO
CF
3 5 To a solution of 2-(acetylthiomethyl)-3,3,3-trifluoropropanoic acid (649 mg, 3 mmol) in MeOH (5 mL) stirring at 25 C was added pellets of potassium hydroxide (421 mg, 7.50 mmol) in four portions over 5 minutes. Reaction was exothermic. Then Mel was added in once, the reaction mixture was then heated at 65 C for 18 hours. The reaction was then 10 cooled down and quenched with 2N HCl until acidic, and the aqueous layer extracted with chloroform (4 x 20 mL). Combined organic layer was dried, concentrated in vacuo, purified with flash chromatography (0-20% MeOH/DCM), to give 3,3,3-trifluoro-2 (methylthiomethyl)propanoic acid (410 mg, 2.179 mmol, 72.6 % yield) as a light yellow oil: IH NMR (400 MHz, CDCl 3 ) 6 10.95 (s, 1H), 3.49 - 3.37 (m, 1H), 3.02 (dd, J = 13.8, 10.8 Hz, 15 1H), 2.90 (dd, J = 13.8, 4.0 Hz, 1H), 2.18 (s, 3H); 1 3 C NMR (101 MHz, CDCl 3 ) 6 172.04 (q, J = 2.8 Hz), 123.55 (q, J = 281.2 Hz), 50.89 (q, J = 27.5 Hz), 29.62 (q, J = 2.3 Hz), 15.85; 19F NMR (376 MHz, CDCl 3 ) 6 -67.98. Example 63: Preparation of 3-(methylthio)pentanoic acid 20 0 HO S S,S-dimethyl carbonodithioate (1.467 g, 12.00 mmol) was added with vigorous stirring to a solution of (E)-pent-2-enoic acid (2.002 g, 20 mmol) in 30% KOH solution (prepared from 25 potassium hydroxide (3.87 g, 69 mmol) and Water (10 mL)). The reaction mixture was slowly heated to 90'C over a period of 20-30 min. Heating was continued for 3 hours before the reaction was cooled down to 25 C and quenched slowly with HCl. The mixture was then extracted with DCM (3 x 30 mL), combined organic layer dried and concentrated to give 3 (methylthio)pentanoic acid (2.7g, 18.22 mmol, 91 % yield) as light orange oil: IR (Thin film) 30 2975, 1701 cm-1; 'H NMR (400 MHz, CDCl 3 ) 6 2.92 (qd, J= 7.3, 5.6 Hz, 1H), 2.63 (d, J= 90 7.2 Hz, 2H), 2.08 (s, 3H), 1.75 - 1.51 (m, 2H), 1.03 (t, J= 7.4 Hz, 3H); 1C NMR (101 MHz, CDCl 3 ) 6 178.14, 43.95, 39.78, 27.04, 12.95, 11.29; EIMS m/z 148. 4-methyl-3-(methylthio)pentanoic acid was prepared as described in Example 63 and isolated 5 as a colorless oil: IR (Thin film) 2960, 1704 cm-1; 1H NMR (400 MHz, CDCl 3 ) 6 2.88 (ddd, J = 9.1, 5.4, 4.7 Hz, 1H), 2.68 (dd, J= 16.0, 5.5 Hz, 1H), 2.55 (dd, J= 16.0, 9.1 Hz, 1H), 2.13 (s, 3H), 2.01 - 1.90 (m, 1H), 1.03 (d, J= 6.8 Hz, 3H), 0.99 (d, J= 6.8 Hz, 3H); EIMS m/z 162. 10 Example 64: Preparation of ethyl 1-(hydroxymethyl)cyclopropanecarboxylate 0 HO O A IM solution of lithium aluminum tri-tert-butoxyhydride in tetrahydrofuran (70.90 mL, 15 70.90 mmol) was added to a stirred solution of diethyl cyclopropane-1,1'-dicarboxylate (6 g, 32.20 mmol) in tetrahydrofuran (129 mL) at 23 'C. The resulting solution was heated to 65 'C and stirred for 24 h. The cooled reaction mixture was diluted with a 10% solution of sodium bisulfate (275 mL) and extracted with ethyl acetate. The combined organic layers were dried (MgS04), filtered, and concentrated to dryness to give the desired product as a 20 pale yellow oil (4.60, 91%): 'H NMR (300 MHz, CDCl 3 ) 6 4.16 (q, J = 7 Hz, 2H), 3.62 (s, 2H), 2.60 (br s, 1H), 1.22-1.30 (m, 5H), 0.87 (dd, J = 7, 4 Hz, 2H). Example 65: Preparation of ethyl 1 ((methylsulfonyloxy)methyl)cyclopropanecarboxylate 25 o 0 0 Triethylamine (5.57 mL, 40.00 mmol) and methanesulfonyl chloride (2.85 mL, 36.60 mmol) were sequentially added to a stirred solution of ethyl 1 30 (hydroxymethyl)cyclopropanecarboxylate (4.80 g, 33.30 mmol) in dichloromethane (83 mL) 91 at 23 'C. The resulting bright yellow solution was stirred at 23 'C for 20 h. The reaction mixture was diluted with water and extracted with dichloromethane. The combined organic layers were dried (MgSO4), filtered, and concentrated to dryness to give the desired product as a brown oil (6.92 g, 94%): 'H NMR (300 MHz, CDCl 3 ) 6 4.33 (s, 2H), 4.16 (q, J= 7 Hz, 5 2H), 3.08 (s, 3H), 1.43 (dd, J= 7, 4 Hz, 2H), 1.26 (t, J= 7 Hz, 3H), 1.04 (dd, J= 7, 4 Hz, 2H). Example 66: Preparation of ethyl 1-(methylthiomethyl)cyclopropanecarboxylate 0 10 Sodium methanethiolate (4.36 g, 62.30 mmol) was added to a stirred solution of ethyl 1 ((methylsulfonyloxy)methyl) cyclopropanecarboxylate (6.92 g, 31.10 mmol) in NN dimethylformamide (62.30 mL) at 23 'C. The resulting brown suspension was stirred at 23 'C 15 for 18 h. The reaction mixture was diluted with water and extracted with diethyl ether. The combined organic layers were dried (MgSO 4 ), filtered, and concentrated by rotary evaporation to afford the title compound as a brown oil (5.43 g, 100%): 'H NMR (300 MHz, CDCl 3 ) 6 4.14 (q, J= 7 Hz, 2H), 2.83 (s, 2H), 2.16 (s, 3H), 1.31 (dd, J= 7, 4 Hz, 2H), 1.25 (t, J= 7 Hz, 3H), 0.89 (dd, J= 7, 4 Hz, 2H). 20 Example 67: Preparation of 1-(methylthiomethyl)cyclopropanecarboxylic acid 0 S - OH 25 A 50% solution of sodium hydroxide (12.63 mL, 243 mmol) was added to a stirred solution of ethyl 1-(methylthiomethyl)cyclopropanecarboxylate (5.43 g, 31.20 mmol) in absolute ethanol (62.30 mL) at 23 'C. The resulting solution was stirred at 23 'C for 20 h. The reaction mixture was diluted with a 0.5 M solution of sodium hydroxide and washed with dichloromethane. The aqueous layer was acidified to pH~1 with concentrated hydrochloric 30 acid and extracted with dichloromethane. The combined organic layers were dried (Na 2 SO4), 92 filtered, and concentrated and concentrated to dryness to give the desired product as a light brown oil (2.10 g, 46%): 'H NMR (300 MHz, CDCl 3 ) 6 2.82 (s, 2H), 2.17 (s, 3H), 1.41 (dd, J = 7, 4 Hz, 2H), 0.99 (dd, J= 7, 4 Hz, 2H). 5 Example 68: Preparation of 2,2-dimethyl-3-(methylthio)propanoic acid 0 S - OH 2,2-Dimethyl-3-(methylthio)propanoic acid can be prepared as demonstrated in the literature 10 (reference Musker, W. K.; et al. J. Org. Chem. 1996, 51, 1026-1029). Sodium methanethiolate (1.0 g, 14 mmol, 2.0 equiv) was added to a stirred solution of 3-chloro-2,2 dimethylpropanoic acid (1.0 g, 7.2 mmol, 1.0 equiv) in NN-dimethylformamide (3.7 mL) at 0 GC. The resulting brown suspension was allowed to warm to 23 'C and stirred for 24 h. The reaction mixture was diluted with a saturated solution of sodium bicarbonate (300 mL) and 15 washed with diethyl ether (3 x 75 mL). The aqueous layer was acidified to pH~1 with concentrated hydrochloric acid and extracted with diethyl ether (3 x 75 mL). The combined organic layers were dried (sodium sulfate), gravity filtered, and concentrated to afford a colorless oil (1.2 g, 99% crude yield). 'H NMR (300 MHz, CDCl 3 ) 6 2.76 (s, 2H), 2.16 (s, 3H), 1.30 (s, 6H). 20 Example 69: Preparation of 4,4,4-trifluoro-3-(methylthio)butanoic acid o SMe HO
CF
3 25 To a 100 mL round bottom flask was added (E)-4,4,4-trifluorobut-2-enoic acid (8 g, 57.1 mmol) and Methanol (24 mL), the solution was stirred in a water bath, then sodium methanethiolate (10.01 g, 143 mmol) was added in three portions. Vigorous bubbling was observed, the mixture was stirred at 25 C overnight, NMR showed no more starting material. To the reaction mixture was added 2 N HCl until acidic. The mixture was extracted with 30 chloroform (5 x 50 mL), combined organic layer was dried over Na 2
SO
4 , concentrated in 93 vacuo and further dried under high vacuum until there was no weight loss to give 4,4,4 trifluoro-3-(methylthio)butanoic acid (10.68 g, 56.8 mmol, 99 % yield) as a colorless oil: 'H NMR (400 MHz, CDCl 3 ) 6 10.88 (s, 1H), 3.53 (dqd, J= 10.5, 8.3, 4.0 Hz, 1H), 2.96 (dd, J= 16.9, 4.0 Hz, 1H), 2.65 (dd, J = 16.9, 10.4 Hz, 1H), 2.29 (s, 3H); 1C NMR (101 MHz, 5 CDCl3) 6 175.78 (s), 126.61 (q, JC-F= 278.8 Hz), 44.99 (q, JC-F = 30.3Hz), 34.12 (d, JC-F = 1.7 Hz), 15.95 (s); EIMS m/z 162. Example 70: Preparation of 3-methyl-3-methylsulfanyl-butyric acid 0 10 3-methyl-3-methylsulfanyl-butyric acid was made using the procedures disclosed in J. Chem Soc Perkin 1, 1992, 10, 1215-21). 15 Example 71: Preparation of 3-methylsulfanyl-butyric acid 0 HOS 3-Methylsulfanyl-butyric acid was made using the procedures disclosed in Synthetic 20 Comm., 1985, 15 (7), 623-32. Example 72: Preparation of tetrahydro-thiophene-3-carboxylic acid 0 0 LJ H S 25 Tetrahydro-thiophene-3-carboxylic acid was made using the procedures disclosed in Heterocycles, 2007, 74, 397-409. Example 73: Preparation of 2-methyl-3-methylsulfanyl-butyric acid 94 0 Hi I 2-Methyl-3-methylsulfanyl-butyric acid was made as described in J. Chem Soc Perkin 1, 1992, 5 10,1215-21. Example 74: Preparation of (1S,2S)-2-(methylthio)cyclopropanecarboxylic acid 0 H 10 (1S,2S)-2-(Methylthio)cyclopropanecarboxylic acid was made using the procedures disclosed in Synthetic Comm., 2003, 33 (5); 801-807. Example 75: Preparation of 2-(2-(methylthio)ethoxy)propanoic acid 15 0 HO S 2-(2-(Methylthio)ethoxy)propanoic acid was made as described in WO 2007/064316 Al. 20 Example 76: Preparation of 2-((tetrahydrofuran-3-yl)oxy)propanoic acid 0 H O 1O 0 2-((Tetrahydrofuran-3-yl)oxy)propanoic acid was made as described in WO 2007/064316 Al. 25 Example 77: BIOASSAYS ON GREEN PEACH APHID ("GPA") (Myzus persicae) (MYZUPE). GPA is the most significant aphid pest of peach trees, causing decreased growth, 95 shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, 5 daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other plants. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses. GPA has developed resistance to many pesticides. Certain molecules disclosed in this document were tested against GPA using 10 procedures described in the following example. In the reporting of the results, "Table 3: GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA) Rating Table" was used (See Table Section). Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) true leaves, were used as test substrate. The seedlings were infested with 20-50 GPA (wingless adult and 15 nymph stages) one day prior to chemical application. Four pots with individual seedlings were used for each treatment. Test compounds (2 mg) were dissolved in 2 mL of acetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm test compound. The stock solutions were diluted 5X with 0.025% Tween 20 in H 2 0 to obtain the solution at 200 ppm test compound. A hand-held aspirator-type sprayer was used for spraying a solution to 20 both sides of cabbage leaves until runoff. Reference plants (solvent check) were sprayed with the diluent only containing 20% by volume of acetone/methanol (1:1) solvent. Treated plants were held in a holding room for three days at approximately 25 'C and ambient relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott's 25 correction formula (W.S. Abbott, "A Method of Computing the Effectiveness of an Insecticide" J. Econ. Entomol. 18 (1925), pp.265-267) as follows. Corrected % Control = 100 * (X - Y) / X where X = No. of live aphids on solvent check plants and 30 Y = No. of live aphids on treated plants The results are indicated in the table entitled "Table 4. Biological Data for GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA)" (See Table Section). 96 Example 78: Insecticidal test for sweetpotato whitefly-crawler (Bemisia tabaci) (BEMITA) in foliar spray assay Cotton plants grown in 3-inch pots, with 1 small (3-5 cm) true leaf, were used as test substrate. The plants were placed in a room with whitefly adults. Adults were allowed to 5 deposit eggs for 2-3 days. After a 2-3 day egg-laying period, plants were taken from the adult whitefly room. Adults were blown off leaves using a hand-held Devilbiss sprayer (23 psi). Plants with egg infestation (100-300 eggs per plant) were placed in a holding room for 5-6 days at 82 'F and 50% RH for egg hatch and crawler stage to develop. Four cotton plants were used for each treatment. Compounds (2 mg) were dissolved in 1 mL of acetone solvent, 10 forming stock solutions of 2000 ppm. The stock solutions were diluted 1OX with 0.025% Tween 20 in H 2 0 to obtain a test solution at 200 ppm. A hand-held Devilbiss sprayer was used for spraying a solution to both sides of cotton leaf until runoff. Reference plants (solvent check) were sprayed with the diluent only. Treated plants were held in a holding room for 8-9 days at approximately 82'F and 50% RH prior to grading. Evaluation was conducted by 15 counting the number of live nymphs per plant under a microscope. Insecticidal activity was measured by using Abbott's correction formula and presented in "Table 4. Biological Data for GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA)" (see column "BEMITA"): Corrected % Control = 100 * (X - Y) / X 20 where X = No. of live nymphs on solvent check plants Y = No. of live nymphs on treated plants PESTICIDALLY ACCEPTABLE ACID ADDITION SALTS, SALT DERIVATIVES, SOLVATES, ESTER DERIVATIVES, POLYMORPHS, ISOTOPES AND RADIONUCLIDES 25 Molecules of Formula One may be formulated into pesticidally acceptable acid addition salts. By way of a non-limiting example, an amine function can form salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, and 30 hydroxyethanesulfonic acids. Additionally, by way of a non-limiting example, an acid function can form salts including those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnesium. 97 Molecules of Formula One may be formulated into salt derivatives. By way of a non limiting example, a salt derivative can be prepared by contacting a free base with a sufficient amount of the desired acid to produce a salt. A free base may be regenerated by treating the salt with a suitable dilute aqueous base solution such as dilute aqueous sodium hydroxide 5 (NaOH), potassium carbonate, ammonia, and sodium bicarbonate. As an example, in many cases, a pesticide, such as 2,4-D, is made more water-soluble by converting it to its dimethylamine salt.. Molecules of Formula One may be formulated into stable complexes with a solvent, such that the complex remains intact after the non-complexed solvent is removed. These 10 complexes are often referred to as "solvates." However, it is particularly desirable to form stable hydrates with water as the solvent. Molecules of Formula One may be made into ester derivatives. These ester derivatives can then be applied in the same manner as the invention disclosed in this document is applied. Molecules of Formula One may be made as various crystal polymorphs. 15 Polymorphism is important in the development of agrochemicals since different crystal polymorphs or structures of the same molecule can have vastly different physical properties and biological performances. Molecules of Formula One may be made with different isotopes. Of particular importance are molecules having 2fH (also known as deuterium) in place of 1H. 20 Molecules of Formula One may be made with different radionuclides. Of particular importance are molecules having 1C. STEREOISOMERS Molecules of Formula One may exist as one or more stereoisomers. Thus, certain 25 molecules can be produced as racemic mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the other stereoisomers. Individual stereoisomers may be obtained by known selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures. Certain molecules disclosed in this document can exist as two or more isomers. 30 The various isomers include geometric isomers, diastereomers, and enantiomers. Thus, the molecules disclosed in this document include geometric isomers, racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the 98 present disclosure are drawn in only one geometric form for clarity, but are intended to represent all geometric forms of the molecule. COMBINATIONS 5 Molecules of Formula One may also be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more compounds having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, or virucidal properties. Additionally, the molecules of Formula One may also be used in combination (such as, in a compositional 10 mixture, or a simultaneous or sequential application) with compounds that are antifeedants, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammal repellents, mating disrupters, plant activators, plant growth regulators, or synergists. Examples of such compounds in the above groups that may be used with the Molecules of Formula One are - (3-ethoxypropyl)mercury bromide, 1,2-dichloropropane, 1,3 15 dichloropropene, 1-methylcyclopropene, 1-naphthol, 2-(octylthio)ethanol, 2,3,5-tri iodobenzoic acid, 2,3,6-TBA, 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6 TBA-potassium, 2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-T isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl, 2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium, 20 2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D, 2,4-D-2-butoxypropyl, 2,4-D-2 ethylhexyl, 2,4-D-3-butoxypropyl, 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl, 2,4 D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 25 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4 D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2 hydroxypropyl)ammonium, 2,4-D-trolamine, 2iP, 2-methoxyethylmercury chloride, 2 phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPA 30 sodium, 4-CPB, 4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate, 8 phenylmercurioxyquinoline, abamectin, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetophos, acetoprole, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrep, acrinathrin, acrolein, 99 acrylonitrile, acypetacs, acypetacs-copper, acypetacs-zine, alachlor, alanycarb, albendazole, aldicarb, aldimorph, aldoxycarb, aldrin, allethrin, allicin, allidochlor, allosamidin, alloxydim, alloxydim-sodium, allyl alcohol, allyxycarb, alorac, alpha-cypermethrin, alpha-endosulfan, ametoctradin, ametridione, ametryn, amibuzin, amicarbazone, amicarthiazol, amidithion, 5 amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium, aminopyralid-tris(2 hydroxypropyl)ammonium, amiprofos-methyl, amiprophos, amisulbrom, amiton, amiton oxalate, amitraz, amitrole, ammonium sulfamate, ammonium a-naphthaleneacetate, amobam, ampropylfos, anabasine, ancymidol, anilazine, anilofos, anisuron, anthraquinone, antu, 10 apholate, aramite, arsenous oxide, asomate, aspirin, asulam, asulam-potassium, asulam sodium, athidathion, atraton, atrazine, aureofungin, aviglycine, aviglycine hydrochloride, azaconazole, azadirachtin, azafenidin, azamethiphos, azimsulfuron, azinphos-ethyl, azinphos methyl, aziprotryne, azithiram, azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban, barium hexafluorosilicate, barium polysulfide, barthrin, BCPC, 15 beflubutamid, benalaxyl, benalaxyl-M, benazolin, benazolin-dimethylammonium, benazolin ethyl, benazolin-potassium, bencarbazone, benclothiaz, bendiocarb, benfluralin, benfuracarb, benfuresate, benodanil, benomyl, benoxacor, benoxafos, benquinox, bensulfuron, bensulfuron-methyl, bensulide, bensultap, bentaluron, bentazone, bentazone-sodium, benthiavalicarb, benthiavalicarb-isopropyl, benthiazole, bentranil, benzadox, benzadox 20 ammonium, benzalkonium chloride, benzamacril, benzamacril-isobutyl, benzamorf, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzohydroxamic acid, benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, benzyladenine, berberine, berberine chloride, beta-cyfluthrin, beta-cypermethrin, bethoxazin, bicyclopyrone, bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos, bilanafos-sodium, 25 binapacryl, bingqingxiao, bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bisazir, bismerthiazol, bispyribac, bispyribac-sodium, bistrifluron, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid, brassinolide, brassinolide-ethyl, brevicomin, brodifacoum, brofenvalerate, brofluthrinate, bromacil, bromacil-lithium, bromacil-sodium, bromadiolone, bromethalin, bromethrin, bromfenvinfos, 30 bromoacetamide, bromobonil, bromobutide, bromocyclen, bromo-DDT, bromofenoxim, bromophos, bromophos-ethyl, bromopropylate, bromothalonil, bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, bromuconazole, bronopol, bucarpolate, bufencarb, buminafos, bupirimate, 100 buprofezin, Burgundy mixture, busulfan, butacarb, butachlor, butafenacil, butamifos, butathiofos, butenachlor, butethrin, buthidazole, buthiobate, buthiuron, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butroxydim, buturon, butylamine, butylate, cacodylic acid, cadusafos, cafenstrole, calcium arsenate, calcium chlorate, calcium 5 cyanamide, calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor, captafol, captan, carbamorph, carbanolate, carbaryl, carbasulam, carbendazim, carbendazim benzenesulfonate, carbendazim sulfite, carbetamide, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, carboxazole, carboxide, carboxin, carfentrazone, carfentrazone-ethyl, carpropamid, cartap, cartap hydrochloride, carvacrol, carvone, CDEA, 10 cellocidin, CEPC, ceralure, Cheshunt mixture, chinomethionat, chitosan, chlobenthiazone, chlomethoxyfen, chloralose, chloramben, chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium, chloramben-sodium, chloramine phosphorus, chloramphenicol, chloraniformethan, chloranil, chloranocryl, chlorantraniliprole, chlorazifop, chlorazifop-propargyl, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen, 15 chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorempenthrin, chlorethoxyfos, chloreturon, chlorfenac, chlorfenac ammonium, chlorfenac-sodium, chlorfenapyr, chlorfenazole, chlorfenethol, chlorfenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfluazuron, chlorflurazole, chlorfluren, chlorfluren-methyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, 20 chlorimuron-ethyl, chlormephos, chlormequat, chlormequat chloride, chlornidine, chlomitrofen, chlorobenzilate, chlorodinitronaphthalenes, chloroform, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophacinone-sodium, chloropicrin, chloropon, chloropropylate, chlorothalonil, chlorotoluron, chloroxuron, chloroxynil, chlorphonium, chlorphonium chloride, chlorphoxim, chlorprazophos, chlorprocarb, 25 chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, chlorthiophos, chlozolinate, choline chloride, chromafenozide, cinerin I, cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, ciobutide, cisanilide, cismethrin, clethodim, climbazole, cliodinate, clodinafop, clodinafop-propargyl, cloethocarb, clofencet, clofencet-potassium, clofentezine, clofibric 30 acid, clofop, clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(2 hydroxypropyl)ammonium, cloquintocet, cloquintocet-mexyl, cloransulam, cloransulam methyl, closantel, clothianidin, clotrimazole, cloxyfonac, cloxyfonac-sodium, CMA, 101 codlelure, colophonate, copper acetate, copper acetoarsenite, copper arsenate, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, coumachlor, coumafuryl, coumaphos, coumatetralyl, coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, 5 crimidine, crotamiton, crotoxyphos, crufomate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam, cuprous oxide, curcumenol, cyanamide, cyanatryn, cyanazine, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalofop, cyhalofop-butyl, 10 cyhalothrin, cyhexatin, cymiazole, cymiazole hydrochloride, cymoxanil, cyometrinil, cypendazole, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin, cyprazine, cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid, cyprosulfamide, cyromazine, cythioate, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, daminozide, dayoutong, dazomet, dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, 15 DDT, debacarb, decafentin, decarbofuran, dehydroacetic acid, delachlor, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, desmedipham, desmetryn, d-fanshiluquebingjuzhi, diafenthiuron, dialifos, di-allate, diamidafos, diatomaceous earth, diazinon, dibutyl phthalate, dibutyl succinate, dicamba, dicamba-diglycolamine, dicamba 20 dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-trolamine, dicapthon, dichlobenil, dichlofenthion, dichlofluanid, dichlone, dichloralurea, dichlorbenzuron, dichlorflurenol, dichlorflurenol-methyl, dichlormate, dichlormid, dichlorophen, dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop 25 ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P, dichlorprop-P-2 ethylhexyl, dichlorprop-P-dimethylammonium, dichlorprop-potassium, dichlorprop-sodium, dichlorvos, dichlozoline, diclobutrazol, diclocymet, diclofop, diclofop-methyl, diclomezine, diclomezine-sodium, dicloran, diclosulam, dicofol, dicoumarol, dicresyl, dicrotophos, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat, diethamquat dichloride, diethatyl, 30 diethatyl-ethyl, diethofencarb, dietholate, diethyl pyrocarbonate, diethyltoluamide, difenacoum, difenoconazole, difenopenten, difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate, difethialone, diflovidazin, diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr-sodium, diflumetorim, dikegulac, dikegulac-sodium, dilor, 102 dimatif, dimefluthrin, dimefox, dimefuron, dimepiperate, dimetachlone, dimetan, dimethacarb, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate, dimethyl phthalate, dimethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin, dinex, dinex-diclexine, 5 dingjunezuo, diniconazole, diniconazole-M, dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium, dinoseb-trolamine, dinosulfon, dinotefuran, dinoterb, dinoterb acetate, dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion, diphacinone, diphacinone-sodium, diphenamid, diphenyl sulfone, diphenylamine, 10 dipropalin, dipropetryn, dipyrithione, diquat, diquat dibromide, disparlure, disul, disulfiram, disulfoton, disul-sodium, ditalimfos, dithianon, dithicrofos, dithioether, dithiopyr, diuron, d limonene, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin hydrochloride, dodicin-sodium, dodine, dofenapyn, dominicalure, doramectin, drazoxolon, DSMA, dufulin, 15 EBEP, EBP, ecdysterone, edifenphos, eglinazine, eglinazine-ethyl, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothal, endothal-diammonium, endothal dipotassium, endothal-disodium, endothion, endrin, enestroburin, EPN, epocholeone, epofenonane, epoxiconazole, eprinomectin, epronaz, EPTC, erbon, ergocalciferol, erlujixiancaoan, esd6pall6thrine, esfenvalerate, esprocarb, etacelasil, etaconazole, etaphos, 20 etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethaprochlor, ethephon, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl, ethofumesate, ethohexadiol, ethoprophos, ethoxyfen, ethoxyfen ethyl, ethoxyquin, ethoxysulfuron, ethychlozate, ethyl formate, ethyl a-naphthaleneacetate, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, ethylicin, 25 ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etinofen, etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos, eugenol, EXD, famoxadone, famphur, fenamidone, fenaminosulf, fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorazole-ethyl, 30 fenchlorphos, fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitropan, fenitrothion, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypropyl, fenoprop butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop potassium, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, 103 fenoxaprop-P-ethyl, fenoxasulfone, fenoxycarb, fenpiclonil, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate, fenridazon, fenridazon potassium, fenridazon-propyl, fenson, fensulfothion, fenteracol, fenthiaprop, fenthiaprop ethyl, fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride, fentin hydroxide, 5 fentrazamide, fentrifanil, fenuron, fenuron TCA, fenvalerate, ferbam, ferimzone, ferrous sulfate, fipronil, flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl, flamprop-M isopropyl, flamprop-M-methyl, flazasulfuron, flocoumafen, flometoquin, flonicamid, florasulam, fluacrypyrim, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop P-butyl, fluazinam, fluazolate, fluazuron, flubendiamide, flubenzimine, flucarbazone, 10 flucarbazone-sodium, flucetosulfuron, fluchloralin, flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerim, flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr-ethyl, flufiprole, flumethrin, flumetover, flumetralin, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, flumorph, fluometuron, fluopicolide, fluopyram, fluorbenside, fluoridamid, fluoroacetamide, 15 fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluotrimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate, flupropanate-sodium, flupyradifurone, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron methyl-sodium, fluquinconazole, flurazole, flurenol, flurenol-butyl, flurenol-methyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurprimidol, 20 flursulamid, flurtamone, flusilazole, flusulfamide, fluthiacet, fluthiacet-methyl, flutianil, flutolanil, flutriafol, fluvalinate, fluxapyroxad, fluxofenim, folpet, fomesafen, fomesafen sodium, fonofos, foramsulfuron, forchlorfenuron, formaldehyde, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosamine, fosamine ammonium, fosetyl, fosetyl-aluminium, fosmethilan, fospirate, fosthiazate, fosthietan, 25 frontalin, fuberidazole, fucaojing, fucaomi, funaihecaoling, fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr, furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin, furfural, furilazole, furmecyclox, furophanate, furyloxyfen, gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellins, gliftor, glufosinate, glufosinate ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyodin, 30 glyoxime, glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate isopropylammonium, glyphosate-monoammonium, glyphosate-potassium, glyphosate sesquisodium, glyphosate-trimesium, glyphosine, gossyplure, grandlure, griseofulvin, guazatine, guazatine acetates, halacrinate, halfenprox, halofenozide, halosafen, halosulfuron, 104 halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop P, haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium, HCH, hemel, hempa, HEOD, heptachlor, heptenophos, heptopargil, heterophos, hexachloroacetone, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumuron, hexaflurate, hexalure, 5 hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf, huancaiwo, huangcaoling, huanjunzuo, hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanide, hydroprene, hymexazol, hyquincarb, IAA, IBA, icaridin, imazalil, imazalil nitrate, imazalil sulfate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, 10 imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr ammonium, imazosulfuron, imibenconazole, imicyafos, imidacloprid, imidaclothiz, iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate, imiprothrin, inabenfide, indanofan, indaziflam, indoxacarb, inezin, iodobonil, iodocarb, iodomethane, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, 15 ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarbazone, iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, isamidofos, isazofos, isobenzan, isocarbamid, isocarbophos, isocil, isodrin, isofenphos, isofenphos-methyl, isolan, isomethiozin, isonoruron, isopolinate, isoprocarb, isopropalin, isoprothiolane, isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron, 20 isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen-ethyl, isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izopamfos, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan, jiecaoxi, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone Ill, kadethrin, karbutilate, karetazan, karetazan-potassium, kasugamycin, kasugamycin hydrochloride, 25 kejunlin, kelevan, ketospiradox, ketospiradox-potassium, kinetin, kinoprene, kresoxim methyl, kuicaoxi, lactofen, lambda-cyhalothrin, latilure, lead arsenate, lenacil, lepimectin, leptophos, lindane, lineatin, linuron, lirimfos, litlure, looplure, lufenuron, lvdingjunzhi, lvxiancaolin, lythidathion, MAA, malathion, maleic hydrazide, malonoben, maltodextrin, MAMA, mancopper, mancozeb, mandipropamid, maneb, matrine, mazidox, MCPA, MCPA 30 2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mebenil, mecarbam, mecarbinzid, mecarphon, 105 mecoprop, mecoprop-2-ethylhexyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-2 ethylhexyl, mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medimeform, medinoterb, 5 medinoterb acetate, medlure, mefenacet, mefenpyr, mefenpyr-diethyl, mefluidide, mefluidide diolamine, mefluidide-potassium, megatomoic acid, menazon, mepanipyrim, meperfluthrin, mephenate, mephosfolan, mepiquat, mepiquat chloride, mepiquat pentaborate, mepronil, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, merphos, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, mesulfen, mesulfenfos, 10 metaflumizone, metalaxyl, metalaxyl-M, metaldehyde, metam, metam-ammonium, metamifop, metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron, metazoxolon, metconazole, metepa, metflurazon, methabenzthiazuron, methacrifos, methalpropalin, methamidophos, methasulfocarb, methazole, methfuroxam, methidathion, methiobencarb, methiocarb, methiopyrisulfuron, methiotepa, methiozolin, methiuron, 15 methocrotophos, methometon, methomyl, methoprene, methoprotryne, methoquin-butyl, methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methyl apholate, methyl bromide, methyl eugenol, methyl iodide, methyl isothiocyanate, methylacetophos, methylchloroform, methyldymron, methylene chloride, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, methylneodecanamide, 20 metiram, metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb, metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone, metribuzin, metsulfovax, metsulfuron, metsulfuron-methyl, mevinphos, mexacarbate, mieshuan, milbemectin, milbemycin oxime, milneb, mipafox, mirex, MNAF, moguchun, molinate, molosultap, monalide, monisouron, monochloroacetic acid, monocrotophos, monolinuron, 25 monosulfuron, monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquat dichloride, moroxydine, moroxydine hydrochloride, morphothion, morzid, moxidectin, MSMA, muscalure, myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulphonanilide, nabam, naftalofos, naled, naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthoxyacetic acids, naproanilide, napropamide, naptalam, naptalam-sodium, natamycin, 30 neburon, niclosamide, niclosamide-olamine, nicosulfuron, nicotine, nifluridide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl, norbormide, norflurazon, nornicotine, noruron, novaluron, noviflumuron, nuarimol, OCH, octachlorodipropyl ether, octhilinone, ofurace, omethoate, orbencarb, 106 orfralure, ortho-dichlorobenzene, orthosulfamuron, oryctalure, orysastrobin, oryzalin, osthol, ostramone, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxine-copper, oxolinic acid, oxpoconazole, oxpoconazole fumarate, oxycarboxin, oxydemeton-methyl, 5 oxydeprofos, oxydisulfoton, oxyfluorfen, oxymatrine, oxytetracycline, oxytetracycline hydrochloride, paclobutrazol, paichongding, para-dichlorobenzene, parafluron, paraquat, paraquat dichloride, paraquat dimetilsulfate, parathion, parathion-methyl, parinol, pebulate, pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin, penflufen, penfluron, penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad, pentmethrin, pentoxazone, 10 perfluidone, permethrin, pethoxamid, phenamacril, phenazine oxide, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenothrin, phenproxide, phenthoate, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phorate, phosacetim, phosalone, phosdiphen, phosfolan, phosfolan-methyl, phosglycin, 15 phosmet, phosnichlor, phosphamidon, phosphine, phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide, picloram, picloram-2-ethylhexyl, picloram-isoctyl, picloram methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram-tris(2 hydroxypropyl)ammonium, picolinafen, picoxystrobin, pindone, pindone-sodium, pinoxaden, piperalin, piperonyl butoxide, piperonyl cyclonene, piperophos, piproctanyl, piproctanyl 20 bromide, piprotal, pirimetaphos, pirimicarb, pirimioxyphos, pirimiphos-ethyl, pirimiphos methyl, plifenate, polycarbamate, polyoxins, polyoxorim, polyoxorim-zinc, polythialan, potassium arsenite, potassium azide, potassium cyanate, potassium gibberellate, potassium naphthenate, potassium polysulfide, potassium thiocyanate, potassium a-naphthaleneacetate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, pretilachlor, primidophos, 25 primisulfuron, primisulfuron-methyl, probenazole, prochloraz, prochloraz-manganese, proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol, profluralin, profluthrin, profoxydim, proglinazine, proglinazine-ethyl, prohexadione, prohexadione calcium, prohydrojasmon, promacyl, promecarb, prometon, prometryn, promurit, propachlor, propamidine, propamidine dihydrochloride, propamocarb, propamocarb hydrochloride, 30 propanil, propaphos, propaquizafop, propargite, proparthrin, propazine, propetamphos, propham, propiconazole, propineb, propisochlor, propoxur, propoxycarbazone, propoxycarbazone-sodium, propyl isome, propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin, prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothiocarb 107 hydrochloride, prothioconazole, prothiofos, prothoate, protrifenbute, proxan, proxan-sodium, prynachlor, pydanon, pymetrozine, pyracarbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyraflufen-ethyl, pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotole, pyrazolynate, pyrazophos, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazothion, 5 pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl, pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol, pyridalyl, pyridaphenthion, pyridate, pyridinitril, pyrifenox, pyrifluquinazon, pyriftalid, pyrimethanil, pyrimidifen, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxyfen, pyrithiobac, pyrithiobac 10 sodium, pyrolan, pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur, quassia, quinacetol, quinacetol sulfate, quinalphos, quinalphos-methyl, quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine, quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P tefuryl, quwenzhi, quyingding, rabenzazole, rafoxanide, rebemide, resmethrin, rhodethanil, 15 rhodojaponin-I, ribavirin, rimsulfuron, rotenone, ryania, saflufenacil, saijunmao, saisentong, salicylanilide, sanguinarine, santonin, schradan, scilliroside, sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz, semiamitraz chloride, sesamex, sesamolin, sethoxydim, shuangjiaancaolin, siduron, siglure, silafluofen, silatrane, silica gel, silthiofam, simazine, simeconazole, simeton, simetryn, sintofen, SMA, S-metolachlor, sodium arsenite, sodium 20 azide, sodium chlorate, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, sodium thiocyanate, sodium a-naphthaleneacetate, sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine, streptomycin, streptomycin sesquisulfate, strychnine, sulcatol, sulcofuron, sulcofuron-sodium, sulcotrione, sulfallate, 25 sulfentrazone, sulfiram, sulfluramid, sulfometuron, sulfometuron-methyl, sulfosulfuron, sulfotep, sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglycapin, sulprofos, sultropen, swep, tau-fluvalinate, tavron, tazimcarb, TCA, TCA-ammonium, TCA calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium, TDE, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, 30 tecoram, teflubenzuron, tefluthrin, tefuryltrione, tembotrione, temephos, tepa, TEPP, tepraloxydim, terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuthylazine, terbutryn, tetcyclacis, tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, tetrafluron, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetrasul, 108 thallium sulfate, thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid, thiadifluor, thiamethoxam, thiapronil, thiazafluron, thiazopyr, thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, thiocyclam, thiocyclam 5 hydrochloride, thiocyclam oxalate, thiodiazole-copper, thiodicarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon, thionazin, thiophanate, thiophanate-methyl, thioquinox, thiosemicarbazide, thiosultap, thiosultap-diammonium, thiosultap-disodium, thiosultap monosodium, thiotepa, thiram, thuringiensin, tiadinil, tiaojiean, tiocarbazil, tioclorim, tioxymid, tirpate, tolclofos-methyl, tolfenpyrad, tolylfluanid, tolylmercury acetate, 10 topramezone, tralkoxydim, tralocythrin, tralomethrin, tralopyril, transfluthrin, transpermethrin, tretamine, triacontanol, triadimefon, triadimenol, triafamone, tri-allate, triamiphos, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, triazbutil, triaziflam, triazophos, triazoxide, tribenuron, tribenuron-methyl, tribufos, tributyltin oxide, tricamba, trichlamide, trichlorfon, trichlormetaphos-3, trichloronat, triclopyr, triclopyr-butotyl, 15 triclopyr-ethyl, triclopyr-triethylammonium, tricyclazole, tridemorph, tridiphane, trietazine, trifenmorph, trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium, triflumizole, triflumuron, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, trifop methyl, trifopsime, triforine, trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac, trinexapac-ethyl, triprene, tripropindan, triptolide, tritac, triticonazole, 20 tritosulfuron, trunc-call, uniconazole, uniconazole-P, urbacide, uredepa, valerate, validamycin, valifenalate, valone, vamidothion, vangard, vaniliprole, vernolate, vinclozolin, warfarin, warfarin-potassium, warfarin-sodium, xiaochongliulin, xinjunan, xiwojunan, XMC, xylachlor, xylenols, xylylcarb, yishijing, zarilamid, zeatin, zengxiaoan, zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zineb, ziram, zolaprofos, zoxamide, 25 zuomihuanglong, a-chlorohydrin, a-ecdysone, a-multistriatin, and a-naphthaleneacetic acid. For more information consult the "COMPENDIUM OF PESTICIDE COMMON NAMES" located at http://www.alanwood.netipesticides/index.html. Also consult "THE PESTICIDE MANUAL" 14th Edition, edited by C D S Tomlin, copyright 2006 by British Crop Production Council, or its prior or more recent editions. 30 BIOPESTICIDES Molecules of Formula One may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more 109 biopesticides. The term "biopesticide" is used for microbial biological pest control agents that are applied in a similar manner to chemical pesticides. Commonly these are bacterial, but there are also examples of fungal control agents, including Trichoderma spp. and Ampelomyces quisqualis (a control agent for grape powdery mildew). Bacillus subtilis are 5 used to control plant pathogens. Weeds and rodents have also been controlled with microbial agents. One well-known insecticide example is Bacillus thuringiensis, a bacterial disease of Lepidoptera, Coleoptera, and Diptera. Because it has little effect on other organisms, it is considered more environmentally friendly than synthetic pesticides. Biological insecticides include products based on: 10 1. entomopathogenic fungi (e.g. Metarhizium anisopliae); 2. entomopathogenic nematodes (e.g. Steinernema feltiae); and 3. entomopathogenic viruses (e.g. Cydia pomonella granulovirus). Other examples of entomopathogenic organisms include, but are not limited to, baculoviruses, bacteria and other prokaryotic organisms, fungi, protozoa and Microsproridia. 15 Biologically derived insecticides include, but not limited to, rotenone, veratridine, as well as microbial toxins; insect tolerant or resistant plant varieties; and organisms modified by recombinant DNA technology to either produce insecticides or to convey an insect resistant property to the genetically modified organism. In one embodiment, the molecules of Formula One may be used with one or more biopesticides in the area of seed treatments and soil 20 amendments. The Manual of Biocontrol Agents gives a review of the available biological insecticide (and other biology-based control) products. Copping L.G. (ed.) (2004). The Manual of Biocontrol Agents (formerly the Biopesticide Manual) 3rd Edition. British Crop Production Council (BCPC), Farnham, Surrey UK. 25 OTHER ACTIVE COMPOUNDS Molecules of Formula One may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more of the following: 1. 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa- 1-azaspiro[4,5]dec-3-en-2-one; 30 2. 3-(4'-chloro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa- 1-azaspiro[4,5]dec-3 en-2-one; 3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone; 4. 4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone; 110 5. 3-chloro-N2-[(1S)- 1-methyl-2-(methylsulfonyl)ethyl] -N1- [2-methyl-4- [1,2,2,2 tetrafluoro- 1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide; 6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide; 7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; 5 8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide; 9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide; 10. 2-cyano-6-fluoro-3-methoxy-NN-dimethyl-benzenesulfonamide; 11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide; 12. 2-cyano-3-difluoromethoxy-NN-dimethylbenzenesulfon-amide; 10 13. 3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl] -1 -methyl- 1H-pyrazole-4 carboxamide; 14. N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-a,a,a-trifluoro-p-tolyl) hydrazone; 15. N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-a,a,a trifluoro-p-tolyl) hydrazone nicotine; 15 16. O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]} S-methyl thiocarbonate; 17. (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine; 18. 1-(6-chloropyridin-3 -ylmethyl)-7-methyl-8-nitro- 1,2,3,5,6,7-hexahydro-imidazo[ 1,2 a]pyridin-5-ol; 20 19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate; and 20. N-Ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro alpha, alpha, alpha-trifluoro-p-tolyl)hydrazone. SYNERGISTIC MIXTURES 25 Molecules of Formula One may be used with certain active compounds to form synergistic mixtures where the mode of action of such compounds compared to the mode of action of the molecules of Formula One are the same, similar, or different. Examples of modes of action include, but are not limited to: acetylcholinesterase inhibitor; sodium channel modulator; chitin biosynthesis inhibitor; GABA and glutamate-gated chloride channel 30 antagonist; GABA and glutamate-gated chloride channel agonist; acetylcholine receptor agonist; acetylcholine receptor antagonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholine receptor; Midgut membrane disrupter; oxidative phosphorylation disrupter, and ryanodine receptor (RyRs). Generally, weight ratios of the molecules of 111 Formula One in a synergistic mixture with another compound are from about 10:1 to about 1:10, in another embodiment from about 5:1 to about 1:5, and in another embodiment from about 3:1, and in another embodiment about 1:1. 5 FORMULATIONS A pesticide is rarely suitable for application in its pure form. It is usually necessary to add other substances so that the pesticide can be used at the required concentration and in an appropriate form, permitting ease of application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, 10 concentrated emulsions, dusts, emulsifiable concentrates, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra low volume solutions. For further information on formulation types see "Catalogue of Pesticide Formulation Types and International Coding System" Technical Monograph n 0 2, 15 5th Edition by CropLife International (2002). Pesticides are applied most often as aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrates, or aqueous 20 suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants. The concentration of the pesticide is usually from about 10% to about 90% by weight. The carrier is usually selected from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 25 10% of the wettable powder, are found among sulfonated lignins, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phenols. Emulsifiable concentrates of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier 30 that is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic 112 solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are selected from conventional anionic and non-ionic surfactants. Aqueous suspensions comprise suspensions of water-insoluble pesticides dispersed in 5 an aqueous carrier at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. Ingredients, such as inorganic salts and synthetic or natural gums may also be added, to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing 10 the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer. Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. 15 Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size. 20 Dusts containing a pesticide are prepared by intimately mixing the pesticide in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide. They can be applied as a seed dressing or as a foliage application with a dust blower machine. It is equally practical to apply a pesticide in the form of a solution in an appropriate 25 organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry. Pesticides can also be applied in the form of an aerosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressure generating propellant mixture. The aerosol composition is packaged in a container from 30 which the mixture is dispensed through an atomizing valve. Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When the pests eat the bait they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. They can be used in pest harborages. 113 Fumigants are pesticides that have a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest's respiratory system or being 5 absorbed through the pest's cuticle. Fumigants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in special chambers. Pesticides can be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various types. By altering the chemistry of the polymer or by changing factors in the processing, microcapsules can be formed of various sizes, solubility, wall 10 thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingredient within is released, which in turn, affects the residual performance, speed of action, and odor of the product. Oil solution concentrates are made by dissolving pesticide in a solvent that will hold the pesticide in solution. Oil solutions of a pesticide usually provide faster knockdown and 15 kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide. Other advantages of oil solutions include better storage stability, better penetration of crevices, and better adhesion to greasy surfaces. Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises 20 oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one compound which is agriculturally active, and is individually coated with a monolamellar or oligolamellar layer comprising: (1) at least one non-ionic lipophilic surface-active agent, (2) at least one non ionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein 25 the globules having a mean particle diameter of less than 800 nanometers. Further information on the embodiment is disclosed in U.S. patent publication 20070027034 published February 1, 2007, having Patent Application serial number 11/495,228. For ease of use, this embodiment will be referred to as "OIWE". For further information consult "Insect Pest Management" 2nd Edition by D. Dent, 30 copyright CAB International (2000). Additionally, for more detailed information consult "Handbook of Pest Control - The Behavior, Life History, and Control of Household Pests" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc. 114 OTHER FORMULATION COMPONENTS Generally, when the molecules disclosed in Formula One are used in a formulation, such formulation can also contain other components. These components include, but are not limited to, (this is a non-exhaustive and non-mutually exclusive list) wetters, spreaders, 5 stickers, penetrants, buffers, sequestering agents, drift reduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith. A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the 10 surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of 15 wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauryl sulfate; sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates. A dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from reaggregating. 20 Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water dispersible granules. Surfactants that are used as dispersing agents have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of 25 particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Non-ionics such as 30 alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersing agents. These have very long hydrophobic 'backbones' and a large number of ethylene oxide chains 115 forming the 'teeth' of a 'comb' surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersing agents used in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate 5 formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers. An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends 10 contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oil soluble calcium salt of dodecylbenzenesulfonic acid. A range of hydrophile-lipophile balance ("HLB") values from 8 to 18 will normally provide good stable emulsions. Emulsion stability can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant. 15 A solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobic part of the micelle. The types of surfactants usually used for solubilization are non-ionics, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyl oleate esters. 20 Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to spray-tank mixes to improve the biological performance of the pesticide on the target. The types of surfactants used for bioenhancement depend generally on the nature and mode of action of the pesticide. However, they are often non-ionics such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates. 25 A carrier or diluent in an agricultural formulation is a material added to the pesticide to give a product of the required strength. Carriers are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and water dispersible granules. 30 Organic solvents are used mainly in the formulation of emulsifiable concentrates, oil in-water emulsions, suspoemulsions, and ultra low volume formulations, and to a lesser extent, granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are aliphatic paraffinic oils such as kerosene or refined paraffins. The second main 116 group (and the most common) comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power. 5 Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils. Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble 10 particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds or 15 are synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum. 20 Microorganisms can cause spoilage of formulated products. Therefore preservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt; methyl p hydroxybenzoate; and 1,2-benzisothiazolin-3 -one (BIT). 25 The presence of surfactants often causes water-based formulations to foam during mixing operations in production and in application through a spray tank. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane, while 30 the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface. 117 "Green" agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection formulations. Green agents are biodegradable and generally derived from natural and/or sustainable sources, e.g. plant and animal sources. Specific examples are: vegetable oils, seed oils, and esters thereof, also alkoxylated alkyl 5 polyglucosides. For further information, see "Chemistry and Technology of Agrochemical Formulations" edited by D.A. Knowles, copyright 1998 by Kluwer Academic Publishers. Also see "Insecticides in Agriculture and Environment - Retrospects and Prospects" by A.S. Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag. 10 PESTS In general, the molecules of Formula One may be used to control pests e.g. beetles, earwigs, cockroaches, flies. aphids, scales, whiteflies, leafhoppers, ants, wasps, termites, moths, butterflies, lice, grasshoppers, locusts, crickets, fleas, thrips, bristletails, mites, ticks, 15 nematodes, and symphylans. In another embodiment, the molecules of Formula One may be used to control pests in the Phyla Nematoda and/or Arthropoda. In another embodiment, the molecules of Formula One may be used to control pests in the Subphyla Chelicerata, Myriapoda, and/or Hexapoda. 20 In another embodiment, the molecules of Formula One may be used to control pests in the Classes of Arachnida, Symphyla, and/or Insecta. In another embodiment, the molecules of Formula One may be used to control pests of the Order Anoplura. A non-exhaustive list of particular genera includes, but is not limited to, Haematopinus spp., Hoplopleura spp., Linognathus spp., Pediculus spp., and Polyplax 25 spp. A non-exhaustive list of particular species includes, but is not limited to, Haematopinus asini, Haematopinus suis, Linognathus setosus, Linognathus ovillus, Pediculus humanus capitis, Pediculus humanus humanus, and Pthirus pubis. In another embodiment, the molecules of Formula One may be used to control pests in the Order Coleoptera. A non-exhaustive list of particular genera includes, but is not limited 30 to, Acanthoscelides spp., Agriotes spp., Anthonomus spp., Apion spp., Apogonia spp., Aulacophora spp., Bruchus spp., Cerosterna spp., Cerotoma spp., Ceutorhynchus spp., Chaetocnema spp., Colaspis spp., Ctenicera spp., Curculio spp., Cyclocephala spp., Diabrotica spp., Hypera spp., Ips spp., Lyctus spp., Megascelis spp., Meligethes spp., 118 Otiorhynchus spp., Pantomorus spp., Phyllophaga spp., Phyllotreta spp., Rhizotrogus spp., Rhynchites spp., Rhynchophorus spp., Scolytus spp., Sphenophorus spp., Sitophilus spp., and Tribolium spp. A non-exhaustive list of particular species includes, but is not limited to, Acanthoscelides obtectus, Agrilus planipennis, Anoplophora glabripennis, Anthonomus 5 grandis, Ataenius spretulus, Atomaria linearis, Bothynoderes punctiventris, Bruchus pisorum, Callosobruchus maculatus, Carpophilus hemipterus, Cassida vittata, Cerotoma trifurcata, Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderus scalaris, Conoderus stigmosus, Conotrachelus nenuphar, Cotinis nitida, Crioceris asparagi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptolestes turcicus, Cylindrocopturus adspersus, 10 Deporaus marginatus, Dermestes lardarius, Dermestes maculatus, Epilachna varivestis, Faustinus cubae, Hylobius pales, Hypera postica, Hypothenemus hampei, Lasioderma serricorne, Leptinotarsa decemlineata, Liogenysfuscus, Liogenys suturalis, Lissorhoptrus oryzophilus, Maecolaspis joliveti, Melanotus communis, Meligethes aeneus, Melolontha melolontha, Oberea brevis, Oberea linearis, Oryctes rhinoceros, Oryzaephilus mercator, 15 Oryzaephilus surinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga cuyabana, Popilliajaponica, Prostephanus truncatus, Rhyzopertha dominica,, Sitona lineatus, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum, Tribolium castaneum, Tribolium confusum, Trogoderma variabile, and Zabrus tenebrioides. In another embodiment, the molecules of Formula One may be used to control pests of 20 the Order Dermaptera. In another embodiment, the molecules of Formula One may be used to control pests of the Order Blattaria. A non-exhaustive list of particular species includes, but is not limited to, Blattella germanica, Blatta orientalis, Parcoblatta pennsylvanica, Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplanetafuliginosa, Pycnoscelus 25 surinamensis, and Supella longipalpa. In another embodiment, the molecules of Formula One may be used to control pests of the Order Diptera. A non-exhaustive list of particular genera includes, but is not limited to, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Bactrocera spp., Ceratitis spp., Chrysops spp., Cochliomyia spp., Contarinia spp., Culex spp., Dasineura spp., Delia spp., 30 Drosophila spp., Fannia spp., Hylemyia spp., Liriomyza spp., Musca spp., Phorbia spp., Tabanus spp., and Tipula spp. A non-exhaustive list of particular species includes, but is not limited to, Agromyza frontella, Anastrepha suspensa, Anastrepha ludens, Anastrepha obliqa, Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera invadens, Bactrocera zonata, 119 Ceratitis capitata, Dasineura brassicae, Delia platura, Fannia canicularis, Fannia scalaris, Gasterophilus intestinalis, Gracillia perseae, Haematobia irritans, Hypoderma lineatum, Liriomyza brassicae, Melophagus ovinus, Musca autumnalis, Musca domestica, Oestrus ovis, Oscinella frit, Pegomya betae, Psila rosae, Rhagoletis cerasi, Rhagoletis pomonella, 5 Rhagoletis mendax, Sitodiplosis mosellana, and Stomoxys calcitrans. In another embodiment, the molecules of Formula One may be used to control pests of the Order Hemiptera. A non-exhaustive list of particular genera includes, but is not limited to, Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia spp., Ceroplastes spp., Chionaspis spp., Chrysomphalus spp., Coccus spp., Empoasca spp., Lepidosaphes spp., 10 Lagynotomus spp., Lygus spp., Macrosiphum spp., Nephotettix spp., Nezara spp., Philaenus spp., Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp., Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp., Toxoptera spp., Trialeurodes spp., Triatoma spp. and Unaspis spp. A non-exhaustive list of particular species includes, but is not limited to, Acrosternum hilare, Acyrthosiphon pisum, Aleyrodes proletella, Aleurodicus 15 dispersus, Aleurothrixusfloccosus, Amrasca biguttula biguttula, Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphis pomi, Aulacorthum solani, Bemisia argentifolii, Bemisia tabaci, Blissus leucopterus, Brachycorynella asparagi, Brevennia rehi, Brevicoryne brassicae, Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus, Cimex lectularius, Dagbertusfasciatus, Dichelopsfurcatus, Diuraphis noxia, Diaphorina citri, Dysaphis 20 plantaginea, Dysdercus suturellus, Edessa meditabunda, Eriosoma lanigerum, Eurygaster maura, Euschistus heros, Euschistus servus, Helopeltis antonii, Helopeltis theivora, Icerya purchasi, Idioscopus nitidulus, Laodelphax striatellus, Leptocorisa oratorius, Leptocorisa varicornis, Lygus hesperus, Maconellicoccus hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium, Macrosiphum rosae, Macrosteles quadrilineatus, Mahanarva 25 frimbiolata, Metopolophium dirhodum, Mictis longicornis, Myzus persicae, Nephotettix cinctipes, Neurocolpus longirostris, Nezara viridula, Nilaparvata lugens, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis, Phylloxera vitifoliae, Physokermes piceae,, Phytocoris californicus, Phytocoris relativus, Piezodorus guildinii, Poecilocapsus lineatus, Psallus vaccinicola, Pseudacysta perseae, Pseudococcus brevipes, Quadraspidiotus 30 perniciosus, Rhopalosiphum maidis, Rhopalosiphum padi, Saissetia oleae, Scaptocoris castanea, Schizaphis graminum, Sitobion avenae, Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodes abutiloneus, Unaspis yanonensis, and Zulia entrerriana. 120 In another embodiment, the molecules of Formula One may be used to control pests of the Order Hymenoptera. A non-exhaustive list of particular genera includes, but is not limited to, Acromyrmex spp., Atta spp., Camponotus spp., Diprion spp., Formica spp., Monomorium spp., Neodiprion spp., Pogonomyrmex spp., Polistes spp., Solenopsis spp., 5 Vespula spp., and Xylocopa spp. A non-exhaustive list of particular species includes, but is not limited to, Athalia rosae, Atta texana, Iridomyrmex humilis, Monomorium minimum, Monomorium pharaonis, Solenopsis invicta, Solenopsis geminata, Solenopsis molesta, Solenopsis richtery, Solenopsis xyloni, and Tapinoma sessile. In another embodiment, the molecules of Formula One may be used to control pests of 10 the Order Isoptera. A non-exhaustive list of particular genera includes, but is not limited to, Coptotermes spp., Cornitermes spp., Cryptotermes spp., Heterotermes spp., Kalotermes spp., Incisitermes spp., Macrotermes spp., Marginitermes spp., Microcerotermes spp., Procornitermes spp., Reticulitermes spp., Schedorhinotermes spp., and Zootermopsis spp. A non-exhaustive list of particular species includes, but is not limited to, Coptotermes 15 curvignathus, Coptotermes frenchi, Coptotermes formosanus, Heterotermes aureus, Microtermes obesi, Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes tibialis, and Reticulitermes virginicus. In another embodiment, the molecules of Formula One may be used to control pests of 20 the Order Lepidoptera. A non-exhaustive list of particular genera includes, but is not limited to, Adoxophyes spp., Agrotis spp., Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp., Diatraea spp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gortyna spp., Helicoverpa spp., Heliothis spp., Indarbela spp., Lithocolletis spp., Loxagrotis spp., Malacosoma spp., 25 Peridroma spp., Phyllonorycter spp., Pseudaletia spp., Sesamia spp., Spodoptera spp., Synanthedon spp., and Yponomeuta spp. A non-exhaustive list of particular species includes, but is not limited to, Achaea janata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbia cuneana, Amyelois transitella, Anacamptodes defectaria, Anarsia lineatella, Anomis sabulifera, Anticarsia gemmatalis, Archips argyrospila, Archips rosana, Argyrotaenia 30 citrana, Autographa gamma, Bonagota cranaodes, Borbo cinnara, Bucculatrix thurberiella, Capua reticulana, Carposina niponensis, Chlumetia transversa, Choristoneura rosaceana, Cnaphalocrocis medinalis, Conopomorpha cramerella, Cossus cossus, Cydia caryana, Cydia funebrana, Cydia molesta, Cydia nigricana, Cydia pomonella, Darna diducta, Diatraea 121 saccharalis, Diatraea grandiosella, Earias insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpus lignosellus, Ephestia cautella, Ephestia elutella, Ephestia kuehniella, Epinotia aporema, Epiphyas postvittana, Erionota thrax, Eupoecilia ambiguella, Euxoa auxiliaris, Grapholita molesta, Hedylepta indicata, Helicoverpa armigera, 5 Helicoverpa zea, Heliothis virescens, Hellula undalis, Keiferia lycopersicella, Leucinodes orbonalis, Leucoptera coffeella, Leucoptera malifoliella, Lobesia botrana, Loxagrotis albicosta, Lymantria dispar, Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae, Maruca testulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis, Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydia vesulia, Pandemis cerasana, 10 Pandemis heparana, Papilio demodocus, Pectinophora gossypiella, Peridroma saucia, Perileucoptera coffeella, Phthorimaea operculella, Phyllocnistis citrella, Pieris rapae, Plathypena scabra, Plodia interpunctella, Plutella xylostella, Polychrosis viteana, Prays endocarpa, Prays oleae, Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia nu, Scirpophaga incertulas, Sesamia inferens, Sesamia nonagrioides, Setora nitens, Sitotroga 15 cerealella, Sparganothis pilleriana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera eridania, Thecla basilides, Tineola bisselliella, Trichoplusia ni, Tuta absoluta, Zeuzera coffeae, and Zeuzera pyrina. In another embodiment, the molecules of Formula One may be used to control pests of the Order Mallophaga. A non-exhaustive list of particular genera includes, but is not limited 20 to, Anaticola spp., Bovicola spp., Chelopistes spp., Goniodes spp., Menacanthus spp., and Trichodectes spp. A non-exhaustive list of particular species includes, but is not limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis, Chelopistes meleagridis, Goniodes dissimilis, Goniodes gigas, Menacanthus stramineus, Menopon gallinae, and Trichodectes canis. 25 In another embodiment, the molecules of Formula One may be used to control pests of the Order Orthoptera. A non-exhaustive list of particular genera includes, but is not limited to, Melanoplus spp., and Pterophylla spp. A non-exhaustive list of particular species includes, but is not limited to, Anabrus simplex, Gryllotalpa africana, Gryllotalpa australis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla, Locusta migratoria, Microcentrum 30 retinerve, Schistocerca gregaria, and Scudderiafurcata. In another embodiment, the molecules of Formula One may be used to control pests of the Order Siphonaptera. A non-exhaustive list of particular species includes, but is not 122 limited to, Ceratophyllus gallinae, Ceratophyllus niger, Ctenocephalides canis, Ctenocephalidesfelis, and Pulex irritans. In another embodiment, the molecules of Formula One may be used to control pests of the Order Thysanoptera. A non-exhaustive list of particular genera includes, but is not 5 limited to, Caliothrips spp., Frankliniella spp., Scirtothrips spp., and Thrips spp. A non exhaustive list of particular sp. includes, but is not limited to, Frankliniellafusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella williamsi, Heliothrips haemorrhoidalis, Rhipiphorothrips cruentatus, Scirtothrips citri, Scirtothrips dorsalis, and Taeniothrips rhopalantennalis, Thrips hawaiiensis, Thrips nigropilosus, Thrips orientalis, 10 Thrips tabaci. In another embodiment, the molecules of Formula One may be used to control pests of the Order Thysanura. A non-exhaustive list of particular genera includes, but is not limited to, Lepisma spp. and Thermobia spp. In another embodiment, the molecules of Formula One may be used to control pests of 15 the Order Acarina. A non-exhaustive list of particular genera includes, but is not limited to, Acarus spp., Aculops spp., Boophilus spp., Demodex spp., Dermacentor spp., Epitrimerus spp., Eriophyes spp., Ixodes spp., Oligonychus spp., Panonychus spp., Rhizoglyphus spp., and Tetranychus spp. A non-exhaustive list of particular species includes, but is not limited to, Acarapis woodi, Acarus siro, Aceria mangiferae, Aculops lycopersici, Aculus pelekassi, 20 Aculus schlechtendali, Amblyomma americanum, Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentor variabilis, Dermatophagoides pteronyssinus, Eotetranychus carpini, Notoedres cati, Oligonychus coffeae, Oligonychus ilicis, Panonychus citri, Panonychus ulmi, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalus sanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychus urticae, and Varroa destructor. 25 In another embodiment, the molecules of Formula One may be used to control pest of the Order Symphyla. A non-exhaustive list of particular sp. includes, but is not limited to, Scutigerella immaculata. In another embodiment, the molecules of Formula One may be used to control pests of the Phylum Nematoda. A non-exhaustive list of particular genera includes, but is not limited 30 to, Aphelenchoides spp., Belonolaimus spp., Criconemella spp., Ditylenchus spp., Heterodera spp., Hirschmanniella spp., Hoplolaimus spp., Meloidogyne spp., Pratylenchus spp., and Radopholus spp. A non-exhaustive list of particular sp. includes, but is not limited to, 123 Dirofilaria immitis, Heterodera zeae, Meloidogyne incognita, Meloidogynejavanica, Onchocerca volvulus, Radopholus similis, and Rotylenchulus reniformis. For additional information consult "HANDBOOK OF PEST CONTROL - THE BEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS" by Arnold Mallis, 9th 5 Edition, copyright 2004 by GIE Media Inc. APPLICATIONS Molecules of Formula One are generally used in amounts from about 0.01 grams per hectare to about 5000 grams per hectare to provide control. Amounts from about 0.1 grams 10 per hectare to about 500 grams per hectare are generally preferred, and amounts from about 1 gram per hectare to about 50 grams per hectare are generally more preferred. The area to which a molecule of Formula One is applied can be any area inhabited (or maybe inhabited, or traversed by) a pest, for example: where crops, trees, fruits, cereals, fodder species, vines, turf and ornamental plants, are growing; where domesticated animals 15 are residing; the interior or exterior surfaces of buildings (such as places where grains are stored), the materials of construction used in building (such as impregnated wood), and the soil around buildings. Particular crop areas to use a molecule of Formula One include areas where apples, corn, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, crucifers, pears, tobacco, 20 almonds, sugar beets, beans and other valuable crops are growing or the seeds thereof are going to be planted. It is also advantageous to use ammonium sulfate with a molecule of Formula One when growing various plants. Controlling pests generally means that pest populations, pest activity, or both, are reduced in an area. This can come about when: pest populations are repulsed from an area; 25 when pests are incapacitated in or around an area; or pests are exterminated, in whole, or in part, in or around an area. Of course, a combination of these results can occur. Generally, pest populations, activity, or both are desirably reduced more than fifty percent, preferably more than 90 percent. Generally, the area is not in or on a human; consequently, the locus is generally a non-human area. 30 The molecules of Formula One may be used in mixtures, applied simultaneously or sequentially, alone or with other compounds to enhance plant vigor (e.g. to grow a better root system, to better withstand stressful growing conditions). Such other compounds are, for example, compounds that modulate plant ethylene receptors, most notably 1 124 methylcyclopropene (also known as 1 -MCP). Furthermore, such molecules may be used during times when pest activity is low, such as before the plants that are growing begin to produce valuable agricultural commodities. Such times include the early planting season when pest pressure is usually low. 5 The molecules of Formula One can be applied to the foliar and fruiting portions of plants to control pests. The molecules will either come in direct contact with the pest, or the pest will consume the pesticide when eating leaf, fruit mass, or extracting sap, that contains the pesticide. The molecules of Formula One can also be applied to the soil, and when applied in this manner, root and stem feeding pests can be controlled. The roots can absorb a 10 molecule taking it up into the foliar portions of the plant to control above ground chewing and sap feeding pests. Generally, with baits, the baits are placed in the ground where, for example, termites can come into contact with, and/or be attracted to, the bait. Baits can also be applied to a surface of a building, (horizontal, vertical, or slant surface) where, for example, ants, termites, 15 cockroaches, and flies, can come into contact with, and/or be attracted to, the bait. Baits can comprise a molecule of Formula One. The molecules of Formula One can be encapsulated inside, or placed on the surface of a capsule. The size of the capsules can range from nanometer size (about 100-900 nanometers in diameter) to micrometer size (about 10-900 microns in diameter). 20 Because of the unique ability of the eggs of some pests to resist certain pesticides, repeated applications of the molecules of Formula One may be desirable to control newly emerged larvae. Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying (for example by spraying an area) the molecules of Formula 25 One to a different portion of the plant. For example, control of foliar-feeding insects can be achieved by drip irrigation or furrow application, by treating the soil with for example pre- or post-planting soil drench, or by treating the seeds of a plant before planting. Seed treatment can be applied to all types of seeds, including those from which plants genetically modified to express specialized traits will germinate. Representative examples 30 include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, those expressing herbicide resistance, such as "Roundup Ready" seed, or those with "stacked" foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, drought resistance, or any other beneficial traits. 125 Furthermore, such seed treatments with the molecules of Formula One may further enhance the ability of a plant to better withstand stressful growing conditions. This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time. Generally, about 1 gram of the molecules of Formula One to about 500 grams per 100,000 seeds is 5 expected to provide good benefits, amounts from about 10 grams to about 100 grams per 100,000 seeds is expected to provide better benefits, and amounts from about 25 grams to about 75 grams per 100,000 seeds is expected to provide even better benefits. It should be readily apparent that the molecules of Formula One may be used on, in, or around plants genetically modified to express specialized traits, such as Bacillus thuringiensis 10 or other insecticidal toxins, or those expressing herbicide resistance, or those with "stacked" foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, or any other beneficial traits. The molecules of Formula One may be used for controlling endoparasites and ectoparasites in the veterinary medicine sector or in the field of non-human animal keeping. 15 The molecules of Formula One are applied, such as by oral administration in the form of, for example, tablets, capsules, drinks, granules, by dermal application in the form of, for example, dipping, spraying, pouring on, spotting on, and dusting, and by parenteral administration in the form of, for example, an injection. The molecules of Formula One may also be employed advantageously in livestock 20 keeping, for example, cattle, sheep, pigs, chickens, and geese. They may also be employed advantageously in pets such as, horses, dogs, and cats. Particular pests to control would be fleas and ticks that are bothersome to such animals. Suitable formulations are administered orally to the animals with the drinking water or feed. The dosages and formulations that are suitable depend on the species. 25 The molecules of Formula One may also be used for controlling parasitic worms, especially of the intestine, in the animals listed above. The molecules of Formula One may also be employed in therapeutic methods for human health care. Such methods include, but are limited to, oral administration in the form of, for example, tablets, capsules, drinks, granules, and by dermal application. 30 Pests around the world have been migrating to new environments (for such pest) and thereafter becoming a new invasive species in such new environment. The molecules of Formula One may also be used on such new invasive species to control them in such new environment. 126 The molecules of Formula One may also be used in an area where plants, such as crops, are growing (e.g. pre-planting, planting, pre-harvesting) and where there are low levels (even no actual presence) of pests that can commercially damage such plants. The use of such molecules in such area is to benefit the plants being grown in the area. Such benefits, may 5 include, but are not limited to, improving the health of a plant, improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingredients), improving the vigor of a plant (e.g. improved plant growth and/or greener leaves), improving the quality of a plant (e.g. improved content or composition of certain ingredients), and improving the tolerance to abiotic and/or biotic stress of the plant. 10 Before a pesticide can be used or sold commercially, such pesticide undergoes lengthy evaluation processes by various governmental authorities (local, regional, state, national, and international). Voluminous data requirements are specified by regulatory authorities and must be addressed through data generation and submission by the product registrant or by a third party on the product registrant's behalf, often using a computer with a connection to the 15 World Wide Web. These governmental authorities then review such data and if a determination of safety is concluded, provide the potential user or seller with product registration approval. Thereafter, in that locality where the product registration is granted and supported, such user or seller may use or sell such pesticide. A molecule according to Formula One can be tested to determine its efficacy against 20 pests. Furthermore, mode of action studies can be conducted to determine if said molecule has a different mode of action than other pesticides. Thereafter, such acquired data can be disseminated, such as by the internet, to third parties. The headings in this document are for convenience only and must not be used to interpret any portion hereof. 25 TABLE SECTION Table 1: Compound number, appearance, and structure Com pound Appearance Structure No. 127
CH
3 N-N/ CH3 N 1 yellow gum N H 3
CH
3 NN N-N CH3 O CH 3 N \IC H 3 3 yellow gum NH C3 N-N / ClH 3 N 4 yellow oil N CH 3 128
/CH
3 F F N-N N-N F N 5 yellow oil NI' CH 3 N CH30, 0 CH\ 7 yellow gum N N-N 0 C H / N H CH 3 CO C HH, 8 yellow gum N 129 C H N-N/ 0 CH 3 ZN 9 beige gum NH3 C H NN/ C30 CH, N-NC 10 colorless gum N Br CH3 CH3 O N-N
CH
3 "7N 12 colorless glass ClH 3 N Br CH 3
H
3 C N-N O CH 3 "N N
CH
3 18 Brown oil N
CH
3 130
H
3 C\ 0N-N
CH
3 N 19 Yellow oil N CH 3
H
3 C \ O N-N
CH
3 20 Yellow oil C H CH 3 N H 3 C \ -0 H N-N N 21 Yellow oil N H 3 22 clear oil
CH
3 1- 3 C N 131 f~l30
CH
3 23 clear oil N/ CH 3 IH3 C N 0 CH 0 24
C
3 N H, C' N 25
H
3 C" 0 N :
H
3 c H 3 C'N~ CH, N N
H
3 C N 26 HC N/j H 3 C N-N
H
3 C 132 N s0 N N/ 27 I
H
3 C N--N
H
3 C N 0 0 N Y 28
H
3 C N'N
H
3 C N 0 N-s N 29
H
3 C N--N
H
3 C N 0 0 N 30HH3C N-N 30 H 3
CH
3 C 133
CH
3 / 0 0 N-N N- S L 31 H"3 C N 0 CH IS CH 32 Gold syrup N H 0 N- C H 3 N 33 Brown solid N H N O
CH
3 N N
CH
3 34 Off white solid N H N 134 o
CH
3 N
CH
3 N CH3 35 Off white solid - N 0 N F 36 Off white solid NF F N 0 37 White solid N CN H 3C--O 0 38 Off white solid I NH N 135
H
3 C-S 0 39 White solid N N N N0 Pale yellow N H solid CN 41 Brown thick N / CH3 mass N H 0 CH3 N N CH 3 Pale yellow N CH 3 semi solid C H3 N 136 0 .N -F Pale yellow N N F F 43 solid CH3F F
H
3 C-S 0 44I N 44 White solid N N N \C H 3 O C H 1 \ / N H Brown thick N N
CH
3 mass
CH
3 N
H
3 C H 33 N ~ CH 3 46 Pale yellow N N
CH
3 thick mass 0
CH
3 N 137
H
3 C
CH
3 N N 47 Pale yellow N thick mass N
H
3 C-S
H
3 C / 48 Pale green N thick mass
H
3 C-S O N
-CH
3 49 Pale yellow N / solid
CH
3 H 3
C
N 50 Brown thick NCH 3 mass 0 CfH 3 N 138
H
3 C-S 0 Np 51 Pale yellow N C H3 thick mass N
CH
3 N 0 NN 52 tan solid
CH
3 N 53 White Solid N H H 3C CH 3 /CH 3 0 /C S N N
CH
3 54 Clear Oil N / 3 139 0
CH
3 N White Semi N CH 3 Solid
H
3 C N
H
3 C 0 s' CH3
N
56 Brown Solid N N O
H
3 C CH 3 N O CH 3 57 White Solid H N
CH
3 o CH 3
CH
3
N
N H CH 3 58 Clear Oil N 140
CH
3 0 CH 3 N NCH3 59 White Solid I H
CH
3 0
CH
3
N
N N CH 3 60 White Solid N H CH 3 I N
CH
3 0 CH 3 S
N
61 Light Yellow N / H Solid I
H
3 C CH 3 H
S-CH
3 N
H
3 C 0 62 Clear Oil N N N 141
H
3 C 63 Light Yellow N H CH 3 Solid NN C3OH 3 C H 64 White Solid N H NO F -N /- F 65 White Solid H CH 3 N a
S-CH
3 H N -- 66 White Semi Solid NN 142 O
H
3 C CH3 Yellow Semi o CH 3 67 N / \ Solid
CH
3 I N
H
3 C CH 3 Cl O
CH
3 N- -O 68 Clear Oil N / N CH 3
CH
3 N C' 0 69 Dark Brown N \ CH3 Oil I clI N F F CN O 70 Viscous Pale N / N\ CH 3 Yellow Oil C H 3 143 Cl O Cl NN 71 White Solid N I aN'
H
3 C /CH 3 / 3 C White Semi Solid N N CH 3
H
3 C N
CH
3 0 CH 3 NCH 73 White Semi N CH3 Solid
CH
3 N CH3 0 /CH3 N-N 74 Clear Oil
CH
3 144 CH3 0 / CH 3 NS White Semi N CH 3 Solid CH 3 N
CH
3 0
CH
3 sCH3 NN 76 Clear Oil N C H CH 3 C H 3 Cl O /CH3 N 77 White Solid N H N CI 0 C3 S N 78 White Solid N/j N 145 C1 0 CH3 N N / H CH 3 79 White Solid I S Cl o ClH- 3 80 White Solid N / 4 C H 3 F F 0 F 81 White Solid N / N N. H3 I N F FF
F
0 F N 82 White Solid N 146 146 F F 0
CH
3 83 White Solid N H CH 3 I N F F
F
0
CH
3 N 84 White Solid N / NH CH 3 N
CH
3 0 /H3 S F N 85 Off-White H 85 SolidI N
CH
3 O H 3 C CH 3 -' O CH 3 86 Yellow Solid N N 7H 3 C 147
CH
3 O H 3 C CH 3 N CH 3 87 Yellow Solid N
CH
3 F F F 0
CH
3 N 88 White Solid N / N\ CH
CH
3 N
CH
3 0
H
3 C CH 3 - CH 3 89 White Solid N N
CH
3
H
3 C N
CH
3 O H 3 C CH 3 S\ CH 3 90 Clear Oil N 148 F F 0 / H 3 N F Faint Yellow N 91 Oil N C H
CH
3 I N F F
O
0 /FC H 3 Faint Yellow IN 92 Oil N CH3
CH
3 I N
CH
3 0 CH 3
N
93 White Solid N / ClH 3 H I3 C N CH3 0 / CH 3 S
N-
NN 94 Clear Oil N N4
CH
3 149 CH3 0 / CH 3 S aN. 95 Clear Oil N CH3 0
/CH
3 S
N
96 Yellow Solid N I aN-H 3 C CH3 0
/CH
3 N-N 97 Yellow Oil / N H- 3
H
3 C N cl- 3 0 Id- 3
N
N/-N 98 Yellow Oil 3 C H3 150 99 Yellow Solid N N C N NC O SH 100 Clear Oil C H . 33 N
CH
3
CH
3 0 N-- 0 101 Clear Oil N C CN I
H
3 C
CH
3
CH
3 0 s N-- 0 102 Clear Oil N - CH 3 5H 3 C N 151
CH
3
CH
3 0 S- 0 N-- 0 103 Clear Oil N N HC
H
3 C
CH
3
CH
3 o s- 0 N-- 0 104 Faint Yellow I N CH3 Oil N C/ 3
H
3 C/ N
CH
3 0 CH3 S 15 Off-White F N 105 SolidICH N 0 C3 S 106 Faint Yellow N Oil N
CH
3 I N 152
CH
3 0
CH
3
N
N H 107 White Solid N H CH 3 CH3 / H S Cl 3C N 108 Clear Oil 13 N ' a N H CH3 N O H3C CH3 N- O CH3 N N N 109 Yellow Solid N~ OCH3
H
3 C O
H
3 C CH3 N---- CH 3 110 Brown Oil N
CH
3 Br N 153
CH
3 O H3C CH3 O CH3 F N/~N 111 Yellow Solid FTN CH3 O H3CCH O CH3 112 Brown Oil H NO
CH
3 0 /H3 S NN N/ 113 Yellow Oil CH3 I aN- Br CH3 O H 3 C CH 3 F N N O CH3 N 114 Brown Oil CH3 154 CH3 O H 3 C CH3 O" CH3 115 Light Brown F N N Solid CH3 NT
CH
3 O H3C H3 NCH3 116 Yellow Solid F N/ N
H
3 C O /CH3 N N
CH
3 117 Yellow Oil CH3 NO 0 H N -C I 118 Brown Oil NB CH3 H3 Br 155
CH
3 0 CH 3 S F N N 119 Brown Oil CH 3
CH
3
CH
3 0 /CH 3 NS F N g CH 3 120 Brown Oil CH 3
CH
3
CH
3 0 CH 3 N X -N 121 Off-White F N / CH CH 3 Solid N
CH
3 N
CH
3 Faint Yellow F N \ CH 3 122 Solid
CH
3 N 156 CH3 0 CH, F__ N/ N 123 Clear Oil K-
H
3 C
CH
3 0 CH3 F N
CH
3 124 Yellow Solid
H
3 C
CH
3 CH3 rN"
H
3 C N N H CH3 126 Yellow Oil 5C H 3 157
CH
3 0 CH 3 127 Yellow Oil N C H 3
CH
3 0 CH3 S NN Neon Yellow / N 128 Oil I
CH
3
N
CH
3 0 /3 N-N NI 19 Neon Yellow / g CUH 3 19Oil F CH 3
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3 C N CH, 0 130 Pink Solid N / H N 158
CH
3 0 /H3 131 Red Oil N CH 3
CH
3 0 CH3 S N/ N 132 Yellow Oil
CH
3 Br Cl O / CH 3 0 3 133 Yellow Oil N/CH 3
H
3 C N Cl 0
/CH
3 NN N/N 134 Clear Oil
H
3 C N 159 O H 3 C CH3 - O CH 3 135 Off-White N / N Solid F 0O
H
3 C CH 3 CH3 H 3 C CH3 N N _N CHA Fj_ N/N 136 Yellow Oil FNCH3 I 3 N HH 1 3 C /CIA 3
CH
0 / N. 137 Yellow Oil 143 F F
CH
3 O F S 138 Yellow Oil F NN
CH
3 160
CH
3 0 /H3 S Faint Yellow N / 139 Oil C CH3 NN N /
CH-
3 140 Faint Yellow NC C H3 I N
H
3 C
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CH
3 O
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3 N O 141 Light Yellow | N Solid
CH
2 N Cl 0 C 3 F N/-N
CH
3 142 Clear Oil H3C N 161
CH
3
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3 O S NN 143 Colorless Oil |N
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2 N
CH
3
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3 O S 144 Colorless Oil |NN CH3
CH
2 N N H- /-C H N- N H ) 145 White Solid CH3 O H3C CH3
OCH
3 146 Gray Oil N C H 3 162 F
CH
3 F N O F 147 Colorless Oil N/ N NN CH 2
CH
3 O CH3 I -N CH 3 148 White Solid N / CXH N
H
3 C CH 3
CH
3 0
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3 149 Yellow Solid F N / N C- H 2 N ci 0 H 3C CH 3
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3 150 White Solid F N H N 163
H
3 C CH 3
N
151 Clear Oil N C H CH 3 I3 ON C H -CH3 F N 153 Whe SOl
CH
3 CH3 0 F F 152 F a Oai l N / \ C N
CH
3 0 F NF /3 F 15 aWite Olidg N CHI Oil CH 3 1 6 164 CH3 0 /CH3 N 3S I / N
CH
3 155 Clear Oil
H
3 C C30H3C /CH3 N 156 Clear Oil N /) CH 3 N
H
3 C C H 3 C / H 157 Clear Oil N
H
3 C N
CH
3 F F 158 Clear Oil N I aN'H 3 C 165
CH
3 o F 3NOF 159 Clear Oil N
CH
3
H
3 C cl O CH 3 N.. F N X N 160 White Solid H 3 C NF Cl O H 3 C CH 3 N0 161 Brown Oil F N / "r H 3 C N ci0H 3 C CH 3 N0 Light Brown Fr N / _N Solid CH 3 N 166 Cl O
CH
3 F N / N 163 White Solid CH 3 H3C 3NO
CH
3 N3 C 164 White SolidN I H 3 C0CH
N
165 White Solid I N / H3
CH
3 H 166 Yellow OilN3 N I aN
H
3 C 167 CI 0 CH3 FN 167 Grey Oil F N C ci F Cl O F N: _ 168 Faint Purple F N Oil
H
3 C N C Hj\ /CH 3 N NN 169 White Solid
H
3 C
CH
3 N-N 170 White Solid N N 8H 3 C 168
CH
3
CH
3 o N- N H 171 White Solid N N Cl 0 H 3 C CH3 O CH 3 172 White Solid N H Cl
CH
3 F N CH 3 173 White Solid F N
CH
3 N CI 0 H S N.. F N 174 Clear Oil
CH
3 N 169 C1 0 / H3 N F N \ CH 3 175 White Solid CH 3 ci 0CH 3 NO 176 Yellow Oil CH 3 N NO /CH 3 N F-N 177 White Solid
CH
3 N CI 0 FF N F_ N F 178 Yellow Oil ClH 3 N 170 ci 0F F 179 White Solid
CH
3 N Cl 0 FF I F F N N H 180 Yellow Solid F N / CH3
H
3 C
H
3 C /CH 3 Faint Yellow F N / N\ C H3 181 Oil H3CH 3 N ci0H 3 C H N 12 Faint Yellow FNCH 3 182 Oil
H
3 C 171
H
3 C C 3 H IN 183 Yellow Oil F N CH 3
H
3 C /CH 3
CH
3 C S N 184 Colorless Oil F N ! N
CH
2 N CH3 S /CH 3 N 185 White Solid F N N CH 3 I \- C H 2 N CHP CH, / N
CIH
3 F N 186 White Solid 172
CH
3 0 F NO F F N X -N cn 187 Yellow Solid H 3 C CH3 N F N F 1F N _N N 188 Yellow Oil H3C N S
N
F N/ N CH 3 189 Yellow Oil
H
3 C NY
CH
3 0 S CH3 N F N/ N 190 Yellow Oil H 3 C 173
N
3 O /CH 3 CH 3 0 NN F- N 191 Yellow Oil F N H3 NN 113CCH N Fj N / 193 Yellow Solid CH3 N 3NO F N . - F F__ N/ 194 White Solid F CH3 N 17F
CH
3 0 S-_CH F N N 195 White Solid CH 3 NO 0
CH
3 NN N / N CH 3 196 Tan Solid N H H3 Cl Ns C H S 0 N 197 White Solid N / NH C 3 C 1H3 S 198 Tan Solid N CIH N H 175 C1 O H 3 C CH 3 X4CH 3 199 Gold Solid N / N N HH CCH Cl 0HCCH 3 200 Yellow Oil N _N
CH
3 N SCH3 CH 3 201 Gold Oil C1 Cl O
CH
3 N White Semi N/ N> CH 202 Solid N / H 3
H
3 C N 176
H
3 C S 203 Yellow Oil N H3C N
H
3 C CH Os NN 204 Yellow Oil N C N H _N AND Enantiomer N c i 0 ......... s 205 Yellow Oil N N
H
3 C N Cl O F ci 0 FF NF 206 Yellow Oil N
H
3 C N 177 F N N_, NCH 3 207 White Solid N CH 3 CCO C l /CH 3 NN 13 N 28 WieSldN x Cl- 3 209 Yellow Oil / C H13 N ci O / CH 3 N N 210 Yellow Oil 3 17 178 N /3 H C; 212 Yellow Oil N ci F 213 Yellow Oil CH 3 N ci F F N 0 N / _N 214 Yellow Oil
CH
3 N 1790
CH
3 CH 3 O S N - 215 Clear Oil F N _N /CH 3 Cream Colored FN CH3 216 Sld FN H N Cl 3 Solid FN
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3
H
3 C N CH3 CHP S N 217 Clear Oil F N N CH3 II
CH
3 H3 N 0 218 Clear Oil F ,, N/ N CH
H
3 C N 180
CH
3
CH
3 0 0 -0 219 Clear Oil F N / N CH 3
H
3 C N F F C H 0
CH
3 0 220 Yellow Oil F N N
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3 C N
CH
2
CH
3 C NI N H 2 221 White Solid N 1H 3 C N
CH
2 CH30/ 222 White SolidH N 181 Br OH 3 C CH 3 N OX CH3 223 White Solid F N H N F F F
CH
3 0 CH 3 224 Colorless Oil N ClH 3 N
CH
3 0 CH3 -N ' -F 225 Light Yellow H 3 F F Oil I H 3 C F F C H3 O N aN 3/s 226 White Solid
CH
3 N 182 F F F
CH
3 0 FF F 227 White Solid _N F CH3O N F F F
CH
3 0 F N- F 228 Colorless Oil CH F N F CH F
CH
3 0 F N. F N CF 229 Colorless Oil a N / H, 3 F N
CH
3 0 F
CH
3 N 230 Colorless Oil N CH3CH 3 N 183 Cl
CH
3 O N- % 231 Colorless Oil N / C N \CH 3 F
CH
3 0 F N 0 23 White Solid N3 N C 232 White Solid N H F F CH F
N-
233 White Solid NI N Ia CH 3
C
3
CH
3 N N CH 234 White Solid I 3N 184
CH
3 F 1N F 235 Colorless Oil N \ CH 3 CH3 O F N 13F F N FF N/ \ OH 236 Colorless Oil C H 3 F F F
CH
3 0 F N N / _N F 237 White Solid O H
H
3 C F F N- F F F
CH
3 0 CH3 238 Colorless Oil N / N
H
3 C N 185
CH
3 0 CH 3 N F 3/F 239 Colorless Oil /H3 F F N
CT
3 0 240 White Solid N
H
3 C N F F F
CT
3 0 F F 241 Colorless Oil NC F N86
H
3 C N F
CH
3 0 FF N F 242 Colorless Oil N / N 0 <F F 186 F F
CH
3 0 FF N F F 243 Colorless Oil NC3N
CH
3 F INN NH C H 3 244 White Solid CH 3
H
3 C N H 3 C Cl C H3 O 245 White Solid N C c N CH 3
H
3 C N
CH
3 0 / x ,)F N 246 Colorless Oil N
H
3 C N 187 F F CH30 F 247 White Solid N N
CH
3 ) N H 3 248 Colorless Oil
H
3 C N CH 3 O N F N3 249 White Solid H 3 C
CH
3 0 0 CH 3 C H\\ /CH S NNN F N CH 3 250 Clear Oil H 3 C N 188 F
CH
3 O F N 251 Brown Oil F N/ N N C - 7 H 2 N Br o CH 3 S N 252 Off White 252 Solid _N
CH
3 Br 0 S Off White c 253 Solid F N H Br 0 H3C CH 3
CH
3 254 Brown Solid F N \CH3 189 CH2 CN O 255 White Solid N / N Cl O C HH 3 256 White Solid N/~
NN
CH
3 NCl 0 257 White Solid N ClOH 3 C
CH
3 -CH3 NN 258 BritoOil N N ci 0 HC H 190 F F F
CH
3 0 CH3 N 259 White Solid N F N H3C N
H
3 C
CH
3 0 CH 3 CH3 0 F, 261 White Solid I jiH 3 >) N F F F
CH
3 0 F N3 F 262 White Solid _N F F N HC
H
3 C 191 F F F
CH
3 0 F
N
4 N F 263 Colorless Oil F N FFF
H
3 C F
CH
3 0 F 3NOF F 264 Colorless Oil F NH CX H N C F N CH0F
CH
3 265 White Solid F N
CH
3 N
H
3 C Cl CH3 0 Colorless N Semi-Solid F N N CH 3 12 3 C 192 CH, 0 0 0 F N 267 Colorless Oil F N N , F F
CH
3 0 F 2d N N N H 268 White Solid F N 3CHC H 3 C N F
CH
3 0 0 F ZH 3 269 White Solid H C N9 N3 F F -N 270 White SolidN 3 193
CH
3 0 13OHF 271 Colorless Oil F 3NO N 272 White Solid FN H3FFFC3 S H 3 C F F N F
CH
3 0 274 Colorless Oil 1 F, N X- NH F N NC H F
H
3 0 194 273 Colorless Oil CH3 F N N CH 3 N I,-
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3 C 19
CH
3
H
3 C O N.N.... C N /N 0 HF 275 W hite Solid FN : H 3 C F F
H
3 HC N
CH
3 0 H3 N2 0 F N/N 276 White Solid F N F
CH
3 Br 0 S Brown c 277 Amorphous F ,I N/ \CH3 SolidCH CHP\ N-H YH 278 White Solid
CH
3 N9 195
CH
3 CHP N NH 279 White Solid N N\
CH
3 N CH~ CH 2 N C H f 280 White Solid N N
CH
3 CH3 0 0C CH3 281 Orange Foam N N I H Cl O S N 282 Colorless Oil N N C H 2 N 196
CH
3 N NO
CH
3 283 Colorless Oil N / N CH 3 C H 2 N cH 0 C3 285 Clear Oil NO ClH 3 C~ H2 N CH3 0 286 Yellow Oil F N / N H3 C N9 197
CH
3 CH3 S IN 287 Yellow Oil N O NC N 288 Yellow Oil N > I~ ~ HN 3 C-< H 3 S CH3 CH3 NN 288 Yellow Oil N O NH CH 3 N/N 289 Dark YellowN3 Oil I N
CH
3
CH
3 C3 S N / H 290 Yellow Oil Ia 0 _
CH
3 198
H
3 C Cl OH3C
CH
3
N
291 Clear Oil N N
CCH
3 22 Tn SH 3 C CHC 0
CH
3
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3 , S ,H 292 Tan Solid NH3 CH3
CH
3 0 N / NO 293 Clear Oil NH3 H3
CH
3 0 F /Z F 294 Yellow Oil ICN H 3
CH
3 199 CH, -N 0 I 0 295 White Semi-
CH
3
CH
3 Solid N F F CI 0 F 296 Colorless Oil NN C H 2 N Br O CH3 N N F N H 297 White Solid N
CH
3 Br 0 N 298 White Solid F N / H N 200 Br 0CH 2 N 299 White Solid F N X _N CH N I- N_ N/ N 300 White Solid
CH
3 N
CH
3 Cl O N N 301 White Solid N
CH
3 N
CH
2 Cl 0 C HN 302 White Solid2
CH
3 N 201 F F F Cl O
CH
3 303 Colorless Oil N: N
H
3 C N 304 Light Yellow N 3 N F F Oil I
H
3 C NN 305 White Solid N /) N F F F CI F 0F 306 Grey Solid NN F cy
H
3 C N 202 C1 F -N F 307 Colorless Oil
H
3 C N N Cl C 308 Colorless Oil NN CH3
H
3 C N Cl F N- F N F 309 Colorless Oil N OH N
H
3 C F F N F F Light Yellow 310 Semi-Solid N /N CH3
H
3 C 203 F F 311 Colorless Oil N F F F
H
3 C N F F ci 0F N N 312 White Solid N N N N H CCH3 NO H N Cl0 NS N N CH3 313 Light Yellow
H
3 C 33 Solid N3
CH
3 0 /H3 S
N.-
IN 314 Faint Yellow N N Oil N 204 CH3 0 CH3 N 315 Faint Yellow N C H 3 315Oil N
CH
3 O
CH
3
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Faint Yellow / N CNH 316 Solid N 1~ Br 0 H 3 C CH 3 OCH3 317 White Solid N H N
CH
3 CI 0 318 Brown Solid F N H N 205 C ~ /CH 2 N 319 Brown Solid F N H _N Cl O
CHH
3 NN N 320 Yellow Solid
H
3 C N
CH
3 N N 321 Yellow Solid N
H
3 C N
CH
2 Cl 0 N N 322 Yellow Solid N N
H
3 C N 206
H
3 C
CH
3 o CH3 323 Colorless Oil N C N\
CH
3 C N CH 3 324 White Solid N
H
3 C -N
OH
0 HCH3 CH 3 C N0 325 W ite olid F,,,, , N NHHC N O CH 3 I: 326 Colorless Oil _N I aN
H
3 C 207
CH
3 0 H 3 C F / N FF 327 White Solid F F
NC
3 C F F
CH
3 CI 0 S N N 0 N - C1 O 328 White Foam N / CH 3 CHH3 N- Cl O S /_ N 329 White Foam N / N\ 3 S C 3 N Cl 0 s N.- 0 330 White Foam NCH
H
3 C N 208 C H3 Cl 0 sO 331 White Foam N N CH 3
H
3 C
H
3 C CH 3 Cl O
CH
3 Clear Yellow N O 332 Oil N /F F CN F Cl O CH, 333 Clear Oil N
H
3 C N CI 0\/-CH 3 F, N 334 Light Brown H Solid N 209 Cl 0 N CH3 335 White Solid N CH 3 N ci 0CH 3 C3l _C/ CH 3 N N 336 White Solid
CH
3 N C l 0
-
H Pale Yellow N N H 37Oil
CH
3 I N ClO N 338 Clear Oil
H
3 C N 210 F F N O 339 Clear Oil N
H
3 C N
H
2 C 0 3 C3
CH
3 O>CH3 340 White Solid F N H I CH 30 3 /CH 3 C H 3 C N 341 Yellow Oil N
CH
3 0 N ~ N 342 Yellow Oil N N 211
CH
3 0 F F 3N F N/N 343 Yellow Oil N N C
CH
3 0 F N F N /CH 344 Yellow Oil N \C H Cl O H N- CN 345 Yellow Solid N C 212 3 N N ci /--H 3 N:/_ >- s/ 346 White Solid
H
3 C N 212 S
CH
3 I S N/:: 347 Pale Yellow H Oil IH 3 C N Cl Ci O N 348 Brown Solid NH I 349 Beige Solid N N N
CH
3 Br 0 S N3 350 Colorless Oil F N / \
CH
3 N 213 Br O CH 3 N < | N CH 3 351 White Solid F NH3
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3 N
H
2 H3C CH3 O H3 352 Yellow Solid F N ClH 3 N NCH
H
2 C 0
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3 s NN 354 Yellow Oil F N / CH 3 N 214
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2 C 0 CH3 355 Yellow Solid F \ CH3 35 Yllw il FN \CH3
CIT
3 N H 2 C C H 3 N / 356 Yellow Oil F N N Br O F N/N 357 Yellow Oil F N F Br 0 F 38 Off-WhiteN 38 Solid F \ / N 215 Br 0 S NN /N 0 Off White F N \CH 3 39Solid I N\ H N, C1 0 H 3 C CH 3 N
-
O i C H 3 360 White Solid N N
CH
3 ci0H 3 C CH- 3 ClHH N ---- O CH3 361 Tan Solid N N N I 0 N /N 362 Clear Oil H3C N1 216 0CH Cl o N ~ S I 0 363 Clear Oil N I
H
3 C N Cl SCH 3 NN 364 Yellow Oil N
CH
3
H
3 C N ci0 H 365 Yellow Oil N/N NN 366 Yellow Oil NN
CH
3 N
CH
3 217 ci 0/CH 3 367 leaCl / /CHN N N-NC 367 Clear Oil C H N N S CH 368 White Solid
H
3 C N 0 H 33C C 369 Light Brown F N N Oil H3 NN
H
3 C CH- 3 N Br 0 S 370 Colorless Gum F N / \
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3 N 218 C
H
3 B r 0 " S N3 371 Colorless Gum F N
CH
3 N cl S / CH 3 S
N
aNN 372 Yellow Oil N
H
3 C Cl O H 3 C
CH
3 N S 373 White Solid N
H
3 C N Ni 0 N)WN 374 Beige Solid N N 219 CH3 O / CH3 N H
H
3 376 White Solid F I
CH
3 O N 376 White Solid F N H NN
CH
3 0 NN F N 378 White Solid F NClH 3 220 Cl O N- N 379 White Solid N HC
NCH
3 N CH3 O H3C CH3 OCH3 N6 %AH/ 380 White Solid F ND D N Cl O H 3 C CH 3 381 White Solid N/ ND D F F N 382 Clear Oil N N I aN
H
3 C N21 221 Cl O /CH 3 -N r aN / NH 383 Pale Yellow N H 3 C 0 83Oil N S
CH
3 en 3 0
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3 NI 0 384 Colorless Oil NCH3 N -N ) FN N \ 385 White Solid CH 3 N CH3 O/CH 3 F / N 386 White Solid FCH N 3 222 3 222 3
CH
2 NCH3 O NN 387 White Solid F N CxH3
CH
3 N C H3 0
NH
3 0 Br F N Br 388 White Solid C H3 N DD
CH
3 o N 3 S 389 Colorless Oil N CH 3
H
3 C N D
CH
3 0 D D 390 Off-White F NCH Solid
H
3 C 223 D S 391 Colorless Oil N CH3 CH 3
ICH
3 ND D S 392 Colorless Oil N CH 3 SHCH 3 N 393 Colorless Oil ND
H
3 C N
CH
3 0 /CH3 I D Fr N 394 Colorless Oil F N ,
H
3 C N 224 Cl Br N -N N \ Br 395 Pink Solid C H 3 I N Cl O /C H 3 N-N 396 Colorless Oil CH3
CH
3 0
CH
3 N N Fr 397 Colorless Oil Nr C1H3 0 / CH 3 N N 398 White Solid F
CH
3 225 Br o
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3 N N CH 3 399 White Solid F N H7 CH 3 NN
CH
3 CH3 N-N 400 Yellow Oil N / N CH 3
CH
3
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3 CH3 401 Yellow Oil
H
3 C O Ns
CH
3
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3 3 N2 / 2 402 Yellow Oil0 226 CH3 CH3 ClCI 3 NS N CH- 3 403 Yellow Oil 0 N
H
3 C
H
2 C 0
CH
3 404 Yellow Solid F N / C 3 N N 405 Colorless Oil N /3 406 Colorless Oil N D CH 3 N 227 Cl O /CH 3 N/N Pale Yellow N0H 3 C 0 407Oil N
CH
3 H I3 C 408 Yellow Oil F N H I F F F 409 White Solid FI S CH 3
CH
3 N' N N/ N 410 Orange Oil s N
CH
3 228
CH
3 0 -H 411 Beige Solid FN
H
3 C
CH
3
CH
3 O N ...
412 White Solid F N N 14 3 C N
CH
3 C I H 3 C0 N Br 0 H 3 C CH 3 414 Yellow Oil N / N
CH
3 N 229
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3 C CH 3 C1O
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3 N /O N 415 Off-White
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3 C N CH 3 416 Yellow Oil F N /H3
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3 N
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3 C H o 3 O C H, S 417 Yellow Oil F N /
CH
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3 C 0 CH 418 Yellow Solid FIN
CH
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3 N 230
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H
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419 Yellow Oil F N / CH H C CH 3 N
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3 C o ,CH 3
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420 Yellow Oil F N / \ H CH 3 N HC S
CH
3 0 421 Light Yellow N 41Oil F/N / _N N f 3 C
H
3 C S 422 Light Yellow N 0s Oil IN acy
H
3 C N 231 0
CH
3 0
CH
3 Light Yellow FN/ N 3Oil F N
H
3 C N CH3 O F NNO 424 Tan Solid
H
3 C F F 425 Colorless Oil IH 3 C N ci 0 F N F 426 Colorless Oil H 3 C 23 232 CH, Cl O H S NN 427 Yellow Oil N C H H C N /C H 2
N
N/-N 428 Yellow Oil H 3 C Cl O - -- H N I :- Y N / C
CH
3 429 Yellow Oil I I '
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3 C N cl 0 N / -N SCH3 Light Yellow C1H 3 Oil N 0 233 Br o H 3 C CH 3 OCH3 431 White Solid N/N N Cl 0 SCH N/N 432 Yellow Oil
H
3 C N N N
CH
3 433 Yellow Oil Cl 3 N
H
3 C CH 3
CH
3 N N 434 White Solid F N / H I2 N' 234 HO 0 CH3 435 White Solid F N / N Fr N ZH
CH
3 N 0 F/>
CH
3 436 White Solid
CH
3 N ci 0 /CH3 437 Yellow Oil N CH3 I aN 0 C H 3 Cl S / CH 3 438 Yellow Oil N CH 3CH3 N3 235I
CH
3 0 NN F N CH 439 White Solid
CH
3 N
CH
3 Y CH 3 FN 440 White Solid CH 3 N CH3 F F N1F
N
441 YelowSoidCH 3 N CH Ho 442 White Solid FN
CH
3 N 236
CH
3 0 F N 443 White Solid CH 3 N'
CH
3 O H N KN7/ N 444 Brown Solid CH 3 Cl O
CH
3 N N7/ N 445 Brown Solid CH 3 CH3 O CH3 NN
CH
3 H3 N N7 N 446 Yellow Solid HCH 3 237 Cl O CH3 N. N 7 N 4) N CH 3 447 Dark Oil CH 3
CH
3
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3 N N HN 448 Brown Solid CH3 Cl3 N- Cu 3 N H 449 Tan Solid N CH 3 N N 7 CH 3 Cl 0 N S CH3 450 White Oil O CH 3 N CH 3
CH
3 238 ci O
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3 451 Yellow Oil N /0 N Cn 3 N
CH
3 Br o CH 3 S NN a N N\ 452 Colorless Oil C H 3 N Br o CH 3 S
N
453 White Solid N \ H3 CH 3 Br O
CH
3 N < | N CH 3 454 White Solid N:
\CH
3 N 239 F F Br 0 F
N
455 Colorless Gum N
CH
3 N H 3 ClO N/N 456 Yellow Oil N
CH
3 N Cl 0 N: S ,CH 3 N 457 White Oil O CH3 N O\ C H 3 AND Enantiomer
CH
3 Br 0 mS 458 White Solid N
CH
3 I N 240
H
3 C
CH
3 Br 0 S N r 459 Colorless Oil NN/ \ N. CH 3 I N Br 0 S-CH 3 N 460 White Solid
CH
3 N F F Br 0 F 461 Colorless Gum / N CH 3 a I ' CH 3 N
CH
3 Br 0 S N3 462 White Solid N / N
H
3 C N 241
CH
3 Br 0 S N3CH 463 White Solid N N CH H 3 C N F F Br 0 F 464 Colorless Gum / N CH3 I N Br O
CH
3
N.---
I -N CH 3 465 White Solid N
H
3 C N AND Enantiomer
CH
3 Br 0 mS 466 White Solid N N C 24
CH
3 I N 242
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3 C
CH
3 Br 0 S NN 467 Colorless Gum N N Br S-H H N Br 0
S-CH
3 N | -NCH Light Yellow N / N H 468Solid C 3 I N Br 0 S-CH 3 469 White Solid N / NCH 3 N 40 Light Yellow a N / N 470 Oil N40 243 Cl O CH3 NNH 471 Light Yellow N / CH D Oil H 3 C C H C H3 NN 472 Light Yellow F N / D 1 Oil
H
3 C N4 Light Purple FrN N DCH 43 Solid H3 HC Cl 0 N / -N 474 Yellow Oil I 0
CH
3 N cH 3 244 Cl 0 N: S ,CH3 N / -NS 475 Light Yellow O CH3 Oil N CH 3
CH
3 Br 0 S-CH 3 N N
CH
3 476 White Solid
CH
3 N CH3 0 N- N CH 3 477 Off-white Solid
CH
3 N /CH 3 No S 478 Clear Oil N 5H 3 C 245 Cl S /CH 3 N- N NN N 479 Beige Solid
H
3 C N H N C N. 480 White Solid I aN'H 3 C Cl Light Yellow N 481 Oil N
H
3 C Cl 0
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H
3 C C H 3
CH
3 N Clear Viscous N 483 Oil N I aN'
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3 C
H
3 CH 3
CH
3 484 Clear Viscous N /N Oil I aN'
H
3 C Cl 0 N N S C H 3 485 White Oil 0
CH
3 N O O CH 3 CI CH3 NN 486 Off White N/ Solid
H
3 C 247
CH
3 O CH 3 N--N C H 3 487 Off-white Gum C3 N
H
3 C CH 3 Cl O YCH3 N O 488 Light Yellow N Solid
H
3 C
H
3 C
CH
3 0 NX CH3 F, NN 489 Yellow Solid H N F F F CI 0 Light Yellow 1 CH 3 490 Oil NI _
CH
3 N 248 F F F CI 0 N
CH
3 491 Light Yellow C H 491 OilN
H
3 C Cl O
CH
3 NN -N N /OCH3 492 White Solid CH 3 N F F F 0 CH3 Light Orange N N 493 Oi _
H
3 C N Cl O CH3 I 0 494 Yellow Oil N 9H 3 C 249 C \\ CH 3 495 Clear Oil N I aN'H 3 C Cl 0 N N S 496 Light Yellow
CH
3 OilH3 N4 0
H
3 C Cl 0
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3 N 4 9 8 L ig h t Y e llo w C OilH3 N 0
H
3 C N - P-Kc I N CH 3 N:/ 498 Light Yellow 2 Oil N 0
H
3 C 250
H
3 C Cl 0 0 499 Colorless Oil N / N CH 3
H
3 C N
CH
3 CI 0 NN H 500 Beige Solid N N C H 3 CI 0 501 White Solid N I a 111 H 3 C N
CH
3 0 502 Thick Yellow H Oil N/ N I aN'H 3 C 251
H
3 C
CH
3 N N N N 503 Beige Solid N
H
3 C
H
3 C
CH
3 N N 504 BegColid Nu CO N Br 0
N
N/N S\ 505 Colorless Gum H 3 C F CH 3 F F ci 0
/CH
3 N 506 Clear N N Colorless Oil I N 252 Cl 0 / CH 3 NNS Clear N CH 3 507 Colorless Oil N C ' O / C H 3 508 Clear N Colorless Oil I N!' C H3 O N 510e YellowiNCH 9 GCH3 N~ I l / H N /3H C 2 53
CH
3 510 Yellow Oil\_ N (cl-I 3
H
3 C 253 Cl O / CH 3 N 511 W hite OilNO 3 O--C
H
3 Cl o 512 Pale Yellow N/N Oil H3C N
CH
3 513 Thick Clear N Oil H 3 C Cl 0 H 3 C CH 3
\.!!CH
3 514 White Solid N / N
H
3 C N 254 Cl 0 NSN CH3 N N-I~ 515 White Oil N 0
H
3 C Cl Dark Brown Cl O F 517 White Solid N S-CH3 NN 518 White Solid N N 2 5 5t S 1 3 C 255 S-IH 519 White Solid N H1 3 C N 0
CH
3 N..N 520 Brown Gum N C H3
CH
3 N CI 0
-
H N:/ -N c 521 Beige SolidN H N N i 0 N
CH
3 522 White Solid N CH3 6H 3 C 256 O H3C CH3 O CH3 523 Yellow Solid F N
NTCH
3 /i S NN Light Brown N Solid
H
3 C H 3 C O /CH3
N
Faint Yellow N 525 Solid F N / N 0 /CH3
N
Faint Yellow N 526 Solid F N / \ C3 CH I c 3 N 257 0 CH,
N..-
527 Yellow Oil F / N N OC
H
3 N
H
3 C S 52 FLight Brown F 5 30 Oil FN O H3 Ny
N
Faint Yellow N 529 Solid FN / H\ N ci 0F F NF 530 Clear OilN H
CH
3 258 F F ci 0 F 531 Yellow Oil N 3 N 0 -- s
CH
3 CO S0CH3 N /
CH
3 532 White Solid 0
H
3 C CN S0CH3 N 533 Orange Oil 0
H
3 C Cl 0
-
H N/ 534 Red Oil N 259 Cl 0 N CH 3 N C N O 535 White Oil I N Hn Cl i 536 White Solid N /12
H
3 C N F F 537 Clear Oil N _
H
3 C NN H Cl 538 White Solid2
H
3 C N 260 Cl o CH 3 N N C H3 539 Clear Oil
H
3 C Cl 0 F F 540 Clear Oil N
H
3 C
CH
3 c i O S NCl 0 N: Light Yellow N N Oil N
I
N 0
H
3 C N NO OCH3 I 0 542 Colorless Oil NC H/ N 261 Cl
CH
3 N 543 White Solid NC/H3 Cl O :/N
CH
3 544 White Solid N H CH3 Cl O S-CH3 NN 545 White Puffy N Solid IH aNC NN 546 Brown Solid N Br 546 CH 3 262 Cl 0 N N SC HN 547 Yellow Oil I H 3 H3C I 0S N N l / H
CH
3 548 White-Yellow H CH3 Oil N
CH
3 Cl O
CH
3 549 Colorless Oil N N
CH
3 I N
CH
3 Cl O CH3
N
550 Colorless Oil NN
H
3 C NH 263 F F F 551 Colorless Oil N
CH
3 I N F F F Cl N CH3
N
552 Colorless Oil NN I N ci ~ F I F 553 Colorless Oil
NO
3 N4 ci 0 F CIA 3 N / NF 554 Colorless Oil I N 264 cl F F F 555 Yellow Oil N
CH
3 N'
H
3 C N N 556 Pale Yellow 1- N Gum \C H3 CH 3 N
H
3 C N....N CH 3 Pale Yellow N N
CH
3 Gum 0 CH 3 N 558 Faint Yellow N Oil
H
3 c 265 Cl Faint Yellow Oil H 3 N 0 0 560 Yellow Solid F N H CH3 561 W hite Solid FN*, C HH H C H 3 N H3C -CH3 CH NN N / CHH NN 562 B row n G um C H 3 N
CH
3 266 0 CH 563 Pale Yellow N'N Gum -N CH3
CH
3 N CH3 0 564 Pale Yellow \C H3 \C H3 N'N Pale Yellow N 565 Gum N CH30 3
CH
3 0o H N'N Pale Yellow N CH3 566 Gum N 267 3 CH3 O N..--N CH 3 567 Off-white F 1/ 3C H 3 56N CH3 Solid ICH 3 N
CH
3 N N F 1F F 568 Pale Yellow C3 Cii, GumI N ci 0 F CH, N NF F 569 Colorless Oil 3 N F F F Cl O
CH
3 White Semi- N Solid N
H
3 C 268 Cl O CH3 N N 571 White Semi- H3 F F Solid N Oil N F F Cl o F F F CN OF 572 Colorless Oil N F N F Cl 0 F N N F CI 0 F NF FF 574 Colorless Oil NI N CH 3 269 F Cl 0 F 575 Colorless Oil N N F N
H
3 C
CH
3
CH
3 N-Cl 0CH3 576 Colorless Oil N
CH
3
H
3 C CH 3 Cl 0
CH
3 577 Colorless Oil N a I -'-V CH3
N
Br 0 CH 3 NC S N33 578 Colorless Oil
NH
3 C N7 270 Cl 0
CH
3 N S 579 Colorless Oil N H 3 C
CH
3 I aN-H 3 C Cl 0 CH 3 N S 580 Colorless Oil CH3 H3C CH 3 NHN OHHC N 0 CH, N/N 581 Colorless Solid
H
3 C N ci N NN 582 Clear Oil N
H
3 C N 271 O HI 583 Brown Oil
H
3 C N Cl0 Dark Yellow Oil N aN 14 3 C N I 585 White Solid N / > H 3 C 1 3 C N 586 Yellow Solid N / N Br 2 2 3 C 272 N _4/ N 587 Purple Solid N CH 3 cl 0 Dark Yellow 588 _i N/ N
CH
3 N H 3 C CI N 589 Colorless Solid N N
H
3 C N
H
3 C
CH
3 Ci O
CH
3
N
590 Brown Solid N
---
N 273
CH
3 C H N;C_- CH 3 Light Yellow N N Solid N N cl 0 N CH3 N
CH
3 592 Brown Oil N NN N cl 0N0 N/N\ 59 Faint Yellow CH3 Solid 2N 27_N H3C CH 595 White solid O H3 N y-CH3
H
3 C 275 Table 2: Compound number and analytical data Com pound MP IR (m) MASS 'HNMR NMR (OC) I c No. 6 9.00 (s, 1H), 8.58 (br, 1H), 8.08 (br d, J= 7.0 Hz, 1H), 7.35 (br dd, J = 7.3, 4.8 Hz, 1H), 6.58 (br s, 0.5 H), 6.49 (br s, 0.5 H), 1668.7 305 3.89-3.79 (m, 3H), 3.25 (s, 3H), 2.96 2.80 (m, 1H), 2.42- 2.40 (m, 1H), 2.02-1.99 (m, 3H), 2.62 (m, 1H), 1.15 (d, J= 6.0 Hz, 3H). 6 9.01 (s, 1H), 8.51 (d, J= 3.8 Hz, 1H), 8.15 (br d, J= 8.0 Hz, 1H), 7.45 (dd, J= 7.9, 2 117- 1670.5 258.9 4.8 Hz, 1H), 6.98 120 (s, 1H), 3.73 (s, 3H), 3.12 (s, 3H), 2.36 (septet, J= 6.5 Hz, 1H), 0.98 (d, J= 6.3 Hz, 6H). 276 6 9.02 (s, 1H), 8.51 (d, J= 3.8 Hz, 1H), 8.16 (ddd, Ji = 7.8 Hz, J2= J3 3 1654.9 319.6 unresolved, 1H), 7.44 (dd, J= 7.8, 4.8 Hz, 1H), 6.99 (s, 1H), 3.75 (s, 3H), 3.10 (s, 3H); 2.07(s, 2H), 1.03 (s, 6H). 6 9.00 (s, 1H), 8.52 (dd, J= 4.5, 1.0 Hz, 1H), 8.14 (ddd, Ji = 8.0 Hz, J2= J3 unresolved, 1H), 4 1676.9 292.2 7.45 (dd, J= 8.1, 5.1 Hz, 1H), 6.93 (s, 1H), 3.76 (m, 3H), 3.14 (s, 3H), 2.65 (t, J= 7.1 Hz, 2H), 2.36 (br, 2H), 1.95 (s, 3H). 6 8.99 (s, 1H), 8.53 (dd, J= 4.8, 1.2 Hz, 1H), 8.13 (ddd, J= 6.1, 1.8 Hz, J3 = 5 1691.6 299.5 unresolved, 1H), 7.46 (dd, J= 7.9, 4.8 Hz, 1H), 6.96 (s, 1H), 3.77 (s, 3H), 3.42 (q, J= 10.6 Hz, 2H ), 3.16 (s, 3H). 277 6 8.99 (s, 1H), 8.56 (d, J= 3.2 Hz, 1H), 8.08 (ddd, J= 7.8, 1.8, 1.8 Hz, 1H), 7.34 6 1735.6, 1678.1 303 (dd, J= 7.8, 4.8 Hz, 1H), 6.52 (s, 1H), 3.85 (s, 3H), 3.68 (s, 3H), 3.24 (s, 3H), 2.67 (br, 2H), 2.37 (br, 2H). 6 8.99 (d, J= 1.5 Hz, 1H), 8.57 (dd, J= 4.8, 1.5 Hz, 1H), 8.08 (ddd, J = 8.1, 2.1, 2.1 Hz, 1H), 7.34 (dd, J= 7.9, 4.8 Hz, 1H), 7 1665.3 307.6 6.52 (s, 1H), 4.88 (br t, J= 5.5 Hz, 1H), 3.80 (s, 3H), 3.41 (q, J= 6.3 Hz, 2H), 3.24 (s, 3H), 2.61 (t, J= 6.3 Hz, 2H), 2.06 (s, 3H). 6 8.97 (br, 1H), 8.55 (br, 1H), 8.06 (ddd, J= 8.1, 1.8, 1.8 Hz, 1H), 7.33 (br dd, J = 7.9, 4.8 8 1722.4 308.7 Hz, 1H), 6.43 (s, 1H), 4.31 (br, 2H), 3.14 (s, 3H), 3.78 (s, 3H), 3.28 (s, 3H), 2.70 (br, 2H), 2.13 (br, 3H). 278 6 9.18 (s, 1H), 8.64 (br d, J= 2.8 Hz, 1H), 8.21 (ddd, J= 7.9, 1.8, 1.8 Hz, 1H), 7.38 9 1691.6 327.3 (dd, J= 7.8, 4.8 Hz, 1H), 3.83 (s, 3H), 2.90-2.83 (m, 1H), 2.79-2.73 (m, 1H), 2.53-2.45 (m, 1H), 2.33-2.25 (m, 1H), 2.06 (s, 3H). 6 9.19 (s, 1H), 8.64 (br, 1H), 8.21 (d, J= 7.9 Hz, 1H), 7.39 (dd, J= 7.1, 4.5 Hz, 1H), 10 1685.9 371 3.83 (s, 3H), 2.90 2.83 (m, 1H), 2.79-2.72 (m, 1H), 2.53-2.45 (m, 1H), 2.33-2.25 (m, 1H), 2.06 (s, 3H). 6 9.19 (s, 1H), 8.64 (br d, J= 2.8 Hz, 1H), 8.49 (d, J = 6.7 Hz, 1H), 8.21 (ddd, J= 7.9, 1.8, 1.8 Hz, 1H), 12 1686.7 340.3 3.83 (s, 3H), 3.25 (s, 3H), 2.35 (septet, J= 6.7 Hz, 1H), 1.15 (d, J= 6.7 Hz, 1H), 1.11 (d, J= 6.6 Hz, 6H). 279 'H NMR (400 MHz, DMSO) 6 8.79 (s, 1H), 8.67 (dd, J= 4.8, 1.3 Hz, 1H), 8.03 (brd, J= 7.8 Hz, 1H), 7.56 (dd, J= 18 1655 305.3 7.8, 5.0 Hz, 1H), 6.60 (s, 1H), 3.87 (s, 3H), 3.15 (s, 3H), 2.94-2.89 (m, 1H), 2.75-2.70 (m, 1H), 2.38-2.33 (m, 1H), 1980 (s, 3H), 1.06 (d, J= 6.5 Hz, 3H). 8.73 (s, 1H), 8.70 (d, J= 4.0 Hz, 1H), 7.77 (d, J= 8.1 Hz, 1H), 7.44 (dd, J= 6.6, 5.1 19 1662 291.5 Hz, 1H), 6.21 (s, 1H), 3.87 (s, 3H), 3.29 (s, 3H), 2.82 (t, J= 7. Hz, 2H), 2.64 (t, J= 7.6 Hz, 2H), 2.08 (s, 3H). 'H NMR (400 MHz, DMSO) 6 8.79 (br, 1H), 8.66 (dd, J= 4.8, 1.5 Hz, 1H), 8.04 (brd, J= 7.6 Hz, 20 1660.7 260.3 1H), 7.55 (dd, J= 7.3, 4.8 Hz, 1H), 6.59 (br, 1H), 3.66 (s, 3H), 3.13 (br, 3H), 2.77 (br, 1H), 1.00 (d, J= 5.5 Hz, 6H). 280 'H NMR (400 MHz, DMSO) 6 8.79 (d, J= 2.1 Hz, 1H), 8.66 (dd, J= 4.8, 1.2 Hz, 1H), 8.03 (ddd, J = 1.8, J2 and J3 21 1641.4 319.3 unresolved, 1H), 7.56 (dd, J= 8.1, 5.1 Hz, 1H), 6.59 (s, 1H), 3.87 (s, 3H), 3.10 (s, 3H), 2.67 (s, 2H), 2.03 (s, 3H), 1.10 (s, 6H). 'H NMR (300 MHz, CDCl3) 6 8.64 (bs, 1H), 8.49 (bs, 1H), 8.07 (d, 1H), 7.42-7.2 (m, 22 1H), 6.0 (s, 1H), 5.37-5.09 (m, 1H), 3.7 (s, 3H), 3.10 2.89 (m, 1H), 1.32 (d. 6H), 1.11 (d, 6H). H NMR (300 MHz, CDCl3) 6 9.00 (bs, 1H), 8.57 (s, 1H), 8.09 (dd, J = 7.9 Hz, 1H), 7.34 (dd, 1H), 23 273.3 (M+1) 6.48 (s, 1H), 4.00 (m, 1H), 3.76 (s, 3H), 3.36 (m, 1H), 2.33 (m, 1H), 1.17 (t, J= 7.1 Hz, 3H), 1.08 (t, J= 6.7 Hz, 6H). 281 6 8.95 (d, J= 1.6 Hz, 1H), 8.57 (dd, J= 4.8, 1.6 Hz, 1H), 8.01 (dt, J= 7.9, 1.9 Hz, 1H), 7.34 (ddd, J= 7.9, 24 1675 341.3 (M+1) 4.9, 0.8 Hz, 1H), 6.43 (s, 1H), 5.90 (s, 1H), 3.83 (s, 3H), 3.31 (s, 3H), 2.53 - 2.17 (m, 2H), 1.09 (d, J= 131.0 Hz, 6H). 6 8.96 (s, 0.4H), 8.78 (s, 0.6H), 8.55 (d, J= 3.3 Hz, 1H), 8.04 (d, J = 7.9 Hz, 0.4H), 7.96 (d, J= 7.9 Hz, 0.6H), 7.41 7.29 (m, 4H), 7.13 - 7.09 (m, 1H), 7.09 (s, 0.6H), 25 1669 381.3 (M+1) 6.59 (s, 0.H), 4.86 (s, 1H), 3.84 (s, 2H), 3.17 (s, 2H), 3.13 (s, 1H), 3.09 - 2.91 (m, 2H), 2.83 (m, 2H), 2.69 (dd, J= 12.9, 4.8 Hz, 0.5H), 2.54 (dd, J= 12.9, 4.1 Hz, 0.5H), 1.99 (s, 1H), 1.96 (s, 2H). 282 6 8.97 (s, 1H), 8.58 (d, J= 3.4 Hz, 1H), 8.07 (m, 1H), 7.35 (dd, J= 7.8, 4.9 Hz, 1H), 6.50 (s, 1H), 4.54 26 1673 354.4 (M+1) 3.75 (i, 2IH), 9 (s, 2H), 3.46 (s, 1H), 3.13 (s, 2H), 2.92 (s, 1H), 2.47 (s, 3H), 2.30 (s, 3H), 1.20 (d, J= 6.8 Hz, 3H). 6 8.92 (s, 1H), 8.58 - 8.47 (m, 2H), 8.10 - 7.96 27 1650 300.2 (M+1) (m, 2H 7.30 dd, 1H), 6.30 (s, 1H), 3.80 (s, 3H), 3.43 (s, 3H). 6 9.00 (d, J= 1.7 Hz, 1H), 8.59 (dd, J= 4.8, 1.6 Hz, 1H), 8.09 (ddd, J = 6.4, 4.1, 2.2 Hz, 28 1668 284.2 (M+1) 1H), 7.88 (s, 1H), 7.39 - 7.33 (m, 1H), 6.57 (s, 1H), 6.55 (s, 1H), 3.75 (s, 3H), 3.43 (s, 3H). 283 6 9.02 (d, J= 1.7 Hz, 1H), 8.60 (dd, J= 4.8, 1.6 Hz, 1H), 8.37 (d, J= 1.8 Hz, 1H), 8.16 29 1637 300.2 (M+1) - 8.08 (d, JH), 7.3 8 (dd, J = 4.8, 0.7 Hz, 1H), 7.36 (d, J= 1.8 Hz, 1H), 6.66 (s, 1H), 3.70 (s, 3H), 3.45 (s, 3H). 6 8.99 (d, J= 1.6 Hz, 1H), 8.57 (dd, J= 4.8, 1.6 Hz, 1H), 8.21 - 7.93 (m, 1H), 7.34 (m,, 30 1657.04 343.3 (M+1) 1H), 6.50 (s, 1H), 6.20 (bs, 1H), 6.18 (d, 1H), 3.74 (s, 3H), 3.52 (s, 2H), 3.39 (s, 3H), 1.96 (s, 3H). 6 9.00 (d, J= 1.8 Hz, 1H), 8.74 8.37 (m, 1H), 8.14 (d, J= 8.0 Hz, 1H), 7.80 - 7.56 31 1691 426 (M+1) (m, H), 7.19 (d, J= 15.5 Hz, 1H), 6.98 (s, 1H), 3.78 (s, 4H), 3.15 (s, 2H), 2.80 (s, 3H), 2.54 (s, 3H). 284 8.99 (br, 1H), 8.59 (br d, J= 2.5 Hz, 1H), 8.19 (br s, 1H), 8.06 (ddd, J = 8.0, 2.5, 1.3 Hz, 32 1641.1 305.2 1H), 7.76 (s, 1H), 7.44 (dd, J= 8.4, 4.8 Hz, 1H), 3.31 (s, 3H), 2.67 (s, 2H), 2.13 (s, 3H), 1.29 (s, 6H). 'H NMR (300 MHz, CDC13) 6 9.01 (d, J= 2.0 Hz, 1H), 8.52 (m, 160- 2H), 8.03 (dd, J= 33 165 203.1 7.1, 1.2 Hz, 1H), 7.63 (s, J= 13.0 Hz, 1H), 7.41 (dd, J= 8.3, 4.7 Hz, 1H), 7.32 (s, 1H), 2.16 (s, 3H). IH NMR (300 MHz, CDC13) 6 9.01 (s, 1H), 8.59 (s, 1H), 8.53-8.23 34 130- 231.2 (m, 1H), 8.02 (d, J 135 = 8.8 Hz, 1H), 7.68 (s, 1H), 7.40 7.38 (m, 2H), 2.57 (m, 1H), 1.44 1.10 (m, 6H). 285 IH NMR (300 MHz, CDC13) 6 9.0 (s, 1H), 8.60 101- (d, J= 15.1 Hz, 35 105 245.1 1H), 8.49 (m, 1H), 8.12 - 7.94 (m, 1H), 7.70 (s, 1H), 7.51 - 7.31 (m, 2H), 1.34 (s, 9H). IH NMR (300 MHz, DMSO) 6 10.68 (s, 1H), 9.10 (d, 1H), 8.73 (d, J = 20.0 Hz, 1H), 175- 8.60 - 8.43 (m, 36 180 271 1H), 8.24 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.84 (d, J= 20.2 Hz, 1H), 7.73 - 7.39 (m, 1H), 3.53 (q, J= 11.2 Hz, 2H). H NMR (300 MHz, CDC13) 6 9.04 (d, J= 2.5 Hz, 1H), 8.73 (s, 1H), 8.55 (dd, J= 170- 4.7, 1.3 Hz, 1H), 37 175 265 8.09 - 7.95 (m, 2H), 7.94 - 7.85 (m, 2H), 7.80 (s, 1H), 7.60-7.49 (m, 14.5, 7.1 Hz, 3H), 7.42 (dd, J= 8.3, 4.8 Hz, 1H). 286 'H NMR (300 MHz, CDC13) 6 9.01 (d, J= 2.3 Hz, 1H), 8.56 (s, 1H), 8.53 (dd, J= 4.7, 1.2 Hz, 1H), 8.34 (s, 1H), 8.02 38 85-90 247.1 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.66 (s, 1H), 7.40 (dd, J = 8.2, 4.7 Hz, 1H), 3.74 (t, J= 5.6 Hz, 2H), 3.47 (s, 3H), 2.67 (t, J= 5.6 Hz, 2H). IH NMR (300 MHz, CDC13) 6 9.01 (bs, 1H), 8.56 (s, 1H), 8.54 (d, J = 4.3 Hz, 1H), 140- 8.03(d, 1H), 7.81 39 146 263.1 (bs, 1H), 7.65 (d, J 6= 16.0 Hz, 1H), 7.40 (dd, J= 8.2, 4.8 Hz, 1H), 2.93 (t, J= 19.6, 12.7 Hz, 2H), 2.71 (t, 2H), 2.18 (s, 3H). IH NMR (300 MHz, CDC13) 6 9.14 (d, 1H), 9.05 (d, J= 2.4 Hz, 1H), 8.81 (dd, J= 3.4 Hz, 1H), 8.73 40 160- 266 (s, 1H), 8.57 (d, J 163 = 3.7 Hz, 1H), 8.26 (d, J= 8.1 Hz, 2H), 8.07 (d, J = 8.3 Hz, 1H), 7.84 (s, 1H), 7.46 (ddd, J= 17.0, 8.0, 4.8 Hz, 2H). 287 'H NMR (300 MHz, CDC13) 6 8.95 (bs, 0.2H), 8.83 (bs, 0.8H), 8.63 (bs, 0.2H), 8.57 (bs, 0.8H), 8.11 - 7.80 (m, 41 1650.91 321.4 1H), 7.62 - 7.11 (m, 8H), 5.01 (s, 0.4H), 4.81 (s, 1.6), 2.96 - 2.82 (m, 0.2H), 2.80 2.62 (m, 0.8H), 1.18 (d, 1.2H), 1.10 (d, J= 6.7 Hz, 4.8H). 'H NMR (300 MHz, CDC13) 6 9.01-8.93(m, 1H), 8.67 (s, 0.4H), 8.61 (d, J= 4.2 Hz, 0.6H), 8.54 (d, 0.4H), 8.08-8.02 (m, 1H), 7.96 (s, 0.6H), 7.80 (s, 42 1650.55 245.1 0.4H), 7.70 (s, 0.6H), 7.47-7.37 (m, 1H), 3.49 (s, 1.2H), 3.26 (s, 2.8H), 3.06-2.98 (m, 0.4H), 2.86 2.70 (m, 0.6H), 1.25 (d, J= 6.1 Hz, 2.4H), 1.09 (d, J= 6.6 Hz, 3.6H). 288 'H NMR (300 MHz, CDC13) 6 9.00, 8.99 (d, J= 7.6, 2.6 Hz, 1H), 8.65 (s, 0.2H) 8.63(d, 0.8H), 8.55 (d, J= 3.4 126- Hz, 0.2H), 8.10 43 128 285.1 8.07 (m, 1H), 7.99 (bs, 0.8H) 7.79 (s, 0.2H), 7.71 (s, 0.8H), 7.43 m, J= 18.7, 8.3, 4.7 Hz, 1H), 3.54 - 3.35 (m, 1.0H), 3.31 (s, 2.4H), 3.14 (q, J= 10.0 Hz, 1.6H). H NMR (300 MHz, CDC13) 6 9.00, 8.99 (d, J= 5.7 Hz, 1H), 8.72 - 8.40 (m, 1H), 8.03 (m, J= 18.9, 11.0 Hz, 2H), 7.79 44 68-70 277 (s, 0.4H), 7.71 (s, 0.6H), 7.60 - 7.35 (m, 1H), 3.45 (s, 1.2H), 3.29 (s, 1.8H), 3.07 - 2.73 (m, 2H), 2.55 (t, J = 7.3 Hz, 2H), 2.19 (s, 1.2H), 2.07 (s, 1.8H). 'H NMR (300 MHz, CDC13) 6 9.01 (d, J= 2.5 Hz, 1H), 8.59 (dd, J= 4.8, 1.4 Hz, 45 1635.19 259.1 1H), 8.26 (s, 1H), 8.07 (ddd, J= 8.3, 2.6, 1.5 Hz, 1H), 7.76 (s, 1H), 7.45 (dd, J= 8.3, 4.7 Hz, 1H), 3.39 (s, 3H), 1.29 (s, 9H). 289 'H NMR (300 MHz, CDC3) 6 9.11 (bs, 1H), 8.63 (d, J= 4.2 Hz, 1H), 8.31 (bd, J= 8.4 Hz, 1H), 7.92 46 1641.96 273.1 (m, J= 14.8 Hz, 2H), 7.92(s, 1H), 5.02 (m, J= 13.5, 6.7 Hz, 1H), 2.52 (m, J= 13.4, 6.7 Hz, 1H), 1.14 0.89 (m, 12H). IH NMR (300 MHz, CDC3) 6 9.01 (d, J= 2.6 Hz, 1H), 8.62 (d, J = 3.2 Hz, 1H), 8.16-8.06 (m, 1H), 47 1649.15 305.1 7.89 (s, 1H), 7.61 (s, 1H), 7.47 (dd, J = 8.3, 4.7 Hz, 1H), 5.17 - 4.91 (m, 1H), 2.8 (t, 2H), 2.4 (t, 2H), 2.05 (s, 3H), 1.07 (d, J = 6.7 Hz, 6H). 290 'H NMR (300 MHz, CDC3) 6 9.12 (d, 0.3H), 9.07 (d, J= 2.3 Hz, 0.7H), 8.63 (d, 0.7H),), 8.59 (d, J = 5.0 Hz, 0.3H), 8.30 - 8.19 (m, 1H), 8.00 (s, 1H), 7.76 (s, 0.3H), 7.70 (s, 0.7H), 48 1649.64 305.1 11H)6 3656 (n1 (m, 2H), 2.79 (t, J = 7.3 Hz, 2H), 2.49 (t, J= 7.3 Hz, 2H), 2.18 (s, 0.9H), 2.06 (s, 2.11H), 1.84 - 1.68 (m, 0.6H), 1.67 1.47 (m, 1.4H), 1.02 (t, J= 7.5 Hz, 0.9H), 0.9(t, J= 7.4 Hz, 2.11H). 6 9.01 (d, J= 2.3 Hz, 0.5H), 8.98 (d, J = 2.5 Hz,0.5H), 8.63 - 8.57 (m, 1H), 8.54 (d, J= 5.6 Hz, 0.5H), 8.07-8.02 (m, J= 15.9, 5.2 Hz, 1H), 124- 7.94 (s, 0.5H), 49 126 217.1 7.78 (s, 0.5H), 7.70 (s, 0.5H), 7.45 (dd, J= 8.3, 4.7 Hz, 0.5H), 7.40 (dd, J= 8.3, 4.7 Hz, 0.5H), 3.44 (s, 1.5H), 3.27 (s, 1.5H), 2.33 (s, 1.5H), 2.04 (s, 21.5H). 291 6 8.99 (d, J= 2.5 Hz, 1H), 8.71 8.45 (m, 1H), 8.07-8.02(m, 1H), 7.92 (s, 1H), 7.69 (d, J= 16.1 Hz, 1H), 7.54 - 7.35 (m, 1H), 3.81 50 1643.65 273.1 3.66 (m,.2H), 3.69 - 3.51 (m, 1.8H), 2.96 (bs, 0.2H), 2.70-2.68 (m, 0.8H), 1.69 1.51(m, 2H), 1.05 (dd, J= 19.7, 6.8 Hz, 6H), 0.96 0.82 (m, 3H). 6 9.01, 8.99 (t, J= 4.8 Hz, 1H), 8.67 (s, 0.25H), 8.61 (dd, J= 4.7, 1.2 Hz, 0.75H), 8.54 (d, J= 3.8 Hz, 0.25H), 8.12 7.98 (m, 1.75H), 7.80 (s, 0.25H), 7.74 (s, 0.75H), 7.46 (dd, J= 8.3, 4.7 Hz, 0.75H), 7.39 (dd, J= 8.2, 51 1648.53 291.1 4.8 Hz, 0.25H), 3.49 (s, 0.75H), 3.29 (s, 2.25H), 3.2-3.1 (m, 0.25H), 3.05 2.82 (m, 2H), 2.63 (dd, J= 13.0, 6.2 Hz, 0.25H), 2.45 (dd, J= 12.0, 4.3 Hz, 0.75H), 2.17 (s 0.75H), 2.03 (s 2.25H), 1.32 (d, J = 6.8 Hz, 0.75H), 1.14 (d, J= 6.5 Hz, 2.25H). 292 6 9.0-8.5 (m, 5H), 52 100- 280.51 8.0-7.6 (m, 3H), 103 7.49 - 7.32 (m, 2H), 3.44 (bs 3H). 'H NMR (400 MHz, CDCl3) 6 9.01 (s, 1H), 8.61 (s, 1H), 8.53 (s, ESIMS m/z 1H), 8.01 (ddd, J (thin film) 1640.83 292.2 = 8.3, 2.5, 1.3 Hz, ([M+2H]*), 1H), 7.96 (s, 1H), 289.23 ([M-H]-) 7.72 (s, 1H), 7.39 (dd, J = 8.3, 4.7 Hz, 1H), 2.82 (s, 2H), 2.15 (s, 3H), 1.40 (s, 6H). IH NMR (400 MHz, CDCl3) 6 9.01 (t, J= 4.3 Hz, 1H), 8.60 (s, 1H), 8.53 (dd, J= 4.7, 1.3 Hz, 1H), 8.01 ESIMS m/z 278 (ddd, J = 8.3, 2.6, 54 (thin film) 1663 ([M+2H]+), 275 1.5 Hz, 1H), 7.79 ([M-H]-) (bs, 1H), 7.70 (s, S 1H), 7.40 (dd, J= 8.3, 4.8 Hz, 1H), 2.88 (dt, J= 11.4, 5.8 Hz, 1H), 2.73 2.56 (m, 2H), 2.15 (s, 3H), 1.34 (d, J = 6.7 Hz, 3H). 293 'H NMR (400 MHz, CDCl3) 6 9.03 (bs, 1H), 8.68 (bs, 1H), 8.07 (d, J = 8.3 Hz, 1H), 7.93 (s, 1H), 7.74 ESIM m~z260 (s, H), 7.67 (s, 55 (thin film) 1651 ESIMS m260 H), 7.50 (d, J = 21.1 Hz, 1H), 3.69 (q, J = 7.1 Hz, 2H), 2.67 (dt, J = 13.4, 6.7 Hz, 1H), 1.15 (t, J= 7.1 Hz, 3H), 1.07 (d, J = 6.7 Hz, 6H). IH NMR (400 MHz, CDCl3) 6 9.10 (s, 1H), 9.00 (d, J= 2.5 Hz, 1H), 8.57 (s, 1H), 8.52 (dd, J= 4.8, ESIMS m/z 278 1.4 Hz, 1H), 8.00 56 (thin film) 1678 ([M+2H]*), 275 (ddd, J = 8.3, 2.6, ([M-H]-) 1.5 Hz, 1H), 7.69 (s, 1H), 7.49 - 7.35 (m, 1H), 3.26 (m, 1H), 2.62 (m, 2H), 2.13 (s, 3H), 1.37 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 9.02 (d, J= 2.2 Hz, 1H), 8.51 (t, J ESIMS m/z = 8.7 Hz, 1H), 57 1 8- 261([M+H]S ) 8.37 (s, 1H), 8.30 112 259 ([M-H]-)' (s, 1H), 7.98 (ddd, J = 8.3, 2.4, 1.3 Hz, 1H), 7.68 (s, 1H), 7.36 (dd, J = 8.2, 4.8 Hz, 1H), 1.52 (s, 9H). 294 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.55 (s, 1H), 8.48 (dd, J = 4.7, 1.4 Hz, 1H), 58 (thin film) 1659 ESIMS m/z 304 7.97 (ddd, J = 8.3, ([M+2H]*) 2.7, 1.5 Hz, 1H), 7.93 (bs, 1H), 7.36 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 2.83 (s, 2H), 2.37 (s, 3H), 2.18 (s, 3H), 1.41 (s, 6H). 'H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.4 Hz, 1H), 8.55 (s, 1H), 8.48 (dd, J = 4.7, 1.4 Hz, 1H), ESIMS m/z 292 7.97 (ddd, J = 8.3, 59 109- ([M+2H]*), 289 2.7, 1.5 Hz, 1H), 113 ([M-H]-) 7.54 (s, 1H), 7.36 (ddd, J = 8.4, 4.7, 0.6 Hz, 1H), 2.94 2.80 (m, 1H), 2.75 - 2.62 (m, 2H), 2.36 (s, 3H), 2.17 (s, 3H), 1.35(d, 3H). H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.55 (s, 1H), 8.48 (dd, J = ESIMS m/z 246 4.7, 1.3 Hz, 1H), 60 168- ([M+2H]), 243 7.97 (ddd, J = 8.3, 173 ([M-H]-) 2.6, 1.4 Hz, 1H), 7.43 - 7.31 (m, 1H), 6.97 (bs, 1H), 2.59 (hept, J = 6.9 Hz, 1H), 2.34 (s, 3H), 1.29 (d, J = 6.9 Hz, 6H). 295 'H NMR (400 MHz, CDC 3 ) 6 8.97 (d, J= 2.5 Hz, 1H), 8.53 (s, 1H), 8.49 (dd, J = 4.7, 1.4 Hz, 1H), 128- ESIMS m/z 278 8.02 - 7.91 (m, 61 133 ([M+2H]) 1H), 7.57 (bs, 1H), 7.36 (ddd, J = 8.3, 4.7, 0.5 Hz, 1H), 2.91 (t, J = 6.7 Hz, 2H), 2.72 (dd, J = 8.0, 5.5 Hz, 2H), 2.35 (s, 3H), 2.20 (s, 3H). H NMR (400 MHz, CDC3) 6 8.73 (d, J= 2.3 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz, ESIM m~z306 1H), 7.86 - 7.79 62 (thin film) 1659 ESIMS m/z 306 2H), 7.75 (s, 1H), 7.44 (ddd, J = 8.2, 4.8, 0.6 Hz, 1H), 2.82 (s, 2H), 2.28 (s, 3H), 2.17 (s, 3H), 1.39 (s, 6H). 296 'H NMR (400 MHz, CDC3) 6 9.01 (t, J = 3.7 Hz, 1H), 8.59 (d, J = 11.1 Hz, 1H), 8.53 (dd, J = 4.7, 1.4 Hz, 1H), 8.21 (s, 1H), 8.01 (ddt, J = 8.3, 2.8, 1.4 122- ESIMS m/z 292 Hz, 1H), 7.71 63 142 ([M+2H]) 7.66 (m, 1H), 7.39 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.10 2.87 (m, 1H), 2.65 (qd, J = 7.0, 5.2 Hz, 1H), 2.50 (dq, J = 14.0, 7.0 Hz, 1H), 2.15 (d, J = 17.6 Hz, 3H), 1.34 (dd, J= 11.7, 7.0 Hz, 6H). H NMR (400 MHz, CDC3) 6 8.95 (s, 1H), 8.47 (dd, J = 4.7, 1.2 Hz, 1H), 8.26 (s, 64 121- ESIMS m/z 275 1H), 7.96 (ddd, J 124 ([M+H]*) = 8.3, 2.7, 1.5 Hz, 1H), 7.35 (dd, J = 8.3, 4.7 Hz, 1H), 6.16 (s, 1H), 2.30 (s, 3H), 1.54 (s, 9H). 297 'H NMR (400 MHz, CDCl3) 6 9.00 (d, J= 2.4 Hz, 1H), 8.62 8.47 (m, 2H), 8.01 (ddd, J = 8.3, 2.7, 144 - ESIMS m/z 1.5 Hz, 1H), 7.68 65 145 300([M+2H] ) (s, 1H), 7.53 (bs, 1H), 7.40 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 2.92 - 2.61 (m, 2H), 2.32 2.05 (m, 1H), 1.38 (d, J= 6.6 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.74 (d, J= 2.3 Hz, 1H), 8.63 (dd, J = 4.7, 1.3 Hz, 1H), 7.89 - 7.75 66 (thin film) 1650 ESIMS m/z 278 (m, 2H), 7.52 (d, J ([M+2H]*) = 14.4 Hz, 1H), 7.50 - 7.39 (m, 1H), 2.90 (t, J = 6.9 Hz, 2H), 2.69 (t, J= 6.9 Hz, 2H), 2.30 (s, 3H), 2.18 (s, 3H). 'H NMR (400 MHz, CDCl3) 6 8.98 (bs, 1H), 8.52 (d, J= 3.8 Hz, 1H), 8.32 (s, 67 (thin film) 1703 ESIMS m/z 275 0.5H), 8.13 - 7.97 ([M+H]*) (m, 1H), 7.84 (s, 0.5H), 7.74 (s, 1H), 7.39 (dd, J= 8.0, 4.8 Hz, 1H), 3.30 (s, 3H), 1.56 (s, 9H). 298 'H NMR (400 MHz, CDCl3) 6 8.92 (d, J= 2.6 Hz, 1H), 8.57 (d, J = 3.5 Hz, 1H), 8.02 (d, J= 7.4 68 (IR thin film) 1682 ESIMS m/z 351 Hz, 1H), 7.85 (bs, ([M+H]*) 1H), 7.47 - 7.32 (m, 1H), 3.40 (d, J = 7.4 Hz, 2H), 1.84 - 1.72 (m, 1H), 1.57 (s, 9H), 0.94 (d, J= 6.7 Hz, 6H). 'H NMR (400 MHz, CDCl3) 6 8.87 (s, 1H), 8.61 (d, J= 4.1 Hz, 1H), 8.00 (ddd, J = 8.4, 2.6, 1.4 Hz, 1H), 7.50 - 7.40 69 (IR thin film) 1662 ESIMS m/z 348 (m, 2H), 7.12 (dd, ([M+H]+) J= 5.1, 1.1 Hz, 1H), 6.92 (dd, J= 5.1, 3.4 Hz, 1H), 6.79 (d, J= 2.8 Hz, 1H), 3.23 (s, 3H), 3.19 (t, J= 7.2 Hz, 2H), 2.52 (t, J= 7.2 Hz, 2H). 1 C NMR (101 H NMR (400 MHz, CDCl 3 ) MHz, CDCl3) 6 6 171.35, 8.94 (d, J= 2.5 148.99, Hz, 1H), 8.67 - 140.22, IR thin film) ESIMS m/z 365 8.63 (m, 1H), 8.03 135.62, 70 1665 ([M+H]*), 363 (s, 1H), 8.02 - 7.99 132.10, ([M-H]-) (m, 1H), 7.50 - 129.01, 7.45 (m, 1H), 4.07 126.56, - 3.92 (m, 1H), 126.18, 3.28 (s, 3H), 1.63 - 124.54, 1.59 (m, 3H). 124.18, 39.70, 37.71, 19.66. 299 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.64 (dd, J = 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, 71 85-86 ESIMS m/z 313 1H), 7.98 (s, 1H), ([M+H]+) 7.47 (ddd, J = 8.4, 4.8, 0.6 Hz, 1H), 3.80 (t, J = 6.7 Hz, 2H), 3.74 (q, J = 7.1 Hz, 2H), 2.64 (t, J = 6.7 Hz, 2H), 1.18 (t, J = 7.2 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 9.01 (d, J= 2.5 Hz, 1H), 8.60 (dd, J = 4.7, 1.2 Hz, 1H), 8.13 - 8.01 72 (thin film) 1630 7. (s, H), 7.52 7.41 (m, 1H), 3.66 (q, J = 7.1 Hz, 2H), 2.59 (s, 2H), 2.12 (s, 3H), 1.23 (s, 6H), 1.18 (t, J = 6.7 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.56 (dd, J= 4.7, 1.1 Hz, 1H), 8.04 (ddd, J ESIM m~z258 = 8.3, 2.6, 1.4 Hz, 73 (thin film) 1600 ESIMS m/z H), 7.94 (s, 1H), 7.43 (dd, J = 8.2, 4.7 Hz, 1H), 3.21 (s, 3H), 2.65 (hept, J= 6.7 Hz, 1H), 2.27 (s, 3H), 1.07 (d, J= 6.8 Hz, 6H). 300 'H NMR (400 MHz, CDCl3) 6 8.94 (bs, 1H), 8.57 (d, J= 3.9 Hz, 1H), 8.15 - 7.97 ESIM m~z291 (in, H), 7.91 (s, 74 (thin film) 1654 ESIMS m/z 291 1H), 7.43 (dd, J= 8.3, 4.7 Hz, 1H), 3.24 (s, 3H), 2.79 (t, J= 7.3 Hz, 2H), 2.45 (t, J= 7.3 Hz, 2H), 2.28 (s, 3H), 2.06 (s, 3H). H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.5 Hz, 75 (thin film) 1649 ESIMS m/z 305 1H), 8.03 (s, 1H), ([M+H]*) 7.43 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.25 (s, 3H), 2.95 2.72 (m, 2H), 2.53 - 2.38 (m, 1H), 2.37 (s, 3H), 2.01 (s, 3H), 1.13 (d, J = 6.6 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.5 Hz, 1H), 8.56 (dd, J= 4.7, 1.4 Hz, ESIM m~z319 1H), 8.05 - 8.01 76 (thin film) 1630 ESIMS m/z 319 I H), 7.99 (s, 1H), 7.46 - 7.37 (m, 1H), 3.19 (s, 3H), 2.71 (s, 2H), 2.31 (s, 3H), 2.14 (s, 3H), 1.19 (s, 6H). 301 'H NMR (400 MHz, CDC13) 6 8.97 (d, J= 2.6 Hz, 1H), 8.66 (s, 1H), 8.55 (dd, J = 173- ESIMS m/z 264 7.8 (13 Hz, H), 2.7, 1.4 Hz, 1H), 7.51 - 7.31 (m, 1H), 7.21 (s, 1H), 2.63 (hept, J= 6.9 Hz, 1H), 1.30 (d, J = 6.9 Hz, 6H). IH NMR (400 MHz, CDC13) 6 8.97 (d, J= 2.5 Hz, 1H), 8.64 (s, 1H), 8.55 (dd, J= 4.7, 1.3 Hz, 1H), 140- ESIMS 7.99 (ddd, J= 8.3, 78 143 m/z297([M+H]) 72.7, 14 Hz, H) (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 2.91 (dd, J= 10.3, 3.5 Hz, 2H), 2.75 (dd, J= 10.3, 3.6 Hz, 2H), 2.19 (s, 3H). IH NMR (400 MHz, CDC13) 6 8.98 (d, J= 2.4 Hz, 1H), 8.67 (s, 1H), 8.55 (dd, J= 4.7, 1.4 Hz, 1H), 8.11 (s, 1H), 7.98 (ddd, J= 8.3, 2.7, 79 119- ESIMS m/z 311 1.4 Hz, 1H), 7.40 124 ([M+H]*) (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 2.89 (dd, J= 12.8, 8.6 Hz, 1H), 2.82 2.71 (m, 1H), 2.68 (dd, J= 12.8, 5.0 Hz, 1H), 2.15 (s, 3H), 1.35 (d, J= 6.8 Hz, 3H). 302 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.68 (s, 0.3H), 8.65 (s, 0.7H), 8.54 (dd, J = 4.7, 1.3 Hz, 1H), 8.41 (bs, 0.7H), 8.03 - 7.94 (m, 80 83-90 ESIMS m/z 325 1H), 7.85 (bs, ([M+H]*) 0.3H), 7.40 (dd, J = 8.3, 4.8 Hz, 1H), 3.07 - 2.90 (m, 1H), 2.74 (qd, J= 7.0, 5.1 Hz, 0.7H), 2.63 (dq, J= 13.9, 6.9 Hz, 0.3H), 2.19 (s, 2H), 2.14 (s, 1H), 1.41 - 1.25 (m, 6H). IH NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.63 (s, 1H), 8.56 (dd, J= 4.7, 1.4 Hz, 1H), 112- ESIMS m/z 333 7.99 (ddd, J= 8.3, 81 122 ([M+H] ) 2.7, 1.5 Hz, 1H), 7.40 (ddd, J= 8.4, 4.8, 0.6 Hz, 1H), 7.19 (s, 1H), 2.56 (t, J= 7.2 Hz, 2H), 2.34 - 2.14 (m, 2H), 2.12 - 1.91 (m, 2H). 303 'H NMR (400 MHz, CDC13) 6 9.01 (dd, J= 7.4, 2.3 Hz, 1H), 8.84 (d, J= 0.4 Hz, 1H), 8.62 (dd, J= 109.5- ESIMS m/z 331 4.8, 1.4 Hz, 1H), 82 111.5 ([M+H]*) 8.12 (s, 1H), 8.07 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 2.90 (t, J= 6.5 Hz, 2H), 2.75 (t, J= 6.7 Hz, 2H), 2.18 (s, 3H). IH NMR (400 MHz, CDC13) 6 9.02 (d, J= 2.4 Hz, 1H), 8.85 (s, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 107.5- ESIMS m/z 345 8.06 (ddd, J= 8.3, 83 110.5 ([M+H]*) 2.7, 1.5 Hz, 1H), 7.89 (s, 1H), 7.44 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 2.93 2.81 (m, 1H), 2.75 - 2.63 (m, 2H), 2.16 (s, 3H), 1.34 (t, J= 6.2 Hz, 3H). IH NMR (400 MHz, CDC13) 6 9.02 (d, J= 2.4 Hz, 1H), 8.90 8.80 (m, 1H), 8.62 (dd, J= 4.8, 1.4 157.5- ESIMS m/z 299 Hz, 1H), 8.06 84 160.0 ([M+H]) (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 7.37 (s, 1H), 2.61 (hept, J= 6.9 Hz, 1H), 1.29 (d, J= 6.9 Hz, 6H). 304 'H NMR (400 MHz, CDC13) 6 8.79 - 8.74 (m, 1H), 8.55 (s, 1H), 8.34 (d, J= 2.5 135.0- ESIMS m/z 295 Hz, 1H), 7.79 (dt, 85 136.0 ([M+H] ) J = 9.7, 2.4 Hz, 1H), 7.62 (s, 1H), 2.91 (t, J= 6.7 Hz, 2H), 2.72 (t, J= 6.7 Hz, 2H), 2.35 (s, 3H), 2.20 (s, 3H). H NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.4 Hz, 1H), 8.51 (dd, J= 4.7, 1.3 Hz, 1H), 8.02 (s, 1H), 86 74.0- ESIMS m/z 303 7.76 (d, J= 37.6 77.0 ([M+H]*) Hz, 1H), 7.38 (dd, J= 8.3, 4.7 Hz, 1H), 3.58 (q, J= 13.0, 6.2 Hz, 2H), 2.25 (s, 3H), 1.44 (s, 9H), 1.16 (t, J = 7.1 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.2 Hz, 1H), 8.50 (dd, J= 4.7, 1.3 Hz, 1H), 8.00 (d, J= 72.5- ESIMS m/z 317 8.3 Hz, 1H), 7.79 87 74.5 ([M+H]*) (s, 1H), 7.38 (dd, J = 8.2, 4.7 Hz, 1H), 3.48 (t, J= 8.0 Hz, 2H), 2.25 (s, 3H), 1.63 - 1.52 (m, 2H), 1.43 (s, 9H), 0.91 (t, J= 7.4 Hz, 3H). 305 'H NMR (400 MHz, CDC13) 6 8.99 (d, J= 2.3 Hz, 1H), 8.69 (d, J = 4.1 Hz, 1H), 8.12 (d, J= 8.3 88 118.0- ESIMS m/z 313 Hz, 1H), 8.04 (d, J 119.5 ([M+H]*) = 0.7 Hz, 1H), 7.50 (dd, J= 8.2, 4.8 Hz, 1H), 3.23 (s, 3H), 2.59 (hept, J= 6.3 Hz, 1H), 1.08 (d, J= 6.7 Hz, 6H). 'H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.1 Hz, 1H), 8.51 (dd, J= 4.7, 1.2 Hz, 1H), 8.03 (ddd, J 89 92-95 ESIMS m/z 317 = 8.3, 2.4, 1.4 Hz, ([M+H]*) 1H), 7.74 (s, 1H), 7.39 (dd, J= 8.3, 4.7 Hz, 1H), 4.64 (s, 1H), 2.21 (s, 3H), 1.41 (s, 9H), 1.10 (d, J= 6.7 Hz, 6H). H NMR (400 MHz, CDC13) 6 8.93 (s, 1H), 8.50 (dd, J= 4.7, 1.1 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 7.87 (s, 1H), 7.38 90 (thin film) 1689 ESIMS m/z 329 (dd, J = 8.3, 4.7 ([M+H]*) Hz, 1H), 3.41 (d, J = 6.9 Hz, 2H), 2.28 (s, 3H), 1.44 (s, 9H), 1.11 - 0.96 (m, 1H), 0.49 (q, J = 5.1 Hz, 2H), 0.24 - 0.14 (m, 2H). 306 'H NMR (400 MHz, CDCl3) 6 9.00 (d, J= 2.5 Hz, 1H), 8.70 (dd, J= 4.7, 1.3 Hz, 1H), 8.13 (ddd, J 91 (thin film) 1569 ESIMS m/z 345 = 8.4, 2.6, 1.4 Hz, ([M+H]*) 1H), 8.10 (s, 1H), 7.51 (dd, J= 8.3, 4.7 Hz, 1H), 3.26 (s, 3H), 2.79 (t, J = 7.3 Hz, 2H), 2.45 (t, J = 7.3 Hz, 2H), 2.06 (s, 3H). 'H NMR (400 MHz, CDCl3) 6 9.00 (d, J= 2.5 Hz, 1H), 8.69 (dd, J= 4.7, 1.1 Hz, 1H), 8.18 (s, 1H), 8.12 (ddd, J= 8.3, 92 (thin film) 1658 ESIMS m/z 359 2.6, 1.4 Hz, 1H), ([M+H]*) 7.50 (dt, J= 13.2, 6.6 Hz, 1H), 3.27 (s, 3H), 2.90 - 2.68 (m, 2H), 2.51 (dd, J= 12.5, 5.0 Hz, 1H), 2.03 (s, 3H), 1.13 (d, J= 6.6 Hz, 3H). 307 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.56 (dd, J = 4.7, 1.3 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 127.0- ESIMS mz 271 I 7. 86 (s, 1H), 4.8, 0.5 Hz, 1H), 3.67 (app s, 2H), 2.55 (hept, J = 6.7 Hz, 1H), 2.26 (s, 3H), 1.13 (t, J = 7.1 Hz, 3H), 1.06 (d, J= 6.7 Hz, 6H). H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.57 (dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.89 (s, 1H), 94 thin film) 1650 ESIMS m/z 319 7.43 (ddd, J = 8.3, ([M+H]*) 4.8, 0.6 Hz, 1H), 3.59 (s, 2H), 2.78 (t, J= 7.3 Hz, 2H), 2.41 (t, J = 7.3 Hz, 2H), 2.27 (s, 3H), 2.05 (s, 3H), 1.64 - 1.49 (m, 2H), 0.92 (t, J = 7.4 Hz, 3H). 308 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.94 (s, 1H), ESIMS m/z 332 7.43 (ddd, J= 8.3, 95 (thin film) 1651 ([M+H] ) 4.8, 0.6 Hz, 1H), 3.53 (app s, 2H), 2.79 (t, J= 7.3 Hz, 2H), 2.43 (t, J= 7.2 Hz, 2H), 2.30 (s, 3H), 2.06 (s, 3H), 1.05 - 0.92 (m, 1H), 0.54 0.42 (m, 2H), 0.27 - 0.14 (m, 2H). IH NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 70.0- ESIMS m/z 305 1H), 7.90 (s, 1H), 96 72.5 ([M+H]) 7.43 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 3.70 (app s, 2H), 2.78 (t, J= 7.3 Hz, 2H), 2.41 (t, J= 7.3 Hz, 2H), 2.28 (s, 3H), 2.05 (s, 3H), 1.15 (t, J= 7.2 Hz, 3H). 309 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.3 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.96 (s, 1H), 7.43 (ddd, J= 8.3, ESIMS ~z 319 4.8, 0.7 Hz, 1 H), 97 (thin film) 1647 ESIMS m/z 319 3.71 (s, 2H), 2.88 (dd, J= 12.6, 9.4 Hz, 1H), 2.73 (d, J = 4.1 Hz, 1H), 2.42 (dd, J= 12.8, 5.1 Hz, 1H), 2.31 (s, 3H), 2.01 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H), 1.12 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.99 (dd, J= 7.9, 2.6 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.06 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.83 ESIMS m/z 319 (s, 1H), 7.44 (ddd, 98 (thin film) 1647 ([M+H]J) J 8.3, 4.8, 0.6 Hz, 1H), 5.15 4.97 (m, 1H), 2.77 (t, J= 7.3 Hz, 2H), 2.45 - 2.27 (m, 2H), 2.26 (s, 3H), 2.04 (s, 3H), 1.15 (d, J= 6.6 Hz, 3H), 1.01 (d, J= 6.8 Hz, 3H). 310 'H NMR (400 MHz, CDC3) 6 9.06 (d, J= 2.2 Hz, 1H), 8.77 (s, 1H), 8.52 (dd, J= 4.7, 1.4 Hz, 1H), 8.09 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 124.0- ESIMS m/z 339 7.81 (s, 1H), 7.69 99 126.0 ([M+H] ) (dt, J= 8.1, 1.7 Hz, 2H), 7.58 7.49 (m, 2H), 7.49 - 7.43 (m, 1H), 7.39 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 2.89 (t, J= 6.8 Hz, 2H), 2.69 (t, J= 6.8 Hz, 2H), 2.15 (s, 3H). H NMR (400 MHz, CDC3) 6 9.05 (d, J= 2.5 Hz, 1H), 8.60 (dd, J= 4.7, 1.3 Hz, 1H), 8.16 (ddd, J 100 (thin film) 1710 ESIMS m/z 442 = 8.3, 2.6, 1.4 Hz, ([M+H]*) 1H), 8.09 (s, 1H), 7.67 (dt, J= 8.5, 2.2 Hz, 2H), 7.51 7.36 (m, 4H), 2.96 (t, J= 6.9 Hz, 4H), 2.74 (t, J= 7.0 Hz, 4H), 2.03 (s, 6H). 311 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.3 Hz, 1H), 8.57 (d, J = 4.7 Hz, 1H), 8.03 (ddd, J= 8.3, 2.4, 1.3 Hz, 1H), ESIMS m/z 321 7.94 (s, 1H), 7.42 101 (thin film) 1652 ([M+H] ) (dd, J= 8.3, 4.8 Hz, 1H), 3.70 (s, 2H), 3.14 (dt, J= 13.2, 7.7 Hz, 1H), 2.94 - 2.81 (m, 1H), 2.74 - 2.53 (m, 5H), 2.28 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDCl3) 6 9.11 - 8.94 (m, 1H), 8.59 - 8.48 (m, 1H), 8.21 7.95 (m, 2H), 7.46 102 (thin film) 1647 ESIMS m/z 335 - 7.34 (m, 1H), ([M+H]*) 4.35 - 3.81 (m, 0.5H), 3.34 - 3.05 (m, 2.5H), 2.74 2.52 (m, 4H), 2.35 - 2.27 (m, 3H), 1.24 - 1.11 (m, 6H). IH NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.4 Hz, 1H), 8.64 8.54 (m, 1H), 8.04 (ddd, J= 8.3, 2.5, ESIMS m/z 337 1.4 Hz, 1H), 7.96 103 (thin film) 1656 ([M+H] ) (s, 1H), 7.43 (dd, J = 8.3, 4.7 Hz, 1H), 3.70 (s, 2H), 3.41 (t, J= 6.9 Hz, 2H), 2.96 (s, 3H), 2.66 (t, J= 6.5 Hz, 2H), 2.28 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H). 312 'H NMR (400 MHz, CDC3) 6 9.01 (s, 1H), 8.56 (dd, J= 4.7, 1.3 Hz, 1H), 8.09 (s, 1H), 8.01 (d, J= 8.1 Hz, 1H), 7.41 (dd, J= 8.3, 4.7 104 (thin film) 1656 ESIMS m/z 351 Hz, 1H), 4.16 (s, ([M+H]*) 0.5H), 3.84 (dd, J = 13.7, 10.7 Hz, 1H), 3.45 - 3.09 (m, 1.5H), 3.07 2.91 (m, 4H), 2.86 (dd, J= 13.7, 2.7 Hz, 1H), 2.32 (s, 3H), 1.19 - 1.11 (m, 6H). 'H NMR (400 MHz, CDC3) 6 8.75 (d, J= 1.7 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 53.0- ESIMS m/z 309 '.1H), 7.85 105 55.5 ([M+H] ) (dt, J= 9.4, 2.4 Hz, 1H), 3.23 (s, 3H), 2.79 (t, J= 7.3 Hz, 2H), 2.44 (t, J= 7.3 Hz, 2H), 2.28 (s, 3H), 2.06 (s, 3H). H NMR (400 MHz, CDC3) 6 9.05 (d, J= 2.3 Hz, 1H), 8.61 (dd, J= 4.7, 1.4 Hz, 1H), 8.16 (ddd, J ESIM m~z353= 8.3, 2.7, 1.5 Hz, 106 (thin film) 1659 ESIMS m/z H), 8.07 (s, 1H), 7.84 - 7.77 (m, 2H), 7.52 - 7.38 (m, 4H), 3.31 (s, 3H), 2.69 (t, J= 7.2 Hz, 2H), 2.46 (t, J= 7.1 Hz, 2H), 1.92 (s, 3H). 313 'H NMR (400 MHz, CDCl3) 6 8.52 (dd, J= 4.8, 1.6 Hz, 1H), 8.21 (s, 1H), 7.62 (dt, J 107 144- ESIMS m/z 258 = 46.6, 23.3 Hz, 147 ([M+H]*) 1H), 7.25 - 7.19 (m, 1H), 6.89 (s, 1H), 2.60 (m, 1H), 2.56 (s, 3H), 2.33 (s, 3H), 1.29 (d, J = 6.9 Hz, 6H). H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.66 (s, 1H), 8.54 (dd, J= ESIMS ~z 325 4.7, 1.3 Hz, I1H), 108 (thin film) 1668 ESIMS m/z 325 8.06 (s, 1H), 8.01 - 7.94 (m, 1H), 7.39 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 2.83 (s, 2H), 2.17 (s, 3H), 1.41 (s, 6H). H NMR (400 MHz, CDCl3) 6 8.90 (d, J= 2.3 Hz, 1H), 8.68 (dd, J= 4.8, 1.5 Hz, 109 109- ESIMS m/z 395 1H), 7.94 (ddd, J 115 ([M+H]*) = 8.2, 2.5, 1.5 Hz, 1H), 7.70 (s, 1H), 7.47 (dtd, J= 11.0, 5.6, 5.5, 4.8 Hz, 1H), 1.49 (s, 18H). 314 IH NMR (400 MHz, CDCl3) 6 8.89 (s, 1H), 8.68 (d, J= 4.1 Hz, ESIMS m/z 352 1H), 7.93 (ddd, J 110 (thin film) 1697 ([M-H]-) 8.2, 2.5, 1.5 Hz, 1H), 7.69 (s, 1H), 7.46 (dd, J= 8.1, 4.8 Hz, 1H), 3.22 (s, 3H), 1.44 (s, 9H). H NMR (400 MHz, CDCl3) 6 8.75 (s, 1H), 8.32 131.5- ESIMS m/z 293 (d, J= 2.5 Hz, 133.0 ([M+H] ) 1H), 8.28 (s, 1H), 7.77 (dt, J= 9.7, 2.4 Hz, 1H), 6.15 (s, 1H), 2.29 (s, 3H), 1.54 (s, 9H). H NMR (400 MHz, CDCl3) 6 8.88 (s, 1H), 8.34 (d, J= 2.5 Hz, ESIMS ~ 337 1H1), 7.83 (d, J = 112 (thin film) 1698 ESIMS m/z 37 9.9 Hz, 1H), 5.99 (s, 1H1), 4.37 (q, J = 7.0 Hz, 2H), 2.17 (s, 3H), 1.50 (s, 9H), 1.37 (t, J = 7.1 Hz, 3H). 315 'H NMR (400 MHz, CDCl3) 6 8.93 (d, J= 2.4 Hz, 1H), 8.73 (dd, J = 4.8, 1.3 Hz, 1H), 7.97 (ddd, J ESIM m~z357 8.2, 2.4, 1.5 Hz, 113 (thin film) 1661 ESI m/z 7 H), 7.77 (s, 1H), 7.51 (dd, J = 8.2, 4.8 Hz, 1H), 3.25 (s, 3H), 2.80 (t, J = 7.4 Hz, 2H), 2.47 (t, J = 7.4 Hz, 2H), 2.08 (s, 3H). 'H NMR (400 MHz, CDCl3) 6 8.95 - 8.86 (m, 1H), 8.35 (s, 1H), ESIMS ~z 351 7.92 - 7.79 (in, 114 (thin film) 1703 ESIMS m/z 351 H), 4.28 (qd, = 7.1, 1.6 Hz, 2H), 3.15 (s, 3H), 2.15 (s, 3H), 1.55 1.41 (m, 9H), 1.39 (t, J= 7.1 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.71 (d, J= 0.9 93.5- ESIMS m/z 307 Hz, 1H), 8.36 (d, J 115 95.5 ([M+H]*) = 2.5 Hz, 1H), 8.02 (s, 1H), 7.91 7.74 (m, 2H), 3.20 (s, 3H), 2.27 (s, 3H), 1.45 (s, 9H). 316 IH NMR (400 MHz, CDC13) 6 8.72 (s, 1H), 8.36 (d, J= 2.5 Hz, 116 112.0- ESIMS m/z 321 1H), 7.82 (m, 2H), 114.0 ([M+H]*) 3.58 (dd, J= 13.3, 6.4 Hz, 2H), 2.24 (s, 3H), 1.44 (s, 9H), 1.16 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.93 (d, J= 2.2 Hz, 1H), 8.73 (dd, J= 4.8, 1.5 Hz, 1H), 7.96 (ddd, J = 8.2, 2.6, 1.5 Hz, 1H), 7.80 (s, 1H), 117 (thin film) 1662 ESIMS m/z 371 7.50 (ddd, J= 8.2, ([M+2]*) 4.8, 0.7 Hz, 1H), 3.27 (s, 3H), 2.87 (dd, J= 12.9, 8.5 Hz, 1H), 2.81 2.66 (m, 1H), 2.46 (dd, J= 12.9, 5.7 Hz, 1H), 2.02 (s, 3H), 1.17 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.3 Hz, 1H), 8.73 (dd, J= 4.8, 1.2 Hz, 1H), 8.00 (ddd, J ESIM m~z325 = 8.2, 2.5, 1.5 Hz, 118 (thin film) 1658 ESIMS m/z 1H), 7.76 (d, J= 2.6 Hz, 1H), 7.52 (dd, J= 8.2, 4.8 Hz, 1H), 3.23 (s, 3H), 2.59 (hept, J = 6.7 Hz, 1H), 1.10 (d, J= 6.7 Hz, 6H). 317 'H NMR (400 MHz, CDC3) 6 8.91 (d, J= 4.1 Hz, 1H), 8.40 (d, J = 2.5 Hz, 1H), 7.91 - 7.84 (m, ESIMS mz 35 111), 4.42 - 4.27 119 (thin film) 1663 ESIMS m/z 33 (m, 1), 4.26 4.16 (m, 1H), 3.23 (s, 3H), 2.89 - 2.72 (m, 2H), 2.60 2.39 (m, 2H), 2.19 (s, 3H), 2.08 (s, 3H), 1.42 (t, J= 7.0 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.92 (d, J= 7.6 Hz, 1H), 8.40 (t, J = 2.3 Hz, 1H), 7.88 (dt, J= 9.8, 2.3 Hz, 1H), 4.66 (dq, J= 9.0, 7.0 Hz, 0.5H), 4.35 (dq, J= 9.2, 7.1 Hz, 0.5H), 4.19 4.08 (m, 1H), 3.24 (thin fim) 1661 ESIMS m/z 367 (s, 1.5d), 3.24 (s, 120 (thnfl) 61 (M+H]+) 1.511), 2.95 (dd, J = 12.8, 8.7 Hz, 0.5H), 2.91 - 2.75 (m, 1.5H), 2.48 2.38 (m, 1H), 2.27 (s, 1.5H), 2.21 (s, 1.5H), 2.06 (s, 1.5H), 1.96 (s, 1.5H), 1.41 (app qd, J= 6.8, 2.7 Hz, 3H), 1.20 (d, J = 6.5 Hz, 1.5H), 1.09 (d, J= 6.8 Hz, 1.5H). 318 'H NMR (400 MHz, CDC13) 6 8.75 (d, J= 1.6 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.97 (s, 1H), 7.85 (dt, J= 9.4, 2.4 121 102.5- ESIMS m/z 323 Hz, 1H), 3.24 (s, 105.0 ([M+H]*) 3H), 2.88 (dd, J = 12.6, 9.4 Hz, 1H), 2.84 - 2.71 (m, 1H), 2.44 (dd, J = 12.6, 4.8 Hz, 1H), 2.31 (s, 3H), 2.01 (s, 3H), 1.13 (d, J = 6.7 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.75 (d, J= 1.2 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 116.5- ESIMS m/z 277 7.92 (s, 1H), 7.85 122 119.5 ([M+H]*) (dt, J = 9.4, 2.3 Hz, 1H), 3.21 (s, 3H), 2.61 (hept, J = 6.7 Hz, 1H), 2.27 (s, 3H), 1.07 (d, J= 6.7 Hz, 6H). 'H NMR (400 MHz, CDC13) 6 8.79 (d, J= 1.5 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.98 (s, 1H), 7.88 123 (thin film) 1650 ESIMS m/z 323 (dt, J= 9.4, 2.3 ([M+H]*) Hz, 1H), 3.69 (s, 2H), 2.78 (t, J= 7.3 Hz, 2H), 2.41 (t, J= 7.3 Hz, 2H), 2.28 (s, 3H), 2.05 (s, 3H), 1.16 (t, J = 7.2 Hz, 3H). 319 'H NMR (400 MHz, CDC13) 6 8.76 (d, J= 1.6 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.93 (s, 1H), 7.85 (dt, J= 9.4, 2.4 124 87.0- ESIMS m/z 337 2Hz),2.870 (s, 12.7, 9.5 Hz, 1H), 2.69 (s, 1H), 2.43 (dd, J= 12.8, 5.0 Hz, 1H), 2.30 (s, 3H), 2.01 (s, 3H), 1.15 (t, J= 7.1 Hz, 3H), 1.12 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.76 (d, J= 1.0 Hz, 1H), 8.42 (d, J = 2.4 Hz, 1H), 139.0- ESIMS m/z 291 7.88 (s, 1H), 7.88 125 141.0 ([M+H] ) 7.83 (m, 1H), 3.67 (s, 2H), 2.52 (hept, J= 6.7 Hz, 1H), 2.26 (s, 3H), 1.13 (t, J= 7.1 Hz, 3H), 1.06 (d, J= 6.7 Hz, 6H). H NMR (400 MHz, CDC13) 6 8.52 (dd, J= 4.8, 1.6 Hz, 1H), 8.21 (s, 1H), 7.74 (s, 1H), 7.65 (dd, J= ESIMS m/z 8.0, 1.6 Hz, 1H), 126 (thin film) 1647 305([M+H] ) 7.27 - 7.16 (m, 1H), 2.93 - 2.82 (m, 1H), 2.74 2.61 (m, 2H), 2.56 (s, 3H), 2.34 (s, 3H), 2.16 (s, 3H), 1.34 (d, J= 6.6 Hz, 3H). 320 'H NMR (400 MHz, CDCl3) 6 8.51 (dd, J= 4.8, 1.6 Hz, 1H), 8.32 (s, 1H), 8.19 (s, 1H), 7.65 (dd, J= 127 (thin film) 1654 ESIMS m/z 291 15.0, 7.5 Hz, 1H), ([M+H]*) 7.29 - 7.20 (m, 1H), 2.88 (t, J= 6.8 Hz, 2H), 2.70 (t, J= 6.9 Hz, 2H), 2.55 (s, 3H), 2.32 (s, 3H), 2.15 (s, 3H). 'H NMR (400 MHz, CDCl3) 6 8.97 (t, J = 2.0 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 7.99 (ddt, J= 8.3, 128 (thin film) 1666 ESIMS m/z 309 2.7, 1.4 Hz, 1H), ([M+H]*) 7.45 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 3.22 (s, 3H), 2.91 2.73 (m, 2H), 2.55 - 2.38 (m, 2H), 2.25 (s, 3H), 2.08 (s, 3H). H NMR (400 MHz, CDCl3) 6 8.97 (dt, J= 3.9, 2.1 Hz, 1H), 8.62 (dd, J= 4.7, 1.2 Hz, 1H), 8.04 ESIMS m/z 323 7.95 (m, 1H), 7.50 129 (thin film) 1667 ([M+H] ) - 7.42 (m, 1H), 3.24 (s, 3H), 2.95 - 2.69 (m, 2H), 2.51 - 2.38 (m, 1H), 2.36 - 2.23 (m, 3H), 2.07 1.96 (m, 3H), 1.20 - 1.13 (m, 3H). 321 IH NMR (400 MHz, CDCl3) 6 8.97(d, J= 1.4 Hz, 1H), 8.46 (d, J= ESIMS m/z 275 4.1 Hz, 1H), 8.27 130 ([M+H]*) (s, 1H), 8.04-7.88 (m, 1H), 7.33 (dd, J= 8.3, 4.8 Hz, 1H), 7.12 (s, 1H), 2.28 (s, 3H), 1.49 (s, 9H). H NMR (400 MHz, CDC13) 6 8.90 (app dd, J= 9.1, 2.4 Hz, 1H), 8.70 (app d, J= 4.8 Hz, 1H), 8.00 7.89 (m, 1H), 7.48 (app dd, J= 8.2, ESIMS m/z 385 4.8 Hz, 1H), 3.23 131 (thin film) 1663 ([M+2]*) (s, 2H), 3.22 (s, 1H), 2.92 - 2.81 (m, 1H), 2.70 2.58 (m, 1H), 2.53 - 2.42 (m, 1H), 2.38 (s, 2H), 2.30 (s, 1H), 2.03 (s, 2H), 1.97 (s, 1H), 1.19 (app t, J= 6.5 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.91 (d, J= 2.2 Hz, 1H), 8.69 (dd, J= 4.8, 1.5 Hz, 1H), 7.95 (ddd, J 132 (thin film) 1667 ESIMS m/z 371 = 8.2, 2.6, 1.5 Hz, ([M+2]*) 1H), 7.48 (ddd, J = 8.2, 4.8, 0.7 Hz, 1H), 3.22 (s, 3H), 2.88 - 2.73 (m, 2H), 2.50 - 2.32 (m, 2H), 2.30 (s, 3H), 2.08 (s, 3H). 322 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.3 Hz, 1H), 8.08 - 8.01 (m, 1H), 8.01 (s, ESIMS m/z 339 1H), 7.46 (dd, J= 133 (thin film) 1651 ([M+H] ) 8.3, 4.8 Hz, 1H), 3.74 (bd, J= 82.2 Hz, 2H), 2.86 (dd, J= 12.8, 8.9 Hz, 1H), 2.70 (s, 1H), 2.47 (dd, J= 12.8, 5.4 Hz, 1H), 2.02 (s, 3H), 1.26 - 1.08 (m, 6H). H NMR (400 MHz, CDCl3) 6 8.95 (s, 1H), 8.63 (d, J= 4.3 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, ESIMS m/z 325 1H), 7.96 (s, 1H), 134 (thin film) 1655 ([M+H] ) 7.67 - 7.36 (m, 1H), 3.72 (q, J = 7.2 Hz, 2H), 2.80 (t, J= 7.4 Hz, 2H), 2.45 (t, J= 7.4 Hz, 2H), 2.07 (s, 3H), 1.17 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.97 (t, J = 2.0 Hz, 1H), 8.61 (dd, J= 4.8, 1.4 Hz, 1H), 135 ESIMS m/z 379 7.99 (ddt, J= 8.3, ([M+H]*) 2.6, 1.3 Hz, 1H), 7.57 (d, J= 2.5 Hz, 1H), 7.44 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 1.50 (s, 18H). 323 'H NMR (400 MHz, CDC3) 6 8.76 (d, J= 1.7 Hz, 0.66H), 8.75 (d, J= 1.7 Hz, 0.33H), 8.43 (d, J = 2.6 Hz, 0.33H), 8.42 (d, J= 2.5 Hz, 0.66H), 8.00 (s, 0.66H), 7.90 (s, 0.33H), 7.85 (app ddt, J= 9.4, 3.4, 136 thin film) 1647 ESIMS m/z 337 2.4 Hz, 1H), 3.24 ([M+H]*) (s, 2H), 3.23 (s, 1H), 2.99 - 2.81 (m, 1H), 2.63 2.48 (m, 1H), 2.31 (s, 2H), 2.28 (s, 1H), 2.02 (s, 2H), 2.01 (s, 1H), 1.30 (d, J= 6.7 Hz, 1H), 1.25 (d, J= 6.1 Hz, 1H), 1.23 (d, J= 6.9 Hz, 2H), 1.11 (d, J= 6.8 Hz, 2H). 324 'H NMR (400 MHz, CDC3) 6 8.78 - 8.76 (m, 0.66H), 8.76 (d, J = 1.7 Hz, 0.33H), 8.43 (d, J= 2.6 Hz, 0.33H), 8.42 (d, J= 2.5 Hz, 0.66H), 7.97 (s, 0.66H), 7.89 7.82 (m, 1.33H), 3.70 (app d, J= 137 (thin film) 1645 ESIMS m/z 352 61.9 Hz, 2H), 2.99 ([M+H]*) - 2.80 (m, 1H), 2.49 (dq, J= 9.3, 6.8 Hz, 1H), 2.30 (s, 2H), 2.27 (s, 1H), 2.02 (s, 2H), 2.01 (s, 1H), 1.30 (d, J= 6.7 Hz, 1H), 1.25 (d, J= 5.2 Hz, 1H), 1.22 (d, J= 6.9 Hz, 2H), 1.19 - 1.12 (m, 3H), 1.10 (d, J = 6.8 Hz, 2H). IH NMR (400 MHz, CDC3) 6 8.75 (d, J= 1.7 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 138 (thin film) 1658 ESIMS m/z 264 7.93 (s, 1H), 7.85 ([M+2]+) (dt, J= 9.3, 2.4 Hz, 1H), 3.24 (s, 3H), 3.13 (t, J= 6.7 Hz, 2H), 2.56 (t, J= 6.6 Hz, 2H), 2.27 (s, 3H). 325 'H NMR (400 MHz, CDCl3) 6 8.92 (dd, J= 2.6, 0.5 Hz, 1H), 8.69 (dd, J= 4.8, 1.5 Hz, 1H), 7.96 ESIMS m/z 325 (ddd, J= 8.2, 2.6, 139 (thin film) 1670 EIM 1.5 Hz, 1H), 7.48 ([M]) (ddd, J= 8.2, 4.8, 0.7 Hz, 1H), 3.22 (s, 3H), 2.87 - 2.73 (m, 2H), 2.51 2.32 (m, 2H), 2.28 (s, 3H), 2.08 (s, 3H). H NMR (400 MHz, CDCl3) 6 8.93 (d, J= 2.3 Hz, 0.6H), 8.90 (d, J= 2.3 Hz, 0.4H), 8.69 (app dt, J= 4.8, 1.4 Hz, 1H), 7.99 - 7.90 (m, 1H), 7.48 (app ddd, J= 8.2, 4.8, 0.4 Hz, 1H), 3.23 140 (thin film) 1666 ESIMS m/z 339 (s, 1.8H), 3.23 (s, ([M]) 1.2H), 2.89 (dd, J = 13.0, 8.8 Hz, 0.6H), 2.83 (dd, J = 13.1, 6.4 Hz, 0.4H), 2.72 - 2.59 (m, 1H), 2.53 2.40 (m, 1H), 2.36 (s, 1.8H), 2.29 (s, 1.2H), 2.03 (s, 1.8H), 1.97 (s, 1.2H), 1.18 (app d, J = 6.8 Hz, 3H). 326 'H NMR (DMSO d6) 6 9.03 (d, J= 2.5 Hz, 1H), 8.55 (s, 1H), 8.47 (dd, J = 4.7, 1.3 Hz, 1H), 8.15 (ddd, J= 8.4, 141 63-64 ESIMS m/z 315 2.7, 1.4 Hz, 1H), ([M+H]*). 7.56 - 7.44 (m, 1H), 5.84 (s, 1H), 5.14 (dd, J= 13.3, 7.4 Hz, 2H), 4.09 (d, J= 5.8 Hz, 2H), 2.14 (s, 3H), 1.39 (s, 9H); 'H NMR (400 MHz, CDC13) 6 8.77 (d, J= 1.9 Hz, 1H), 8.49 (d, J = 2.5 Hz, 1H), 8.03 (s, 1H), 7.86 (dt, J= 9.1, 2.4 ESIM m~z357 Hz, H), 3.99 142 (thin film) 1653 ESIMS n/z 3 3.48 (i, 2H), 2.86 (dd, J= 12.8, 9.0 Hz, 1H), 2.75 2.60 (m, 1H), 2.47 (dd, J= 12.8, 5.3 Hz, 1H), 2.03 (s, 3H), 1.57 (s, 3H), 1.20 - 1.13 (m, 6H). 327 H NMR (400 MHz, CDC13) 6 8.93 (d, J= 2.5 13 C NMR (101 Hz, 1H), 8.56 (dd, MHz, CDC1 3 ) J = 4.7, 1.3 Hz, 6 171.57, 1H), 8.05 - 7.97 148.61, (m, 1H), 7.85 (s, 147.12, 1H), 7.42 (dd, J= 139.96, ESIMS m/z 317 8.3, 4.8 Hz, 1H), 132.81, 143 ([M+H] 5.86 (ddt, J= 125.97, 16.6, 10.1, 6.4 Hz, 125.50, 1H), 5.16 (ddd, J 125.11, = 18.5, 13.6, 1.3 124.02, Hz, 2H), 4.23 (s, 118.63, 52.02, 2H), 2.79 (t, J= 33.86, 29.83 7.3 Hz, 2H), 2.44 15.98, 11.25. (t, J= 7.3 Hz, 2H), ' 2.26 (s, 3H), 2.05 (s, 3H); H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.5 13 Hz, 1H), 8.56 (dd, C NMR J= 4.7, 1.4 Hz, (101 MHz, 1H), 8.02 (ddd, J CDC1 3 ) a = 8.3, 2.7, 1.5 Hz, 175.71, 1H), 7.88 (s, 1H), 148.54, 7.42 (ddd, J= 8.3, 147.75, 4.7, 0.5 Hz, 1H), 140.09, 144 ESIMS m/z 331 5.87 (ddt, J= 136.14, ([M+H]*) 16.6, 10.2, 6.3 Hz, 132.82,126.04, 1H), 5.22 - 5.09 125.96, (m, 2H), 4.29 (s, 125.43, 2H), 2.89 (dd, J= 123.93, 12.5, 9.5 Hz, 1H), 118.41, 51.90, 2.77 (s, 1H), 2.44 18.41, 16.58, (dd, J= 12.7, 5.0 15.19, 15.07, Hz, 1H), 2.30 (s, 11.24 3H), 2.01 (s, 3H), 1.14 (d, J= 6.7 Hz, 3H) 328 'H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.3 Hz, 1H), 8.48 8.37 (m, 1H), 8.32 (s, 1H), 7.94 (d, J 197- ESIMS m/z 246 = 8.3 Hz, 1H), 145 200 ([M+H]*), 244 7.52 (br s, 1H), ([M-H]-) 7.41 - 7.25 (m, 1H), 5.79 (br s, 1H), 3.33 - 3.23 (m, 2H), 2.29 (d, J = 2.9 Hz, 3H), 1.16 (dd, J= 8.7, 5.7 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.88 (app d, J= 2.3 Hz, 1H), 8.69 ESIMS m/z 368 8.60 (m, 1H), 7.96 146 ([M+H]*) - 7.86 (m, 1H), 7.48 - 7.39 (m, 1H), 3.18 (app s, 3H), 2.26 (app s, 3H), 1.60 - 1.36 (m, 9H). H NMR (400 1C NMR MHz, CDC13) 6 (101 MHz, 8.94 (d, J = 2.4 CDC1 3 ) 6 Hz, 1H), 8.57 (dd, 170.38, J= 4.7, 1.4 Hz, 148.29, 1H), 8.03 (ddd, J 147.92, = 8.3, 2.7, 1.5 Hz, 140.10, 1H), 7.84 (s, 1H), 136.04, 147 ESIMS m/z 337 7.43 (ddd, J= 8.3, 132.44, ([M+H]*) 4.8, 0.6 Hz, 1H), 126.09, 5.85 (ddt, J= 125.01, 16.7, 10.1, 6.5 Hz, 124.93, 1H), 5.23 - 5.09 123.98, (m, 2H), 4.22 (s, 118.90, 77.34, 2H), 2.59 - 2.43 77.02, 76.70, (m, 2H), 2.41 - 52.22, 29.68, 2.32 (m, 2H), 2.26 29.39, 26.75, (s, 3H). 11.14. 329 'H NMR (400 MHz, CDC13) 6 1 3 C NMR (101 8.94 (d, J = 2.5 MHz, CDC1 3 ) Hz, 1H), 8.56 (dd, S 177.78 J= 4.7, 1.3 Hz, 148.63, 1H), 8.02 (ddd, J 147.7, = 8.3, 2.7, 1.5 Hz, 140.03, 1H), 7.83 (s, 1H), 136.13, ESIMS m/z 285 7.41 (dd, J = 8.4, 136.10, 148 82-89 (IM+H]~ 28 4.7 Hz, H), 5.86 133.10, (ddt, J= 16.6, 125.92, 10.1, 6.4 Hz, 1H), 124.69, 5.13 (ddd, J= 123.95, 18.5, 13.6, 1.3 Hz, 118.26, 77.33, 2H), 4.20 (s, 1H), 77.01, 76.69, 2.59 (dt, J= 13.4, 51.89, 31.16, 6.7 Hz, 1H), 2.25 19.67, 11.16 (s, 3H), 1.07 (d, J = 6.7 Hz, 6H). IH NMR (400 MHz, DMSO-d6) 6 9.01 - 8.87 (m, 1H), 8.60 (s, 1H), 8.49 (d, J= 2.4 ESIMS m/z 333 Hz, 1H), 8.14 (dt, 149 91-92 ([M+H] ) J = 10.4, 2.4 Hz, 1H), 5.84 (s, 1H), 5.24 - 5.08 (m, 2H), 4.08 (d, J= 5.8 Hz, 2H), 2.14 (s, 3H), 1.39 (s, 8H). 330 "C NMR (101 MHz, CDC1 3 ) IH NMR (400 6 160.78, MHz, DMSO-d6) 158.18, 6 'H NMR (400 152.13, 136.90 MHz, CDC13) 6 (d, J= 15.5 195- ESIMS m/z 255 8.76 (s, 1H), 8.39 Hz), 135.65 150 196 ([M-t-Bu] (d, J= 2.5 Hz, (d, J= 24.2 1H), 8.37 (s, 1H), Hz), 134.88 7.79 (dt, J= 9.4, (d, J= 4.0 2.3 Hz, 1H), 6.40 Hz), 121.39, (s, 1H), 1.54 (s, 117.90, 9H). 112.99, 112.76, 81.79, 28.24. H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.0 Hz, 1H), 8.56 (d, J = 4.1 Hz, 1H), 8.02 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.97 (s, 1H), 7.42 151 (thin film) 1653 ESIMS m/z 320 (dd, J= 8.3, 4.7 ([M+2]*) Hz, 1H), 3.24 (s, 3H), 2.94 (dq, J= 9.3, 6.9 Hz, 1H), 2.61 (dq, J= 9.3, 6.8 Hz, 1H), 2.32 (s, 3H), 2.01 (s, 3H), 1.29 - 1.20 (m, 6H), 1.11 (d, J = 6.8 Hz, 3H). 331 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.57 (dd, J= 4.7, 1.3 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, ESIM m~z306 1H), 7.93 (s, 1H), 152 (thin film) 1652 ESI m/z 306 7.43 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 3.30 - 3.19 (m, 4H), 2.49 (dd, J= 15.5, 6.8 Hz, 1H), 2.32 - 2.23 (m, 4H), 2.05 (s, 3H), 1.28 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.57 (d, J = 4.2 Hz, 1H), 93.0- ESIMS m/z 313 8.04 (d, J = 8.3 153 950([M+H]+) Hz, 1H), 7.44 (dd, J= 8.3, 4.7 Hz, 1H), 3.25 (s, 3H), 2.59 - 2.42 (m, 2H), 2.42 - 2.34 (m, 2H), 2.28 (s, 3H). 332 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.58 (dd, J= 4.7, 1.3 Hz, 1H), 8.02 (ddd, J = 8.3, 2.5, 1.4 Hz, ESIMS m/z 328 1H), 7.90 (s, 1H), 154 (thin film) 1663 ([M+2]*) 7.43 (ddd, J= 8.3, 4.8, 0.4 Hz, 1H), 3.24 (s, 3H), 3.01 2.88 (m, 1H), 2.88 - 2.71 (m, 1H), 2.29 (s, 3H), 2.14 1.93 (m, 1H), 1.15 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.56 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J ESIM m~z334 = 8.3, 2.7, 1.5 Hz, 155 (thin film) 1632 EI m/z 1H), 7.98 (s, 1H), 7.43 (ddd, J = 8.3, 4.7, 0.4 Hz, 1H), 3.65 (br s, 2H), 2.69 (s, 2H), 2.30 (s, 3H), 2.14 (s, 3H), 1.19 - 1.11 (m, 9H). 333 'H NMR (400 MHz, CDCl3) 6 9.05 - 8.94 (m, 1H), 8.56 (d, J= 4.1 Hz, 1H), 8.07 8.02 (m, 1H), 8.02 - 7.87 (m, 1H), 156 (thin film) 1646 ESIMS m/z 334 7.49 - 7.37 (m, ([M+2]+) 1H), 4.49 - 3.17 (m, 1H), 3.01 2.77 (m, 1H), 2.61 - 2.39 (m, 1H), 2.35 - 2.24 (m, 3H), 2.00 (s, 3H), 1.35 - 1.07 (m, 9H). 'H NMR (400 MHz, CDCl3) 6 8.98 (s, 1H), 8.57 (d, J= 4.2 Hz, 1H), 8.06 (ddd, J = 8.3, 2.6, 1.4 Hz, 1H), 7.93 (s, 1H), 7.44 (dd, J= 8.3, ESIMS m/z 320 4.7 Hz, 1H), 3.71 157 (thin film) 1650 ([M+2] ) (s, 2H), 3.25 (h, J = 6.8 Hz, 1H), 2.45 (dd, J= 15.5, 6.6 Hz, 1H), 2.27 (s, 3H), 2.23 (dd, J = 15.5, 7.5 Hz, 1H), 2.05 (s, 3H), 1.27 (d, J= 6.8 Hz, 3H), 1.16 (t, J = 7.1 Hz, 3H). 334 'H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.4 Hz, 1H), 8.58 (dd, J= 4.7, 1.2 Hz, 1H), 8.06 (ddd, J ESIM m~z328= 8.3, 2.6, 1.4 Hz, 158 thin film) 1658 ESI m/z 328 H), 7.92 (s, 1H), 7.44 (dd, J= 8.3, 4.7 Hz, 1H), 3.70 (s, 2H), 2.57 - 2.41 (m, 2H), 2.40 2.30 (m, 2H), 2.27 (s, 3H), 1.16 (t, J = 7.2 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.58 (dd, J= 4.7, 1.1 Hz, 1H), 8.02 (d, J= ESIMS m/z 340 7.5 Hz, 1H), 7.88 159 (thin film) 1653 ([M]) (d, J= 16.9 Hz, 1H), 7.50 - 7.38 (m, 1H), 4.46 3.08 (m, 2H), 2.95 - 2.69 (m, 2H), 2.28 (s, 3H), 2.13 1.91 (m, 1H), 1.18 - 1.10 (m, 6H). IH NMR (400 MHz, CDCl3) 6 8.78 (d, J= 1.9 Hz, 1H), 8.50 (d, J = 2.4 Hz, 1H), 8.04 (s, 1H), 7.88 160 90.0- ESIMS m/z 343 (dt, J= 9.1, 2.3 93.0 ([M]) Hz, 1H), 3.72 (q, J = 7.1 Hz, 2H), 2.79 (t, J= 7.4 Hz, 2H), 2.44 (t, J= 7.4 Hz, 2H), 2.07 (s, 3H), 1.16 (t, J = 7.2 Hz, 3H). 335 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.2 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 161 (thin film) 1691 ESIMS m/z 341 7.97 (d, J= 2.5 ([M]) Hz, 1H), 7.85 (d, J = 9.3 Hz, 1H), 3.61 (q, J= 7.1 Hz, 2H), 1.45 (s, 9H), 1.17 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.72 (d, J= 1.8 109.0- ESIMS mz 327 Hz, 1H), 8.43 (d, J 162 120(M)= 2.4 Hz, H), 7.93 (s, 1H), 7.82 (dt, J= 9.2, 2.1 Hz, 1H), 3.23 (s, 3H), 1.46 (s, 9H). H NMR (400 MHz, CDCl3) 6 8.77 (d, J= 1.5 Hz, 1H), 8.49 (d, J = 2.4 Hz, 1H), 3 158.0- ESIMS nz 311 7.96 (s, 1H), 7.87 163 158.0- ESIM z31 (dt, J= 9.1, 2.3 Hz, 1H), 3.70 (s, 2H), 2.51 (hept, J = 6.7 Hz, 1H), 1.15 (t, J= 7.2 Hz, 3H), 1.08 (d, J= 6.7 Hz, 6H). 336 'H NMR (400 MHz, CDC3) 6 8.77 (d, J= 1.9 Hz, 1H), 8.49 (d, J = 2.5 Hz, 1H), 7.99 (s, 1H), 7.87 (dt, J= 9.1, 2.3 109.5- ESIMS m/z 357 Hz, 1HI), 3.85 164 109.5- E IM 3.57 (m, 2H), 3.34 - 3.15 (m, 1H), 2.46 (dd, J= 15.6, 6.4 Hz, 1H), 2.25 (dd, J= 15.6, 7.7 Hz, 1H), 2.07 (s, 3H), 1.28 (d, J= 6.8 Hz, 3H), 1.17 (t, J= 7.2 Hz, 3H). IH NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.56 (dd, J = 4.7, 1.2 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.5 Hz, 125.0- ESIMS m/z 303 1H), 8.01 (s, 1H), 165 127.0 ([M+H] ) 7.43 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 3.24 (s, 3H), 2.54 2.45 (m, 1H), 2.32 (s, 3H), 2.10 (s, 3H), 1.81 - 1.69 (m, 1H), 1.58 1.47 (m, 1H), 1.04 - 0.93 (m, 1H). 337 'H NMR (400 MHz, CDC3) 6 8.99 (d, J= 2.5 Hz, 1H), 8.56 (dd, J= 4.7, 1.3 Hz, 1H), 8.07 (ddd, J = 8.3, 2.6, 1.4 Hz, 1H), 8.00 (s, 1H), 7.44 (ddd, J= 8.3, 166 (thin film) 1642 ESIMS m/z 318 4.8, 0.4 Hz, 1H), ([M+2] ) 3.85 - 3.53 (m, 2H), 2.52 - 2.42 (m, 1H), 2.31 (s, 3H), 2.10 (s, 3H), 1.73 - 1.63 (m, 1H), 1.56 - 1.45 (I, 1H), 1.14 (t, J = 7.1 Hz, 3H), 1.02 - 0.90 (m, 1H). 167 (thin film) 1646 ESIMS m/z 355 338 'H NMR (400 MHz, CDC13) 6 8.79 (d, J= 2.0 Hz, 1H), 8.50 (d, J = 2.5 Hz, 1H), 8.02 (s, 1H), 7.89 168 (thin film) 1663 (dt, J= 9.1, 2.4 Hz, 1H), 3.72 (q, J = 7.1 Hz, 2H), 2.59 - 2.43 (m, 2H), 2.42 - 2.34 (m, 2H), 1.17 (t, J = 7.2 Hz, 3H). IH NMR (400 MHz, CDC13) 6 8.96 (s, 1H), 8.56 (s, 1H), 8.03 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.90 (s, 1H), 7.42 (dd, J= 169 140- ESIMS m/z 274 8.2, 4.7 Hz, 1H), 143 ([M+H]*) 4.37 (s, 1H), 3.66 (q, J= 7.1 Hz, 2H), 3.24 (qd, J= 7.2, 5.7 Hz, 2H), 2.26 (s, 3H), 1.13 (t, J= 7.1 Hz, 3H), 1.07 (t, J= 7.2 Hz, 3H). 339 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.4 Hz, 1H), 8.56 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.89 (s, 1H), 138- ESIMS m/z 288 7.42 (ddd, J= 8.3, 170 140 ([M+H] ) 4.7, 0.6 Hz, 1H), 4.41 (t, J= 5.4 Hz, 1H), 3.66 (q, J= 7.1 Hz, 2H), 3.20 3.10 (m, 2H), 2.26 (s, 3H), 1.47 (tq, J = 14.6, 7.2 Hz, 2H), 1.13 (t, J= 7.1 Hz, 3H), 0.85 (t, J= 7.4 Hz, 3H). IH NMR (400 MHz, CDC3) 6 8.94 (d, J= 2.5 Hz, 1H), 8.50 (dd, J= 4.7, 1.3 Hz, 1H), 8.12 (s, 1H), 7.96 (ddd, J= 8.3, 193-ESIM m~z260 2.7, 1.5 Hz, 1 H), 171 193- ESIMS mz 260 7.37 (ddd, J= 8.4, 4.8, 0.6 Hz, 1H), 6.08 (s, 1H), 4.86 (t, J= 5.4 Hz, 1H), 3.23 (dd, J= 7.0, 1.1 Hz, 2H), 2.28 (s, 3H), 1.60 - 1.47 (m, 2H), 0.93 (t, J = 7.4 Hz, 3H). 340 IH NMR (400 MHz, CDC13) 6 8.96 (bs, 1H), 8.53 (d, J= 4.2 Hz, 172 140- ESIMS m/z 295 1H), 8.36 (bs, 1H), 143 ([M+H]*) 8.04 - 7.90 (m, 1H), 7.38 (dd, J= 8.3, 4.7 Hz, 1H), 6.45 (s, 1H), 1.54 (s, 9H). 'H NMR (400 MHz, CDC13) 6 8.77 (s, 1H), 8.49 (d, J= 2.1 Hz, 3 129.0- ESIMS nz 297 1H), 8.01 (s, 1H), 173 129.0- E IMIm/29 7.87 (dt, J =9.1, 2.2 Hz, 1H), 3.22 (s, 3H), 2.60 (hept, J= 6.6 Hz, 1H), 1.09 (d, J= 6.7 Hz, 6H). H NMR (400 MHz, CDCl3) 6 8.77 (d, J= 2.0 Hz, 1H), 8.49 (d, J = 2.4 Hz, 1H), 174 (thin film) 1658 ESIMS m/z 329 8.08 (s, 1H), 7.88 ([M]) (dt, J= 9.1, 2.4 Hz, 1H), 3.25 (s, 3H), 2.80 (t, J= 7.3 Hz, 2H), 2.48 (t, J= 7.3 Hz, 2H), 2.07 (s, 3H). 341 'H NMR (400 MHz, CDC13) 6 8.76 (d, J= 1.8 Hz, 1H), 8.49 (d, J = 2.4 Hz, 1H), 8.07 (s, 1H), 7.85 (dt, J= 9.1, 2.3 175 89.5- ESIMS m/z 343 Hz, 1H), 3.26 (s, 92.0 ([M]) 3H), 2.87 (dd, J= 12.6, 9.1 Hz, 1H), 2.81 - 2.68 (m, 1H), 2.48 (dd, J= 12.6, 5.2 Hz, 1H), 2.03 (s, 3H), 1.16 (d, J= 6.7 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 8.79 (d, J= 1.5 Hz, 1H), 8.49 (d, J = 2.4 Hz, 1H), 8.10 (s, 1H), 7.89 176 (thin film) 1646 ESIMS m/z 341 (dt, J= 9.1, 2.3 ([M]) Hz, 1H), 3.25 (s, 3H), 2.56 - 2.44 (m, 1H), 2.13 (s, 3H), 1.73 - 1.59 (m, 1H), 1.61 1.49 (m, 1H), 1.07 - 0.95 (m, 1H). IH NMR (400 MHz, CDCl3) 6 8.77 (d, J= 2.0 Hz, 1H), 8.49 (d, J = 2.5 Hz, 1H), 8.07 (s, 1H), 7.87 77(85.5- ESIMS J= 9.1, 2.3 177 85.5- ESIM mz Hz, 1H), 3.31 3.18 (m, 4H), 2.51 (dd, J= 15.6, 6.5 Hz, 1H), 2.29 (dd, J= 15.6, 7.6 Hz, 1H), 2.07 (s, 3H), 1.29 (d, J= 6.8 Hz, 3H). 342 IH NMR (400 MHz, CDCl3) 6 8.78 (d, J= 2.0 Hz, 1H), 8.50 (d, J 178 (thin film) 1666 ESIMS m/z 351 = 2.5 Hz, 1H), ([M]) 8.06 (s, 1H), 7.88 (dt, J= 9.1, 2.4 Hz, 1H), 3.26 (s, 3H), 2.58 - 2.37 (m, 4H). H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 2.0 Hz, 1H), 8.50 (d, J = 2.4 Hz, 1H), 107.0- ESIMS m/z 367 7.96 (s, 1H), 7.84 179 108.5 ([M+2] ) (dt, J= 9.0, 2.3 Hz, 1H), 3.25 (s, 3H), 2.93 - 2.67 (m, 2H), 2.12 1.94 (m, 1H), 1.19 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 2.0 Hz, 1H), 8.50 (d, J = 2.5 Hz, 1H), 7.93 (s, 1H), 7.89 180 132.0- ESIMS m/z 379 7.80 (m, 1H), 4.08 135.0 ([M]) - 3.30 (m, 2H), 2.86 - 2.65 (m, 2H), 2.12 - 1.93 (I, 1H), 1.19 (d, J = 6.4 Hz, 3H), 1.16 (t, J= 7.2 Hz, 3H). 343 'H NMR (400 MHz, CDC3) 6 8.77 (d, J= 1.9 Hz, 0.66H), 8.76 (d, J= 1.9 Hz, 0.33H), 8.50 (d, J = 2.7 Hz, 0.33H), 8.49 (d, J= 2.5 Hz, 0.66H), 8.11 (s, 0.66H), 8.00 (s, 0.33H), 7.92 181 (thin film) 1654 ESIMS m/z 357 7.81 (m, 1H), 3.26 ([M]) (s, 2H), 3.25 (s, 1H), 3.03 - 2.79 (m, 1H), 2.66 2.40 (m, 1H), 2.04 (s, 2H), 2.02 (s, 1H), 1.31 (d, J= 6.7 Hz, 1H), 1.28 (d, J= 6.8 Hz, 1H), 1.24 (d, J= 6.9 Hz, 2H), 1.15 (d, J= 6.8 Hz, 2H). H NMR (400 MHz, CDC3) 6 8.79 (d, J= 2.0 Hz, 0.66H), 8.77 (d, J= 2.0 Hz, 0.33H), 8.50 (d, J = 2.6 Hz, 0.33H), 8.49 (d, J= 2.5 Hz, 0.66H), 8.08 (s, 0.66H), 7.95 (s, ESIM m~z371 0.3311), 7.92 182 (thin film) 1633 ESIMS m/z 371 ., H), 4.03 ([M]) - 3.46 (m, 2H), 3.03 - 2.78 (m, 1H), 2.59 - 2.33 (m, 1H), 2.04 (s, 2H), 2.02 (s, 1H), 1.32 (d, J= 6.7 Hz, 1H), 1.27 (d, J = 6.2 Hz, 1H), 1.23 (d, J= 6.9 Hz, 2H), 1.18 1.12 (m, 5H). 344 'H NMR (400 MHz, CDC13) 6 8.73 (d, J= 2.0 Hz, 1H), 8.46 (d, J = 2.4 Hz, 1H), 7.87 (d, J= 4.9 ESIMS m/z 323 Hz, 1H), 7.84 (dt, 183 J = 9.2, 2.4 Hz, ([IM]) 1H), 5.93 - 5.76 (m, 1H), 3.73 (q, J = 7.1 Hz, 2H), 1.72 (s, 3H), 1.58 (dd, J= 6.9, 0.9 Hz, 3H), 1.17 (t, J = 7.1 Hz, 3H). IH NMR (400 13C NMR (101 MHz, CDC13) 6 MHz, CDC1 3 ) 8.77 - 8.70 (m, 6 171.63, 1H), 8.42 (d, J= 149.08, 2.5 Hz, 1H), 7.86 146.12, (s, 1H), 7.84 (dt, J 136.99, = 8 , 2.4 Hz, 1H), 136.01, 5.86 (ddt, J= 135.78, 184 ESIMS m/z 335 16.6, 10.2, 6.4 Hz, 135.15, ([M+H]*) 1H), 5.18 (dd, J= 135.11, 10.1, 1.2 Hz, 1H), 132.63,125.92, 5.13 (dd, J= 17.1, 125.30, 1.4 Hz, 1H), 4.22 118.74, (s, 2H), 2.79 (t, J 113.49, = 7.3 Hz, 2H), 113.26, 51.95, 2.42 (t, J= 7.3 Hz, 33.84, 29.78, 2H), 2.26 (s, 3H), 15.99, 11.24 2.06 (s, 3H). 345 'H NMR (400 MHz, CDC3) 6 8.74 (d, J= 1.7 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.89 (s, 1H), 7.84 (dt, J = 9.4, 2.3 Hz, 1H), 5.86 (ddt, ESIMS m/z 349 J = 16.6, 10.2, 6.3 185 65-66 ([M+H] ) Hz, 1H), 5.23 5.09 (m, 2H), 2.87 (dt, J = 13.0, 9.0 Hz, 1H), 2.77 2.64 (m, 1H), 2.44 (dd, J= 12.8, 4.9 Hz, 1H), 2.30 (s, 3H), 2.01 (s, 3H), 1.13 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.74 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 7.84 (s, 1H), 7.83 (dt, J= 8, 2.3 Hz,1H), 5.85 (ddt, 120-ESIM m~z303J = 16.6, 10.1, 6.4 186 120- ESIMS mz Hz, H), 5.17 (d, = 10.1 Hz, 1H), 5.10 (dd, J= 17.1, 1.4 Hz, 1H), 4.20(s, 1H), 2.56 (dt, J= 13.5, 6.7 Hz, 1H), 2.25 (s, 3H), 1.07 (d, J= 6.7 Hz, 6H). 346 'H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 187 105- (R thin film) 1655 ESIMS m/z 359 7.85 (bs, 2H), 3.21 109 ([M+H]*) (s, 2H), 2.80 (s, 2H), 2.25 (d, J= 20.5 Hz, 3H), 2.00 (dd, J= 13.7, 8.6 Hz, 1H), 1.22 1.00 (m, 6H). 'H NMR (400 MHz, CDCl3) 6 8.74 (t, J= 11.5 Hz, 1H), 8.42 (t, J = 12.9 Hz, 1H), 188 (thin film) 1651 ESIMS m/z 345 8.03 - 7.75 (m, ([M+H]*) 2H), 3.69 (s, 2H), 2.62 - 2.39 (m, 2H), 2.31 (dd, J= 16.0, 8.7 Hz, 2H), 2.26 (s, 3H), 1.15 (t, J= 7.2 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.7 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.97 (s, 1H), 7.90 189 (thin film) 1618 ESIMS m/z 351 7.76 (m, 1H), 2.89 ([M+H]*) (d, J= 5.4 Hz, 2H), 2.68 (s, 2H), 2.26 (d, J = 22.4 Hz, 3H), 2.14 (d, J = 4.9 Hz, 3H), 1.24 - 1.01 (m, 9H). 347 'H NMR (400 MHz, CDC3) 6 8.77 (d, J= 1.6 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.91 (d, J= 19.7 Hz, 1H), 7.87 (dt, J= 9.4, 2.4 Hz, 190 (thin film) 1640 ESIMS m/z 335 1H), 3.70 (s, 2H), ([M+H]*) 2.55 - 2.37 (m, 1H), 2.30 (s, 3H), 2.10 (s, 3H), 1.64 (ddd, J= 8.6, 5.2, 3.6 Hz, 1H), 1.54 1.48 (m, 1H), 1.14 (t, J= 7.2 Hz, 3H), 1.01 - 0.89 (m, 1H). 'H NMR (400 MHz, CDC3) 6 8.73 (t, J= 9.3 Hz, 1H), 8.43 (d, J= 2.5 Hz, 1H), 7.91 (s, 1H), 7.85 (dt, J 191 (thin film) 1649 ESIMS m/z 323 = 9.4, 2.4 Hz, 1H), ([M+H]*) 3.28 - 3.11 (m, 4H), 2.47 (dd, J= 15.5, 6.9 Hz, 1H), 2.31 - 2.19 (m, 4H), 2.06 (s, 3H), 1.28 (d, J= 6.8 Hz, 3H). 348 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.7 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.88 (d, J= 3.3 Hz, 1H), 7.87 ESIMS m/z 337 7.82 (m, 1H), 3.69 192 (thin film) 1642 ([M+H] ) (bs, 2H), 3.25 (h, J = 6.8 Hz, 1H), 2.42 (dd, J= 15.5, 6.8 Hz, 1H), 2.26 (s, 3H), 2.24 - 2.17 (m, 1H), 2.06 (s, 3H), 1.27 (d, J= 6.8 Hz, 3H), 1.15 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 7.88 (s, 1H), 7.83 193 88- ESIMS m/z 345 (dt, J= 9.3, 2.3 100 ([M+H]*) Hz, 1H), 3.23 (s, 3H), 2.96 - 2.69 (m, 2H), 2.25 (d, J = 21.3 Hz, 3H), 2.10 - 1.92 (m, 1H), 1.17 (dd, J= 13.7, 7.0 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.7 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 194 91-95 ESIMS m/z 331 7.91 (s, 1H), 7.85 ([M+H]*) (dt, J= 9.3, 2.4 Hz, 1H), 3.24 (s, 3H), 2.56 - 2.40 (m, 2H), 2.39 2.32 (m, 2H), 2.27 (s, 3H). 349 'H NMR (400 MHz, CDC13) 6 8.76 (d, J= 1.7 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.96 (s, 1H), 7.86 (dt, J= 9.4, 2.3 195 113- ESIMS m/z 321 3H, H) 3.ddd(s, = 8.1, 5.5, 3.6 Hz, 1H), 2.31 (s, 3H), 2.10 (s, 3H), 1.70 (ddd, J= 8.6, 5.2, 3.6 Hz, 1H), 1.55 - 1.49 (m, 1H), 0.97 (ddd, J= 8.5, 5.5, 4.3 Hz, 1H). H NMR (400 MHz, CDC13) 6 8.90 (d, J= 2.3 Hz, 1H), 8.65 (dt, J = 28.7, 14.3 Hz, 1H), 8.34 (s, 1H), 196 147- ESIMS m/z 264 7.93 (ddd, J= 8.2, 149 ([M+H]*) 2.6, 1.5 Hz, 1H), 7.60 - 7.33 (m, 1H), 6.96 (d, J= 28.5 Hz, 1H), 2.60 (hept, J= 6.9 Hz, 1H), 1.30 (d, J= 6.9 Hz, 6H). H NMR (400 MHz, CDC13) 6 8.90 (d, J= 2.3 Hz, 1H), 8.65 (dt, J= 28.9, 14.4 Hz, 1H), 8.34 (s, 1H), 197 101- ESIMS m/z 311 7.94 (ddd, J = 8.2, 105 ([M+H]*) 2.5, 1.5 Hz, 1H), 7.64 - 7.34 (m, 2H), 3.00 - 2.76 (m, 1H), 2.73 2.58 (m, 2H), 2.18 (s, 3H), 1.32 (t, J = 22.1 Hz, 3H). 350 'H NMR (400 MHz, CDC13) 6 8.90 (d, J= 2.3 Hz, 1H), 8.64 (dt, J= 39.7, 19.8 Hz, 1H), 8.42 - 8.16 (m, 1H), 7.93 198 105- ESIMS m/z 297 (ddd, J= 8.2, 2.5, 116 ([M+H]*) 1.5 Hz, 1H), 7.62 (s, 1H), 7.47 (ddd, J= 13.7, 11.3, 5.2 Hz, 1H), 2.91 (t, J = 6.8 Hz, 2H), 2.73 (t, J= 6.9 Hz, 2H), 2.27 - 2.07 (m, 3H). H NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.5 Hz, 1H), 8.68 8.50 (m, 1H), 8.02 ESIMS ~z 323 (d, J = 7.6 Hz, 199 79-84 ESIMS mz 323 1H), 7.88 (bs, 1H), 7.42 (dd, J= 8.2, 4.6 Hz, 1H), 3.61 (q, J= 7.1 Hz, 2H), 1.44 (s, 9H), 1.17 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.91 (d, J= 2.5 Hz, 1H), 8.64 ESIMS m/z 309 8.48 (m, 1H), 8.01 200 (thin film) 1693 ([M+H] ) (d, J= 7.5 Hz, 1H), 7.90 (s, 1H), 7.41 (dd, J= 8.3, 4.8 Hz, 1H), 3.23 (s, 3H), 1.58 - 1.25 (m, 9H). 351 'H NMR (400 MHz, CDCl3) 6 8.90 (d, J= 2.1 Hz, 1H), 8.64 (dd, J= 17.1, 16.2 Hz, 1H), 8.34 (d, J= ESIMS m/z 325 3.6 Hz, 1H), 8.01 201 (thin film) 1663 ([M+H] ) 7.88 (m, 1H), 7.85 (s, 1H), 7.46 (ddd, J = 8.2, 4.8, 0.5 Hz, 1H), 2.91 2.75 (m, 2H), 2.16 (d, J= 15.0 Hz, 3H), 1.52 - 1.31 (m, 6H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.62 (d, J = 4.7 Hz, 1H), 8.05 (ddd, J= 8.4, ESIMS ~z 293 2.6, 1.4 Hz, I1H), 202 (thin film) 1651, ESIMS m/z 293 794 (s, 1H), 7.55 7.35 (m, 1H), 3.70 (bs, 2H), 2.53 (dt, J= 13.4, 6.7 Hz, 1H), 1.15 (t, J= 7.2 Hz, 3H), 1.08 (d, J= 6.7 Hz, 6H). 352 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.3 Hz, 1H), 8.63 (d, J = 3.8 Hz, 1H), 8.05 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H), 7.57 ESIMS m/z 339 7.37 (m, 1H), 3.72 203 (thin film) 1649 ([M+H] ) (dt, J= 13.9, 6.6 Hz, 2H), 3.40 3.14 (m, 1H), 2.48 (dd, J= 15.6, 6.3 Hz, 1H), 2.26 (dd, J= 15.6, 7.7 Hz, 1H), 2.06 (s, 3H), 1.29 (d, J= 6.8 Hz, 3H), 1.17 (t, J = 7.2 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 9.03 - 8.80 (m, 1H), 8.56 (d, J= 60.5 Hz, 1H), 8.12 - 7.73 (m, 2H), 7.44 (dt, J= 30.2, 204 (IR thin film) 1651 ESIMS m/z 353 15.2 Hz, 1H), 3.96 ([M+H]*) - 3.43 (m, 2H), 2.90 (dt, J= 54.3, 23.6 Hz, 1H), 2.46 (dd, J= 38.2, 29.0 Hz, 1H), 2.02 (d, J = 4.1 Hz, 2H), 1.72 (s, 1H), 1.35 1.10 (m, 9H). 353 'H NMR (400 MHz, CDCl3) 6 9.00 (bs, 1H), 8.66 (bs, 1H), 8.05 (t, J = 13.3 Hz, 1H), 8.00 (s, 1H), 7.46 ESIMS m/z (t, J= 28.3 Hz, 205 (thin film) 1646 337[M+H]*) 1H), 3.84 - 3.49 (m, 2H), 2.66 2.38 (m, 1H), 2.12 (s, 3H), 1.71 - 1.43 (m, 2H), 1.15 (t, J = 7.2 Hz, 3H), 1.05 - 0.92 (m, 1H). H NMR (400 MHz, CDCl3) 6 8.96 (s, 1H), 8.64 (d, J= 4.2 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.4 Hz, 206 (thin film) 1663 ESIMS m/z 347 1H), 7.96 (s, 1H), ([M+H]*) 7.55 - 7.38 (m, 1H), 3.72 (q, J= 7.2 Hz, 2H), 2.60 2.43 (m, 2H), 2.43 - 2.30 (m, 2H), 1.17 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.6 Hz, 1H), 8.64 (dd, J= 4.7, 1.3 Hz, 207 98- ESIMS m/z 361 18 H), 8.01 d, J (s, 1H), 7.52 - 7.38 (m, 1H), 3.60 (bs, 2H), 2.90 - 2.58 (m, 2H), 2.00 m, 1H), 1.26 - 1.05 (m, 6H). 354 'H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.4 Hz, 1H), 8.62 (d, J = 4.0 Hz, 1H), 112- ESIMS m/z 279 8.04 (d, J= 7.2 208 120 ([M+H]*) Hz, 1H), 7.96 (s, S1H), 7.46 (dd, J= 8.3, 4.8 Hz, 1H), 3.23 (s, 3H), 2.62 (dt, J= 13.4, 6.7 Hz, 1H), 1.09 (d, J = 6.7 Hz, 6H). IH NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.6 Hz, 1H), 8.61 (dt, J= 34.2, 17.1 Hz, 1H), 8.28 - 7.77 (m, 2H), 7.64 ESIMS m/z 325 7.35 (m, 1H), 3.27 209 (thin film) 1655 ([M+H] ) (s, 3H), 2.87 (dd, J = 12.5, 9.0 Hz, 1H), 2.81 - 2.67 (m, 1H), 2.46 (dt, J= 42.8, 21.4 Hz, 1H), 2.04 (s, J= 8.9 Hz, 3H), 1.17 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.8, 1.3 Hz, ESIMSm~z 3 1 H), 8.12 - 8.00 210 (thin film) 1660 ESIMS mz 311 I1H), 7.99 (s, S 1H), 7.46 (dd, J = 7.9, 4.8 Hz, 1H), 3.25 (s, 3H), 2.80 (t, J= 7.4 Hz, 2H), 2.48 (t, J= 7.4 Hz, 2H), 2.07 (s, 3H). 355 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, ESIMS m/z 325 1H), 7.99 (s, 1H), 211 (thin film) 1657 ([M+H] ) 7.66 - 7.38 (m, 1H), 3.31-3.30 (m, 4H), 2.52 (dd, J= 15.6, 6.4 Hz, 1H), 2.30 (dd, J= 15.6, 7.7 Hz, 1H), 2.06 (s, 3H), 1.27 (d, J = 16.2, 7.0 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.3 Hz, 1H), 8.63 (d, J = 3.8 Hz, 1H), 8.05 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H), 7.57 ESIMS m/z 339 7.37 (m, 1H), 3.72 212 (thin film) 1649 ([M+H] (dt, J= 13.9, 6.6 Hz, 2H), 3.40 3.14 (m, 1H), 2.48 (dd, J= 15.6, 6.3 Hz, 1H), 2.26 (dd, J= 15.6, 7.7 Hz, 1H), 2.06 (s, 3H), 1.29 (d, J= 6.8 Hz, 3H), 1.17 (t, J = 7.2 Hz, 3H). 356 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.3 Hz, 1H), 8.06 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 8.03 (s, 1H), 213 (thin film) 1651 ESIMS m/z 323 7.47 (dd, J= 8.1, ([M+H]*) 4.6 Hz, 1H), 3.25 (s, 3H), 2.58 - 2.40 (m, 1H), 2.13 (s, 3H), 1.69 (ddd, J = 8.6, 5.2, 3.6 Hz, 1H), 1.60 - 1.48 (m,1H), 1.00 (ddd, J= 27.8, 17.7, 13.9 Hz, 1H). 'H NMR (400 MHz, CDC3) 6 8.92 (t, J = 13.0 Hz, 1H), 8.80 8.58 (m, 1H), 8.02 (ddd, J= 8.3, 2.6, 214 (thin film) 1661 ESIMS m/z 348 1.3 Hz, 1H), 7.94 ([M+2H] , (s, 1H), 7.51 - 7.39 (m, 1H), 3.27 (d, J = 12.6 Hz, 3H), 2.98 - 2.59 (m, 2H), 2.22 - 1.92 (I, 1H), 1.19 (d, J = 6.8 Hz, 3H). 357 'H NMR (400 MHz, CDC13) 6 8.57 (bs, 1H), 8.19 (t, J= 13.5 Hz, 1H), 7.80 (s, 1H), 7.65 (ddd, J= 17.4, 9.8, 2.7 Hz, 1H), 3.69-2.99 (m, 215 (IR thin film) 1641 ESIMS m/z 363 2H), 2.82-2.38 (m, ([M+H]*) 2H), 2.21 (dt, J= 15.9, 7.9 Hz, 1H), 2.20-2.03 (m, 3H), 1.80 (t, J= 17.1 Hz, 3H), 0.98-0.83 (m, 3H), 0.85-0.68 (m, 1H), 0.39-0.17 (m, 2H), 0.09-0.10 (m, 2H). 'H NMR (400 MHz, CDCl3) 6 8.78 (bs, 1H), 8.43 (d, J= 2.5 Hz, 1H), 7.91-7.79 (m, 2H), 5.06 (tt, J = 13.4, 6.7 Hz, 1H), 2.97 (dd, J = 12.5, 8.1 Hz, 0.5H), 216 95- ESIMS m/z 351 2.79 (dd, J = 12.6, 103 ([M+H]*) 9.8 Hz, 0.5H), 2.68-2.55 (m, 0.5H), 2.52-2.35 (m, 1.5H), 2.34 (s, 1.2H), 2.26 (s, 1.8H), 2.06 (s, 1.3H), 1.93 (s, 1.7H), 1.22-1.09 (m, 6H), 1.10-0.95 (m, 3H). 358 'H NMR (400 MHz, CDC3) 6 8.76 (d, J= 1.7 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.93 (s, 1H), 7.85 (dt, J= 9.4, 2.3 Hz, 1H), 3.97-3.14 217 (R thin film) 1648 ESIMS m/z 351 (m, 2H), 2.88 (dd, ([M+H]*) J = 12.3, 9.8 Hz, 1H), 2.71 (s, 1H), 2.43 (dd, J= 12.8 4.9 Hz, 1H), 2.30 (s, 3H), 2.01 (s, 3H), 1.64-1.48 (m, 2H), 1.16-1.08 (m, 3H), 0.98-0.86 (m, 3H). 'H NMR (400 MHz, CDC3) 6 8.88 - 8.77 (m, 1H), 8.44 - 8.38 (m, 1H), 8.20 8.05 (m, 1H), 7.90 218 (thin film) 1648 ESIMS m/z 353 - 7.80 (m, 1H), ([M+H]*) 4.53 - 3.31 (m, 2H), 3.30 - 3.05 (m, 2H), 2.76 2.53 (m, 4H), 2.36 - 2.26 (m, 3H), 1.24 - 1.12 (m, 6H). 359 'H NMR (400 MHz, CDCl3) 6 8.82 (s, 1H), 8.42 (d, J= 2.4 Hz, 1H), 8.14 (s, 1H), 7.88 - 7.81 (m, 1H), 4.13 (s, 219 (thin film) 1654 ESIMS m/z 369 0.5H), 3.84 (dd, J ([M+H]*) = 13.7, 10.7 Hz, 1H), 3.29 (s, 1.5H), 3.01 - 2.92 (m, 4H), 2.88 (dd, J= 13.7, 2.7 Hz, 1H), 2.32 (s, 3H), 1.21 - 1.10 (m, 6H). 'H NMR (400 MHz, CDCl3) 6 8.77 (d, J= 1.7 Hz, 1H), 8.43 (d, J = 2.4 Hz, 1H), 7.90 (s, 1H), 7.86 220 (thin film) 1652 ESIMS m/z 359 (dt, J= 9.4, 2.4 ([M+H]*) Hz, 1H), 3.68 (d, J = 5.9 Hz, 2H), 2.26 (s, 3H), 2.23 2.05 (m, 4H), 1.92 - 1.82 (m, 2H), 1.15 (t, J= 7.2 Hz, 3H). 360 'H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.5 Hz, 1H), 8.56 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.91 (s, 1H), 7.42 (ddd, J= 8.4, 108- ESIMS m/z 286 4.8, 0.6 Hz, 1H), 221 111 ([M+H] ) 5.82 (ddt, J = 17.1, 10.2, 5.6 Hz, 1H), 5.14 - 4.97 (m, 2H), 4.49 (t, J = 5.5 Hz, 1H), 3.83 (tt, J= 5.7, 1.5 Hz, 2H), 3.67 (q, J= 7.1 Hz, 2H), 2.27 (s, 3H), 1.14 (t, J= 7.1 Hz, 3H). IH NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.5 Hz, 1H), 8.48 (dd, J= 4.7, 1.4 Hz, 1H), 8.14 (s, 1H), 7.94 (ddd, J= 8.3, 222 188- ESIMS m/z 258 2.7, 1.5 Hz, 1H), 192 ([M+H]*) 7.35 (ddd, J= 8.3, 4.7, 0.5 Hz, 1H), 6.53 (s, 1H), 5.93 5.79 (m, 1H), 5.26 - 5.02 (m, 3H), 3.89 (tt, J= 5.8, 1.5 Hz, 2H), 2.26 (s, 3H). 361 'H NMR (400 MHz, CDC13) 6 8.77 (d, J= 1.9 Hz, 1H), 8.44 (t, J = 4.4 Hz, 1H), 184- ESIMS m/z 301 8.03 (s, 1H), 7.87 223 185 ([M+t-Bu+H], (dt, J= 9.3, 2.4 Hz, 1H), 4.44 (s, 2H), 2.56 - 2.42 (m, 3H), 2.36 (dd, J= 12.7, 5.5 Hz, 2H), 2.30 (s, 3H), 2.27 (s, 1H). IH NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.2 Hz, 1H), 8.58 (d, J = 3.9 Hz, 1H), 8.03 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.90 (s, 1H), 7.43 224 ESIMS m/z 360 (dd, J= 8.1, 4.6 ([M+H]*) Hz, 1H), 3.77 (dqd, J= 17.2, 8.6, 3.7 Hz, 1H), 3.28 (s, 3H), 2.56 (dd, J = 16.3, 3.7 Hz, 1H), 2.44 (dd, J= 16.3, 10.0 Hz, 1H), 2.29 (s, 3H), 2.28 (s, 3H). H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.4 Hz, 1H), 8.59 (dd, J= 4.7, 1.2 Hz, 1H), 8.09 - 7.84 ESIM m~z360 (in, 2H), 7.44 225 (thin film) 1669 ESIMS mz 360 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 3.68 3.52 (m, 1H), 3.31 (s, 3H), 3.18 (t, J = 12.4 Hz, 1H), 2.87 - 2.67 (m, 1H), 2.34 (s, 3H), 2.08 (s, 3H). 362 'H NMR (400 MHz, CDC13) 6 1 3 C NMR (101 8.93 (d, J= 2.2 MHz, CDC1 3 ) Hz, 1H), 8.58 (d, J 6172.48 = 3.9 Hz, 1H), 148.05, 8.02 (ddd, J= 8.3, 147.99, 2.6, 1.4 Hz, 1H), 140.07, 226 99- ESIMS m/z 289 7.86 (s, 1H), 7.44 136.00, 101 ([M+H]*) (dd, J= 8.4, 4.7 126.24, Hz, 1H), 4.16 (p, J 126.12, = 9.1 Hz, 1H), 124.45, 3.71 (t, J= 9.2 Hz, 124.03, 42.15, 2H), 3.20 (s, 3H), 37.41, 27.83, 2.76 (dd, J= 13.3, 11.04. 5.0 Hz, 2H), 2.25 (s, 3H). 'H NMR (400 MHz, CDC13) 6 8.96 (d, J =2.5 Hz, 1H), 8.59 (dd, J =4.7, 1.2 Hz, 1H), 8.04 (ddd, J 105- ESIMS m/z 381 =8.3, 2.6, 1.4 Hz, 227 107 ([M+H] ) 1H), 7.92 (s, 1H), 7.44 (ddd, J =8.3, 4.8, 0.6 Hz, 1H), 4.16 - 3.94 (m, 1H), 3.27 (s, 3H), 2.55 (d, J =5.7 Hz, 2H), 2.27 (s, 3H). H NMR (400 MHz, CDC13) 6 8.94 (d, J =2.5 Hz, 1H), 8.58 (dd, J =4.7, 1.4 Hz, 1H), 8.03 (ddd, J ESIMS ~ 429 = 8.3, 2.7, 1.5 Hz, 228 (thin film) 1664 ESIMS m/z 429 '7.89 (s, 1H), 7.43 (ddd, J =8.3, 4.8, 0.6 Hz, 1H), 3.24 (s, 3H), 2.64 2.48 (m, 2H), 2.39 (dd, J =9.2, 6.4 Hz, 2H), 2.27 (s, 3H). 363 'H NMR (400 MHz, CDC13) 6 8.94 (d, J =2.5 Hz, 1H), 8.58 (dd, J =4.7, 1.3 Hz, 1H), 8.03 (ddd, J ESIM m~z413 =8.3, 2.7, 1.5 Hz, 229 ESIMS m/z 413 '7.89 (s, 1H), 'H 7.43 (ddd, J =8.3, 4.8, 0.6 Hz, 1H), 3.24 (s, 3H), 2.60 2.45 (m, 2H), 2.40 (dd, J =9.8, 5.7 Hz, 2H), 2.26 (s, 3H). H NMR (400 MHz, CDC13) 6 8.92 (d, J =2.5 Hz, 1H), 8.53 (dd, J =4.7, 1.2 Hz, ESIMS m/z 277 1H), 8.01 (ddd, J 230 ([M+H]=) 8.3, 2.6, 1.5 Hz, 1H), 7.86 (s, 1H), 7.39 (dd, J =8.3, 4.6 Hz, 1H), 3.24 (s, 3H), 2.27 (s, 3H), 1.56 (d, J =21.3 Hz, 6H). 1 C NMR (101 'H NMR (400 MHz, CDC1 3 ) MHz, CDC13) 6 6 174.28, 8.85 (s, 1H), 8.57 148.35, (dd, J=4.7, 1.1 147.80, Hz, 1H), 7.91 (d, J 140.47, =7.2 Hz, 1H), 139.98, ESIMS m/z 355 7.52 - 7.31 (m, 136.03, 231 ([M+H]*) 2H), 7.25 - 7.14 132.72, (m, 2H), 7.03 - 128.79, 6.90 (m, 2H), 3.67 128.69, (d, J =5.7 Hz, 126.86, 1H), 3.19 (s, 3H), 125.85, 1.98 (s, 3H), 1.39 124.88, (d, J =7.0 Hz, 123.98, 42.93, 3H). 37.51, 20.46, 10.69. 364 'H NMR (400 MHz, CDC3) 6 8.87 (d, J =2.5 Hz, 1H), 8.57 (dd, J =4.7, 1.3 Hz, 1H), 7.97 (ddd, J =8.3, 2.7, 1.5 Hz, 1H), 7.68 (s, 1H), 232 57-59 ESIMS m/z 391 7.42 (ddd, J =8.3, ([M+H]*) 4.8, 0.6 Hz, 1H), 7.28 (t, J =7.9 Hz, 1H), 7.09 (dd, J =8.3, 1.1 Hz, 1H), 7.03 (d, J =7.7 Hz, 1H), 6.96 (s, 1H), 3.57 (s, 2H), 3.23 (s, 3H), 2.14 (s, 3H). 'H NMR (400 MHz, CDC3) 6 8.89 (d, J =2.5 Hz, 1H), 8.55 (dd, J =4.7, 1.4 Hz, 179- ESIMS m/z 365 1H), 7.95 (d, J 233 181 ([M+H] ) 8.0 Hz, 1H), 7.83 (s, 1H), 7.40 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 7.04 (s, 1H), 3.81 (s, 3H), 3.37 (s, 3H), 2.19 (s, 3H). 365 "C NMR (101 H NMR (400 MHz, CDC1 3 ) MHz, CDC13) 6 6 159.59, 8.94 (d, J =2.5 154.79, Hz, 1H), 8.55 (dd, 148.41, J =4.7, 1.4 Hz, 147.61, 1H), 8.02 (ddd, J 146.31, 100- ESIMS mz 343 =8.3, 2.7, 1.5 Hz, 140.04, 234 102 ([M+H] ) 1H), 7.91 (s, 1H), 136.20, 7.41 (ddd, J =8.3, 127.79, 4.7, 0.6 Hz, 1H), 125.90, 6.37 (s, 1H), 6.13 124.35, (d, J=3.2 Hz, 123.93, 1H), 3.53 (s, 2H), 117.73, 3.38 (s, 3H), 2.22 108.90, 38.56, (s, 3H). 30.20, 15.42, 11.02. H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.5 Hz, 1H), 8.58 (dd, J = 4.7, 1.4 Hz, 1H), 8.03 (ddd, J 235 (thin film) 1654 ESIMS m/z = 8.3, 2.7, 1.5 Hz, 307([M+H]*) 1H), 7.85 (s, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.24 (s, 3H), 3.02 2.77 (m, 3H), 2.59 - 2.38 (m, 2H), 2.25 (s, 3H). IH NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.4 Hz, 1H), 8.60 (dd, J = 4.7, 1.2 Hz, ESIMS m/z 397 8H), 8.18 (s, 1H), 236 ([M+H]+) 8.03 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.91 (s, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 3.29 (s, 3H), 2.70 (s, 2H), 2.28 (s, 3H). 366 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.61 (dd, J = 4.7, 1.3 Hz, 1H), 8.22 (s, 1H), 8.03 (ddd, J= 8.3, 237 1169 ESIMS m/z 411 2.7 1 )5 Hz, 1H), 27 114 (thin film) 1629 (IIM+H] + . (dd, J =8., 748 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 4.09 3.83 (m, 1H), 3.58 - 3.30 (m, 1H), 2.79 - 2.51 (m, 2H), 2.28 (s, 3H), 1.19 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.58 (dd, J = 4.7, 1.3 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.88 (s, 1H), 7.43 (ddd, J = 8.3, 238 ESIMS m/z 373 4.8, 0.6 Hz, 1H), ([M+H]*) 3.77 (tdd, J = 17.3, 8.6, 3.8 Hz, 2H), 3.67 (brs, 1H), 2.54 (dd, J= 16.3, 3.6 Hz, 1H), 2.37 (dd, J = 24.4, 8.2 Hz, 1H), 2.29 (s, 3H), 2.28 (s, 3H), 1.17 (t, J= 7.2 Hz, 3H). 367 'H NMR (400 MHz, CDC3) 6 8.96 (s, 1H), 8.59 (d, J= 4.2 Hz, 1H), 8.11 - 7.78 (m, 2H), 7.44 (dd, J = 8.3, 4.7 Hz, 1H), 4.21 (s, 1H), 3.52 (dd, J= 19.2, ESIMS m/z 373 11.9 Hz, 1H), 3.37 239 (thin film) 1666 ([M+H] ) 3.10 (m, 2H), 2.76 (dd, J = 34.4, 11.6 Hz, 1H), 2.28 (s, 3H), 2.08 (s, 3H), 1.19 (t, J= 7.1 Hz, 3H). (Compound spectrum shows two rotamers; only the major one is reported) H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.5 Hz, 1H), 8.58 (dd, 1 C NMR (101 J = 4.7, 1.3 Hz, MHz, CDCl 3 ) 1H), 8.04 (ddd, J 6 171.90, = 8.3, 2.7, 1.5 Hz, 148.46, 1H), 7.84 (s, 1H), 147.96, 103- ESIMS m/z 303 7.44 (ddd, J = 8.3, 140.05, 240 105 ([M+H] ) 4.8, 0.4 Hz, 1H), 135.98, 4.10 (p, J = 9.1 126.08, Hz, 1H), 3.70 (t, J 125.15, = 9.1 Hz, 2H), 124.31, 3.68 - 3.46 (m, 124.03, 44.01, 2H), 2.75 (dd, J= 42.41, 27.81, 13.3, 5.0 Hz, 2H), 12.95, 11.16. 2.24 (s, 3H), 1.13 (t, J = 7.2 Hz, 3H). 368 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.59 (dd, J = 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.88 (s, 1H), 241 ESIMS m/z 395 7.44 (ddd, J = 8.3, ([M+H]*) 4.8, 0.6 Hz, 1H), 4.05 (dtd, J = 14.1, 8.4, 2.6 Hz, 1H), 3.97 - 3.43 (m, 2H), 2.51 (d, J = 5.5 Hz, 2H), 2.26 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H). 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.58 (dd, J = 4.7, 1.3 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 242 (thin film) 1661 ESIMS m/z 443 1H), 7.87 (s, 1H), ([M+H]*) 7.44 (ddd, J = 8.3, 4.7, 0.5 Hz, 1H), 3.80 - 3.52 (m, 2H), 2.65 - 2.47 (m, 2H), 2.40 2.31 (m, 2H), 2.26 (s, 3H), 1.15 (t, J = 7.2 Hz, 3H). 369 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.58 (dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, ESIMS mz 42 11H), 7.87 (s, 1H), 243 (thin film) 1660 ESIMS m/z 427 7.44 (ddd, J = 8.4, 4.8, 0.6 Hz, 1H), 3.69 (d, J= 6.8 Hz, 2H), 2.62 2.45 (m, 2H), 2.42 - 2.31 (m, 2H), 2.26 (s, 3H), 1.15 (t, J = 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.93 (s, 1H), 8.53 (d, J= 4.0 Hz, 1H), 8.02 (ddd, J = 8.3, 2.6, 1.4 Hz, 244 64-68 ESIMS m/z 291 1H), 7.82 (s, 1H), ([M+H]*) 7.40 (dd, J = 8.3, 4.7 Hz, 1H), 3.98 (s, 1H), 3.30 (s, 1H), 2.26 (s, 3H), 1.58 (s, 3H), 1.53 (s, 3H), 1.17 (t, J = 7.0 Hz, 3H). 370 'H NMR (400 MHz, CDC3) 6 8.82 (brs, 1H), 8.57 (d, J= 3.8 Hz, 1H), 7.87 (brs, 1H), 7.41 (dd, J = 8.2, 4.8 Hz, 1H), 245 114- (thin film) 1656 ESIMS m/z 370 7.20 (d, J = 8.4 116 ([M+H]*) Hz, 2H), 6.97 (d, J = 8.3 Hz, 3H), 3.88 (brs, 1H), 3.54 (brs, 2H), 2.21 (brs, 3H), 1.38 (d, J= 6.9 Hz, 3H), 1.10 (t, J = 7.1 Hz, 3H). 'H NMR (400 MHz, CDC3) 6 8.86 (d, J= 2.5 Hz, 1H), 8.57 (dd, J = 4.7, 1.3 Hz, 1H), 7.96 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.58 (s, 1H), 246 ESIMS m/z 405 7.42 (ddd, J = 8.4, ([M+H]*) 4.8, 0.6 Hz, 1H), 7.27 (t, J= 7.9 Hz, 1H), 7.14 7.05 (m, 1H), 7.05 - 6.92 (m, 2H), 3.68 (brs, 2H), 3.52 (s, 2H), 2.16 (s, 3H), 1.14 (t, J = 7.2 Hz, 3H). 371 'H NMR (400 MHz, CDCl3) 6 8.91 (d, J= 2.1 Hz, 1H), 8.56 (d, J = 4.0 Hz, 1H), 170- ESIMS m/z 379 7.96 (d, J = 8.1 247 172 ([M+H]*) Hz, 1H), 7.84 (s, 1H), 7.40 (dd, J = 8.3, 4.7 Hz, 1H), 7.05 (s, 1H), 4.05 3.56 (m, 5H), 2.16 (s, 3H), 1.23 (t, J = 6.9 Hz, 3H). IH NMR (400 MHz, CDC13) 6 8.96 (d, J= 2.5 Hz, 1H), 8.55 (dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.91 (s, 1H), 248 (thin film) 1653 ESIMS m/z 357 7.42 (ddd, J = 8.4, ([M+H]*) 4.8, 0.6 Hz, 1H), 6.31 (s, 1H), 6.12 (d, J= 3.3 Hz, 1H), 3.95 - 3.72 (m, 2H), 3.53 (s, 2H), 2.20 (s, 3H), 1.96 (s, 3H), 1.25 (t, J= 7.1 Hz, 3H). 372 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.59 (dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 249 80-82 ESIMS m/z 321 1H), 7.83 (s, 1H), ([M+H]*) 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.89 - 3.51 (m, 2H), 2.97 - 2.81 (m, 3H), 2.51 (s, 2H), 2.24 (s, 3H), 1.15 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.80 (dd, J= 43.8, 10.1 Hz, 1H), 8.51 - 8.36 (m, 1H), ESIMS ~z 393 8.11 (d, J = 38.7 250 (thin film) 1649 ESIMS m/z 9 Hz, 1HI), 7.96 7.77 (m, 1H), 4.32 - 3.92 (m, 2H), 3.49 - 3.11 (m, 6H), 2.32 (s, 3H), 1.27 - 1.05 (m, 6H). 'H NMR (400 1 3 C NMR (101 MHz, CDCl3) 6 MHz, CDCl 3 ) 8.75 (d, J= 1.7 6 170.27, Hz, 1H), 8.43 (d, J 148.88, = 2.5 Hz, 1H), 136.14, 7.86 (s, 2H), 5.96 135.91, ESIMS m/z 357 - 5.71(m, 1H), 135.20, 251 ([M+H]*) 5.20 (dd, J= 10.2, 132.35, 1.2 Hz, 1H), 5.13 125.45, (dd, J= 17.1, 1.3 125.15, Hz, 1H), 4.22 (s, 119.03, 2H), 2.50 (dt, J= 113.57, 13.9, 6.1 Hz, 4H), 113.34, 52.17, 2.42 - 2.33 (m, 38.61, 28.27, 2H). 26.76, 11.14. 373 'H NMR (400 MHz, CDC13) 6 8.79 (d, J= 1.8 Hz, 1H), 8.63 (s, ESIMS m/z 1H), 8.42 (d, J = 252 168 359([M]+), 2.5 Hz, 1H), 7.82 169 361([M+2H]*) (dt, J= 9.4, 2.4 Hz, 1H), 7.68 (s, 1H), 2.91 (t, J= 6.9 Hz, 2H), 2.75 (dd, J= 10.2, 3.5 Hz, 2H), 2.20 (s, 3H). H NMR (400 MHz, CDC13) 6 8.78 (d, J= 1.8 Hz, 1H), 8.65 (s, 1H), 8.41 (d, J= ESIMS m/z 373 2.5 Hz, 1H), 7.81 253 106- ([M+H]), 375 (dt, J= 9.3, 2.4 Hz, 107 ([M+2H]*) 1H), 7.66 (s, 1H), 2.87 (dd, J= 14.5, 10.2 Hz, 1H), 2.74 - 2.66 (m, 2H), 2.18 (s, 3H), 1.36(d, J= 6.6 Hz, 4H). 'H NMR (400 MHz, CDC13) 6 8.72 (d, J= 1.9 254 95-96 ESIMS m/z 372 Hz, 1H), 8.44 (d, J ([M+H]*) = 2.5 Hz, 1H), 7.85 (s, 1H), 7.83 (s,1H), 3.22 (s, 3H), 1.45 (s, 9H). 374 'H NMR (400 MHz, CDC3) 6 8.94 (d, J= 2.6 Hz, 1H), 8.49 (dd, J= 4.7, 1.4 Hz, 1H), 8.46 (s, 1H), 8.02 (s, 1H), 7.96 (ddd, J= 8.4, 2.7, ESIMS m/z 278 1.5 Hz, 1H), 7.38 255 221- ([M+H]), 276 (ddd, J = 8.3, 4.8, 223 ([M-H]-) 0.6 Hz, 1H), 6.46 (t, J= 5.6 Hz, 1H), 5.91 (ddt, J= 17.2, 10.5, 5.3 Hz, 1H), 5.24 (dq, J= 17.1, 1.7 Hz, 1H), 5.13 (dq, J= 10.3, 1.5 Hz, 1H), 3.88 (tt, J= 5.6, 1.6 Hz, 2H). H NMR (400 MHz, CDC3) 6 8.94 (d, J= 2.7 Hz, 1H), 8.49 (dd, J= 4.7, 1.3 Hz, 1H), 8.46 (s, 1H), 222- ESIMS m/z 266 7.96 (ddd, J= 8.3, 256 225 ([M+H]*), 264 2.6, 1.4 Hz, 1H), ([M-H]-) 7.88 (s, 1H), 7.38 (dd, J= 8.3, 4.7 Hz, 1H), 6.26 (t, J = 5.2 Hz, 1H), 3.35 - 3.20 (m, 2H), 1.17 (t, J= 7.2 Hz, 3H). 375 'H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.7 Hz, 1H), 8.51 8.39 (m, 2H), 8.02 ESIMS mz 280 - 7.80 (m, 2H), 27 213- ESIMS m/z_280 7.39 - 7.31 (in, 257 (IM+H]), 278 396.33 (s, 1HI), 3.28 - 3.11 (m, 2H), 1.55 (ddd, J = 14.4, 7.3, 4.1 Hz, 2H), 0.95 (td, J= 7.3, 4.2 Hz, 3H). 'H NMR (400 1 3 C NMR (101 MHz, CDC13) 6 MHz, CDC1 3 ) 8.91 (d, J= 2.4 6 170.97, Hz, 1H), 8.56 (dd, 154.09, J= 4.7, 1.4 Hz, 148.02, 1H), 8.01 (ddd, J 139.81, ESIMS m/z 335 = 8.3,2.5, 1.4 Hz, 136.83, 258 ([M+H]*) 1H), 7.87 (s, 1H), 135.90, 7.41 (dd, J= 8.2, 133.69, 4.8 Hz, 1H), 5.96 133.53, - 5.78 (m, 1H), 126.02,124.26, 5.21 - 5.15 (m, 123.96, 2H),4.20 - 4.13 117.87, (m, 2H), 1.46 (s, 106.89, 81.33, 9H). 60.31, 28.08. 376 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.7 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 7.89 (s, 1H), 7.86 (dt, J= 9.4, 2.4 Hz, 1H), 3.77 (tdd, 259 104- (thin film) 1648 ESIMS m/z 391 J = 17.2, 8.6, 3.8 107 ([M+H]*) Hz, 2H), 3.71 3.51 (m, 1H), 2.53 (dd, J= 16.2, 3.6 Hz, 1H), 2.36 (dd, J = 15.1, 9.4 Hz, 1H), 2.29 (s, 3H), 2.27 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.8 Hz, 1H), 8.45 (d, J = 2.5 Hz, 1H), 8.12 - 7.77 (m, 2H), 4.21 (s, 1H), 3.61 - 3.38 (m, ESIMSm~z 3 1 H), 3.36 - 3.09 260 (thin film) 1665 ESIMS m/z 391 2H), 2.76 (dd, J = 35.3, 11.8 Hz, 1H), 2.28 (s, 3H), 2.09 (s, 3H), 1.19 (t, J= 7.1 Hz, 3H). Mixture of two rotational isomers, only the major peaks reported 377 'H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 7.85 (dt, J= 9.3, 2.4 Hz, 1H), 7.82 261 118- (thin film) 1639 ESIMS m/z 321 (s, 1H), 4.08 (p, J 120 ([M+H]*) = 9.1 Hz, 1H), 3.70 (t, J = 9.2 Hz, 2H), 3.68 3.43 (m, 2H), 2.74 (t, J= 9.1 Hz, 2H), 2.24 (s, 3H), 1.13 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 7.85 (dt, J= 9.3, 2.4 Hz, 1H), 7.82 262 109- (thin film) 1657 ESIMS m/z 413 (s, 1H), 4.08 (p, J 111 ([M+H]*) = 9.1 Hz, 1H), 3.70 (t, J = 9.2 Hz, 2H), 3.68 3.43 (m, 1H), 2.74 (t, J= 9.1 Hz, 2H), 2.24 (s, 3H), 1.13 (t, J= 7.2 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), ESIMS m/z 445 7.89 (s, 1H), 7.88 263 (thin film) 1659 ([M+H] ) 7.84 (m, 1H), 3.69 (d, J = 6.8 Hz, 2H), 2.59 - 2.44 (m, 2H), 2.39 2.31 (m, 2H), 2.25 (s, 3H), 1.15 (t, J = 7.2 Hz, 3H). 378 'H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 7.85 (dt, J= 9.3, 2.4 Hz, 1H), 7.82 264 (thin film) 1659 ESIMS m/z 461 (s, 1H), 4.08 (p, J ([M+H]*) = 9.1 Hz, 1H), 3.70 (t, J = 9.2 Hz, 2H), 3.68 3.43 (m, 1H), 2.74 (t, J= 9.1 Hz, 2H), 2.24 (s, 3H), 1.13 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.73 (d, J= 1.5 Hz, 1H), 8.39 (d, J = 2.5 Hz, 1H), 265 105- (thin film) 1634 ESIMS m/z 309 7.87 - 7.80 (m, 107 ([M+H]*) 2H), 3.90 (brs, 1H), 3.31 (brs, 1H), 2.25 (s, 3H), 1.58 (s, 3H), 1.53 (s, 3H), 1.17 (t, J = 7.0 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.58 (brs, 1H), 8.43 (d, J= 2.5 Hz, 1H), 7.73 (brs, 1H), 7.21 (d, J = 266 (thin film) 1599 ESIMS m/z 387 8.4 Hz, 2H), 6.96 ([M+H]*) (d, J = 8.4 Hz, 2H), 4.03 - 3.22 (m, 3H), 2.46 1.98 (m, 3H), 1.38 (d, J= 6.9 Hz, 3H), 1.09 (t, J = 7.1 Hz, 3H). 379 'H NMR (400 MHz, CDCl3) 6 8.64 (d, J= 1.7 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.79 (dt, J= 9.3, 2.4 Hz, 1H), 7.58 267 (thin film) 1654 ESIMS m/z 423 (s, 1H), 7.27 (t, J ([M+H]*) = 7.9 Hz, 1H), 7.15 - 7.06 (m, 1H), 7.00 (d, J = 7.7 Hz, 1H), 6.95 (s, 1H),3.67 (brs, 2H), 3.52 (s, 2H), 2.15 (s, 3H), 1.14 (t, J= 7.2 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.71 (d, J= 1.4 Hz, 1H), 8.41 (d, J 174-ESIM m~z397 = 2.5 Hz, 1H), 268 174 (thin film) 1652 ESIMS m/z 39 7.85 (s, IH), 7.78 (d, J = 9.3 Hz, 1H), 7.07 (s, 1H), 3.82 (s, 5H), 2.16 (s, 3H), 1.22 (t, J = 6.9 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.7 Hz, 1H), 8.41 (d, J = 2.5 Hz, 1H), 7.90 (s, 1H), 7.85 269 (th 10 ESIMS m/z 375 (dt, J= 9.4, 2.4 269 980 (thin film) 1630 ESIM 'H]'+ Hz, 1H), 6.38 (s, S1H), 6.13 (d, J = 3.3 Hz, 1H), 3.81 (d, J= 6.5 Hz, 2H), 3.52 (s, 2H), 2.19 (s, 3H), 1.95 (s, 3H), 1.24 (t, J = 7.1 Hz, 3H). 380 'H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 7.89 - 7.84 (m, 270 77-79 (thin film) 1650 ESIMS m/z 339 1H), 7.84 (s, 1H), ([M+H]*) 3.68 (brs, 2H), 2.98 - 2.73 (m, 3H), 2.48 (ddd, J = 13.9, 8.2, 3.5 Hz, 2H), 2.23 (s, 3H), 1.15 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.9 Hz, 1H), 8.47 (d, J = 2.5 Hz, 1H), ESIM m~z429 8.16 (s, 1H), 7.90 271 (thin film) 1635 ESIMS z 429 '1H), 7.88 - 7.83 (m, 1H), 3.99 (brs, 1H), 3.42 (brs, 1H), 2.63 (brs, 2H), 2.27 (s, 3H), 1.19 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.66 (s, 1H), 8.40 (d, J= 2.5 Hz, 272 18 ESIMS m/z 397 1H), 7.85 - 7.70 272 116- EShMS film 168 (MH+ (mn, 2H), 7.27 (s, 1H), 3.89 (s, 3H), 3.82 (q, J= 7.0 Hz, 2H), 2.16 (s, 3H), 1.24 (t, J = 7.1 Hz, 3H). 381 'H NMR (400 MHz, CDCl3) 6 8.59 (brs, 1H), 8.42 (d, J= 2.5 Hz, 1H), 7.76 (brs, 273 (thin film) 1651 ESIMS m/z 371 1H), 7.03 - 6.85 ([M+H]*) (m, 4H), 3.55 (brs, 3H), 2.25 (brs, 3H), 1.38 (d, J = 6.9 Hz, 3H), 1.09 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.69 (d, J= 1.7 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.78 (dt, J = 9.4, 2.4 Hz, 1H), 7.49 ESIMS m/z 437 (s, 1H), 7.15 (d, J 274 (thin film) 1653 ([M+H]+) = 8.7 Hz, 2H), 7.10 (d, J = 8.1 Hz, 2H), 3.65 (s, 2H), 2.95 (t, J = 7.3 Hz, 2H), 2.37 (t, J= 7.4 Hz, 2H), 2.12 (s, 3H), 1.10 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.7 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), 275 (60 ESIMS m/z 399 7.92 (s, 1H), 7.85 275 114- tinflm 6 ESIMH +/ (dt, J = 9.3, 2.4 Hz, 1H), 3.77 (s, 2H), 3.68 (s, 2H), 2.94 (s, 3H), 2.83 (s, 6H), 2.28 (s, 3H), 1.16 (t, J= 7.2 Hz, 3H). 382 'H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.5 Hz, 1H), 8.59 (dd, J = 4.7, 1.3 Hz, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.5 Hz, 276 83-86 (thin film) 1664 ESIMS m/z 425 1H), 7.85 (s, 1H), ([M+H] ), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 4.00 (brs, 1H), 3.73 (s, 3H), 3.39 (brs, 1H), 2.86 (s, 2H), 2.26 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.76 (s, 1H), 8.49 (d, J= 2.4 Hz, 1H), 8.03 (s, 1H), 7.87 (dt, J= 9.1, ESIMS m/z 388 2.3Hz, 1H), 3.26 277 ([M+H]*) (s, 3H), 2.94 2.83 (m, 1H), 2.73 (dd, J= 14.4, 6.9 Hz, 1H), 2.48 (dd, J= 12.7, 5.3 Hz,1H), 2.03 (s, 3H), 1.17 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.3 Hz, 1H), 8.55 (dd, J= 4.7, 1.4 Hz, 1H), 8.02 (ddd, J 154- ESIMS m/z 260 = 8.3, 2.7, 1.5 Hz, 278 156 ([M+H]*), 258 1H), 7.93 (s, 1H), ([M-H]-) 7.42 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 4.51 (s, 1H), 3.29 3.22 (m, 2H), 3.21 (s, 3H), 2.27 (s, 3H), 1.08 (t, J= 7.2 Hz, 3H). 383 'H NMR (400 MHz, CDC13) 6 8.94 (dd, J= 2.6, 0.4 Hz, 1H), 8.55 (dd, J= 4.7, 1.4 Hz, 1H), 8.01 (ddd, J= 8.3, 2.7, 159- ESIMS m/z 274 1.5 Hz, 1H), 7.92 279 161 ([M+H]*), 272 (s, 1H), 7.42 (ddd, ([M-H]-) J= 8.3, 4.8, 0.7 Hz, 1H), 4.53 (t, J = 5.4 Hz, 1H), 3.21 (s, 3H), 3.19 3.10 (m, 2H), 2.28 (s, 3H), 1.53 - 1.38 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.96 - 8.90 (m, 1H), 8.55 (dd, J= 4.7, 1.4 Hz, 1H), 8.01 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), ESIMS m/z 272 7.93 (s, 1H), 7.41 280 150 ([M+H]), 270 (ddd, J = 8.3, 4.8, 152 ([M-H]-) 0.7 Hz, 1H), 5.82 (ddt, J= 17.1, 10.2, 5.6 Hz, 1H), 5.19 - 4.98 (m, 2H), 4.61 (t, J= 5.5 Hz, 1H), 3.84 (tt, J= 5.8, 1.5 Hz, 2H), 3.23 (s, 3H), 2.28 (s, 3H). 384 'H NMR (400 MHz, CDCl3) 6 8.75 (dd, J= 2.5, 0.5 Hz, 1H), 8.62 (dd, J= 4.8, 1.5 (thin film) ESIMS m/z 275 Hz, 1H), 7.82 281 3268, 2978, 1698. ([M+H]*), 273 (ddd, J= 8.2, 2.6, ([M-H]-) 1.5 Hz, 1H), 7.78 (s, 1H), 7.43 (ddd, J= 8.1, 4.8, 0.6 Hz, 1H), 6.04 (s, 1H), 2.29 (s, 3H), 1.52 (s, 9H). H NMR (400 MHz, CDCl3) 6 8.93 (d, J= 2.5 1C NMR (101 Hz, 1H), 8.62 (dd, MHz, CDCl 3 ) J= 4.7, 1.3 Hz, 6 175.72, 1H), 8.03 (ddd, J 148.64, = 8.4,2.7, 1.4 Hz, 140.81, 1H), 7.93 (d, J = 140.04, 282 ESIMS m/z 338 3.2 Hz, 1H), 7.46 135.64, ([M+H]*) (dd, J= 8.2, 4.7 132.61, Hz, 1H), 5.86 (ddt, 130.03, J= 16.6, 10.2, 6.4 126.26, Hz,1H), 5.25 - 124.10,123.76, 5.10 (m, 2H), 4.26 118.63, 51.53, (s, 2H), 2.81 (t, J 37.19, 18.27, = 7.3 Hz, 2H), 16.55. 2.49 (t, J = 7.3 Hz, 2H), 2.07 (s, 3H). 385 'H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.7, 1.3 Hz, 1C NMR (101 1H), 8.03 (ddd, J MHz, CDC1 3 ) = 8.3,2.7, 1.4 Hz, 6 171.59, 1H), 7.97 (s, 1H), 148.68, 7.45 (dd, J= 8.3, 140.73, 4.8 Hz, 1H), 5.86 140.01, 283 ESIMS m/z 352 (ddt, J = 16.7, 135.62, ([M+H]*) 10.5, 6.3 Hz, 1H), 132.56, 5.18(dd, J= 9.8, 126.44, 8.6 Hz, 2H), 4.41 126.31, - 4.28 (m, 2H), 124.11,123.77, 2.87 (dd, J= 12.7, 118.84, 51.65, 9.1 Hz, 1H), 2.75 33.90, 29.65, (bs, 1H), 2.48 (dd, 15.93. J= 12.7, 5.2 Hz, 1H), 2.02 (s, 3H), 1.18 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.5 Hz, 1H), 8.69 8.56 (m, 1H), 8.04 (ddd, J = 8.4, 2.6, 284 93-94 ESIMS m/z 305 1.4Hz, 1H), 7.90 ([M+H]*) (s, 1H), 7.45 (dd, J = 8.3, 4.8 Hz, 1H), 5.97 - 5.74 (m, 1H), 5.31 - 4.99 (m, 2H), 4.29 (s,2H), 1.10 (d, J= 6.7 Hz, 6H). 386 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.3 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.5 Hz, 285 (thin film) 1654 ESIMS m/z 306 1H), 7.90 (s, 1H), ([M+2]+) 7.43 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 3.78 - 3.63 (m, 2H), 2.57 - 2.47 (m, 2H), 2.28 (s, 3H), 2.09 (s, 3H), 1.93 (s, 3H), 1.90 1.80 (m, 2H). H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.8 Hz, 1H), 8.44 (d, J = 2.5 Hz, 1H), ESIMS m/z 377 7.88 (s, 1H), 7.88 286 (thin film) 1656 ([M+H] ) 7.82 (m, 1H), 3.70 (d, J = 6.0 Hz, 2H), 3.12 (t, J= 6.7 Hz, 2H), 2.51 (t, J= 6.6 Hz, 2H), 1.16 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.4 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, ESIM m~z333 1H), 7.91 (s, 1H), 287 (thin film) 1649 ESIMS m/z 33 7.43 (ddd, J= 8.3, 4.7, 0.5 Hz, 1H), 3.74 (s, 2H), 2.63 2.54 (m, 1H), 2.54 - 2.47 (m, 2H), 2.26 (s, 3H), 2.10 (s, 3H), 1.90 - 1.80 (m, 2H), 1.06 (d, J = 6.7 Hz, 6H). 387 'H NMR (400 MHz, CDC3) 6 8.93 (d, J= 2.4 Hz, 1H), 8.52 (dd, J= 4.7, 1.4 Hz, 1H), 8.01 (ddd, J = 8.3, 2.6, 1.4 Hz, ESIMS m/z 335 1H), 7.85 (s, 1H), 288 (thin film) 1694 ([M+H] ) 7.39 (dd, J= 8.3, 'H 4.7 Hz, 1H), 4.17 (s, 2H), 3.75 - 3.60 (m, 2H), 2.52 (t, J = 7.3 Hz, 2H), 2.25 (s, 3H), 2.09 (s, 3H), 1.95 - 1.81 (m, 2H), 1.43 1.06 (m, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.3 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.91 (s, 1H), ESIMS m/z 366 7.43 (ddd, J= 8.3, 289 (thin film) 1652 ([M+H] ) 4.8, 0.6 Hz, 1H), 3.72 (s, 2H), 2.78 (t, J= 7.2 Hz, 2H), 2.57 - 2.50 (m, 2H), 2.42 (t, J= 7.2 Hz, 2H), 2.28 (s, 3H), 2.10 (s, 3H), 2.05 (s, 3H), 1.91 - 1.81 (m, 2H). 388 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.57 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.6, 1.4 Hz, 1H), 7.95 (s, 1H), 7.43 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 290 (thin film) 1650 ESIMS m/z 380 4.44 - 3.08 (m, ([M+H]*) 2H), 2.95 - 2.82 (m, 1H), 2.81 2.65 (m, 1H), 2.62 - 2.47 (m, 2H), 2.47 - 2.38 (m, 1H), 2.31 (s, 3H), 2.10 (s, 3H), 2.01 (s, 3H), 1.87 (p, J = 7.4 Hz, 2H), 1.12 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.54 (d, J= 2.5 Hz, 1H), 8.58 (dd, J= 4.7, 1.4 Hz, 291 (R thin film) 1684 ESIMS m/z 337 1H), 8.19 - 7.94 ([M+H]*) (m, 1H), 7.80 (bs, 1H), 7.47 - 7.34 (m, 1H), 4.76 4.38 (m, 1H).1.57 (s, 9H), 1.13 (d, J = 6.7 Hz, 6H), 389 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.57 (dd, J= 4.7, 1.3 Hz, 1H), 8.03 (ddd, J = 8.3, 2.6, 1.5 Hz, 1H), 7.99 (s, 1H), 7.43 (dd, J= 8.2, 292 96- (thin film) 1666, ESIMS m/z 4.6 Hz, 1H), 4.10 100 1450 335.2 ([M+H]*) (q, J= 6.5 Hz, 1H), 3.56 (dt, J= 9.1, 6.6 Hz, 1H), 3.45 (dt, J= 9.2, 6.9 Hz, 1H), 3.25 (s, 3H), 2.66 (t, J = 6.8 Hz, 2H), 2.29 (s, 3H), 2.11 (s, 3H), 1.30 (d, J = 6.5 Hz, 3H). IH NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.56 (dd, J= 4.7, 1.2 Hz, 1H), 8.08 (s, 1H), 8.05 (ddd, J= 8.3, ESIMS 2.5, 1.5 Hz, 1H), 293 (thin film) 1665 m/z 319.5 7.42 (dd, J= 8.3, ([M+H]*) 4.8 Hz, 1H), 4.11 (q, J= 6.5 Hz, 1H), 3.59 - 3.44 (m, 4H), 3.37 (s, 3H), 3.24 (s, 3H), 2.29 (s, 3H), 1.29 (d, J= 6.5 Hz, 3H). 390 'H NMR (400 MHz, CDC3) 6 8.94 (d, J= 2.6 Hz, 1H), 8.58 (dd, J= 4.7, 1.3 Hz, 1H), 8.01 (ddd, J = 8.3, 2.6, 1.5 Hz, ESIMS 1), 7.91 (s, 1H), 294 (thin film) 1668 m8z 43 (dd, J - 8.3, (q, J= 6.4 Hz, 1H), 3.87 (dq, J= 12.3, 8.9 Hz, 1H), 3.81 - 3.64 (m, 1H), 3.24 (d, J= 12.2 Hz, 3H), 2.28 (s, 3H), 1.33 (d, J = 6.5 Hz, 3H). 'H NMR (400 MHz, CDC3) 6 8.96 (dd, J= 5.5, 2.5 Hz, 1H), 8.58 (dd, J= 4.7, 1.2 Hz, 1H), 8.03 (tdd, J= 7.0, 2.7, 1.5 Hz, 1H), 7.92 (d, J = 5.3 Hz, 1H), ESIMS 7.43 (dd, J= 8.3, 295 (thin film) 1665 M/Z331.28 Hz, 12, 4.12 Hz, 2H), 3.85 (dd, J= 7.3, 4.0 Hz, 1H), 3.73 (dd, J= 17.8, 10.9 Hz, 3H), 3.25 (s, 3H), 2.29 (d, J= 4.0 Hz, 3H), 2.05 1.81 (m, 2H), 1.29 (d, J= 6.5 Hz, 3H). 391 'H NMR (400 "C NMR (101 MHz, CDCl3) 6 MHz, CDCl 3 ) 8.94 (d, J= 2.6 6 177.38, Hz, 1H), 8.63 (dd, 153.53, J= 4.7, 1.3 Hz, 150.57, 1H), 8.04 (ddd, J 148.69, 296 ESIMS m/z 358 = 8.4,2.7, 1.4 Hz, 140.09, ([M]+) 1H), 7.92 (s, 1H), 126.70, 5.85 (ddt, J = 126.36, 16.7, 10.1, 6.4 Hz, 124.09, 1H), 5.18 (ddd, J 123.64,123.24, = 18.4, 13.6, 1.2 123.15, 72.71, Hz,2H), 2.65 - 37.64, 31.31, 2.29 (m, 4H). 19.49. 'H NMR (400 MHz, DMSO-d6) 6 8.93 (s, 1H), 8.65 (s, 1H), 8.48 (thin film) 3337, ESIMS m/z 330 (d, J = 2.5 Hz, 297 3273, 3079, 3018, ([M+H] +2) 1H), 8.28 (s, 2H), 1631. ' 8.18 (dt, J= 10.3, 2.3 Hz, 1H), 3.14 (q, J= 7.2 Hz, 2H), 1.08 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, DMSO-d6) 6 8.94 (s, 1H), 8.66 (s, 1H), 8.52 (d, J= 2.5 Hz, 1H), 8.22 (dt, J= (thin film) 3322, ESIMS m/z 344 10.3, 2.3 Hz, 1H), 298 2963, 1636. ([M+H] +2). 8.02 (s, 1H), 6.62 (t, J= 5.6 Hz, 1H), 3.07 (dd, J= 12.6, 6.8 Hz, 2H), 1.45 (dd, J= 14.3, 7.2 Hz, 2H), 0.89 (t, J = 7.4 Hz, 3H). 392 'H NMR (400 MHz, DMSO-d6) 6 8.95 (s, 1H), 8.67 (s, 1H), 8.52 (d, J= 2.5 Hz, 1H), 8.22 (dt, J = 10.3, 2.3 Hz, 1H), (thin film) 3329, ESIMS m/z 342 8.13 (s, 1H), 6.73 299 3289, 3074, 1634. ([M+H] ). (t, J = 5.7 Hz, 1H), 5.88 (ddt, J= 17.2, 10.2, 5.1 Hz, 1H), 5.18 (dq, J = 17.2, 1.7 Hz, 1H), 5.12 - 5.06 (m, 1H), 3.76 (dd, J= 7.3, 3.5 Hz, 2H). 'H NMR (400 MHz, DMSO-d6) 6 9.06 (d, J= 2.5 Hz, 1H), 8.84 (s, 1H), 8.56 (dd, J= 4.7, 1.3 Hz, 1H), (thin film) 3251, ESIMS m/z 280 8.7,20 (ddd, J= 8.4, 300 3090, 2973, 1644. ([M+H]*) 75 (dd, Jz H), 4.7 Hz, 1H), 6.36 (t, J= 5.6 Hz, 1H), 3.07 (s, 3H), 3.02 (dd, J= 7.0, 5.8 Hz, 2H), 0.97 (t, J = 7.1 Hz, 3H). 393 'H NMR (400 MHz, DMSO-d6) 6 9.06 (d, J= 2.6 Hz, 1H), 8.84 (s, 1H), 8.56 (dd, J= 4.7, 1.1 Hz, 1H), 8.25 - 8.13 (m, 301 (thin film) 3232, ESIMS m/z 294 1H), 7.58 (dd, J= 3075, 1639. ([M+H]*). 8.4, 4.7 Hz, 1H), 6.34 (t, J= 5.6 Hz, 1H), 3.06 (d, J= 3.2 Hz, 3H), 2.94 (dd, J= 13.4, 6.4 Hz, 2H), 1.45 1.30 (m, 2H), 0.80 (t, J= 7.4 Hz, 3H). 'H NMR (400 MHz, DMSO-d6) 6 9.06 (d, J= 2.6 Hz, 1H), 8.86 (s, 1H), 8.59 - 8.52 (m, 1H), 8.25 8.14 (m, 1H), 7.58 ESIMS ~z 292 (dd, J = 8.4, 4.7 302 (thin film) 3227, ESM S m,' 292 Hz, 1H), 6.56 (t, J 3078, 1635. ([M-H]-). = 5.6 Hz, 1H), 5.77 (ddt, J= 16.9, 10.1, 4.9 Hz, 1H), 5.08 (dd, J= 17.2, 1.7 Hz, 1H), 4.99 (dd, J= 10.3, 1.5 Hz, 1H), 3.62 (t, J= 5.2 Hz, 2H), 3.08 (s, 3H). 394 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.64 (dd, J = 4.7, 1.1 Hz, 1H), 8.06 (ddd, J = 8.4, 2.5, 1.4 Hz, ESIMS m/z 393 1H), 7.98 (s, 1H), 303 (thin film) 1659 ([M+H] ) 7.47 (dd, J = 8.3, 4.8 Hz, 1H), 3.94 3.55 (m, 3H), 2.63 (dd, J= 16.3, 3.7 Hz, 1H), 2.41 (dd, J = 16.3, 9.9 Hz, 1H), 2.29 (s, 3H), 1.19 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.64 (dd, J = 4.7, 1.2 Hz, 1H), 8.21 - 7.90 (m, 2H), 7.47 304 (thin film) 1669 ESIMS m/z 393 (ddd, J = 8.4, 4.8, ([M+H]*) 0.6 Hz, 1H), 4.12 (dd, J= 14.3, 7.1 Hz, 1H), 3.46 (brs, 2H), 3.25 - 3.06 (m, 1H), 2.80 (brs, 1H), 2.10 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H). 395 'H NMR (400 MHz, CDC3) 6 9.01 - 8.88 (m, 1H), 8.64 (dd, J = 4.7, 1.3 Hz, 1H), 8.05 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), ESIMS m/z 323 7.93 (s, 1H), 7.48 305 93-95 (thin film) 1654 ([M+H] ) (ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 4.13 (p, J= 9.1 Hz, 1H), 3.73 (t, J = 9.0 Hz, 2H), 3.70 3.51 (m, 2H), 2.79 (t, J= 9.2 Hz, 2H), 1.15 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.65 (dd, J = 4.7, 1.3 Hz, 1H), 8.07 (ddd, J = 8.3, 2.7, 1.5 Hz, 306 88-89 (thin film) 1666 ESIMS m/z 415 1H), 7.99 (s, 1H), ([M+H]*) 7.48 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 4.17 - 3.94 (m, 1H), 3.86 - 3.59 (m, 2H), 2.57 (d, J = 5.7 Hz, 2H), 1.19 (t, J= 7.2 Hz, 3H). 396 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.64 (dd, J = 4.7, 1.4 Hz, 1H), 8.06 (ddd, J ESIM m~z341= 8.3, 2.7, 1.5 Hz, 307 (thin film) 1657 ESIMS m/z 341 H), 7.94 (s, 1H), 7.48 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.71 (s, 2H), 2.99 2.76 (m, 3H), 2.60 - 2.39 (m, 2H), 1. 17 (t, J= 7.2 Hz, 3H). IH NMR (400 MHz, CDC3) 6 8.77 (brs, 1H), 8.67 - 8.55 (m, 1H), 7.85 (brs, 1H), 7.44 (dd, J = 8.3, 4.7 Hz, 1H), 7.19 (d, J= 8.4 308 (thin film) 1663 ESIMS m/z 389 Hz, 2H), 6.96 (d, J ([M+H]*) = 8.2 Hz, 2H), 3.91 - 3.32 (m, 3H), 1.40 (d, J = 6.9 Hz, 3H), 1.11 (t, J= 7.2 Hz, 3H). (One aromatic proton merged into baseline) 397 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.66 (dd, J = 4.8, 1.4 Hz, 1H), 8.05 (ddd, J 309 (thin film) 1638 ESIMS m/z 431 = 8.3, 2.7, 1.5 Hz, ([M+H]*) 1H), 7.97 (d, J = 5.4 Hz, 2H), 7.49 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 4.05 3.47 (m, 2H), 2.69 (s, 2H), 1.21 (t, J = 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.78 (brs, 1H), 8.62 (dd, J = 4.7, 1.0 Hz, 1H), 7.88 (brs, 1H), 7.44 ESIM m~z373 (dd, J = 8.3, 4.7 310 (thin film) 1657 ESIMS m/z 37 Hz, H), 7.04 (brs, 1H), 7.04 - 6.96 (m, 2H), 6.96 6.84 (m, 2H), 3.84 - 3.32 (m, 3H), 1.40 (d, J= 6.9 Hz, 3H), 1.11 (t, J = 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.64 (dd, J = 4.7, 1.3 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.4 Hz, 311 (thin film) 1666 ESIMS m/z 447 1H), 7.97 (s, 1H), ([M+H]*) 7.47 (ddd, J = 8.3, 4.8, 0.4 Hz, 1H), 3.72 (q, J= 7.2 Hz, 2H), 2.60 2.46 (m, 2H), 2.46 - 2.33 (m, 2H), 1. 17 (t, J = 7.2 Hz, 3H). 398 'H NMR (400 MHz, CDCl3) 6 8.88 (d, J= 1.9 Hz, 1H), 8.60 (d, J = 4.1 Hz, 1H), 7.92 (ddd, J = 8.3, 312 181- (thin film) 1653 ESIMS m/z 399 2.5, 1.3 Hz, 1H), 183 ([M+H]*) 7.86 (s, 1H), 7.42 (dd, J = 8.3, 4.7 Hz, 1H), 7.36 (s, 1H), 3.84 (s, 3H), 3.84 - 3.75 (m, 2H), 1.24 (t, J= 7.1 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.96 (s, 1H), 313 58-61 (thin film) 1636 ESIMS m/z 377 7.45 (ddd, J = 8.3, ([M+H]*) 4.8, 0.6 Hz, 1H), 6.64 (d, J= 3.2 Hz, 1H), 6.16 (d, J = 3.4 Hz, 1H), 3.84 (q, J= 7.1 Hz, 2H), 3.49 (s, 2H), 1.91 (s, 3H), 1.26 (t, J= 7.1 Hz, 3H). 399 'H NMR (400 MHz, CDC3) 6 8.94 (s, 0.75H), 8.91 (s, 0.25H), 8.60 - 8.53 (m, 0.75H), 8.51 (s, 0.25H), 8.07 7.95 (m, 1H), 7.83 (s, 0.25H), 7.80 (s, 0.75H), 7.46 7.33 (m, 1H), 3.34 ESIMS m/z 318 - 3.23 (in, 0.511), 314 (thin film) 1657 ([M2]) 3.14 - 3.00 (in, 1H), 2.91 (s, 0.5H), 2.78 (t, J= 7.2 Hz, 1.5H), 2.47 - 2.30 (m, 1.5H), 2.25 (s, 3H), 2.20 (s, 0.75H), 2.05 (s, 2.25H), 0.99 (s, 0.5H), 0.80 (d, J= 6.7 Hz, 1.5H), 0.72 (s, 0.5H), 0.47 (s, 1.5H). 400 'H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.4 Hz, 0.8H), 8.91 (s, 0.2H), 8.56 (dd, J = 4.7, 1.0 Hz, 0.8H), 8.50 (d, J= 4.2 Hz, 0.2H), 8.06 - 7.96 (m, 1H), 7.84 (s, 1H), 7.42 (dd, J= 8.3, 4.7 Hz, 0.8H), 7.37 (dd, J= 7.9, 4.7 Hz, 0.2H), 3.79 - 3.65 (m, 0.2H), 3.35 - 3.25 315 (thin film) 1654 ESIMS m/z 331 (m, 0.8H), 3.22 ([M+H]*) 3.12 (m, 0.2H), 3.03 - 2.81 (m, 1H), 2.77 - 2.57 (m, 1H), 2.42 (dd, J= 12.8, 5.0 Hz, 0.8H), 2.29 (s, 2.4H), 2.26 (s, 0.6H), 2.18 (s, 0.6H), 2.00 (s, 2.4H), 1.31 (d, J= 6.7 Hz, 0.6H), 1.11 (d, J= 6.7 Hz, 2.4H), 1.00 (d, J= 6.6 Hz, 0.4H), 0.89 - 0.67 (m, 2H), 0.56 - 0.39 (m, 1.6H). 401 'H NMR (400 MHz, CDC3) 6 8.98 - 8.86 (m, 1H), 8.61 - 8.44 (m, 1H), 8.09 7.94 (m, 1H), 7.87 - 7.73 (m, 1H), 7.48 - 7.30 (m, 1H), 3.52 (s, 118.0- ESIMS m/z 385 0.2H), 3.27 (s, 316 120.5 ([M+H]*) 0.8H), 3.11 (s, 0.2H), 2.62 - 2.41 (m, 0.8H), 2.23 (s, 3H), 1.32 - 1.17 (m, 1.2H), 1.06 (d, J= 6.2 Hz, 4.8H), 0.97 (s, 0.4H), 0.79 (d, J= 5.7 Hz, 1.6H), 0.72 (s, 0.4H), 0.44 (s, 1.6H). H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.1 Hz, 1H), 8.54 (dd, J= 4.7, 1.4 Hz, 317 119.0- ESIMS m/z 341 1H), 8.33 (s, 1H), 121.0 ([M+2]*) 7.99 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.38 (dd, J= 8.1, 4.7 Hz, 1H), 6.35 (s, 1H), 1.54 (s, 9H). 402 'H NMR (400 MHz, DMSO-d6) 6 8.94 (s, 1H), 8.71 (s, 1H), 8.52 (d, J= 2.5 Hz, ESIMS m/z 298 1H), 8.22 (dt, J = 318 (thin film) 3319, ([M+H]S), 296 10.3, 2.3 Hz, 1H), 2964, 1638. (MH]) 8.16 (s, 1H), 6.53 (IM-HY) (t, J= 5.7 Hz, 1H), 3.08 (dd, J= 12.7, 6.8 Hz, 2H), 1.52 - 1.38 (m, 2H), 0.88 (t, J = 7.4 Hz, 3H). 'H NMR (400 MHz, DMSO-d6) 6 8.95 (d, J= 1.2 Hz, 1H), 8.72 (s, 1H), 8.52 (d, J = 2.5 Hz, 1H), 8.27 (s, 1H), 8.22 (d, J (thin film) 3311 ESIMS m/z 296 = 10.3 Hz, 1H), 319 3093, 1635' ([M+H]*), 294 6.64 (t, J = 5.7 ([M-H]-) Hz, 1H), 5.88 (ddt, J = 17.2, 10.2, 5.1 Hz, 1H), 5.18 (dq, J = 17.2, 1.7 Hz, 1H), 5.09 (dq, J = 10.3, 1.6 Hz, 1H), 3.83 - 3.67 (m, 2H). 403 'H NMR (400 MHz, DMSO-d6) 6 9.08 (d, J= 2.6 Hz, 1H), 8.85 (s, 1H), 8.56 (dd, J = 4.7, 1.2 Hz, 1H), 8.22 (ddd, J = 8.4, (thin film) 3264, ESIMS m/z 294 2.61.4 Hz, 1H), 320 3071, 2980, 1640. ([M+H]*). .58 H(zdd, - 84 (t, J= 5.6 Hz, 1H), 3.50 (q, J= 7.1 Hz, 2H), 3.07 2.94 (m, 2H), 1.04 (t, J= 7.1 Hz, 3H), 1.00 - 0.92 (t, J = 7.0 Hz, 3H). H NMR (400 MHz, DMSO-d6) 6 9.08 (d, J= 2.5 Hz, 1H), 8.85 (s, 1H), 8.56 (dd, J = 4.7, 1.3 Hz, 1H), 8.22 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), (thin film) 3256, ESIMS m/z 308 7.58 (ddd, J= 8.4, 321 3081, 2960, 1633. ([M+H]*). 4.8 0.5 Hz, 1H), Hz, 1H), 3.50 (q, J = 7.0 Hz, 2H), 2.93 (dd, J = 13.5, 6.3 Hz, 2H), 1.44 1.30 (m, 2H), 1.04 (t, J= 7.1 Hz, 3H), 0.79 (t, J= 7.4 Hz, 3H). 404 'H NMR (400 MHz, DMSO-d6) 6 9.08 (d, J= 2.5 Hz, 1H), 8.87 (s, 1H), 8.56 (dd, J = 4.7, 1.3 Hz, 1H), 8.22 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.62 - 7.52 (m, (thin film) 3260, ESIMS m/z 306 1H), 6.43 (t, J = 322 3067, 1638. ([M+H]). 5.7 Hz, 1H), 5.76 (ddt, J = 17.2, 10.1, 5.0 Hz, 1H), 5.07 (dq, J = 17.2, 1.7 Hz, 1H), 4.98 (dq, J = 10.3, 1.6 Hz, 1H), 3.60 (t, J = 5.3 Hz, 2H), 3.51 (q, J= 7.0 Hz, 2H), 1.05 (t, J = 7.1 Hz, 3H). IH NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.56 (dd, J = 4.7, 1.3 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 323 (thin film) 1650 ESIMS m/z 274 1H), 7.87 (s, 1H), ([M+H]*) 7.42 (ddd, J = 8.4, 4.8, 0.6 Hz, 1H), 3.22 (s, 3H), 2.26 (s, 3H), 2.24 - 2.11 (m, 1H), 2.03 (d, J = 7.0 Hz, 2H), 0.89 (d, J= 6.6 Hz, 6H). 405 'H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.56 (dd, J = 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.6, 1.4 Hz, ESIMS ~ 287 H), 7.84 (s, H), 324 60-63 (thin film) 1647 ESIMS m/z 287 7.43 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.67 (s, 2H), 2.25 (s, 3H), 2.23 - 2.11 (m, 1H), 1.99 (d, J = 7.0 Hz, 2H), 1.14 (t, J= 7.1 Hz, 3H), 0.88 (d, J = 6.6 Hz, 6H). H NMR (400 MHz, CDCl3) 6 8.77 (d, J= 1.6 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.92 - 7.80 (m, 325 74-76 (thin film) 1642 ESIMS m/z 305 2H), 3.67 (s, 2H), ([M+H]*) 2.25 (s, 3H), 2.23 2.11 (m, 1H), 1.97 (d, J= 7.0 Hz, 2H), 1.14 (t, J= 7.1 Hz, 3H), 0.88 (d, J= 6.7 Hz, 6H). 406 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.62 (dd, J = 4.7, 1.3 Hz, 1H), 8.08 (tdd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.93 (s, 1H), 326 (thin film) 1653 ESIMS m/z 307 7.46 (ddd, J = 8.3, ([M+H]*) 4.8, 0.4 Hz, 1H), 3.70 (q, J= 7.0 Hz, 2H), 2.25 2.09 (m, 1H), 2.02 (d, J= 7.0 Hz, 2H), 1.16 (t, J= 7.2 Hz, 3H), 0.90 (d, J= 6.6 Hz, 6H). 'H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.8 Hz, 1H), 8.45 (d, J = 2.5 Hz, 1H), ESIMS m/z 443 7.88 (s, 1H), 7.84 327 90-92 (thin film) 1656 ([M+H]*) (dt, J = 9.3, 2.4 Hz, 1H), 4.00 (brs, 1H), 3.73 (s, 3H), 3.39 (brs, 1H), 2.85 (s, 2H), 2.26 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H). 407 'H NMR (400 MHz, CDC3) 6 9.03 (d, J= 2.5 Hz, 0.6H), 8.99 (d, J= 2.4 Hz, 0.4H), 8.63 - 8.55 (m, 1H), 8.29 (s, 0.6H), 8.21 (s, 328 (thin film) 1651 ESIMS m/z 341 0.4H), 8.06 - 7.98 ([M]) (m, 1H), 7.46 7.38 (m, 1H), 3.38 - 3.23 (m, 4H), 3.22 - 3.12 (m, 1H), 2.76 - 2.56 (m, 4H), 1.26 (d, J = 6.9 Hz, 1.2H), 1.21 (d, J= 6.9 Hz, 1.8H). 'H NMR (400 MHz, CDC3) 6 9.00 (d, J= 2.4 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 8.22 (s, 1H), 8.00 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), 329 (thin film) 1660 ESIMS m/z 357 7.43 (ddd, J= 8.3, ([M]) 4.8, 0.7 Hz, 1H), 3.83 (dd, J= 13.6, 10.8 Hz, 1H), 3.42 - 3.30 (m, 1H), 3.28 (s, 3H), 2.95 (s, 3H), 2.89 (dd, J = 13.7, 2.7 Hz, 1H), 1.21 (d, J= 7.0 Hz, 3H). 408 'H NMR (400 MHz, CDC3) 6 9.04 (d, J= 2.5 Hz, 0.6H), 8.99 (d, J= 2.5 Hz, 0.4H), 8.60 (m, 1H), 8.23 (s, 0.6H), 8.17 (s, 0.4H), 8.06 - 7.97 (m, 1H), 7.47 330 (thin film) 1650 ESIMS m/z 355 7.38 (m, 1H), 4.26 ([M]) - 3.73 (m, 1H), 3.56 - 3.29 (m, 1H), 3.31 - 3.05 (m, 2H), 2.78 2.54 (m, 4H), 1.26 (d, J= 6.7 Hz, 1.2H), 1.22 (d, J= 6.7 Hz, 1.8H), 1.21 - 1.13 (m, 3H). IH NMR (400 MHz, CDC3) 6 9.02 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 8.19 (s, 1H), 8.01 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), ESIMS m/z 371 7.44 (ddd, J= 8.3, 331 (thin film) 1657 ([IM) 4.8, 0.6 Hz, 1H), 4.10 (s, 1H), 3.82 (dd, J= 13.6, 11.0 Hz, 1H), 3.43 3.21 (m, 2H), 2.94 (s, 3H), 2.88 (dd, J = 13.6, 2.5 Hz, 1H), 1.21 (d, J= 7.0 Hz, 3H), 1.17 (t, J= 7.2 Hz, 3H). 409 'H NMR (400 MHz, CDCl3) 6 8.92 (d, J= 2.5 Hz, 1H), 8.58 (dd, J= 4.7, 1.3 Hz, 1H), 8.05 - 7.97 (m, 1H), 7.91 (bs, 332 (R thin film) 1699 ESIMS m/z 385 1H), 7.50 - 7.31 ([M+H]*) (m, 1H). 4.21 3.83 (m, 1H), 3.54 - 3.08 (m, 1H), 1.90 (d, J= 6.9 Hz, OH), 1.58 1.33 (m, 10H), 1.24 - 0.92 (m, 1H), IH NMR (400 MHz, CDCl3) 6 8.93 (bs, 1H), 8.59 (d, J= 4.2 Hz, 1H), 8.03 (ddd, J 333 (JR thin film)1701 = 8.3, 2.6, 1.4 Hz, 1H), 7.89 (s, 1H), 7.443 (dd, J= 8.3, 4.7 Hz, 1H), 3.84 3.54 (m, 5H), 1.19 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, DMSO-d6) 6 8.94 (s, 1H), 8.71 (s, 1H), 8.52 ESIMS ~z 284 (d, J = 2.5 Hz, 334 (thin film) 3272, ESM S m, 284 'H), 8.22 (dt, = 3080, 1642. (IM-H]-) 10.3, 2.4 Hz, 1H), 8.15 (s, 1H), 6.47 (t, J= 5.5 Hz, 1H), 3.21 - 3.07 (m, 2H), 1.07 (t, J = 7.2 Hz, 3H). 410 'H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.4 Hz, 1H), 8.62 (d, J = 3.8 Hz, 1H), 8.15 (s, 1H), 8.03 335 128- ESIMS m/z 311 (d, J = 8.3 Hz, 133 ([M+H]*). 1H), 7.46 (dd, J = 8.3, 4.8 Hz, 1H), 3.34 (q, J= 6.8 Hz, 1H), 3.26 (s, 3H), 2.10 (s, 3H), 1.45 (d, J= 6.9 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 8.91 (d, J= 2.4 Hz, 1H), 8.60 8.55 (m, 1H), 8.01 336 128- ESIMS m/z 309 , 7.5 Hz, 7.42 (dd, J = 8.2, 4.8 Hz, 1H), 3.99 3.84 (m, 2H), 3.28 (s, 3H), 2.06 - 1.79 (m, 1H), 1.06 0.73 (m, 6H). H NMR (400 1C NMR (101 MHz, CDC13) 6 MHz, CDC1 3 ) 8.95 (d, J= 2.5 6 170.00, Hz, 1H), 8.62 (dd, 148.61, J= 4.8, 1.4 Hz, 140.15, 337 ESIMS m/z 297 1H), 8.13 (s, 1H), 140.03, ([M+H]*). 8.04 (ddd, J = 8.3, 135.68, 2.7, 1.4 Hz, 1H), 126.56, 7.50 - 7.43 (m, 126.42, 1H), 3.26 (s, 3H), 125.33, 3.12 (s, 2H), 2.24 124.15, 37.16, (s, 3H). 34.94, 16.22. 411 'H NMR (400 MHz, CDCl3) 6 8.93 (d, J= 2.6 Hz, 1H), 8.58 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J 338 ESIMS m/z 295 = 8.3, 2.6, 1.4 Hz, ([M+H]*) 1H), 7.90 (s, 1H), 7.42 (dd, J= 8.3, 4.8 Hz, 1H), 4.18 (bs, 2H), 3.66 (q, J = 7.1 Hz, 2H), 1.33 - 1.10 (m, 6H). 'H NMR (400 MHz, CDCl3) 6 8.93 (d, J= 2.3 Hz, 1H), 8.60 (d, J = 4.2 Hz, 1H), ESIMS ~z 349 8.03 (d, J = 8.4 339 (IR thin film) 1720 ESIMS m/z 349 Hz, 1H), 7.90 (s, S 1H), 7.44 (dd, J = 8.1, 4.6 Hz, 1H), 4.67 - 4.42 (m, 2H), 3.70 (q, J= 7.2 Hz, 2H), 1.22 (t, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.80 (s, 1H), 8.41 8.30 (m, 2H), 7.84 (dt, J= 9.6, 2.4 340 134.0- ESIMS m/z 305 Hz, 1H), 6.67 (dd, 136.0 ([M+H]*) J= 17.8, 11.4 Hz, 1H), 6.45 (s, 1H), 5.93 (d, J= 17.8 Hz, 1H), 5.51 (dd, J= 11.4, 1.1 Hz, 1H), 1.54 (s, 9H). 412 'H NMR (400 MHz, CDC3) 6 9.00 - 8.87 (m, 1H), 8.61 - 8.46 (m, 1H), 8.08 7.95 (m, 1H), 7.86 - 7.75 (m, 1H), 7.47 - 7.33 (m, 1H), 3.40 - 3.04 (m, 2H), 2.85 (dd, J= 15.9, 7.4 Hz, ESIMS m/z 331 0.33H), 2.43 (dd, J 341 (thin film) 1660 ([M+H]) = 15.5, 6.5 Hz, 0.67H), 2.32 2.11 (m, 5H), 2.05 (s, 2H), 1.41 (d, J = 6.9 Hz, 1H), 1.27 (d, J= 6.7 Hz, 2H), 1.06 0.93 (m, 0.67H), 0.88 - 0.76 (m, 1.33H), 0.77 0.63 (m, 0.67H), 0.56 - 0.38 (m, 1.33H). 'H NMR (400 MHz, CDCl3) 6 9.00 - 8.86 (m, 1H), 8.61 - 8.45 (m, 1H), 8.09 7.92 (m, 1H), 7.85 (s, 1H), 7.51 - 7.32 ESIM mz329 (in, 111), 3.32 342 (thin film) 1646 ESIMS m/z 329 3.16 (i, 1I), 2.66 - 2.44 (m, 1H), 2.31 - 2.21 (m, 4H), 2.08 (s, 2H), 1.69 - 1.49 (m, 2H), 1.23 - 0.88 (m, 1.67H), 0.88 0.71 (m, 2H), 0.58 - 0.39 (m, 1.33H). 413 'H NMR (400 MHz, CDC3) 6 8.98 - 8.87 (m, 1H), 8.62 - 8.46 (m, 1H), 8.07 7.93 (m, 1H), 7.85 - 7.78 (m, 1H), 7.48 - 7.33 (m, 1H), 3.33 - 3.21 ESIMS m/z 339 (m, 0.67H), 3.13 343 thin film) 1661 ([M+H]) 3.04 (m, 0.33H), 3.04 - 2.95 (m, 0.67H), 2.70 2.28 (m, 3.33H), 2.24 (s, 3H), 1.08 0.96 (m, 0.67H), 0.87 - 0.76 (m, 1.33H), 0.76 0.65 (m, 0.67H), 0.55 - 0.39 (m, 1.33H). IH NMR (400 MHz, CDCl3) 6 8.98 - 8.88 (m, 1H), 8.57 (dd, J= 4.7, 1.1 Hz, 0.67H), 8.52 8.48 (m, 0.33H), 8.08 - 7.93 (m, 1H), 7.78 (m, 1H), 7.46 - 7.33 (m, 1H), 3.90 - 3.77 ESIMS m/z 353 (m, 0.33H), 3.30 344 (thin film) 1657 ([M+H] ) 3.19 (m, 0.67H), 3.15 - 3.06 (m, 0.33H), 2.98 2.61 (m, 1.67H), 2.30 - 2.13 (m, 3H), 2.04 - 1.92 (m, 1H), 1.40 1.32 (m, 1H), 1.13 (d, J= 6.6 Hz, 2H), 1.08 - 0.94 (m, 0.67H), 0.93 0.65 (m, 2H), 0.56 - 0.34 (m, 1.33H). 414 'H NMR (400 MHz, CDC13) 6 1C NMR (101 8.92 (d, J= 2.6 MHz, CDC1 3 ) Hz, 1H), 8.60 (dd, 6 157.55, J= 4.7, 1.3 Hz, 148.53, ESIMS m/z 266 1H), 8.04 - 8.00 140.74, 345 ([M+H])2 (m, 1H), 8.00 (s, 139.94, 1H), 7.45 (dd, J = 135.66, 8.3, 4.8 Hz, 1H), 126.17, 4.51 (d, J = 3.8 125.05, Hz, 1H), 3.24 (s, 124.09, 37.11, 3H), 2.80 (d, J = 27.78 4.7 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.96 (d, J= 2.5 Hz, 1H), 8.61 (m, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.99 (s, 1H), 346 76-82 7.45 (ddd, J= 8.3, 4.8, 0.6 Hz, 1H), 3.74 (q, J= 7.2 Hz, 2H), 2.87 (q, J = 7.4 Hz, 2H), 1.26 (t, J= 7.4 Hz, 3H), 1.19 (t, J= 7.2 Hz, 3H) H NMR (400 MHz, CDC13) 6 8.98 (d, J= 2.6 13C NMR (101 Hz, 1H), 8.64 (dd, MHz, CDC1 3 ) J= 4.7, 1.4 Hz, 6 148.76, 1H), 8.09 (s, 1H), 140.35, 8.06 - 8.01 (m, 140.24, 1H), 7.46 (dd, J= 135.58, 347 ESIMS m/z 427 8.3, 4.8 Hz, 1H), 128.34, ([M+H]*). 3.94 - 3.57 (m, 126.41, 3H), 3.13 - 3.01 124.10, 60.39, (m, 1H), 2.95 (dd, 53.43, 44.29 J = 13.3, 6.1 Hz, 33.06, 27.67, 2H), 2.76 - 2.61 21.06, 15.80, (m, 3H), 2.06 (d, J 14.23, 12.89. = 2.2 Hz, 5H), 1.19 (t, J= 7.2 Hz, 3H). 415 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.53 ESIMS m/z 300 8.47 (m, 1H), 8.44 348 250- ([M+H]S), 298 (d, J = 2.3 Hz, 253 ([M-H]-) 1H), 8.08 (s, 1H), 8.00 - 7.93 (m, 1H), 7.41 - 7.33 (m, 1H), 6.75 (s, 1H), 3.72 - 3.56 (m, 4H). H NMR (400 MHz, CDC13) 6 8.93 (d, J= 2.5 Hz, 1H), 8.51 (dd, J= 4.7, 1.3 Hz, 1H), 8.19 (s, 1H), (thin film) 3377, ESIMS m/z 243 7.99 (ddd, J = 8.3, 349 1662. ([M+H]). 2.7, 1.5 Hz, 1H), 7.38 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 3.87 - 3.83 (m, 2H), 2.57 (t, J = 8.1 Hz, 2H), 2.38 (s, 3H), 2.27 - 2.16 (m, 2H). 1 C NMR (101 'H NMR (400 MHz, CDCl 3 ) MHz, CDCl3) 6 6 171.94, 8.76 (d, J= 1.6 137.14, Hz, 1H), 8.50 (d, J 136.91, = 2.4 Hz, 1H), 135.08, 350 ESIMS m/z 374 8.00 (s, 1H), 7.88 129.74, ([M+2H]*) (dt, J= 9.1, 2.3 Hz, 128.83, 1H), 3.25 (s, 3H), 126.10, 2.80 (t, J = 7.4 Hz, 114.00, 2H), 2.46 (t, J= 113.77, 77.34, 7.4 Hz, 2H), 2.07 77.02, 76.70, (s, 3H). 37.13, 33.76, 29.68, 15.96. 416 IH NMR (400 MHz, CDCl3) 6 8.76 (s, 1H), 8.49 (d, J= 2.4 Hz, 142- ESIMS m/z 342 1H), 7.96 (s, 1H), 351 143 ([M+2H]*), 340 7.88 (dt, J= 9.1, ([M]) 2.3Hz, 1H), 3.22 (s, 3H), 2.57 (dd, J = 13.4, 6.7 Hz, 1H), 1.09 (d, J= 6.7 Hz, 6H). 'H NMR (400 MHz, CDC13) 6 8.75 (s, 1H), 8.40 (s, 1H), 7.98 - 7.78 (m, 2H), 6.65 (dd, 352 58.5- ESIMS m/z 319 J= 17.9, 11.4 Hz, 61.5 ([M+H]*) 1 H), 5.94 (dd, J = 17.9, 1.4 Hz, 1H), 5.46 (dd, J= 11.4, 1.4 Hz, 1H), 3.20 (s, 3H), 1.41 (s, 9H). H NMR (400 MHz, CDC13) 6 8.78 (d, J= 1.8 Hz, 1H), 8.46 (d, J = 2.4 Hz, 1H), 7.98 (s, 1H), 7.91 (dt, J= 9.3, 2.4 ESIMS m/z 321 Hz, 1H), 6.67 (dd, 353 (thin film) 1653 ([M+H]*) J= 18.0, 11.5 Hz, 1H), 5.92 (dd, J= 18.0, 1.0 Hz, 1H), 5.52 (dd, J= 11.5, 1.0 Hz, 1H), 3.25 (s, 3H), 2.77 (t, J = 7.3 Hz, 2H), 2.46 (t, J= 7.3 Hz, 2H), 2.04 (s, 3H). 417 'H NMR (400 MHz, CDC3) 6 8.79 (d, J= 1.7 Hz, 1H), 8.45 (d, J = 2.5 Hz, 1H), 8.04 (s, 1H), 7.91 (dt, J= 9.3, 2.4 Hz, 1H), 6.69 (dd, ESIMS mz 335 J = 18.0, 11.5 Hz, 354 (thin film) 1650 ([M+H] ) 1H), 5.99 (d, J= 18.0 Hz, 1H), 5.53 (dd, J= 11.5, 1.1 Hz, 1H), 3.26 (s, 3H), 2.90 - 2.74 (m, 2H), 2.44 (dd, J = 12.0, 4.4 Hz, 1H), 1.99 (s, 3H), 1.12 (d, J= 6.5 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.78 (d, J= 1.0 Hz, 1H), 8.45 (d, J = 2.4 Hz, 1H), 7.94 (s, 1H), 7.90 (dt, J= 9.3, 2.3 112.0- ESIMS m/z 289 Hz, 1H), 6.66 (dd, 355 114.5 ([M+H]) J= 18.0, 11.5 Hz, S1H), 5.91 (dd, J= 18.0, 1.1 Hz, 1H), 5.52 (dd, J= 11.6, 0.8 Hz, 1H), 3.21 (d, J= 6.5 Hz, 3H), 2.73 - 2.56 (m, 1H), 1.05 (d, J = 6.7 Hz, 6H). 418 'H NMR (400 MHz, CDC3) 6 8.79 (d, J= 1.8 Hz, 1H), 8.46 (d, J = 2.5 Hz, 1H), 7.98 (s, 1H), 7.91 (dt, J= 9.3, 2.4 Hz, 1H), 6.66 (dd, J= 18.0, 11.5 Hz, 356 (thin film) 1651 ESIMS m/z 335 1H), 5.92 (dd, J= ([M+H]*) 18.0, 1.0 Hz, 1H), 5.52 (dd, J= 11.5, 1.0 Hz, 1H), 3.30 3.16 (m, 4H), 2.51 (dd, J= 15.7, 6.6 Hz, 1H), 2.27 (dd, J= 15.7, 7.5 Hz, 1H), 2.03 (s, 3H), 1.26 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.80 (d, J= 1.7 Hz, 1H), 8.46 (d, J = 2.5 Hz, 1H), 8.03 (s, 1H), 7.93 (dt, J= 9.3, 2.4 Hz, 1H), 6.69 (dd, J= 18.0, 11.5 Hz, 1H), 5.94 (dd, J= ESIM m~z333 18.0, 1.1 Hz, 1H), 357 (thin film) 1644 ESIMS m/ 5.53 (dd, J= 11.5, 1.1 Hz, 1H), 3.25 (s, 3H), 2.47 (ddd, J= 8.2, 5.5, 3.6 Hz, 1H), 2.08 (s, 3H), 1.73 (ddd, J = 8.6, 5.2, 3.6 Hz, 1H), 1.51 (ddd, J = 8.2, 5.1, 4.4 Hz, 1H), 0.97 (ddd, J = 8.5, 5.5, 4.3 Hz, 1H). 419 IH NMR (400 MHz, CDC13) 6 8.75 (t, J = 9.6 Hz, 1H), 8.51 (d, J= 107- ESIMS m/z 394 2.5 Hz, 1H), 7.98 358 108 ([M+H]*), 396 (s, 1H), 7.89 (dt, ([M+2H]*) J= 9.0, 2.4 Hz, 1H), 3.25 (s, 3H), 2.67 - 2.44 (m, 2H), 2.44 - 2.33 (m, 2H). H NMR (400 MHz, CDC13) 6 8.77 (d, J= 2.0 Hz, 1H), 8.53 (d, J = 2.5 Hz, 1H), ESIMS m/z 400 8.03 (s, 1H), 7.90 359 177- ([M+2H]), 398 (d, J= 9.0 Hz, 1H), 178 (M]-) 3.68 (t, J= 10.4 Hz, 1H), 3.47 3.31 (m, 1H), 3.27 (s, 4H), 2.98 (dd, J = 16.7, 11.8 Hz,1H), 2.60 (s, 1H). H NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.4 Hz, 1H), 8.57 (d, J = 3.6 Hz, 1H), 8.00 (t, J= 14.2 360 ESIMS m/z 337 Hz, 1H), 7.79 (d, J ([M+H]*) = 62.4 Hz, 1H), 7.52 - 7.32 (m, 1H), 3.51 (dt, J= 17.0, 7.9 Hz, 2H), 1.68 - 1.46 (m, 11H), 0.93 (t, J= 7.4 Hz, 3H). 420 'H NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.4 Hz, 1H), 8.57 (d, J = 3.7 Hz, 1H), 8.03 (d, J= 7.3 ESIM m~z349 Hz, 1H), 7.92 (s, 361 62-72 ESIMS m/z 39 1H), 7.42 (dd, s 8.3, 4.7 Hz, 1 H), 3.43 (d, J= 6.9 Hz, 2H), 1.37 (bs, 9H), 1.13 - 0.87 (m, 1H), 0.59 0.39 (m, 2H), 0.29 - 0.09 (m, 2H). IH NMR (400 MHz, CDC13) 6 8.95 (t, J= 9.2 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.20 - 7.86 (m, 2H), 7.59 - 7.33 362 (thin film) 1655 ESIMS m/z 341 (m, 1H), 3.73 (ddt, ([M+H]*) J= 20.5, 13.4, 6.8 Hz, 2H), 3.23 3.06 (m, 1H), 2.94 - 2.81 (m, 1H), 2.74 - 2.62 (m, 2H), 2.59 (s, 3H), 1.25 - 1.07 (m, 3H). H NMR (400 MHz, CDCl3) 6 8.95 (t, J= 11.5 Hz, 1H), 8.64 (dd, J= 4.8, 1.4 Hz, 1H), 8.17 - 7.96 ESIM m~z357 (in, 2H), 7.59 363 (thin film) 1661 ESIMS mz 7.39 (m, 1H), 3.73 (d, J= 7.0 Hz, 2H), 3.44 (dd, J= 22.5, 15.7 Hz, 2H), 2.96 (s, 3H), 2.71 (t, J= 6.9 Hz, 2H), 1.18 (dd, J= 8.8, 5.5 Hz, 3H). 421 'H NMR (400 MHz, CDCl3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.77 8.52 (m, 1H), 8.11 364 (thin film) 1436 ESIMS m/z 355 - 7.89 (m, 2H), ([M+H]*) 7.60 - 7.38 (m, 1H), 4.62 (bs, 1H), 4.02 (bs, 1H), 3.21 - 2.46 (m, 3H), 2.01 (s, 3H), 1.35 1.15 (m, 6H). IH NMR (400 MHz, CDCl3) 6 8.94 (t, J= 8.8 Hz, 1H), 8.62 (dt, J= 17.9, 9.0 Hz, 1H), 8.06 (tdd, J= 8.4, 2.7, 1.5 Hz, 1H), 7.97 (d, J= 3.8 365 (thin film) 1660 ESIMS m/z 339 Hz, 1H), 7.47 ([M+H]*) (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 3.73 3.50 (m, 2H), 2.87 - 2.73 (m, 2H), 2.53 - 2.37 (m, 2H), 2.07 (s, 3H), 1.64 - 1.47 (m, 2H), 0.93 (t, J= 7.4 Hz, 3H). 422 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.62 (d, J = 4.7 Hz, 1H), 8.04 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 8.00 (s, 1H), 7.46 (dd, J= 8.3, 4.8 ESIMS m/z 353 Hz, 1H), 3.71 (dd, 366 (thin film) 1654 ([M+H]*) J 113.8, 59.4 Hz, 2H), 2.86 (dd, J = 12.7, 9.0 Hz, 1H), 2.71 (d, J= 6.6 Hz, 1H), 2.45 (dt, J= 30.4, 15.2 Hz, 1H), 1.57 (dt, J= 14.9, 7.5 Hz, 2H), 1.16 (d, J= 6.7 Hz, 3H), 0.94 (t, J= 7.4 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.95 (t, J= 8.0 Hz, 1H), 8.61 (dd, J= 12.3, 11.3 Hz, 1H), 8.06 (tdd, J= 8.3, 2.7, 1.4 Hz, 1H), 7.96 (d, J= 367 (thin film) 1658 ESIMS m/z 353 3.8 Hz, 1H), 7.47 ([M+H]*) (dd, J= 8.3, 4.7 Hz, 1H), 3.50 (s, 2H), 2.82 (dd, J= 21.9, 14.6 Hz, 2H), 2.47 (t, J= 7.3 Hz, 2H), 2.07 (s, 3H), 1.90 - 1.62 (m, 1H), 0.95 (d, J = 6.7 Hz, 6H). 423 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.61 (dd, J= 4.7, 1.3 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, ESIMS m/z 325 H), 7.99 (s, H), 368 84-92 (IM+H]*) 7.45 (ddd, J= 8.3, 4.8, 0.6 Hz, 1 H), 3.74 (q, J= 7.2 Hz, 2H), 2.85 (t, J = 7.3 Hz, 2H), 1.66 - 1.58 (m, 2H), 1.19 (t, J= 7.2 Hz, 3H), 0.96 (t, J= 7.4 Hz, 3H). IH NMR (400 MHz, CDC3) 6 10.07 (d, J= 0.5 369 ESIMS m/z 321 Hz, 1H), 8.85 (s, ([M+H]*) 1H), 8.52 (s, 1H), 8.28 - 7.88 (m, 2H), 3.26 (s, 3H), 1.49 (s, 9H). H NMR (400 MHz, CDC3) 6 8.76 (d, J= 2.0 Hz, 1H), 8.50 (d, J = 2.5 Hz, 1H), 7.99 (s, 1H), 7.88 ESIMS m/z 388 (d, J= 9.1 Hz, 1H), 370 ([M+2H]*), 386 3.30 - 3.22 (m, ([M]-) 1H), 3.25 (s, 3H), 2.54 - 2.44 (m, 1H), 2.28 (dd, J= 15.6, 7.6 Hz, 1H), 2.07(s, 3H), 1.29 (d, J= 6.8 Hz, 3H). 424 'H NMR (400 "C NMR (101 MHz, CDCl3) 6 MHz, CDCl 3 ) 8.78 (d, J= 1.8 6 172.01, Hz, 1H), 8.50 (d, J 160.77, = 2.4 Hz, 1H), 158.18, ESIMS m/z 386 8.02 (s, 1H), 7.90 136.88, 371 ([M+2H]*), 384 (dt, J= 9.1, 2.3 Hz, 135.14, ([M]) 1H), 3.25 (s, 3H), 129.87, 2.55 - 2.44 (m, 128.91, 1H), 2.12 (s,3H), 126.19, 1.72 - 1.48 (m, 114.04,37.25, 3H), 1.08 - 0.93 24.97, 23.16, (m, 1H). 18.09, 16.47. 'H NMR (400 MHz, CDC13) 6 8.95 (dd, J= 12.3, 2.6 Hz, 1H), 8.65 (dd, J= 4.7, 1.4 Hz, 1H), 8.05 (ddd, J= 8.3, 2.7, 372 (thin film) 1421 ESIMS m/z 341 1.5 Hz, 1H), 7.99 ([M+H]*) (d, J= 7.2 Hz, 1H), 7.53 - 7.43 (m, 1H), 4.29 (s, 2H), 2.97 (t, J= 7.5 Hz, 2H), 2.85 2.62 (m, 2H), 2.04 (s, 3H), 1.29 (td, J = 7.1, 3.4 Hz, 3H). 425 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.61 (dd, J= 4.7, 1.4 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.99 (s, 1H), 103- ESIMS m/z 339 7.44 (ddd, J= 8.3, 373 113 ([M+H] ) 4.8, 0.6 Hz, 1H), 3.73 (q, J= 7.2 Hz, 2H), 3.44 (h, J = 6.9 Hz, 2H), 1.64 - 1.52 (m, 1H), 1.29 (d, J= 6.9 Hz, 2H), 1.19 (t, J= 7.2 Hz, 3H), 0.95 (t, J= 7.4 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.93 (d, J= 2.5 Hz, 1H), 8.51 (dd, J= 4.7, 1.3 Hz, 1H), 8.19 (s, 1H), 167- ESIMS m/z 264 7.99 (ddd, J = 8.3, 374 170 ([M+H]). 2.7, 1.5 Hz, 1H), 7.38 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 3.87 - 3.83 (m, 2H), 2.57 (t, J = 8.1 Hz, 2H), 2.38 (s, 3H), 2.27 - 2.16 (m, 2H). 426 'H NMR (400 MHz, DMSO-d6) 6 8.90 (s, 1H), 8.50 (s, 1H), 8.42 (d, J= 2.4 Hz, (thin film) 3313, ESIMS m/z 262 1H), 8.10 (dt, JH= 375 3113, 2967, 1636. ([M-H]-). 170.6 , 1H, 6.9 (t, J= 5.6 Hz, 1H), 3.19 - 3.04 (m, 2H), 2.20 (s, 3H), 1.06 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, DMSO-d6) 6 8.90 (s, 1H), 8.50 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 8.10 (dt, J = (thin film) 3321, ESIMS m/z 276 10.6, 2.3 Hz, 1H), 376 3288, 1632. ([M-H]-). 7.98 (s, 1H), 6.24 (t, J = 5.7 Hz, 1H), 3.06 (dd, J= 12.9, 6.7 Hz, 2H), 2.21 (s, 3H), 1.53 1.36 (m, 2H), 0.88 (t, J= 7.4 Hz, 3H). H NMR (400 MHz, DMSO-d6) 6 8.90 (s, 1H), 8.51 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 8.12 (t, J = 2.3 Hz, 1H), 8.09 (thin film) 3310 ESIMS m/z 276 (d, J = 2.1 Hz, 377 3103, 16310, ([M+H]*), 274 1H), 6.38 (t, J = ([M-H]-). 5.8 Hz, 1H), 5.87 (ddt, J = 17.2, 10.3, 5.1 Hz, 1H), 5.17 (dq, J= 17.2, 1.7 Hz, 1H), 5.10 5.03 (m, 1H), 3.80 - 3.70 (m, 2H), 2.22 (s, 3H). 427 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.4 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 378 143- (thin film) 1619 ESIMS m/z 329 7.94 (s, 1H), 7.87 145 ([M+H]*) (dt, J = 9.4, 2.4 Hz, 1H), 7.44 (s, 1H), 6.98 (s, 1H), 3.80 (s, 5H), 2.17 (s, 3H), 1.22 (t, J = 7.1 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.94 (s, 1H), 8.63 (s, 1H), 8.05 (ddd, J = 8.3, 2.6, 1.4 379 135- (thin film) 1614 ESIMS m/z331 Hz, 1H), 7.96 (s, 138 ([M+H]*) 1H), 7.51 (s, 1H), 7.46 (dd, J = 8.3, 4.7 Hz, 1H), 7.07 (s, 1H), 3.82 (s, 5H), 1.24 (t, J = 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 ESIMS ~z 310 8.'71 (s, 1H), 8.36 380 97-99 (thin film) 1684 ESIMS m/z (d, J = 2.4 Hz, 1H), 7.98 - 7.74 (m, 2H), 2.27 (s, 3H), 1.45 (s, 9H). 428 IH NMR (400 MHz, CDCl3) 6 8.91 (d, J= 2.5 Hz, 1H), 8.57 (dd, ESIM m~z312 J = 4.7, 1.1 Hz, 381 96-99 (thin film) 1693 ESIMS m/z 312 JH18.01 (d, J = 7.8 Hz, 1H), 7.91 (brs, 1H), 7.41 (dd, J = 8.3, 4.7 Hz, 1H), 1.46 (s, 9H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.0 Hz, 1H), 8.64 (d, J = 4.0 Hz, 1H), 8.05 (ddd, J= 8.4, ESIMS ~z 380 2.7, 1.4 Hz, I1H), 382 (thin film) 1660 ESIMS mz 380 7.97 (s, 1H), 7.47 (dd, J= 8.3, 4.7 Hz, 1H), 3.73 (q, J = 7.2 Hz, 2H), 3.14 (t, J= 6.7 Hz, 2H), 2.58 (t, J= 6.7 Hz, 2H), 1.18 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 8.06 (d, J = 0.8 Hz, 1H), 8.06 8.02 (m, 1H), 7.45 383 (thin film) 2975, ESIMS m/z 427 (ddd, J = 8.3, 4.8, 2916, 1711. ([M+H]*). 0.6 Hz, 1H), 3.44 3.30 (m, 2H), 2.94 (dt, J = 13.2, 8.5 Hz, 2H), 2.54 (ddd, J = 13.2, 6.0, 2.3 Hz, 2H), 2.09 (d, J= 5.3 Hz, 6H), 1.32 (t, J = 6.7 Hz, 6H). 429 "C NMR (101 1H NMR (400 MHz, CDCl 3 ) MHz, Acetone) 6 6 207.75 (s), 9.09 (d, J= 2.5 172.62(s), Hz, 1H), 8.51 (dd, 149.98 (s), J = 5.3, 2.0 Hz, 141.33 (s), 2H), 8.19 (ddd, J 134.8(s), 384 lMSm/z286 = 8.3, 2.7, 1.5 Hz, 130.19 (s), 384H), 7.51 (ddd, 12868(s), = 8.3, 4.7, 0.7 Hz, 126.05 (s), 1H), 3.14 (s, 3H), 125.47 (s), 2.71 - 2.63 (m, 38.29 (s), 2H), 2.36 - 2.30 37.07 (s), (m, 2H), 2.28 (s, 30.00 (s), 3H), 2.09 (s, 3H). 27.64 (s), 11.09 (s). H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 0.9 Hz, 1H), 8.41 (d, J = 2.4 Hz, 1H), 385 (thin film) 3342, ESIMS m/z 278 7.94 (s, 1H), 7.84 2972, 1644. ([M+H]*). (dt, J = 9.4, 2.3 Hz, 1H), 3.30 3.22 (m, 2H), 3.21 (s, 3H), 2.27 (s, 3H), 1.08 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 1.6 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.93 (s, 1H), 7.84 386 (thin film) 3330, ESIMS m/z 292 (dt, J = 9.4, 2.3 1647. ([M+H]*). Hz, 1H), 4.47 (s, 1H), 3.21 (s, 3H), 3.19 - 3.10 (m, 2H), 2.27 (s, 3H), 1.53 - 1.38 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H). 430 'H NMR (400 MHz, CDCl3) 6 8.74 (d, J= 1.4 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.96 (s, 1H), 7.84 (dt, J = 9.4, 2.3 (thin film) 3334 ESIMS m/z 290 Hz, 1H), 5.82 (ddt, 387 3088 1641 ([M+H]*), 288 J = 17.1, 10.2, 5.6 ([M-H]-). Hz, 1H), 5.09 (ddq, J = 10.3, 8.7, 1.5 Hz, 2H), 4.57 (t, J = 5.5 Hz, 1H), 3.84 (tt, J = 5.7, 1.5 Hz, 2H), 3.22 (s, 3H), 2.28 (s, 3H). H NMR (400 MHz, CDCl3) 6 8.77 (s, 1H), 8.46 (s, 1H), 8.05 (d, J = 13.3 Hz, 1H), 7.85 (dt, J= 9.2, 0 ESIMS m/z 422 2.2 Hz, 1H), 4.48 ([M+H] ). (s, 1H), 4.13 (dd, J = 11.7, 9.2 Hz, 1H), 3.57 (dd, J= 9.2, 3.7 Hz, 1H), 3.31 (d, J= 2.9 Hz, 3H), 2.35 (d, J = 4.5 Hz, 3H). 431 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.57 (dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.6, 1.4 Hz, 1H), 7.92 (s, 1H), 7.43 (ddd, J = 8.3, 389 (thin film) 1646 ESIMS m/z 322 4.8, 0.6 Hz, 1H), ([M+H]*) 4.20 - 3.27 (m, 2H), 2.87 (dd, J= 12.6, 9.4 Hz, 1H), 2.72 (s, 1H), 2.42 (dd, J= 12.8, 5.1 Hz, 1H), 2.31 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H), 1.12 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.82 - 8.70 (m, 1H), 8.48 - 8.39 (d, J= 2.5 Hz, 1H), 8.00 - 7.91 (s, 1H), 7.91 - 7.82 ESIMS m/z (m, 1H), 4.13 390 81-84 (thin film) 1646 340([M+H] ) 3.25 (s, 3H), 2.96 2.80 (m, 1H), 2.76 - 2.57 (s, 1H), 2.48 - 2.36 (m, 1H), 2.36 - 2.26 (s, 3H), 1. 19 - 1.13 (m, 3H), 1.13 - 1.08 (d, J= 6.7 Hz, 3H). 432 'H NMR (400 MHz, CDCl3) 6 9.01 - 8.89 (d, J = 2.6 Hz, 1H), 8.67 8.57 (m, 1H), 8.06 - 8.01 (m, 2H), 391 (thin film) 1655 ESIMS m/z 328 7.50 - 7.43 (m, ([M+H]*) 1H), 3.30 - 3.23 (s, 3H), 2.91 - 2.83 (m, 1H), 2.82 2.71 (m, 1H), 2.52 - 2.41 (m, 1H), 1.20 - 1.12 (d, J= 6.6 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.07 - 8.03 (m, 1H), 8.01 (s, 1H), 7.46 (ddd, J ESIMS M/Z xx - 8.3, 4.8, 0.4 Hz, 392 (thin film) 1652 ([MH]) 342 1H), 3.94 - 3.51 (m, 2H), 2.86 (dd, J = 12.8, 8.9 Hz, 1H), 2.76 - 2.63 (m, 1H), 2.47 (dd, J = 12.8, 5.4 Hz, 1H), 1.18 (t, J = 7.2 Hz, 3H), 1.16 (d, J= 6.7 Hz, 3H). 433 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.63 (dd, J = 4.6, 0.9 Hz, 1H), 8.06 (ddd, J 393 (thin film) 1652 ESIMS m/z 327 = 8.4, 2.7, 1.4 Hz, ([M+H]*) 1H), 7.98 (s, 1H), 7.52 - 7.40 (m, 1H), 3.72 (q, J = 7.2 Hz, 2H), 2.78 (s, 2H), 2.06 (s, 3H), 1.17 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.6 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), ESIM m~z325 7.91 (s, 1H), 7.86 394 (thin film) 1642 ESIMS m/]z 325 (dt, J = 9.4, 2.4 Hz, 1H), 3.69 (d, J = 5.0 Hz, 2H), 2.77 (s, 2H), 2.27 (s, 3H), 2.05 (s, 3H), 1.15 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.99 - 8.90 (d, J= 2.6 Hz, 1H), 8.68 8.59 (m, 1H), 8.19 395 (thin film) 1675. ESIMS mz 424 -8.13 (s, 1H), 8.06 395(thn ilm 165. ([MHl+2. - 8.00 (in, 1H), 7.51 - 7.41 (m, 1H), 4.51 - 4.40 (s, 1H), 4.17 - 4.04 (m, 1H), 3.63 3.56 (m, 1H), 3.38 - 3.28 (s, 3H). 434 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J = 4.7, 1.4 Hz, ESIMS m/z 313 1H), 8.05 (ddd, J 396 (thin film) 1654 ([M+H]=) 8.4, 2.7, 1.4 Hz, 1H), 8.01 (s, 1H), 7.47 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 3.25 (s, 3H), 2.79 (s, 2H), 2.07 (s, 3H). 'H NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.6 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 397 (thin film) 1649 ESIMS m/z 312 7.94 (s, 1H), 7.85 ([M+H]*) (dt, J = 9.4, 2.4 Hz, 1H), 2.79 (t, J = 7.3 Hz, 2H), 2.44 (t, J = 7.3 Hz, 2H), 2.28 (s, 3H), 2.06 (s, 3H). IH NMR (400 MHz, CDCl3) 6 8.75 (d, J= 1.7 Hz, 1H), 8.42 (d, J = 2.5 Hz, 1H), 7.97 (s, 1H), 7.85 (dt, J= 9.4, 2.4 398 103- (thin film) 1645 ESIMS m/z 326 Hz, 1H), 2.88 (dd, 105 ([M+H]*) J = 12.6, 9.4 Hz, 1H), 2.85 - 2.70 (m, 1H), 2.44 (dd, J = 12.6, 4.8 Hz, 1H), 2.31 (s, 3H), 2.01 (s, 3H), 1.13 (d, J= 6.7 Hz, 3H). 435 'H NMR (400 MHz, CDC13) 6 8.78 (d, J= 1.8 Hz, 1H), 8.64 (s, 1H), 8.41 (d, J= 399 165.5- ESIMS m/z 329 2.3 Hz, 1H), 7.81 166.5 ([M+2]*) (dt, J = 9.4, 2.4 Hz, 1H), 7.13 (s, 1H), 2.64 (hept, J = 6.9 Hz, 1H), 1.30 (d, J= 6.9 Hz, 6H). H NMR (300 MHz, CDC13) 6 8.93 (d, J= 2.5 Hz, 1H), 8.54 (dd, J= 4.7, 1.2 Hz, 1H), 8.00 (ddd, J = 8.3, 2.6, 1.5 Hz, 1H), 7.89 (s, 1H), 7.40 (dd, J= 8.3, ESIMS m/z 380 4.8 Hz, 1H), 4.32 400 (thin film) 1650 ([M+H] ) - 3.03 (m, 2H), 2.76 (t, J= 7.2 Hz, 2H), 2.57 (dd, J= 12.7, 5.5 Hz, 1H), 2.46 - 2.31 (m, 3H), 2.25 (s, 3H), 2.05 (s, 3H), 2.02 (s, 3H), 1.97 1.84 (m, 1H), 1.03 (d, J= 6.7 Hz, 3H). 436 'H NMR (300 MHz, CDC3) 6 8.92 (d, J= 2.4 Hz, 1H), 8.53 (d, J = 3.9 Hz, 1H), 8.00 (ddd, J= 8.0, 2.3, 1.2 Hz, 1H), 7.92 (s, 1H), 7.39 (dd, J= 8.3, 4.8 401 (thin film) 1650 ESIMS m/z 394 Hz, 1H), 4.26 ([M+H]*) 3.04 (m, 2H), 3.03 - 2.60 (m, 2H), 2.59 - 2.34 (m, 3H), 2.28 (s, 3H), 2.12 - 2.01 (m, 3H), 2.00 - 1.85 (m, 4H), 1.09 (d, J = 6.5 Hz, 3H), 1.01 (d, J= 6.7 Hz, 3H). H NMR (300 MHz, CDC3) 6 8.93 (d, J= 2.6 Hz, 1H), 8.53 (dd, J= 4.7, 1.2 Hz, 1H), 8.00 (ddd, J = 8.3, 2.5, 1.5 Hz, ESIMS m/z 347 1H), 7.87 (s, 1H), 402 (thin film) 1649 ([M+H]+) 7.3 9 (dd, J = 8.4, 4.8 Hz, 1H), 4.38 2.87 (m, 2H), 2.64 - 2.45 (m, 2H), 2.42 - 2.29 (m, 1H), 2.23 (s, 3H), 2.03 (s, 3H), 1.98 1.83 (m, 1H), 1.08 - 0.98 (m, 9H). 437 'H NMR (300 MHz, CDC3) 6 8.90 (d, J= 2.6 Hz, 1H), 8.49 (dd, J= 4.8, 1.3 Hz, 1H), 7.98 (ddd, J = 8.3, 2.5, 1.5 Hz, 1H), 7.82 (d, J= 2.0 Hz, 1H), 7.36 (dd, J= 8.4, 4.8 Hz, 1H), 4.23 ESIMS m/z 349 4.09 (m, 2H), 3.64 403 (thin film) 1694 ([M+H]*) (dd, J= 13.8, 6.7 Hz, 1H), 3.47 (dd, J= 13.8, 7.7 Hz, 1H), 2.53 (dd, J= 12.8, 5.8 Hz, 1H), 2.36 (dd, J= 12.8, 7.5 Hz, 1H), 2.23 (s, 3H), 2.03 (s, 3H), 2.00 - 1.87 (m, 1H), 1.27 1.12 (m, 3H), 1.03 (d, J= 6.7 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.80 (d, J= 1.2 Hz, 1H), 8.67 (s, 1H), 8.38 (d, J= 2.5 Hz, 1H), 7.85 (dt, J= 9.6, 2.3 ESIMS m/z 375 Hz, 1H), 7.24 (s, 404 1[+]) IH), 6.7 3 (dd, J = 17.9, 11.4 Hz, 1H), 5.90 (dd, J= 17.9, 1.0 Hz, 1H), 5.56 (dd, J= 11.4, 1.0 Hz, 1H), 2.66 2.55 (m, 1H), 1.29 (d, J= 6.9 Hz, 6H). 438 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.6 Hz, 1H), 8.63 (dd, J = 4.7, 1.2 Hz, 1H), 8.05 (ddd, J 405 (thin film) 1656 ESIMS m/z 314 = 8.7, 2.6, 1.4 Hz, ([M+H]*) 1H), 8.02 (s, 1H), 7.47 (dd, J = 8.3, 4.8 Hz, 1H), 2.80 (t, J= 7.4 Hz, 2H), 2.49 (t, J = 7.4 Hz, 2H), 2.07 (s, 3H). 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.7, 1.2 Hz, 1H), 8.12 - 8.01 (m, 2H), 7.47 (dd, 406 (thin film) 1651 ESIMS m/z 328 J = 8.3, 4.7 Hz, ([M+H]*) 1H), 2.87 (dd, J= 12.5, 9.0 Hz, 1H), 2.83 - 2.73 (m, 1H), 2.48 (dd, J= 12.5, 5.1 Hz, 1H), 2.02 (s, 3H), 1.17 (d, J= 6.6 Hz, 3H). 439 'H NMR (300 MHz, CDCl3) 6 8.96 - 8.92 (d, J= 2.7 Hz, 1H), 8.64 8.59 (dd, J= 4.9, 1.4 Hz, 1H), 8.07 7.99 (m, 2H), 7.50 - 7.40 (dd, J= 8.4, 4.8 Hz, 1H), 3.39 3.28 (m, 1H), 3.10 407 (thin film) 2916, ESIMS m/z 413 - 2.99 (td, J= 7.2, 1713. ([M+H]*). 3.9 Hz, 2H), 2.96 2.86 (dd, J= 13.2, 8.7 Hz, 1H), 2.86 2.79 (t, J= 7.3 Hz, 2H), 2.58 - 2.48 (dd, J= 13.1, 5.8 Hz, 1H), 2.14 2.12 (s, 3H), 2.09 2.06 (s, 3H), 1.30 1.26 (d, J= 6.9 Hz, 3H). 'H NMR (300 MHz, CDCl3) 6 8.71 (t, J= 1.4 Hz, 1H), 8.35 (d, J= EIMS m/z 320 2.6 Hz, 1H), 7.83 408 (thin film) 1692 ElM (dt, J= 9.5, 2.3 ([IM]) Hz, 2H), 3.18 (s, 3H), 2.65 (q, J= 7.5 Hz, 2H), 1.44 (s, 9H), 1.25 (t, J = 7.1 Hz, 3H). 440 IH NMR (400 MHz, CDCl3) 6 8.64 (s, 1H), 8.41 165- ESIMS m/z 400 (d, J= 2.5 Hz, 409 168 ([M+H] ) 1H), 7.80 (s, 1H), 7.72 (d, J= 9.2 Hz, 1H), 3.40 (s, 3H), 2.63 (s, 3H), 2.26 (s, 3H). H NMR (300 MHz, CDCl3) 6 8.96 - 8.91 (d, J= 2.6 Hz, 1H), 8.65 8.56 (d, J= 4.6 ESIM m~z399 Hz, 1H), 8.06 410 (thin film) 2916, ESMS 397 8.01 (i, 1H), 8.01 1713. ([M-H]-) - 8.01 (s, 1H), 7.49 - 7.40 (dd, J= 8.4, 4.8 Hz, 1H), 3.03 2.97 (m, 4H), 2.84 - 2.78 (t, J= 7.2 Hz, 4H), 2.13 2.10 (s, 6H). H NMR (400 MHz, CDCl3) 6 8.78 - 8.73 (dd, J = 2.0, 1.1 Hz, 1H), 8.44 - 8.38 (d, J= 2.5 Hz, 1H), 7.94 7.90 (s, 1H), 7.89 7.81 (dt, J= 9.4, (thin film) 3336, ESIMS m/z 292 2.3 Hz, 1H), 4.38 411 2973, 1644, 1599. ([M+H]*). 4.31 (m, 1I) 3.69 Hz, 2H), 3.29 3.16 (qd, J= 7.2, 5.6 Hz, 2H), 2.30 2.17 (s, 3H), 1.16 1.10 (t, J= 7.1 Hz, 3H), 1.10 1.04 (t, J = 7.2 Hz, 3H). 441 'H NMR (400 MHz, CDCl3) 6 8.77 - 8.73 (dd, J = 2.4, 1.0 Hz, 1H), 8.43 - 8.39 (d, J= 2.5 Hz, 1H), 7.94 7.91 (s, 1H), 7.88 7.82 (dt, J= 9.4, (thin film) 3340, 2.3 Hz, 1H), 4.44 412 2965, 2931, 1644, ESIMS m/z 306 4.36 (m, 1H), 3.70 1599 ([M+H]*). - 3.59 (q, J= 7.1 Hz, 2H), 3.19 3.09 (ddd, J= 8.1, 7.1, 5.9 Hz, 2H), 2.28 - 2.24 (s, 3H), 1.52 - 1.37 (h, J= 7.4 Hz, 2H), 1.16 1.08 (t, J= 7.1 Hz, 3H), 0.89 - 0.80 (t, J = 7.4 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.81 - 8.67 (dd, J = 2.4, 1.0 Hz, 1H), 8.46 - 8.34 (d, J= 2.5 Hz, 1H), 7.97 7.89 (s, 1H), 7.88 7.75 (dt, J= 9.4, 2.3 Hz, 1H), 5.88 (thin film) 3292, ESIMS m/z 304 5.72 (ddt, J = 413 3084, 1638, 1602. ([M+H]*). 1., 102, 5.6 Hz, (m, 2H), 4.52 4.40 (t, J= 5.7 Hz, 1H), 3.87 - 3.75 (tt, J= 5.7, 1.6 Hz, 2H), 3.71 - 3.58 (q, J= 7.1 Hz, 2H), 2.32 - 2.20 (s, 3H), 1.19 - 1.04 (t, J= 7.1 Hz, 3H). 442 'H NMR (400 MHz, CDCl3) 6 8.95 - 8.89 (d, J= 2.7 Hz, 1H), 8.61 - 8.54 (dd, J= 4.8, 414 ESIMS m/z 354 1.5 Hz, 1H), 8.07 ([M+2H]*) 7.98 (m, 1H), 7.93 - 7.79 (s, 1H), 7.46 - 7.36 (m, 1H), 3.25 - 3.17 (s, 3H), 1.52 1.39 (s, 8H). H NMR (400 MHz, CDC13) 6 8.93 (d, J= 2.5 Hz, 1H), 8.63 8.54 (m, 1H), 8.06 - 7.98 (m, 1H), 85.5- ESIMS m/z 412 77.95 (s, 1H), 7.45 45 875 (MH+ 7.37 (mn, 1H), 4.08 - 3.93 (m, 1H), 3.02 - 2.91 (m, 1H), 2.57 (dd, J= 13.1, 6.5 Hz, 1H), 2.17 (s, 3H), 1.48 (s, 9H), 1.37 (d, J = 6.8 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.76 (s, 1H), 8.43 (s, 1H), 7.93 (s, 1H), 7.87 (dt, J= ESIMS ~z 323 9.4, 2.2 Hz, I1H), 416 thin film) 1653 ESIMS m/z 323 3.23 (s, 3H), 2.78 (t, J = 7.3 Hz, 2H), 2.63 (q, J= 7.6 Hz, 2H), 2.44 (t, J = 7.3 Hz, 2H), 2.05 (s, 3H), 1.32 (t, J= 7.6 Hz, 3H). 443 'H NMR (400 MHz, CDCl3) 6 8.76 (s, 1H), 8.42 (s, 1H), 7.98 (s, 1H), 7.87 (dt, J= 9.4, 2.2 Hz, 1H), 3.24 (s, 3H), 2.87 417 (thin film) 1649 ESIMS m/z 337 (m, 1H), 2.79 (m, ([M+H]*) 1H), 2.67 (q, J = 7.5 Hz, 2H), 2.45 (dd, J= 12.6, 5.0 Hz, 1H), 2.03 (s, 3H), 1.34 (t, J= 7.6 Hz, 3H), 1.13 (d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.76 (s, 1H), 8.41 (s, 1H), 7.92 (s, 105.0- ESIMS m/z 292 1H), 7.87 (d, J= 418 180([M+2]+) 9.4 Hz, 1H), 3.21 (s, 3H), 2.62 (q, J = 7.6 Hz, 3H), 1.32 (t, J= 7.6 Hz, 3H), 1.07 (d, J= 6.7 Hz, 6H). 'H NMR (400 MHz, CDCl3) 6 8.75 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 7.91 (s, 1H), 7.87 (dt, J = 9.4, 2.4 Hz, 1H), 3.33 ESIMS m/z 337 3.13 (m, 1H), 2.63 419 (thin film) 1650 ([M+H] ) (q, J = 7.6 Hz, 2H), 2.47 (dd, J= 15.5, 6.7 Hz, 1H), 2.25 (dd, J = 15.5, 7.3 Hz, 1H), 2.05 (s, 3H), 1.32 (t, J = 7.6 Hz, 3H), 1.27 (d, J= 6.8 Hz, 3H). 444 'H NMR (400 MHz, CDCl3) 6 8.76 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 7.97 (s, 1H), 7.88 (dt, J= 9.4, 2.3 Hz, 1H), 3.23 ESIMS m/z 335 (s, 3H), 2.68 (q, J 420 (thin film) 1643 ([M+H]*) = 7.6 Hz, 2H), 2.48 (ddd, J = 8. 1, 5.5, 3.6 Hz, 1H), 2.10 (s, 3H), 1.74 1.67 (m, 1H), 1.54 - 1.47 (m, 1H), 1.33 (t, J= 7.6 Hz, 3H), 0.99 - 0.92 (m, 1H). H NMR (400 MHz, CDCl3) 6 8.62 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 7.76 (dt, J= 9.4, 2.4 Hz, 1H), 421 (thin film) 1655 ESIMS m/z 385 7.46 (s, 1H), 7.13 ([M+H]*) (d, J= 8.3 Hz, 2H), 6.96 (d, J= 8.2 Hz, 2H), 3.63 (s, 2H), 3.45 (s, 2H), 2.45 (s, 3H), 2.15 (s, 3H), 1.12 (t, J= 7.1 Hz, 3H). 445 'H NMR (400 MHz, CDCl3) 6 8.80 (d, J= 2.6 Hz, 1H), 8.62 (dd, J= 4.7, 1.3 Hz, 1H), 7.90 (ddd, J = 8.3, 2.7, 1.4 Hz, ESIMS m/z 388 1H), 7.44 (dd, J= 422 (thin film) 1661 ([M+H] ) 8.7, 4.8 Hz, 1H), 7.42 (s, 1H), 7.12 (d, J= 8.3 Hz, 2H), 6.97 (d, J= 8.3 Hz, 2H), 3.68 (d, J= 8.3 Hz, 2H), 3.51 (s, 2H), 2.43 (s, 3H), 1.14 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.77 (s, 1H), 8.42 (d, J= 2.5 Hz, 1H), 7.90 (s, 1H), 7.86 (dt, J = 9.4, 1 9 F NMR (376 423 EIMS m/z 332 Hz,MHz, CDC 3 ) (s, 2H), 2.48 (t, J 6 -120.98 (s). = 6.9 Hz, 2H), 2.24 (s, 3H), 2.10 (s, 5H), 1.85 (p, J = 7.0 Hz, 2H), 1.13 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (s, 1H), 8.46 (s, 1H), 8.10 (s, 1H), 8.02 (d, J= 9.2 Hz, 1H), 3.69 19F NMR (376 424 85-86 EIMS m/z 330 (s, 2H), 3.03 (p, J MHz, CDCl 3 ) = 8.2 Hz, 1H), 6 -121.32 (s). 2.56 (dd, J= 18.1, 9.0 Hz, 1H), 2.41 (m, 1H), 2.27 (s, 3H), 2.11 (m, 5H), 1.15 (t, J= 7.2 Hz, 3H). 446 I1H NMR (400 MHz, CDC3) 6 8.62 (s, 1H), 8.39 (d, J= 2.5 Hz, 425 (thin film) 1641 ESIMS m/z 425 1H), 7.71 (s, 2H), ([M+H]*) 7.52 (s, 2H), 7.42 (s, 2H), 3.87 (s, 2H), 2.11 (s, 3H), 1.25 (t, J= 7.0 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.62 (s, 1H), 8.39 (d, J= 2.5 Hz, 426 (thin film) 1649 ESIMS m/z 428 1H), 7.71 (s, 2H), ([M+H]*) 7.52 (s, 2H), 7.42 (s, 2H), 3.87 (s, 2H), 2.11 (s, 3H), 1.25 (t, J= 7.0 Hz, 3H). 447 'H NMR (400 MHz, CDCl3) 6 8.98 - 8.94 (d, J= 2.5 Hz, 1H), 8.65 8.60 (dd, J= 4.7, 1.3 Hz, 1H), 8.08 8.03 (m, 1H), 8.03 - 7.99 (s, 1H), 7.50 - 7.43 (m, 1H), 5.80 - 5.62 (m, 427 (thin film) 3084, ESIMS m/z 365 1H), 5.09 - 4.99 2974, 1653. ([M+H]*). (m, 2H), 3.92 3.73 (s, 1H), 3.69 3.53 (s, 1H), 3.13 2.94 (m, 2H), 2.87 - 2.74 (dd, J= 12.7, 9.1 Hz, 1H), 2.72 - 2.58 (m, 1H), 2.49 - 2.36 (dd, J= 12.7, 5.3 Hz, 1H), 1.20 1.13 (m, 6H). H NMR (400 MHz, CDCl3) 6 8.99 - 8.92 (d, J= 2.5 Hz, 1H), 8.66 8.59 (m, 1H), 8.09 - 8.01 (m, 1H), 7.99 - 7.93 (s, 1H), (thin film) 3086, ESIMS m/z 351 7.51 - 7.43 (m, 428 2975, 1658. ([M+H]*). iH), 5.85 - 5.63 (m, 1H), 5.14 4.98 (m, 2H), 3.77 - 3.63 (m, 2H), 3.14 - 3.03 (m, 2H), 2.82 - 2.70 (m, 2H), 2.46 2.35 (m, 2H), 1.19 - 1.09 (m, 3H). 448 'H NMR (400 MHz, CDC3) 6 8.98 - 8.94 (d, J= 2.5 Hz, 1H), 8.67 8.58 (m, 1H), 8.13 - 8.01 (m, 2H), 7.51 - 7.42 (m, 1H), 5.70 - 5.52 (m, 1H), 5.06 429 (thin film) 3087, ESIMS m/z 351 4.95 (m, 1H), 4.95 2974, 2930, 1656. ([M+H]*). - 4.85 (d, J= 10.0 Hz, 1H), 3.83 3.70 (dd, J= 14.3, 7.2 Hz, 1H), 3.68 3.57 (s, 1H), 3.33 3.23 (m, 1H), 3.19 - 3.07 (m, 2H), 1.48 - 1.42 (d, J= 6.8 Hz, 3H), 1.19 1.15 (m, 31H). IH NMR (400 MHz, CDC3) 6 8.93 - 8.85 (m, 1H), 8.65 - 8.56 (m, 1H), 8.09 8.03 (m, 3H), 8.03 - 7.99 (m, 1H), 430 (thin film) 1719, ESIMS m/z 446 7.64 - 7.51 (m, 1687 ([M+H]*) 1H), 7.50 - 7.37 (m, 3H), 6.15 5.67 (m, 2H), 2.95 - 2.72 (m, 2H), 2.58 - 2.43 (m, 1H), 2.06 - 1.96 (m, 3H), 1.31 1.19 (m, 31H). 449 'H NMR (400 MHz, CDCl3) 6 9.00 - 8.89 (d, J= 2.9 Hz, 1H), 8.64 - 8.49 (d, J = 4.8 100- ESIMS m/z 311 Hz, 1H), 8.11 431 102 ([M+2-t-Bu]3) 7.99 (m, 1H), 7.94 - 7.75 (s, 1H), 7.58 - 7.39 (m, 1H), 3.68 - 3.49 (m, 2H), 1.53 1.30 (s, 9H), 1.23 -1.10 (m, 2H). IH NMR (400 MHz, CDCl3) 6 9.00 - 8.92 (d, J= 2.5 Hz, 1H), 8.67 8.59 (dd, J= 4.7, 1.4 Hz, 1H), 8.11 432 (thin film) 3485, ESIMS m/z 311 8.07 (s, 1H), 8.06 3092, 2976, 1657. ([M+H]*). 8.01 (m, 1H), 7.50 - 7.42 (m, 1H), 3.79 - 3.65 (m, 2H), 3.10 - 3.05 (s, 2H), 2.26 - 2.18 (s, 3H), 1.22 - 1.12 (m, 3H). H NMR (400 MHz, CDCl3) 6 8.97 (s, 1H), 8.61 (s, 1H), 8.09 - 7.94 (m, 2H), 7.51 ESIMS m/z 354 7.36 (m, 1H), 3.39 433 (thin film) 1719 ([M+H] ) - 3.27 (m, 1H), 2.98 - 2.85 (m, 1H), 2.58 - 2.49 (m, 1H), 2.46 (s, 3H), 2.08 (s, 3H), 1.29 (d, J= 6.9 Hz, 3H). 450 IH NMR (400 MHz, CDC3) 6 8.73 (s, 1H), 8.30 (d, J= 2.5 Hz, 434 156.5- ESIMS m/z 319 1H), 8.27 (s, 1H), 158.0 ([M+H]*) 7.76 (dt, J= 9.8, 2.4 Hz, 1H), 6.43 (s, 1H), 1.55 (s, 9H), 1.01 - 0.91 (m, 4H). H NMR (400 MHz, CDC3) 6 8.74 (d, J= 1.1 Hz, 1H), 8.64 (s, 1H), 8.37 - 8.29 144.0- ESIMS m/z 279 (m, 2H), 7.74 (dt, 435 146.0 ([M+H] ) J = 9.5, 2.3 Hz, 1H), 4.95 (d, J = 3.0 Hz, 2H), 3.21 3.06 (m, 1H), 2.63 - 2.48 (m, 1H), 1.26 (d, J= 6.9 Hz, 6H). H NMR (400 MHz, CDC3) 6 8.79 (d, J= 1.2 Hz, 1H), 8.60 (s, 1H), 8.38 (d, J= 436 (thin film) 1659 ESIMS m/z 249 2.5 Hz, 1H), 7.81 ([M+H]*) (dt, J= 9.5, 2.3 Hz, 1H), 7.68 (s, 1H), 7.54 (s, 1H), 2.63 - 2.51 (m, 1H), 1.28 (d, J= 6.9 Hz, 6H). 451 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.7 Hz, 1H), 8.62 (dd, J= 4.8, 1.5 Hz, 1H), 8.08 - 8.01 (m, 2H), 7.49 ESIMS m/z 382 7.41 (m, 1H), 3.43 437 (thin film) 1711 ([M+H] ) - 3.30 (m, 1H), 3.23 (hept, J= 6.8 Hz, 1H), 3.00 2.87 (m, 1H), 2.59 - 2.49 (m, 1H), 2.09 (s, 3H), 1.31 (d, J= 6.8 Hz, 3H), 1.25 - 1.18 (m, 6H). H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.4 Hz, 1H), 8.64 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J ESIM m~z341 = 8.4, 2.7, 1.4 Hz, 438 (JR thin film) 1435 ESIMS m/z3 2H), 7.56 - 7.36 (m, 1H), 3.69 (d, J = 26.2 Hz, 3H), 3.10 (s, 2H), 2.62 (d, J= 12.7 Hz, 1H), 2.02 (s, 3H), 1.27 (d, J= 6.4 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.95 - 8.60 (bs, 1H), 8.55 - 8.26 (d, J= 2.5 Hz, 1H),7.95 (s, 1H), 439 101- ESIMS m/z 275 7.89 - 7.75 (m, 109 ([M+H]*) 1H), 3.39 - 2.94 (s, 3H), 2.42 - 2.23 (s, 3H), 1.34 - 1.07 (m, 1H), 1.08 0.96 (m, 2H), 0.77 - 0.53 (dd, J= 7.8, 3.0 Hz, 2H). 452 'H NMR (400 MHz, CDC13) 6 8.84 - 8.61 (bs, 1H), 8.58 - 8.29 (d, J= 2.4 Hz, 1H), 8.10 - 7.71 440 132- ESIMS m/z 289 (m, 2H), 3.32 139 ([M+H]*) 3.04 (s, 3H), 2.48 2.14 (s, 3H), 1.47 1.29 (m, 1H), 1.27 - 1.09 (m, 2H), 1.05 - 0.91 (d, J= 6.0 Hz, 3H), 0.61 0.41 (m, 1H). IH NMR (400 MHz, CDC13) 6 8.91 - 8.60 (d, J= 1.8 Hz, 1H), 8.56 90- ESIMS m/z 310 8.25 (d, J= 2.5 441 100 ([M+H] ) Hz, 1H), 8.06 7.88 (s, 1H), 7.91 7.72 (m, 1H), 3.29 (s, 3H), 2.46 - 2.06 (m, 5H), 1.66 1.59 (m, 1H). H NMR (400 MHz, CDC13) 6 8.73 (bs, 1H), 8.60 - 8.31 (d, J= 2.5 Hz, 1H), 7.96 ESIMS m/z 288 7.66 (m, 2H), 3.22 442 70-77 ([M+H] ) (s, 3H), 2.25 (s, 3H), 2.17 - 1.92 (d, J= 6.8 Hz, 2H), 1.19 - 0.89 (m, 1H), 0.66 0.34 (m, 2H), 0.05 - 0.00 (m, 2H). 453 IH NMR (400 MHz, CDC13) 6 8.74 (s, 1H), 8.42 (d, J= 2.5 Hz, ESIMS ~ 303 H), 8.13 - 7.64 443 82-88 ESIMS m/z 303 (, 2H), 3.12 1(s, 3H), 2.34 - 2.06 (m, 5H), 1.52 1.46 (m, 2H), 0.5 0.7 (m, 1H), 0.38 (m, 4H). IH NMR (400 MHz, CDC13) 6 9.27 (s, 1H), 9.10 (s, 2H),7.93 (s, 444 87-93 ESIMS m/z 292 1H), 3.24 (s, 3H), ([M+H]*) 2.79 (t, J= 7.3 Hz, 2H), 2.48 (t, J= 7.2 Hz, 2H), 2.29 (s, 3H), 2.06 (s, 3H). H NMR (400 MHz, CDC13) 6 9.23 (s, 1H), 9.2 97- ESIMS m/z 312 (s, 2H), 8.04 (s, 445 104 ([M+H] ) 1H), 3.25 (s, 3H), 2.80 (t, J= 7.3 Hz, 2H), 2.47 (t, J= 7.3 Hz, 2H), 2.08 (s, 3H). 454 'H NMR (400 MHz, CDC13) 6 9.16(s, 1H), 9.10(s, 2H), 7.97 (s, 1H), 3.24 (s, 110- ESIMS m/z 306 3H), 2.95 - 2.82 446 114 ([M+H] ) (m, 1H), 2.82 2.69 (m, 1H), 2.45 (dd, J= 12.6, 4.8 Hz, 1H), 2.33 (s, 3H), 2.02 (s, 3H), 1.13 (d, J= 6.7 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 9.22 (s, 1H), 9.11 (s, 2H), 8.08 (s, 1H), 3.27 (s, 3H), 447 ESIMS m/z 326 2.94 - 2.79 (m, ([M+H]*) 1H), 2.79 - 2.64 (m, 1H), 2.49 (dd, J= 12.6, 5.1 Hz, 1H), 2.04 (s, 3H), 1.17(d, J= 6.7 Hz, 3H). H NMR (400 MHz, CDC13) 6 9.16 (s, 1H), 9.10 118- ESIMS m/z 260 (s, 2H), 7.91 (s, 448 122 ([M+H] ) 1H), 3.21 (s, 3H), 2.60 (dt, J= 13.4, 6.7 Hz, 1H), 2.28 (s, 3H), 1.07 (d, J = 6.7 Hz, 6H). 455 IH NMR (400 MHz, CDCl3) 6 9.22 (s, 1H), 9.12 130- ESIMS m/z 279 (s, 2H), 8.01 (s, 449 139 ([M+H]) 1H), 3.23 (s, 3H), 2.59 (dt, J= 13.3, 6.6 Hz, 1H), 1.09 (d, J= 6.7 Hz, 6H). H NMR (400 MHz, CDC13) 6 8.93 (s, 1H), 8.62 (s, 1H), 8.06 - 8.00 (m, 2H), 7.49 7.43 (m, 1H), 5.80 (thin film) 1737, ESIMS m/z 412 5.39 (m, 2H), 450 1689 ([M+H]*) 2.91 - 2.80 (m, 1H), 2.80 - 2.69 (m, 1H), 2.64 2.53 (m, 1H), 2.53 - 2.43 (m, 1H), 2.01 (s, 3H), 1.58 (s, 3H), 1.21 - 1.17 (m, 6H). IH NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.7 Hz, 1H), 8.58 (dd, J= 4.8, 1.5 Hz, 1H), 8.08 - 7.99 (m, 1H), 7.96 (s, ESIM m~z284 1H), 7.45 - 7.39 451 (thin film) 1747 ESIMS mz 284 i H), 4.34 4.22 (m, 2H), 4.11 - 3.98 (m, 1H), 3.02 - 2.92 (m, 1H), 2.65 - 2.53 (m, 1H), 2.17 (s, 3H), 1.37 (d, J= 6.8 Hz, 3H), 1.28 (t, J= 7.1 Hz, 3H). 456 'H NMR (400 MHz, CDC13) 6 8.99 - 8.89 (d, J= 2.7 Hz, 1H), 8.66 - 8.60 (m, 1H), 452 3499, 3189, 2914, 8.10 - 8.02 (n, (s, 1H), 7.48 7.43 (m, 1H), 3.28 - 3.20 (s, 3H), 2.83 - 2.76 (m, 2H), 2.52 - 2.43 (m, 2H). IH NMR (400 MHz, CDC13) 6 8.98 - 8.91 (d, J= 2.7 Hz, 1H), 8.66 - 8.58 (m, 1H), 8.10 - 8.04 (m, 1H), 8.03 - 7.96 453 90-91 ESIMS m/z 370 (s, 1H), 7.50 ([M+2H]*) 7.41 (dd, J= 8.3, 4.8 Hz, 1H), 3.29 - 3.22 (s, 3H), 2.93 - 2.82 (m, 1H), 2.53 - 2.43 (m, 1 H), 1. 19 1.15 (d, J= 6.6 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 9.11 - 8.83 (d, J= 2.7 Hz, 1H), 8.74 - 8.52 (d, J= 4.6 ESIM m~z322 Hz, H), 8.15 454 130- ES([M ) 322 8.03 (m, HH), 7.99 132 ([M+2H)+] - 7.90 (s, 1H), 7.58 - 7.36 (m, 1H), 3.34 - 3.11 (s, 3H), 2.67 2.48 (m, 1H), 1.17 - 1.00 (d, J= 6.7 Hz, 6H). 457 'H NMR (400 MHz, CDCl3) 6 9.01 - 8.90 (d, J= 2.7 Hz, 1H), 8.67 ESIMS m/z 376 -8.60 (m, 1H), 455 3102,2993,E1651 ([M]), 378 8.01 - 7.93 (s, ([M+2H]*) 1H), 7.54 - 7.43 (m, 1H), 3.32 3.19 (s, 3H), 2.61 - 2.45 (m, 1H), 2.47 - 2.33 (m, 1H). IH NMR (400 MHz, CDC13) 6 8.99 - 8.91 (m, 1H), 8.66 - 8.60 (m, 1H), 8.11 8.07 (s, 1H), 8.07 (thin film) 3434, ESIMS m/z 279 7.99 (m, 1H), 7.50 456 1675. ([M+H]*). - 7.42 (m, 1H), 3.40 - 3.37 (m, 1H), 3.32 - 3.26 (m, 3H), 3.09 3.03 (dd, J= 6.5, 2.4 Hz, 1H), 2.89 2.81 (dd, J= 6.5, 4.1 Hz, 1H). H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.4 Hz, 1H), 8.64 (d, J = 3.7 Hz, 1H), 8.08 - 8.02 (m, 2H), 7.47 (dd, J= 457 (thin film) 1741, ESIMS m/z 384 8.2, 4.8 Hz, 1H), 1684 ([M+H]*) 5.94 - 5.40 (m, 2H), 2.93 - 2.81 (m, 1H), 2.81 2.69 (m, 1H), 2.55 - 2.43 (m, 1H), 2.10 (s, 3H), 2.02 (s, 3H), 1.20 (d, J = 6.5 Hz, 3H). 458 'H NMR (400 MHz, CDC13) 6 9.02 - 8.91 (s, 1H), 8.66 - 8.59 (s, 1H), 8.08 8.04 (m, 1H), 7.52 - 7.42 (m, 2H), 458 97-98 ESIMS m/z 368 3.29 - 3.19 (s, ([M+2H]*) 3H), 2.54 - 2.46 (m, 1H), 2.17 2.09 (s, 3H), 1.71 - 1.62 (m, 1H), 1.56 - 1.50 (m, 1H), 1.08 -0.93 (d, J= 5.5 Hz, 1H). 'H NMR (400 MHz, CDC13) 6 9.01 - 8.91 (m, 1H), 8.75 - 8.55 (m, 1H), 8.10 8.01 (m, 1H), 8.00 - 7.93 (s, 1H), 459 3089, 2966, 2916, ESIMS m/z 370 7.52 - 7.41 (m, 1655 ([M+2H]*) 1H), 3.31 - 3.19 (s, 3H), 2.55 2.43 (m, 1H), 2.34 - 2.21 (m, 1H), 2.09 - 2.02 (s, 3H), 1.34 - 1.23 (d, J= 6.8 Hz, 3H). 8.96 - 8.92 (d, J= 2.8 Hz, 1H), 8.67 - 8.54 (dd, J= 4.8, 1.5 Hz, 1H), 8.12 - 8.06 (s, 460 95-96 ESIMS m/z 342 1H), 8.05 - 7.93 ([M+2H]*) (m, 1H), 7.49 7.42 (m, 1H), 3.29 - 3.21 (s, 3H), 3.13 - 3.07 (s, 2H), 2.27 - 2.19 (s, 3H) 459 'H NMR (400 MHz, CDC13) 6 8.97 - 8.92 (d, J= 2.6 Hz, 1H), 8.68 - 8.62 (dd, J= 4.8, 1.5 Hz, 1H), 8.10 - 7.99 (d, J= 8.5 3091, 2980,2941, ESIMS m/z 392 Hz, 1H), 7.92 461 1661 ([M+2H] ) 7.86 (s, 1H), 7.50 - 7.44 (m, 1H), 3.28 - 3.21 (s, 3H), 2.92 - 2.84 (s, 1H), 2.83 2.67 (m, 1H), 2.10 - 1.95 (m, 1H), 1.24 - 1.17 (d, J= 6.9 Hz, 3H). H NMR (400 MHz, CDC13) 6 9.00 - 8.90 (d, J= 2.7 Hz, 1H), 8.70 - 8.59 (m, 1H), 8.11 - 8.02 (m, ESIMS m/z 368 1H), 7.95 - 7.89 462 91-92 ([M]+), 370 (s, 1H), 7.51 ([M+2H]*) 7.39 (m, 1H), 3.79 - 3.63 (m, 2H), 2.85 - 2.72 (m, 1H), 2.51 - 2.37 (m, 2H), 2.10 2.00 (s, 3H), 1.25 - 1.06 (m, 2H). 460 'H NMR (400 MHz, CDC13) 6 9.01 - 8.91 (d, J= 2.6 Hz, 1H), 8.71 - 8.57 (d, J= 4.8 Hz, 1H), 8.17 8.02 (m, 1H), 8.02 463 102- ESIMS m/z 384 - 7.92 (s, 1H), 104 ([M+2H]*) 7.51 - 7.40 (m, 1H), 2.93 - 2.79 (m, 1H), 2.74 2.59 (s, 1H), 2.53 - 2.35 (m, 1H), 2.03 - 1.98 (s, 3H), 1.22 - 1.10 (m, 6H). H NMR (400 MHz, CDC13) 6 9.02 - 8.90 (d, J= 2.8 Hz, 1H), 8.67 - 8.60 (d, J= 4.7 3092,2975,2935 ESIMS m/z 390 Hz, 1H), 8.12 464 ' 1663' ' ([M]+), 392 8.03 (m, 1H), 7.55 ([M+2H]* - 7.41 (m, 1H), 3.80 - 3.61 (s, 2H), 2.58 - 2.43 (m, 1H), 2.43 2.32 (m, 2H), 1.22 - 1.11 (m, 3H) 'H NMR (400 MHz, CDC13) 6 9.00 - 8.90 (d, J= 2.7 Hz, 1H), 8.65 - 8.57 (d, J= 4.7 Hz, 1H), 8.11 465 142- ESIMS m/z 338 8.01 (m, 1H), 7.93 143 ([M+2H]* - 7.87 (s, 1H), 7.51 - 7.42 (m, 1H), 2.59 - 2.43 (m, 1 H), 1. 19 1.12 (m, 3H), 1.12 - 1.03 (d, J= 6.8 Hz, 6H). 461 'H NMR (400 MHz, CDC13) 6 9.01 - 8.94 (d, J= 2.7 Hz, 1H), 8.69 - 8.59 (d, J= 4.5 Hz, 1H), 8.14 8.05 (m, 1H), 8.02 - 7.93 (s, 1H), 7.52 - 7.39 (dd, J 119- ESIMS mz 382 = 8.3, 4.7 Hz, 466 120 ([M+2H] ) 1H), 3.85 - 3.52 (d, J= 44.3 Hz, 2H),2.59 - 2.43 (s, 1H), 2.17 - 2.10 (s, 3H), 1.65 1.60 (m, 1H), 1.55 - 1.50 (m, 1H), 1.20 - 1.12 (m, 3H),1.04 - 0.93 (d, J= 4.9 Hz, 1H). H NMR (400 MHz, CDC13) 6 8.98 - 8.95 (d, J= 2.7 Hz, 1H), 8.65 - 8.61 (d, J= 4.7 Hz, 1H), 8.09 8.05 (m, 1H), 7.94 - 7.92 (s, 1H), 7.50 - 7.43 (m, 467 3087, 2970, 2917, ESIMS m/z 384 1H), 3.82 - 3.61 1653 ([M+2H]*) (s, 2H), 3.31 3.18 (m, 1H), 2.54 - 2.41 (dd, J= 15.6, 6.3 Hz, 1H), 2.30 - 2.21 (m, 1H), 2.08 - 2.04 (s, 3H), 1.31 1.27 (d, J = 6.8 Hz, 3H), 1.21 1.13 (m, 3H). 462 'H NMR (400 MHz, CDC13) 6 9.03 - 8.88 (d, J = 2.7 Hz, 1H), 8.69 - 8.56 (dd, J= 4.8, 1.5 Hz, 1H), 8.07 ESIMS m/z 354 8.05 (m, 1H), 8.04 468 73-74 ([M]'), 356 - 8.03 (s, 1H), ([M+2H]*) 7.49 - 7.43 (m, 1H), 3.83 - 3.62 (s, 2H), 3.09 3.07 (s, 2H), 2.25 - 2.20 (s, 3H), 1.21 - 1.15 (m, 3H). IH NMR (400 MHz, CDC13) 6 8.97 - 8.94 (d, J= 2.7 Hz, 0.7H), 8.88 - 8.86 (d, J= 2.6 Hz, 0.3H), 8.65 - 8.61 (m, 0.7H), 8.49 - 8.46 (m, 0.3H), 8.08 8.03 (m, 1.7H), 8.01 - 7.95 (m, ESIMS m/z 0.3H), 7.48 - 7.43 469 74-75 368([M]+), 370 (m, 0.7H), 7.39 ([M+2H]*) 7.34 (m, 0.3H), 3.99 - 3.84 (s,0.31H), 3.29 3.19 (s, 0.7H), 3.17 - 3.07 (m, 2H), 1.53 - 1.47 (s, 0.9H), 1.47 1.42 (d, J= 6.9 Hz, 2.1H), 1.35 1.28 (m, 0.9H), 1.20 - 1.14 (m, 2.1H). 463 'H NMR (400 MHz, CDC3) 6 8.89 (d, J= 1.6 Hz, 1H), 8.59 (d, J = 4.1 Hz, 1H), 8.06 (s, 1H), 7.98 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.78 9 ESIMS m/z 416 (dd, J= 5.2, 3.3 47 (hn il)1699 ESIM m/]41 Hz, 2H), 7.53 7.48 (m, 1H), 7.44 - 7.37 (m, 3H), 3.44 - 3.28 (m, 1H), 2.97 (dd, J= 13.2, 8.8 Hz, 1H), 2.59 (dd, J= 13.2, 5.8 Hz, 1H), 2.09 (s, 3H), 1.38 (d, J = 6.8 Hz, 3H). IH NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.2 Hz, 1H), 8.63 (d, J = 4.1 Hz, 1H), 8.05 (s, 1H), 8.05 471 (thin film) 1652 ESIMS m/z 326 8.00 (m, 1H), 7.46 ([M+H]*) (dd, J = 8.3, 4.7 Hz, 1H), 3.27 (s, 3H), 2.86 (d, J = 12.9 Hz, 1H), 2.47 (d, J= 12.9 Hz, 1H), 2.02 (s, 3H), 1.16 (s, 3H). 464 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.63 (dd, J = 4.7, 1.2 Hz, 1H), 8.11 - 7.94 472 (thin film) 1648 ESIMS m/z 340 (m, 2H), 7.53 ([M+H]*) 7.40 (m, 1H), 3.97 - 3.46 (m, 2H), 2.85 (d, J = 13.0 Hz, 1H), 2.46 (d, J = 13.0 Hz, 1H), 2.02 (s, 3H), 1.21 1.13 (m, 6H). 'H NMR (400 MHz, CDCl3) 6 8.76 (d, J= 1.1 Hz, 1H), 8.43 (d, J = 2.5 Hz, 1H), 7.94 (s, 1H), 7.86 (dt, J = 9.4, 2.3 473 85-87 (thin film) 1642 ESIMS m/z 338 Hz, 1H), 4.05 ([M+H]*) 3.30 (m, 2H), 2.87 (d, J= 12.9 Hz, 1H), 2.42 (d, J = 12.9 Hz, 1H), 2.30 (s, 3H), 2.01 (s, 3H), 1.16 (t, J= 7.1 Hz, 3H), 1.11 (s, 3H). H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.62 (dd, J= 4.7, 1.2 Hz, 1H), 8.07 - 8.01 (m, 2H), 7.45 (dd, 474 (thin film) 1677 ESIMS m/z 356 J = 8.3, 4.7 Hz, ([M+H]*) 1H), 5.88 - 4.24 (m, 3H), 3.48 (s, 3H), 2.92 - 2.75 (m, 2H), 2.49 (dd, J= 12.4, 4.8 Hz, 1H), 2.01 (s, 3H), 1.21 (d, J= 6.5 Hz, 3H). 465 'H NMR (400 MHz, CDCl3) 6 9.02 - 8.90 (m, 1H), 8.66 - 8.57 (m, 1H), 8.21 8.00 (m, 2H), 7.47 475 (thin film) 1731, ESIMS m/z 426 (dt, J= 8.4, 4.3 1683 ([M+H]*) Hz, 1H), 5.95 5.35 (m, 2H), 3.04 - 2.70 (m, 2H), 2.56 - 2.42 (m, 1H), 2.06 - 1.95 (m, 3H), 1.29 1.13 (m, 12H). 'H NMR (400 MHz, CDCl3) 6 9.08 - 9.04 (d, J= 2.7 Hz, 1H), 8.96 - 8.92 (s, 1H), 8.63 - 8.58 (m, 121- ESIMS m/z 354 1H), 8.24 - 8.17 476 123 ([M]+), 356 (m, 1H), 7.64 ([M+2H]*) 7.57 (m, 1H), 3.56 - 3.45 (s, 1H), 3.17 - 3.11 (s, 3H), 2.00 - 1.94 (s, 3H),1.35 - 1.27 (d, J= 6.8 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.99 (s, 1H), 8.57 (d, J= 3.8 Hz, 108.1- ESIMS m/z 231 11H), 8.08 (dt, J= 477 110 ([M+H] ) 7.9, 1.9 Hz, 1H), 7.34 (dd, J= 7.7, 4.7 Hz, 1H), 6.49 (s, 1H), 3.79 (s, 3H),3.23 (s, 3H), 1.94 (s, 3H). 466 'H NMR (400 MHz, CDC3) 6 9.02 - 8.93 (d, J= 2.5 Hz, 1H), 8.64 8.58 (m, 1H), 8.11 - 8.04 (ddd, J= 8.3, 2.6, 1.5 Hz, (thin film) 3487, ESIMS m/z 291 1H), 7.98 - 7.94 (s, 478 3103, 1648. ([M+H]*). 1H), 7.70 - 7.65 (s, 1H), 7.49 - 7.42 (m, 1H), 3.78 3.66 (m, 2H), 2.82 - 2.74 (m, 2H), 2.55 - 2.43 (m, 2H), 2.10 - 2.03 (s, 3H), 1.20 - 1.13 (m, 3H). H NMR (400 MHz, CDC3) 6 8.98 - 8.93 (d, J= 2.5 Hz, 1H), 8.65 8.61 (m, 1H), 8.07 - 8.01 (m, 1H), 143- ESIMS m/z 310 8.01 - 7.99 (s, 1H), 479 146 ([M+H]). 7.49 - 7.44 (m, 1 ), 5.67 - 5.53 (s, 1H), 4.28 - 4.13 (m, 2H), 3.74 3.58 (m, 2H), 1.27 - 1.21 (m, 3H), 1.20 - 1.14 (m, 3H). 467 'H NMR (400 MHz, CDCl3) 6 9.03 - 8.97 (d, J= 2.5 Hz, 1H), 8.65 8.58 (dd, J= 4.7, 1.4 Hz, 1H), 8.12 8.03 (m, 1H), 8.02 480 160- ESIMS m/z 276 7.73 -(76 , 1H), 7.50 - 7.43 (m, 1H), 5.69 - 5.59 (s, 1H), 4.28 - 4.16 (m, 2H), 3.70 3.54 (m, 2H), 1.28 - 1.20 (m, 3H), 1.17 - 1.08 (m, 3H). H NMR (400 MHz, CDC13) 6 8.98 - 8.94 (d, J= 2.4 Hz, 1H), 8.65 8.59 (m, 1H), 8.09 - 8.02 (m, 1H), (thin film) 3092, ESIMS m/z 328 7.99 - 7.95 (s, 1H), 481 2972, 1657. ([M+H]*). 1H) 3.7 743 (n (m, 2H), 3.64 3.55 (m, 2H), 2.38 - 2.28 (m, 2H), 2.14 - 2.06 (m, 2H), 1.19 - 1.13 (m, 3H). 468 'H NMR (400 MHz, CDCl3) 6 8.99 - 8.93 (d, J= 2.5 Hz, 1H), 8.65 8.58 (dd, J= 4.7, 1.3 Hz, 1H), 8.14 8.09 (s, 1H), 8.06 104- ESIMS m/z 325 8.01 (m, 1H), 7.50 482 108 ([M+H]). - 7.41 (m, 1H), 3.90 - 3.75 (s, 1H), 3.66 - 3.51 (s, 1H), 3.31 - 3.21 (d, J= 6.7 Hz, 1H), 2.11 2.06 (s, 3H), 1.46 1.40 (d, J= 6.9 Hz, 3H), 1.23 1.12 (m, 3H). H NMR (400 MHz, CDCl3) 6 8.97 - 8.94 (d, J= 2.5 Hz, 1H), 8.63 8.59 (m, 1H), 8.09 - 8.03 (m, 1H), 483 (thin film) 2953, ESIMS m/z 321 7.92 - 7.87 (s, 1H), 1654. ([M+H]*). 7.49 - 7.42 (dd, J = 8.3, 4.8 Hz, 1H), 3.74 - 3.61 (m, 2H), 2.09 - 2.06 (s, 2H), 1.17 - 1.13 (t, J= 7.1 Hz, 3H), 1.03 - 1.00 (s, 9H). 469 'H NMR (300 MHz, CDC3) 6 9.03 - 8.93 (d, J= 2.4 Hz, 1H), 8.62 8.55 (d, J= 4.7 Hz, 1H), 8.11 8.03 (d, J= 8.4 (thin film) 2953, ESIMS m/z 287 Hz, 1H), 7.90 484 1646. ([M+H]*). 7.84 (s, 1H), 7.66 7.59 (s, 1H), 7.49 7.39 (dd, J= 8.4, 4.8 Hz, 1H), 3.75 3.62 (q, J= 7.1 Hz, 2H), 2.16 2.09 (s, 2H), 1.21 1.10 (m, 3H), 1.04 - 0.93 (s, 9H). H NMR (400 MHz, CDC3) 6 9.06 - 8.91 (m, 1H), 8.64 (d, J= 3.9 Hz, 1H), 8.15 - 8.09 (m, 1H), 8.09 - 8.00 (m, 1H), 7.47 (dd, J= 485 (thin film) 1758, ESIMS m/z 428 8.1, 4.7 Hz, 1H), 1689 ([M+H]*) 5.99 - 5.41 (m, 2H), 4.12 (s, 2H), 3.59 (q, J= 7.0 Hz, 2H), 3.00 2.69 (m, 2H), 2.56 - 2.42 (m, 1H), 2.04 - 1.95 (m, 3H), 1.29 - 1.13 (m, 6H). 470 'H NMR (400 MHz, CDCl3) 68.95 (d, J= 2.6 Hz, 1H), 8.62 (dd, J= 4.7, 1.3 Hz, 1H), 8.26 - 7.91 486 101- ESIMS m/z 351 (m, 2H), 7.46 (dd, 110 ([M+H]*) J= 8.3, 4.8 Hz, 1H), 3.82 - 3.44 (m, 2H), 2.42 (s, 2H), 2.13 (s, 3H), 1.33 - 1.01 (m, 5H), 0.71 - 0.45 (m, 2H). H NMR (400 MHz, CDCl3) 6 9.03 (s, 1H), 8.59 (d, J= 3.9 Hz, ESIM m~z273 1 H), 8.18 (dt, J= 487 (IR thin film) 1643 ESIMS m/z 273 8.0, 1.8 Hz, -H), 7.43 (dd, J= 7.8, 5.0 Hz, 1H), 6.53 (s, 1H), 3.76 (s, 3H), 3.18 (s, 3H), 1.12 (s, 9H). 'H NMR (400 MHz, CDCl3) 6 8.98 - 8.86 (d, J= 2.7 Hz, 1H), 8.62 - 8.49 (m, 1H), ESIMS m/z 352 8.05 - 8.00 (m, 488 81-82 ([M]+), 354 1H),7.98 - 7.83 (s, ([M+2H]*) 1H), 7.45 - 7.36 (m, 1H), 3.78 3.63 (m, 2H), 3.61 - 3.50 (m, 2H), 1.49 - 1.33 (s, 9H). 471 'H NMR (300 MHz, CDCl3) 6 8.78 (s, 1H), 8.37 489 121.0- ESIMS m/z 278 (s, 1H), 8.28 (s, 123.0 ([M]) 1H), 7.81 (d, J = 9.6 Hz, 1H), 7.59 (s, 1H), 6.44 (s, 1H), 1.53 (s, 9H). H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.5 Hz, 1H), 8.64 (dd, J = 4.7, 1.2 Hz, 1H), 8.05 (ddd, J = 8.4, 2.7, 1.4 Hz, ESIMS m/z 1H), 7.98 (s, 1H), 490 (thin film) 1664 347([M+H] ) 7.47 (ddd, J = 8.3, 4.8, 0.4 Hz, 1H), 3.26 (s, 3H), 3.02 2.87 (m, 1H), 2.52 (dd, J= 16.3, 4.0 Hz, 1H), 2.13 (dd, J = 16.3, 9.1 Hz, 1H), 1.14 (d, J= 6.9 Hz, 3H). 472 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.64 (dd, J= 4.7, 1.3 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H), ESIMS m/z 361 7.47 (ddd, J= 8.3, 491 (thin film) 1659 ([M+H] ) 4.8, 0.5 Hz, 1H), 3.87 - 3.57 (m, 2H), 3.03 - 2.85 (m, 1H), 2.49 (dd, J= 16.3, 4.2 Hz, 1H), 2.10 (dd, J= 16.3, 9.0 Hz, 1H), 1.17 (t, J= 7.2 Hz, 3H), 1.14 (d, J= 6.9 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.64 (dd, J = 4.7, 1.2 Hz, 1H), 8.10 (s, 1H), 8.04 (ddd, J= 8.3, 492 103- (thin film) 1670 ESIMS m/z 341 2.6, 1.4 Hz, 1H), 106 ([M+H]*) 7.47 (dd, J = 8.3, 4.7 Hz, 1H), 4.01 (t, J= 6.6 Hz, 1H), 3.32 (s, 3H), 3.31 (s, 3H), 2.80 (qd, J = 13.7, 6.6 Hz, 2H), 2.07 (s, 3H). 473 'H NMR (400 MHz, CDC3) 6 9.00 (d, J= 2.3 Hz, 1H), 8.62 (d, J = 4.9 Hz, 1H), 8.08 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.97 (d, J= 0.5 493 (thin film) 1655 ESIMS m/z 359 Hz, 1H), 7.68 (s, ([M+H]*) 1H), 7.46 (dd, J = 8.2, 4.7 Hz, 1H), 3.87 - 3.60 (m, 3H), 2.61 (dd, J = 16.1, 4.0 Hz, 1H), 2.50 (dd, J= 16.1, 9.9 Hz, 1H), 2.29 (s, 3H), 1.19 (t, J = 7.1 Hz, 3H). 'H NMR (400 MHz, CDC3) 6 8.99 (bs, 1H), 8.64 (bs, 1H), 8.16 7.95 (m, 2H), 7.56 - 7.35 (m, 1H), 3.93 - 3.51 (m, 494 (thin film) 1660 ESIMS m/z 355 2H), 3.42 - 3.03 ([M+H]*) (m, 1H), 2.87(m, 0.5H), 2.81 - 2.69 (m, 0.5H), 2.54(s, 1.5H), 2.47 (s, 1.5H), 2.38 - 2.15 (m, 1H), 1.32 1.21 (m, 3H), 1.22 - 1.10 (m, 3H). 474 'H NMR (400 MHz, CDC3) 6 8.97(d, J = 2.4 Hz, 1H),8.63 (bs, 1H), 8.20 - 7.86 (m, 2H), 7.46 (dd, J= 8.3, 4.8 Hz, 1H), 495 (thin film) 1661 ESIMS m/z 370 3.88 - 3.66 (m, ([M+H]*) 2H), 3.66 - 3.48 (m, 1H), 2.96 2.89 (m, 1H), 2.88 (s, 3H), 2.27(dd, J = 16.6, 7.3 Hz, 1H), 1.43 (d, J= 6.9 Hz, 3H), 1.22 1.05 (t, 3H). 'H NMR (400 MHz, CDC3) 6 8.96 - 8.90 (m, 1H), 8.64 - 8.59 (m, 1H), 8.08 8.05 (m, 1H), 8.04 - 7.99 (s, 1H), 496 ESIMS m/z 355 7.50 - 7.40 (m, ([M+H]*) 1H), 3.95 - 3.73 (s, 2H), 3.67 3.53 (s, 2H), 3.38 - 3.30 (s, 3H), 2.83 - 2.77 (m, 2H), 2.54 - 2.43 (m, 2H), 2.10 2.02 (s, 3H). 475 'H NMR (400 MHz, CDC3) 6 9.01 - 8.87 (d, J= 2.6 Hz, 1H), 8.68 - 8.56 (m, 1H), 8.11 - 8.05 (d, J= 1.3 Hz, 1H), 8.03 - 7.95 (m, OH), 7.51 - 7.40 (m, ESIMS m/z 369 1H), 4.49 - 3.86 497 ([M+H]*), 367 (m, 1H), 3.73 ([M-H]-) 3.52 (s, 3H), 3.39 - 3.28 (s, 3H), 2.90 - 2.77 (d, J= 10.2 Hz, 1H), 2.77 - 2.66 (s, 1H), 2.52 - 2.37 (m, 1H), 2.07 - 1.95 (s, 3H), 1.21 1.10 (d, J= 6.5 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.98 -8.90 (d, J= 2.8 Hz, 1H), 8.69 - 8.56 (m, 1H), 8.11 - 8.04 (m, 498 ESIMS m/z 323 1H), 8.04 - 7.97 ([M+H]*) (s, 1H), 3.65 3.53 (s, 2H), 3.37 - 3.31 (s, 3H), 2.63 - 2.45 (m, 3H), 1.24 - 1.17 (d, J= 7.0 Hz, 6H). 476 'H NMR (400 MHz, CDC3) 6 9.02 - 8.92 (dd, J = 2.6, 0.8 Hz, 1H), 8.68 - 8.60 (dd, J = 4.8, 1.5 Hz, 1H), 8.09 - 7.98 (m, 499 ESIMS m/z 321 1H), 7.96 - 7.87 ([M+H]*) (s, 1H), 3.87 3.58 (d, J = 30.0 Hz, 2H), 3.49 3.38 (m, 1H), 2.16 - 2.08 (s, 3H), 1.39 - 1.32 (d, J= 7.0 Hz, 3H), 1.22 - 1.13 (m, 3H). 'H NMR (400 MHz, CDC3) 6 8.95 (s, 1H), 8.62 (d, J= 4.0 Hz, 1H), 8.08 - 8.01 (m, 1H), 7.97 (s, 1H), 7.46 (dd, J= (thin film) 3326, ESIMS m/z 322 8.3, 4.7 Hz, 1H), 500 2959, 2931, 1648. ([M+H]*). 1442 - .32 (1, (m, 2H), 3.27 3.15 (m, 2H), 1.49 - 1.37 (m, 2H), 1.37 - 1.22 (m, 2H), 1.19 - 1.12 (m, 3H), 0.94 0.84 (m, 3H). 477 'H NMR (400 MHz, CDC 3 ) 6 8.95 (s, 1H), 8.62 (d, J= 4.0 Hz, 1H), 8.08 - 8.00 (m, 1H), 7.97 (s, 1H), 7.50 7.40 (m, 1H), 501 (thin film) 3326, ESIMS m/z 336 4.44 - 4.34 (m, 2929, 1645. ([M+H]*). 1H), 3.73 3.62 (m, 2H), 3.24 - 3.14 (m, 2H), 1.50 1.41 (m, 2H), 1.36 - 1.22 (m, 4H), 1.18 1.12 (m, 3H), 0.87 - 0.81 (m, 3H). H NMR (400 MHz, CDC3) 6 8.99 (s, 1H), 8.60 (d, J= 4.0 Hz, 1H), 8.09 - 8.03 (m, 1H), 8.00 (d, J = 0.6 Hz, 1H), 7.72 - 7.67 (m, 502 (thin film) 3354, ESIMS m/z 302 1H), 7.48 - 7.40 2929, 1644. ([M+H]*). (m, 1H), 4.50 (s, 1H), 3.72 - 3.63 (m, 2H), 3.23 3.14 (m, 2H), 1.52 - 1.38 (m, 2H), 1.36 - 1.21 (m, 4H), 1.20 - 1.14 (m, 3H), 0.90 0.82 (m, 3H). 478 'H NMR (400 MHz, CDCl3) 6 8.97 (s, 1H), 8.62 (s, 1H), 8.09 - 8.02 (m, 1H), 7.98 (s, 1H), 7.51 - 7.42 (m, 1H), 4.11 (d, J 503 (thin film) 3269, ESIMS m/z 322 = 8.2 Hz, 1H), 2964, 1647. ([M+H]*). 3.86 - 3.74 (m, 1H), 3.71 - 3.63 (m, 2H), 1.45 1.34 (m, 2H), 1.18 - 1.11 (m, 3H), 1.08 (d, J= 6.6 Hz, 3H), 0.91 0.84 (m, 3H). 'H NMR (400 MHz, CDCl3) 6 9.00 (s, 1H), 8.60 (s, 1H), 8.09 - 8.03 (m, 1H), 8.00 (d, J = 0.6 Hz, 1H), 7.69 (d, J= 0.6 Hz, 1H), 7.45 (dd, 504 93-96 ESIMS m/z 288 1H8.1, 4.6 Hz, 8.2 Hz, 1H), 3.83 3.75 (m, 1H), 3.71 - 3.62 (m, 2H), 1.43 - 1.38 (m, 2H), 1.19 - 1.15 (m, 3H), 1.08 (d, J = 6.6 Hz, 3H), 0.89 - 0.85 (m, 3H). 479 'H NMR (400 MHz, CDCl3) 6 9.01 - 8.89 (d, J= 2.6 Hz, 1H), 8.68 - 8.59 (m, 1H), 8.02 - 7.92 (s, 505 ESIMS m/z 423 1H), 7.51 - 7.42 ([M+H]*) (m, 1H), 3.85 3.67 (m, 1H), 3.36 - 3.22 (s, 3H), 2.69 - 2.56 (m, 1H), 2.51 - 2.37 (m, 1H), 2.37 2.25 (m, 3H). 'H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.8, 1.4 Hz, 1H), 8.10 - 8.02 (m, 1H), 8.00 (s, 506 (thin film) 1657 ESIMS m/z 351 1H), 7.51 - 7.41 ([M+H]*) (m, 1H), 3.55 (bs, 2H), 2.90 - 2.64 (m, 2H), 2.59 2.26 (m, 2H), 2.07 (s, 3H), 1.02 - 0.87 (m, 1H), 0.62 0.35 (m, 2H), 0.27 - 0.07 (m, 2H). 480 'H NMR (400 MHz, CDC13) 6 8.96 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.7, 1.3 Hz, 1H), 8.26 - 7.78 (m, 2H), 7.46 (dd, J= 8.3, 4.8 Hz, 507 (thin film) 1653 ESIMS m/z 365 1H), 3.5 (bs, 2H), ([M+H]*) 2.86 (m, 2H), 2.48 (dd, J= 12.8, 5.4 Hz, 1H), 2.03 (s, 3H), 1.17 (d, J= 6.7 Hz, 3H), 1.09 0.85 (m, 1H), 0.63 - 0.37 (m, 2H), 0.31 - 0.08 (m, 2H). 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.8, 1.4 Hz, 1H), 8.11 - 8.02 (m, 1H), 7.99 (s, 1H), 7.55 - 7.35 ESIMS m/z 365 (m, 1H), 3.51 (bs, 508 thin film) 1655 ([M+H] ) 2H), 3.37 - 3.08 (m, 1H), 2.60 2.38 (m, 1H), 2.38 - 2.20 (m, 1H), 2.07 (s, 3H), 1.29 (d, J= 6.8 Hz, 3H), 1.11 - 0.85 (m, 1H), 0.65 0.40 (m, 2H), 0.36 - 0.11 (m, 2H) 481 'H NMR (400 MHz, CDCl3) 6 8.99 (s, 1H), 8.57 (d, J= 3.6 Hz, 1H), 8.08 (dt, J= ESIMS m/z 273 7.9, 1.9 Hz, I1H), 509 (JR thin film) 1673 ESMS / 7 7.35 (dd, J= 7.8, 4.8 Hz, 1H), 6.47 (s, 1H), 3.77 (s, 3H), 322 (s, 3H), 2.10 (bs, 2H), 1.62 (m, 2H), 1.27 (m, 2H), 0.85 (m, 3H). IH NMR (400 MHz, CDCl3) 6 8.99 - 8.95 (m, 1H), 8.63 (d, J= 4.6 Hz, 1H), 8.25 - 8.15 (m, 1H), 8.06 (d, J= 8.3 Hz, 1H), 7.48 (dd, 510 (thin film) 1740, ESIMS m/z 428 J= 8.1, 4.8 Hz, 1688 ([M+H]*) 1H), 6.16 - 5.34 (m, 2H), 4.94 4.78 (m, 1H), 2.93 - 2.70 (m, 2H), 2.55 - 2.42 (m, 1H), 2.01 (s, 3H), 1.37 - 1.24 (m, 6H), 1.20 (d, J= 6.2 Hz, 3H). 482 'H NMR (400 MHz, CDC3) 6 8.99 (s, 1H), 8.64 (d, J= 3.9 Hz, 1H), 8.16 (s, 1H), 8.10 (dd, J= 8.3, 1.1 Hz, 1H), 7.51 (dd, J= 8.3, 4.8 ESIMS m/z 400 Hz, 1H), 4.63 (s, 51 (hn il)1663 ESIM m/]40 2H), 3.82 - 3.67 (m, 4H), 3.35 (s, 3H), 2.86 (dd, J= 12.4, 8.9 Hz, 1H), 2.80 - 2.65 (m, 1H), 2.47 (dd, J= 12.8, 5.5 Hz, 1H), 2.01 (s, 3H), 1.18 (d, J= 6.6 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.4 Hz, 1H), 8.63 (d, J = 3.8 Hz, 1H), (thin film) 3514, ESIMS m/z 295 8.09 - 8.03 (m, 512 3091,2978, 1676. ([M+H]*). H) .99 (s, 1H), 4.8 Hz, 1H), 3.88 (s, 2H), 3.77 - 3.65 (m, 2H), 3.40 (s, 3H), 1.18 (t, J= 7.2 Hz, 3H). 483 'H NMR (400 MHz, CDC3) 6 8.99 (s, 1H), 8.60 (d, J= 4.1 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 8.00 (d, J= 0.6 Hz, 1H), 7.72 513 (thin film) 3348, ESIMS m/z 288 7.67 (m, 1H), 7.50 2959, 2931, 1644. ([M+H]*). - 7.40 (m, 1H), 4.49 (s, 1H), 3.73 3.59 (m, 2H), 3.26 - 3.12 (m, 2H), 1.50 - 1.37 (m, 2H), 1.35 - 1.22 (m, 2H), 1.21 1.14 (m, 3H), 0.93 - 0.84 (m, 3H). 'H NMR (400 MHz, CDCl3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.60 (dd, J= 4.7, 1.4 Hz, 514 91-93 ESIMS m/z 338 1H), 8.08 - 8.03 ([M+H]*). (m, 1H), 7.97 (s, 1H), 7.47 - 7.41 (i, 1H), 3.69 (q, J = 7.2 Hz, 2H), 1.47 (s, 9H), 1.21 1.13 (m, 3H). 484 'H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.7, 1.3 Hz, 1H), 8.12 (s, 1H), 8.04 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), ESIMS m/z 384 7.46 (ddd, J= 8.3, 515 (thin film) 1664 ([M+H] ) 4.8, 0.5 Hz, 1H), 4.37 - 3.53 (m, 4H), 3.50 (q, J= 6.9 Hz, 2H), 2.97 - 2.79 (m, 1H), 2.79 - 2.64 (m, 1H), 2.47 (dd, J= 12.7, 5.6 Hz, 1H), 2.01 (s, 3H), 1.23 - 1.12 (m, 6H). IH NMR (400 MHz, CDCl3) 6 8.89 (d, J= 1.0 Hz, 1H), 8.62 (d, J = 4.0 Hz, 1H), 8.01 (ddd, J= 8.4, 2.5, 1.4 Hz, 1H), 7.82 (s, 1H), 7.46 (dd, J= 8.3, 4.7 516 (R thin film) 1658 ESIMS m/z 362 Hz, 1H), 7.04 (dd, ([M+H]+) J= 5.1, 0.9 Hz, 1H), 6.85 (dd, J= 5.1, 3.4 Hz, 1H), 6.76 - 6.69 (m, 1H), 3.23 (s, 3H), 2.84 (t, J= 7.3 Hz, 2H), 2.24 (t, J= 7.3 Hz, 2H), 2.00 (p, J= 7.3 Hz, 2H). 485 'H NMR (400 MHz, CDC13) 6 8.97 (d, J= 2.3 Hz, 1H), 8.61 (s, 1H), 8.56 (dd, J= 163.5 4.7, 1.4 Hz, 1H), 517 - ESIMS m/z 320 7.99 (ddd, J= 8.3, 166.5 ([M+H]*) 2.7, 1.5 Hz, 1 H), 7.41 (ddd, J= 8.4, 4.8, 0.7 Hz, 1H), 7.18 (s, 1H), 2.78 - 2.68 (m, 2H), 2.68 - 2.54 (m, 2H). 'H NMR (400 MHz, CDC13) 6 8.99 (d, J= 2.5 Hz, 1H), 8.59 (dd, J= 4.7, 1.3 Hz, 1H), 8.09 - 8.04 (m, 1H), 8.04 ESIMS m/z 306 8.01 (m, 1H), 7.72 518 53-56 (M+H]*). (s, 1H), 7.47 - 7.41 (m, 1H), 4.97 (d, J = 5.2 Hz, 1H), 3.74 - 3.61 (m, 2H), 3.46 - 3.34 (m, 2H), 2.67 2.57 (m, 2H), 2.08 (s, 3H), 1.25 - 1.12 (m, 3H). 486 'H NMR (400 MHz, CDC13) 6 8.95 (d, J= 2.6 Hz, 1H), 8.61 (dd, J= 4.7, 1.3 Hz, 1H), 8.07 - 8.01 (m, 1H), 8.00 (s, 519 110- ESIMS m/z 340 1H), 7.48 - 7.42 112 ([M+H]*). (m, 1H), 4.94 4.83 (m, 1H), 3.74 - 3.59 (m, 2H), 3.46 - 3.34 (m, 2H), 2.67 - 2.56 (m, 2H), 2.07 (s, 3H), 1.21 - 1.08 (m, 3H). 'H NMR (400 MHz, CDCl3) 6 9.00 (s, 1H), 8.57 (bs, 1H), 8.10 (dt, J= 8.0, 1.9 Hz, 1H), 7.34 (dd, J= ESIM m~z273 7.7, 4.7 Hz, 520 (IR thin film) 1672 ESIMS m/z 273 1H),6.47 (s, IH), 4.02 (q, J= 7.3 Hz, 2H), 3.22 (s, 3H), 2.45 (dt, J= 13.4, 6.7 Hz, 1H), 1.51 (t, J= 7.3 Hz, 3H), 1.09 (dd, J= 6.5, 4.1 Hz, 6H). 487 'H NMR (400 MHz, CDC13) 6 8.96 (d, J= 2.6 Hz, 1H), 8.62 (dd, J= 4.7, 1.3 Hz, 1H), 8.15 (s, 1H), 8.09 - 8.01 (m, 115- ESIMS m/z 351 1H), 7.50 - 7.41 521 118 ([M+H]). (m, 1H), 3.72 (s, 1H), 3.46 - 3.19 (m, 2H), 2.09 (s, 3H), 1.45 (d, J= 6.9 Hz, 3H), 1.05 0.90 (m, 1H), 0.58 - 0.42 (m, 2H), 0.29 - 0.13 (m, 2H). IH NMR (400 MHz, CDC13) 6 8.97 (s, 1H), 8.65 (s, 1H), 8.09 - 8.01 (m, 1H), 7.98 (s, 522 92-95 ESIMS m/z 309 I, 752 -3.45 3.83 (m, 1H), 3.79 (s, 1H), 3.67 (s, 1H), 3.28 (s, 3H), 1.34 - 1.25 (m, 3H), 1.18 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.67 (d, J= 0.9 Hz, 1H), 8.33 (d, J 119.0- ESIMS mz 334 = 2.5 Hz, 1H), 523 121.0 ([M+2]*) 7.94 - 7.73 (m, 2H), 3.25 (s, 3H), 1.86 - 1.72 (m, 1H), 1.45 (s, 9H), 1.04 - 0.92 (m, 4H). 488 'H NMR (400 MHz, CDC13) 6 8.79 (s, 1H), 8.58 (dd, J= 4.7, 1.2 Hz, 1H), 7.92 (d, J 524 109.5- ESIMS m/z 334 = 7.6 Hz, 1H), 111.0 ([M+H]+) 7.69 (s, 1H), 7.41 (dd, J= 8.3, 4.8 Hz, 1H), 7.18 (s, 1H), 6.86 (s, 1H), 3.41 (s, 3H), 2.32 (s, 3H). H NMR (400 MHz, CDC13) 6 8.72 (d, J= 1.6 Hz, 1H), 8.40 (d, J = 2.5 Hz, 1H), 7.93 (s, 1H), 7.82 525 92.0- ESIMS m/z 336 (dt, J= 9.5, 2.4 94-0 ([M+2]*) Hz, 1H), 3.29 (s, 3H), 2.80 (t, J= 7.3 Hz, 2H), 2.52 (t, J= 7.3 Hz, 2H), 2.06 (s, 3H), 1.80 1.70 (m, 1H), 1.07 - 0.99 (m, 4H). H NMR (400 MHz, CDC13) 6 8.72 (dd, J= 1.2, 0.8 Hz, 1H), 8.39 (d, J= 2.5 Hz, 1H), 7.96 (s, 1H), 7.82 (dt, J= 9.5, 526 105.0- ESIMS m/z 350 2.4 Hz, 1H), 3.30 107.0 ([M+2]*) (s, 3H), 2.96 - 2.78 (m, 2H), 2.53 2.39 (m, 1H), 2.01 (s, 3H), 1.87 - 1.75 (I, 1H), 1.16 (d, J = 6.6 Hz, 3H), 1.14 - 0.94 (m, 4H). 489 'H NMR (300 MHz, CDCl3) 6 8.70 (s, 1H), 8.36 (d, J= 2.4 Hz, 1H), 7.89 (s, 1H), ESIMS ~z 304 7.80 (dt, J = 9.5, 527 (thin film) 1651 ESIM mz 304 2.3 Hz, H), 3.24 (s, 3H), 2.77 - 2.62 (m, 1H), 1.76 1.64 (m, 1H), 1.07 (d, J= 6.7 Hz, 6H), 1.03 - 0.93 (m, 4H). H NMR (300 MHz, CDCl3) 6 8.69 (d, J= 1.7 Hz, 1H), 8.37 (d, J = 2.6 Hz, 1H), 7.88 (s, 1H), 7.79 (dt, J= 9.5, 2.3 ESIM m~z350 Hz, H), 3.33 528 (thin film) 1651 ESIMS m/ 350 3.13 (m, 4H), 2.54 ' (dd, J= 15.6, 6.5 Hz, 1H), 2.30 (dd, J= 15.6, 7.6 Hz, 1H), 2.03 (s, 3H), 1.80 - 1.65 (m, 1H), 1.27 (d, J= 6.7 Hz, 3H), 1.07 0.90 (m, 4H). IH NMR (400 MHz, CDCl3) 6 8.73 (d, J= 1.5 Hz, 1H), 8.40 (d, J = 2.5 Hz, 1H), 7.96 (s, 1H), 7.83 112.5- ESIMS m/z 348 (dt, J= 9.4, 2.3 529 114.5 ([M+2] ) Hz, 1H), 3.29 (s, 3H), 2.50 (ddd, J = 8.1, 5.5, 3.6 Hz, 1H), 2.11 (s, 3H), 1.85 - 1.74 (m, 2H), 1.57 - 1.48 (m, 1 H), 1. 12 0.94 (m, 5H). 490 'H NMR (400 MHz, CDCl3) 6 8.97 - 8.92 (m, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.07 - 8.01 (m, 2H), 7.46 (ddd, J 530 (thin film) 1720 ESIMS m/z 436 = 8.4, 4.8, 0.7 Hz, ([M+H]*) 1H), 3.32 - 3.18 (m, 1H), 3.18 3.01 (m, 2H), 2.94 - 2.85 (m, 1H), 2.62 - 2.48 (m, 3H), 2.07 (s, 3H), 1.27 (d, J= 6.8 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 9.10 - 8.83 (m, 1H), 8.76 - 8.52 (m, 1H), 8.07 8.01 (m, 2H), 7.51 - 7.41 (m, 1H), 531 (thin film) 1720 ESIMS m/z 450 3.35 - 3.20 (m, ([M+H]*) 1H), 2.95 - 2.83 (m, 3H), 2.59 2.47 (m, 1H), 2.28 - 2.13 (m, 2H), 2.07 (s, 3H), 2.03 - 1.91 (m, 2H), 1.27 (d, J= 6.8 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.4 Hz, 1H), 8.62 (d, J = 3.8 Hz, 1H), 8.14 (s, 1H), 8.07 532 80-83 ESIMS m/z 355 7.98 (m, 1H), 7.49 ([M+H]*). - 7.40 (m, 1H), 4.19 (s, 1H), 3.69 3.44 (m, 3H), 3.35 (s, 3H), 3.33 (br s, 1H), 2.08 (s, 3H), 1.45 (d, J= 6.9 Hz, 3H). 491 'H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.4 Hz, 1H), 8.64 8.59 (m, 1H), 8.11 533 (thin film) 3095, ESIMS m/z 341 (s, 1H), 8.06 - 7.99 2920, 1663. ([M+H]*). (m, 1H), 7.48 7.42 (m, 1H), 3.91 (br s, 2H), 3.60 (s, 2H), 3.35 (s, 3H), 3.13 (s, 2H), 2.21 (s, 3H). H NMR (400 MHz, CDCl3) 6 8.98 (s, 1H), 8.65 (s, 1H), 8.11 (s, 1H), 8.05 (d, J = (thin film) 3082, ESIMS m/z 337 8.3 Hz, 1H), 7.47 534 3004, 2919, 1657. ([M+H]). 1H), 3.1 (s, 2H), 2.23 (s, 3H), 1.05 0.92 (m, 1H), 0.54 - 0.44 (m, 2H), 0.26 - 0.13 (m, 2H). IH NMR (400 MHz, CDCl3) 6 9.00 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.7, 1.2 Hz, 1H), 8.25 (s, 1H), 8.07 (ddd, J= 8.3, 2.4, 1.3 Hz, 1H), 535 (thin film) 3423, ESIMS m/z 356 7.47 (dd, J = 8.3, 1654 ([M+H]*) 4.7 Hz, 1H), 4.47 - 3.70 (m, 3H), 3.65 - 3.09 (m, 2H), 2.91 - 2.68 (m, 2H), 2.48 (dd, J= 12.4, 5.0 Hz, 1H), 2.01 (s, 3H), 1.18 (d, J= 6.5 Hz, 3H). 492 'H NMR (400 MHz, CDC13) 6 8.92 (d, J= 2.6 Hz, 1H), 8.74 8.49 (m, 1H), 8.09 536 64-71 ESIMS m/z 291 - 7.95 (m, 1H), ([M+H]*) 7.86 (s, 1H), 7.52 7.36 (m, 1H), 5.12 (s, 2H), 3.92 - 3.60 (m, 2H), 1.89 (bs, 3H), 1.29 - 1.03 (m, 3H). H NMR (400 MHz, CDC13) 6 8.95(d, J= 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.13 - 7.99 (m, ESIMS m/z 360 1H), 7.94 (s, 1H), 537 ESM+H] ) 7.55 - 7.34 (m, 1H), 3.87 - 3.46 (m, 2H), 2.28 2.19 (m, 2H), 2.19 - 2.05 (m, 2H), 1.95 - 1.83 (m, 2H), 1.20 - 1.10 (m, 3H). H NMR (400 MHz, CDC13) 6 8.96 (d, J= 2.5 Hz, 1H), 8.67 8.54 (m, 1H), 8.06 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 8.01 (s, 1H), 7.46 (dd, J 538 111- ESIMS m/z 291 =8.3, 4.7 Hz, 1H), 119 ([M+H]*) 3.73 (q, J= 7.2 Hz, 2H), 1.46 (ddd, J= 12.6, 8.1, 4.7 Hz, 1H), 1.16 (t, J= 7.2 Hz, 3H), 1.004 (t, J= 3.7 Hz, 2H), 0.71 (dd, J= 7.7, 3.0 Hz, 2H). 493 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.8.62 (d, J= 4.6 Hz, 1H), 8.07 (d, J= 7.2 Hz, 1H), 8.02 7.98 (s, 1H), 7.45 539 ESIMS m/z 305 (dd, J= 8.3, 4.8 ([M+H]*) Hz, 1H), 3.71 (tt, J = 13.2, 6.6 Hz, 2H), 1.45 - 1.35 (m, 1H), 1.28 1.21 (m, 1H), 1.21 - 1.07 (m, 4H), 1.04 - 0.96 (d, J= 6.0 Hz, 3H), 0.54 (t, J= 8.7 Hz, 1H). 'H NMR (400 MHz, CDC3) 6 8.97 (d, J= 2.5 Hz, 1H), 8.64 (dd, J= 4.8, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 8.00 (s, 1H), 540 ESIMS m/z 327 7.479 (ddd, J = ([M+H]*) 8.3, 4.8, 0.7 Hz, 1H), 3.94 (dq, J= 14.3, 7.2 Hz, 1H), 3.59 (dq, J= 14.2, 7.2 Hz, 1H), 2.35 - 2.09 (m, 2H), 1.67 - 1.53 (m, 1H), 1.18 (t, J= 7.2 Hz, 3H). 494 'H NMR (400 MHz, CDC3) 6 9.02 - 8.93 (d, J= 2.7 Hz, 1H), 8.70 - 8.58 (m, 1H), 8.11 - 8.05 (s, 1H),8.06 - 8.04 (m, 1H), 7.52 ESIMS m/z 367 7.44 (m, 1H), 3.70 541 ([M+H] ) (m, 2H), 3.60 3.51 (m, 2H), 3.38 - 3.26 (s, 3H), 2.60 -2.42 (m, 1H), 2.18 - 2.05 (s, 3H), 1.72 1.61 (m, 1H), 1.55 - 1.48 (m, 1H), 1.11 - 0.87 (m, 1H). IH NMR (400 MHz, CDCT3) 6 1 3 C NMR (101 9.03 (dd, J = 4.9, MHz, CDC1 3 ) 2.6 Hz, 2H), 8.61 6 207.86 (s), (m, 2H), 8.16 (d, J 172.25 (s), = 3.2 Hz, 1H), 148.49 (s), 8.11 (dddd, J = 141.08 (s), 8.4, 4.1, 2.6, 1.3 140.03 (s), 542 ESIMS m/z 321 Hz, 2H), 7.50 (dt, 135.83 (s), ([M+H]+) J = 8.5, 4.4 Hz, 126.81 (s), 2H), 3.66 (q, J = 126.45 (s), 7.0 Hz, 3H), 2.76 124.20 (d, J = (t, J = 6.2 Hz, 8.3 Hz), 44.00 4H), 2.37 (t, J = (s), 38.42 (s), 6.1 Hz, 3H), 2.17 30.09 (s), (s, 35H), 1.12 (td, 27.89 (s), J = 7.1, 1.3 Hz, 13.15 (s). 3H). 495 'H NMR (400 MHz, CDC13) 6 8.96 (d, J= 2.6 Hz, 1H), 8.64 (dd, J = 4.7, 1.4 Hz, 1H), 8.05 (ddd, J ESIMS m/z 323 - 8.3, 2.7, 1.4 Hz, 543 117- ([M+H]+), 321 1H), 7.98 (s, 1H), 120 ([M-H]) 7.47 (ddd, J = 8.4, 4.8, 0.6 Hz, 1H), 3.80 (t, J = 6.7 Hz, 2H), 3.74 (q, J = 7.1 Hz, 2H), 2.64 (t, J = 6.7 Hz, 2H), 1.18 (t, J = 7.2 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.98 (d, J= 2.4 Hz, 1H), 8.63 (s, ESIMS m/z 297 i1H), 8.58 - 8.53 132 (IM+H], 295 7.96 (, H), 7.43 - 7.37 (m, 1H), 3.59 - 3.48 (m, 1H), 2.18 (s, 3H), 1.59 (d, J= 7.3 Hz, 3H). H NMR (400 MHz, CDCl3) 6 9.06 - 8.90 (m, 1H), 8.74 (s, 1H), 545 (thin film) 3178, ESIMS m/z 283 8.64 (s, 1H), 8.57 2923, 1676. ([M+H]*). 8.45 (m, 1H), 8.05 - 7.90 (m, 1H), 7.46 - 7.33 (m, 1H), 3.41 (s, 2H), 2.24 (s, 3H). 496 IH NMR (400 MHz, CDCl3) 6 8.82 (s, 1H), 8.60 (d, J= 4.1 Hz, 135.0- ESIMS m/z 413 1H), 7.95 (d, J = 546 136.5 ([M+H]+) 7.4 Hz, 1H), 7.71 (s, 1H), 7.43 (dd, J = 8.3, 4.8 Hz, 1H), 6.69 (s, 1H), 3.38 (s, 3H), 2.47 (s, 3H). H NMR (400 MHz, CDC13) 6 8.97 (d, J= 2.3 Hz, 1H), 8.64 (dd, J= 4.7, 1.4 Hz, 1H), 8.15 (s, 1H), 8.04 (ddd, J= 8.3, 2.7, 1.4 Hz, 1H), (thin film) 1739, ESIMS m/z 398 7.47 (ddd, J= 8.3, 547 1669 ([M+H]) 4.8, 0.7 Hz, 1H), 4.50 - 3.40 (m, 4H), 2.84 (dd, J= 12.7, 8.9 Hz, 1H), 2.78 - 2.63 (m, 1H), 2.46 (dd, J= 12.7, 5.4 Hz, 1H), 2.03 (s, 3H), 2.01 (s, 3H), 1.16 (d, J = 6.6 Hz, 3H). 497 'H NMR (400 MHz, CDCl3) 6 9.56 (s, 1H), 9.27 (s, 1H), 8.99 (d, J = 2.3 Hz, 1H), 8.58 (dd, J= 4.7, 1.4 Hz, 1H), 8.00 (ddd, J= 8.3, 2.7, 548 (thin film) 1583 ESIMS m/z 328 1.4 Hz, 1H), 7.42 ([M+H]*) (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 3.19 - 3.05 (m, 1H), 3.00 (dd, J= 13.2, 8.1 Hz, 1H), 2.78 (dd, J= 13.2, 5.2 Hz, 1H), 2.15 (s, 3H), 1.44 (d, J= 6.7 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 8.02 (s, 1H), 549 (thin film) 1657 ESIMS m/z 340 7.46 (ddd, J= 8.3, ([M+H]*) 4.8, 0.6 Hz, 1H), 3.26 (s, 3H), 3.06 (td, J= 13.0, 7.4 Hz, 1H), 2.43 (ddd, J= 22.2, 15.7, 7.0 Hz, 2H), 2.03 (s, 3H), 1.69 1.45 (m, 2H), 0.97 (t, J= 7.3 Hz, 3H). 498 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.06 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.99 (s, 1H), 7.47 (ddd, J= 8.4, 4.8, 0.6 Hz, 1H), 550 (thin film) 1654 ESIMS m/z 353 3.73 (ddt, J= ([M+H]*) 20.4, 13.3, 6.7 Hz, 2H), 3.18 - 2.99 (m, 1H), 2.44 (dd, J= 15.7, 7.3 Hz, 1H), 2.36 (dd, J= 15.7, 6.6 Hz, 1H), 2.03 (s, 3H), 1.69 1.41 (m, 2H), 1.17 (t, J= 7.2 Hz, 3H), 0.97 (t, J= 7.3 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.4 Hz, 1H), 8.64 (dd, J= 4.8, 1.4 Hz, 1H), 8.05 (ddd, J = 8.4, 2.7, 1.5 Hz, ESIMS m/z 379 1H), 8.01 (s, 1H), 551 (thin film) 1667 ([M+H]+) 7.47 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.83 - 3.69 (m, 1H), 3.30 (s, 3H), 2.64 (dd, J= 16.4, 3.6 Hz, 1H), 2.46 (dd, J= 16.4, 10.1 Hz, 1H), 2.29 (s, 3H). 499 'H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 8.11 - 8.04 (m, 1H), 8.02 (d, J = 13.3 Hz, 1H), 7.46 (ddd, J= 8.4, ESIMS ~z 419 4.8, 0.6 Hz, 1 H), 552 (thin film) 1665 ESIMS m 419 3.85 -3.69 (in, 1H), 3.60 (s, 2H), 2.64 (dd, J= 16.4, 3.7 Hz, 1H), 2.42 (dd, J= 16.4, 9.9 Hz, 1H), 2.28 (s, 3H), 1.09 - 0.89 (m, 1H), 0.51 (d, J = 8.2 Hz, 2H), 0.20 (t, J= 5.1 Hz, 2H). H NMR (400 MHz, CDCl3) 6 8.95 (d, J= 2.5 Hz, 1H), 8.63 (dd, J= 4.7, 1.3 Hz, 1H), 8.05 (ddd, J 553 (thin film) 1663 ESIMS m/z 329 = 8.4, 2.7, 1.5 Hz, ([M+H]*) 1H), 8.01 (s, 1H), 7.52 - 7.43 (m, 1H), 3.25 (s, 3H), 2.43 - 2.35 (m, 2H), 2.35 - 2.13 (m, 2H), 1.59 (t, J = 18.4 Hz, 3H). 500 'H NMR (400 MHz, CDC3) 6 8.94 (d, J= 2.6 Hz, 1H), 8.61 (dd, J= 4.7, 1.3 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.99 (s, 1H), 7.45 (ddd, J= 8.4, 554 (thin film) 1661 ESIMS m/z 369 4.8, 0.5 Hz, 11H), ([M+H]*) 3.52 (s, 2H), 2.45 2.33 (m, 2H), 2.23 (ddd, J= 23.9, 16.3, 7.3 Hz, 2H), 1.58 (t, J= 18.4 Hz, 3H), 0.96 (tt, J = 7.8, 4.8 Hz, 1H), 0.56 - 0.42 (m, 2H), 0.18 (q, J= 4.7 Hz, 2H). 3 C NMR (101 1H NMR (400 MHz, CDC1 3 ) MHz, CDC3) 6 6167.08, 8.96 (d, J= 2.5 148.99, Hz, 1H), 8.65 (dd, 135.51, ESIMS m/z 351 J= 4.8, 1.4 Hz, 131.88, ([M+H]*). 1H), 8.06 (s, 1H), 128.75, 8.05 - 8.03 (m, 126.53, 1H), 7.54 - 7.41 125.99, (m, 1H), 3.70 (s, 124.65, 2H), 3.29 (s, 3H). 124.19, 37.84, 33.12. 501 'H NMR (400 MHz, CDC3) 6 9.00 (s, 1H), 8.57 (dd, J= 4.8, 1.6 Hz, 1H), 8.10 (dt, J= 8.0, 2.0 Hz, 1H), 7.34 (dd, J= ESIMS ~z 305 7.2, 4.8 Hz, 1 H), 556 (IR thin film) 1375 ESIMS m/z 305 6.48 (s, 1H), 4.05 (q, J= 7.3 Hz, 2H), 3.25 (s, 3H), 2.78 (dt, J= 6.8, 3.2 Hz, 2H), 2.50 (bs, 1H), 2.31 (s, 1H), 2.05 (s, 3H), 1.52 (t, J= 7.3 Hz, 3H) H NMR (400 MHz, CDCl3) 6 9.01 (s, 1H), 8.56 (d, J= 4.0 Hz, 1H), 8.12 (dt, J= 7.9, 1.9 Hz, 1H), 7.34 (dd, J= 7.8, ESIMS m/z 288 4.8 Hz, 1H), 6.44 557 (IR thin film) 1675 ([M+2H] ) (s, 1H), 4.34 (dt, J = 13.2, 6.6 Hz, 1H), 3.21 (s, 3H), 2.44 (dt, J= 13.4, 6.7 Hz, 1H), 1.52 (dd, J= 8.6, 6.7 Hz, 6H), 1.09 (dd, J= 6.7, 3.7 Hz, 6H) 502 'H NMR (400 MHz, CDC3) 6 8.88 (d, J= 2.6 Hz, 1H), 8.61 (dd, J= 4.7, 1.3 Hz, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.47 - 7.40 (m, 2H), 7.12 (dd, 558 (thin film) 1657 ESIMS m/z 362 J= 5.1, 1.1 Hz, ([M+H]*) 1H), 6.92 (dd, J= 5.1, 3.4 Hz, 1H), 6.78 (dd, J= 3.3, 0.8 Hz, 1H), 3.70 (dd, J= 14.5, 7.7 Hz, 2H), 3.18 (t, J = 7.2 Hz, 2H), 2.48 (t, J= 7.2 Hz, 2H), 1.14 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.91 (d, J= 2.4 Hz, 1H), 8.62 (dd, J= 4.7, 1.4 Hz, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.81 (s, 1H), 7.46 (ddd, J= 8.3, 4.8, 0.5 Hz, 1H), 559 (thin film) 1658 ESIMS m/z 376 7.04 (dd, J= 5.1, ([M+H]*) 1.1 Hz, 1H), 6.85 (dd, J= 5.1, 3.4 Hz, 1H), 6.77 6.70 (m, 1H), 3.70 (q, J= 7.1 Hz, 2H), 2.84 (t, J= 7.2 Hz, 2H), 2.26 2.15 (m, 2H), 2.00 (p, J= 7.5 Hz, 2H), 1.15 (t, J= 7.2 Hz, 3H). 503 'H NMR (300 MHz, CDC13) 6 10.12 (s, 1H), 9.14 (s, 1H), 8.90 (d, J = 2.0 Hz, 1H), 140.0- ESIMS m/z 277 8.82 (s, 1H), 8.51 560 142.0 ([M+H] ) (d, J = 2.5 Hz, S1H), 7.92 (dt, J= 9.2, 2.4 Hz, 1H), 2.65 (dt, J= 13.8, 6.9 Hz, 1H), 1.31 (d, J= 6.9 Hz, 6H). 'H NMR (400 MHz, CDC13) 6 8.79 (s, 1H), 8.67 (s, 1H), 8.40 (s, 172.0- ESIMS m/z 298 11H), 7.80 (dt, J= 561 177.0 ([M+H] ) 9.4, 2.3 Hz, 1H), 7.42 (s, 1H), 4.77 (s, 2H), 2.63 (hept, J= 6.9 Hz, 1H), 1.30 (d, J= 6.9 Hz, 6H). H NMR (400 MHz, CDC13) 6 9.01 (s, 1H), 8.56 (bs, 1H), 8.14 (d, J = 7.9 Hz, 1H), 7.36 (dd, J= 7.9, 4.8 Hz, 1H), 6.45 ESIMS m/z 319 (s, 1H), 4.37 (dt, J 562 (IR thin film) 1677 ([M+H]) 13.2, 6.6 Hz, 1H), 3.24 (s, 3H), 2.85-2.67 (m, 2H), 2.64 - 2.41 (m, 1H), 2.35 - 2.21 (m, 1H), 2.05 (s, 3H), 1.57 - 1.48 (d, J= 20.2 Hz, 6H). 504 'H NMR (400 MHz, CDCl3) 6 9.09 (d, J= 1.7 Hz, 1H), 8.61(d, J = 3.3 Hz, 1H), 8.20 (dt, J= 7.9, 563 (IR thin film) 1675 ESIMS m/z 322 1.9 Hz, 11H), 7.52 ([M+2H] ) - 7.46 (m, 4H), 7.45 - 7.33 (m, 2H), 6.69 (s, 1H), 3.22 (s, 3H), 2.43 (dt, J= 13.3, 6.7 Hz, 1H), 1.06 (bs, 3H), 0.73 (bs,3H). 'H NMR (400 MHz, CDCl3) 6 9.00 (d, J= 1.5 Hz, 1H), 8.58 (dd, J= 4.8, 1.6 Hz, 1H), 8.09 (dt, J= 8.0, 1.8 Hz, 1H), 7.35 (dd, J= 7.9, 564 (IR thin film) 1675 ESIMS m/z 305 4.8 Hz, 1H), 6.49 ([M+H]*) (s, 1H), 4.13 3.93 (m, 1H), 3.80 (s, 3H), 3.50 3.30 (m, 1H), 2.87 - 2.68 (m, 2H), 2.53 - 2.15 (m, 2H), 2.05 (s, 3H), 1.19 (t, J= 7.2 Hz, 3H). 505 'H NMR (400 MHz, CDCl3) 6 9.00 (d, J= 1.5 Hz, 1H), 8.57 (dd, J= 4.8, 1.6 Hz, 1H), 8.10 (dt, J= 7.9, 1.8 Hz, 1H), 7.35 (dd, J= 7.6, 4.5 Hz, 1H), 6.52 ESIM m~z331 (s, H), 3.83 (s, 565 (IR thin film) 1673 ESIMS m/z 331 3H), 3.5 7 (qd, J= 13.9, 7.4 Hz, 2H), 2.90 - 2.65 (m, 2H), 2.53 - 2.34 (m, 1H), 2.34 2.19 (m, 1H), 2.05 (s, 3H), 1.00 (ddd, J = 12.7, 7.7, 4.9 Hz, 1H), 0.62 0.39 (m, 2H), 0.33 - 0.06 (m, 2H). IH NMR (400 MHz, CDCl 3 ) 6 9.00 (d, J= 1.6 Hz, 1H), 8.57 (dd, J= 4.8, 1.6 Hz, 1H), 8.23-7.93 (m, 1H), 7.35 (dd, J= 7.9, 4.8 Hz, 1H), 6.51 (s, 0.40, H), 6.50 (s, 0.6) 3.92 ESIMS m/z 345 (s, 1.60 H), 3.82 566 ([+]) (s, 1.40H), 3.72 3.35 (m, 2H), 3.06 - 2.70 (m, 1H), 2.63 - 2.28 (m, 2H), 2.05 (s, 1.60H), 1.95 (s, 1.40H), 1.15 (m, 3H), 1.01 (td, J= 7.6, 4.8 Hz, 1H), 0.51 (d, J= 8.3 Hz, 2H), 0.30 0.08 (m, 2H). 506 IH NMR (400 MHz, CDC13) 6 8.80 (s, 1H), 8.43 (s, 1H), 7.82 (ddd, 109.5- ESIMS m/z 277 J 9.5, 2.7, 1.7 567 111.1 ([M+H] ) Hz, 1H), 6.50 (s, 1H), 3.77 (s, 3H), 3.22 (s, 3H), 2.43 (dt, J= 13.5, 6.8 Hz, 1H), 1.09 (d, J = 6.7 Hz, 6H). 'H NMR (400 MHz, CDCl3) 6 8.79 (s, 1H), 8.43 (d, J= 2.6 Hz, 1H), 7.82 (ddd, J 568 (IR thin film) 1676 ESIMS m/z 309 = 9.5, 2.7, 1.7 Hz, ([M+H]*) 1H), 6.51 (s, 1H), 3.81 (s, 3H), 3.25 (s, 3H), 2.85 2.70 (m, 2H), 2.53 - 2.23 (m, 2H) 2.05 (s, 3H). 1 C NMR (101 MHz, CDCl 3 ) H NMR (400 6 171.71 (s), MHz, CDCl3) 6 148.66 (s), 9.01 (s, 1H), 8.61 140.88 (s), (s, 1H), 8.53 (s, 140.06 (s), 1H), 8.01 (ddd, J 135.68 (s), 569 ESIMS m/z 343 = 8.3, 2.5, 1.3 Hz, 126.37 (s), ([M+H]*) 1H), 7.96 (s, 1H), 123.93 (m), 7.72 (s, 1H), 7.39 44.06 (s), (dd, J = 8.3, 4.7 33.29 (t, J= Hz, 1H), 2.82 (s, 25.2 Hz), 2H), 2.15 (s, 3H), 26.85 (t, J= 1.40 (s, 6H). 4.1 Hz), 23.79 (t, J= 27.6 Hz), 13.07 (s). 507 'H NMR (400 MHz, CDCl3) 6 8.98 (d, J= 2.3 Hz, 1H), 8.63 (td, J= 4.8, 2.4 Hz, 1H), 8.14 - 8.01 (m, 2H), 7.46 (ddd, J= 8.3, 4.8, 570 (R thin film) 1652 ESIMS m/z 409 0.7 Hz, 1H), 4.26 ([M+H]*) (dd, J= 17.2, 8.4 Hz, 1H), 3.89 3.61 (m, 2H), 3.01 (dd, J= 17.6, 8.2 Hz, 1H), 2.77 (s, 2H), 2.48 (dd, J= 17.7, 3.3 Hz, 1H), 1.19 (t, J= 7.2 Hz, 3H). 'H NMR (400 MHz, CDCl3) 6 9.04 (d, J= 13.4 Hz, 1H), 8.61 (dt, J= 6.0, 3.1 Hz, 1H), 8.41 (s, 1H), 8.05 (dddd, J= 7.8, 6.2, 2.6, 1.4 ESIMS m/z 409 Hz, 1H), 7.44 (dt, 571 (JR thin film) 1671 ([M+H] ) J = 13.4, 6.7 Hz, 1H), 4.41 - 3.90 (m, 2H), 3.56 3.18 (m, 2H), 3.14 - 2.84 (m, 1H), 2.70 (d, J= 7.1 Hz, 3H), 1.23 1.13 (m, 3H). (Signals of both diastereomers) 508 IH NMR (400 MHz, CDCl3) 6 8.97 (s, 1H), 8.65 (s, 1H), 8.06 (dd, J 572 (IR thin film) 1667 ESIMS m/z 383 = 8.3, 1.2 Hz, 1H), ([M+H] ), 8.00 (s, 1H), 7.48 (dd, J= 7.8, 4.5 Hz, 1H), 3.26 (s, 3H), 2.53 - 2.32 (m, 4H). H NMR (400 MHz, CDCl3) 6 8.96 (s, 1H), 8.64 (d, J= 4.3 Hz, 1H), 8.07 (ddd, J ESIMS m/z 397 = 8.3, 2.7, 1.4 Hz, 573(IRthi flm)1E6SIMH+ m/ IH), 7.98 (s, 1H), 7.48 (dd, J= 8.3, 4.7 Hz, 1H), 3.72 (q, J= 7.2 Hz, 2H), 2.55 - 2.35 (m, 4H), 1.17 (t, J = 7.2 Hz, 3H). IH NMR (400 MHz, CDCl3) 6 8.96 (s, 1H), 8.65 (s, 1H), 8.06 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.96 (s, 574 (IR thin film) 1667 ESIMS m/z 411 1H), 7.48 (dd, J= ([M+H] ), 8.2, 4.7 Hz, 1H), 3.70 - 3.52 (m, 2H), 2.57 - 2.34 (m, 4H), 1.61 (s, 3H), 1.60 - 1.52 (m, 2H), 0.93 (t, J = 7.4 Hz, 3H). 509 'H NMR (400 MHz, CDC3) 6 8.96 (s, 1H), 8.64 (s, 1H), 8.07 (ddd, J= 8.3, 2.6, 1.3 Hz, 1H), 8.00 (s, ESIMS m/z 423 11H), 7.47 (dd, J= 575 (IR thin film) 1669 ([M+H] ) 8.2, 4.7 Hz, 1H), 3.55 (s, 2H), 2.58 2.36 (m, 4H), 1.63 (s, 2H), 0.97 (tt, J = 7.8, 4.9 Hz, 1H), 0.59 - 0.44 (m, 2H), 0.20 (q, J= 4.8 Hz, 2H). H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.3 Hz, 1H), 8.06 - 8.02 (m, 2H), 7.51 7.41 (m, 1H), 3.27 576 (IR thin film) 1657 ESIMS m/z 353 (s, 3H), 3.06 (td, J ([M+H]*) = 7.0, 4.2 Hz, 1H), 2.43 (d, J= 7.1 Hz, 2H), 2.11 (s, 3H), 1.91 (dtd, J= 13.5, 6.7, 4.3 Hz, 1H), 0.96 (d, J= 6.8 Hz, 3H), 0.88 (d, J= 6.8 Hz, 3H). 510 'H NMR (400 MHz, CDC3) 6 8.96 (d, J= 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 8.02 (s, 1H), 7.46 (ddd, J= 8.4, 4.8, 0.6 Hz, 1H), 577 (IR thin fil m ) 1655 ESIMS m/z 367 3.88 - 3.59 (m, ([M+H]*) 2H), 3.06 (ddd, J = 7.8, 6.2, 4.2 Hz, 1H), 2.39 (dd, J= 7.0, 2.0 Hz, 2H), 2.11 (s, 3H), 1.90 (dtd, J= 13.5, 6.8, 4.2 Hz, 1H), 1.17 (t, J= 7.2 Hz, 3H), 0.95 (d, J= 6.7 Hz, 3H), 0.88 (d, J = 6.8 Hz, 3H). H NMR (400 MHz, CDC3) 6 8.95 (d, J= 2.7 Hz, 1H), 8.63 (d, J = 4.8 Hz, 1H), 8.05 (d, J= 11.1 Hz, 1H), 8.01 (s, EIMS (m/z) 396 1H), 7.50 - 7.42 578 ([M+]+), 398 (m, 1H), 3.26 (s, ([M+2]+) 3H), 2.93 - 2.76 (m, 2H), 2.71 (m, 1H), 2.55 - 2.47 (m, 1H), 1.22 (d, J = 2.9 Hz, 3H), 1.21 (d, J= 2.9 Hz, 3H), 1.18 (d, J = 6.7 Hz, 3H). 511 'H NMR (400 MHz, CDC13) 6 8.94 (d, J= 2.7 Hz, 1H), 8.62 (dd, J= 4.8, 1.5 Hz, 1H), 8.04 (s, 1H), 8.03 - 8.06 (m, 579 EIMS (m/z) 353 1H), 7.49 - 7.44 ([M+]+) (m, 1H), 3.26 (s, 3H), 2.95 - 2.77 (m, 2H), 2.76 2.69 (m, 1H), 2.55 - 2.48 (m, 1H), 1.23 - 1.20 (m, 6H), 1.17 (d, J= 6.7 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 8.97 - 8.94 (m, 0.7H), 8.87 (dd, J = 2.8, 0.7 Hz, 0.3H), 8.62 (dd, J = 4.8, 1.4 Hz, 0.7H), 8.47 (dd, J = 4.8, 1.5 Hz, 0.3H), 8.07 - 8.03 EIMS (m/s) 367 (m, 0.7H), 8.02 (s, 580 ([M+1]+) 1H), 7.98 - 7.94 (m, 0.3H), 7.49 7.44 (m, 0.7H), 7.36 (d, J= 0.7 Hz, 0.3H), 3.85 (bs, 1H), 3.60 (bs, 1H), 2.92 - 2.75 (m, 2H), 2.65 (m, 1H), 2.58 - 2.42 (m, 1H), 1.23 1.18 (m, 6H), 1.18 - 1.15 (m, 6H). 512 'H NMR (400 MHz, CDCl3) 6 8.97 (s, 1H), 8.64 (dd, J= 4.7, 1.3 Hz, 1H), 8.06 (s, 1H), 7.98 (s, 1H), ESIMS m/z 7.47 (dd, J= 8.2, 581 51-53 420.9([M+H]*), 4.8 Hz, 1H), 3.55 419.0([M-H]-) (m, 5H), 3.22 (m, 1H), 2.95 (d, J= 8.5 Hz, 1H), 2.18 (m, 1H), 1.94 (s, 1H), 1.43 (s, 9H), 1.16 (t, J= 7.1 Hz, 3H). H NMR (400 MHz, CDC13) 6 8.91 (d, J= 2.5 Hz, 1H), 8.62 (dd, J= 4.7, 1.1 Hz, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.63 (s, 1H), ESIMS m/z 360 7.45 (dd, J= 8.3, 582 (IR thin film) 1659 ([M+H]+) 4.8 Hz, 1H), 7.35 (d, J= 1.6 Hz, 1H), 5.98 (d, J= 0.8 Hz, 1H), 4.34 (t, J= 6.6 Hz, 2H), 3.67 (dd, J= 12.7, 5.8 Hz, 2H), 2.73 (t, J= 5.7 Hz, 2H), 2.31 (s, 3H), 1.10 (t, J= 7.2 Hz, 3H). 513 'H NMR (400 MHz, CDC3) 6 8.61 - 8.51 (m, 2H), 8.00 (s, 1H), 7.69 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.43 (d, J= 7.9 Hz, 1H), 7.40 (JR thin film) ESIMS m/z 395 7.33 (m, 2H), 7.14 583 3302, 1652 ([M+H]+) 7.0 (, J=2. Hz, 1H), 6.98 6.92 (m, 1H), 6.78 (s, 1H), 3.63 (s, 2H), 3.12 (t, J= 7.0 Hz, 2H), 2.52 (t, J= 7.1 Hz, 2H), 1.06 (t, J= 7.2 Hz, 3H). H NMR (400 MHz, CDCl3) 6 8.94 (d, J= 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.2 Hz, 1H), 8.43 (d, J= 4.1 Hz, 1H), 8.04 (ddd, J= 8.4, 2.7, 1.4 Hz, 1H), 7.91 (s, 1H), 7.57 (td, J ESIMS m/z 371 = '7.7, 1.7 Hz, 1H), 584 (IR thin film) 1656 ([M+H]+) 7.46 (dd, J= 8.3, 4.6 Hz, 1H), 7.15 (d, J= 7.8 Hz, 1H), 7.05 (dd, J= 7.1, 5.2 Hz, 1H), 3.69 (q, J= 7.1 Hz, 2H), 2.79 (t, J = 7.5 Hz, 2H), 2.22 (t, J= 7.3 Hz, 2H), 2.13 - 1.99 (m, 2H), 1.14 (t, J = 7.2 Hz, 3H). 514 'H NMR (400 MHz, CDC13) 6 8.82 (s, 1H), 8.58 (d, J= 4.0 Hz, 1H), 7.94 (d, J= 148.0- ESIMS m/z 348 8.7 Hz, 1H), 7.74 585 149.0 ([M+H]+) (s, 1H), 7.41 (dd, J = 8.3, 4.8 Hz, 1H), 7.15 (s, 1H), 6.85 (s, 1H), 3.94 - 3.76 (m, 2H), 2.33 (s, 3H), 1.25 (t, J= 7.1 Hz, 3H). 'H NMR (400 MHz, CDC13) 6 8.85 (s, 1H), 8.60 (d, J= 4.7 Hz, 1H), 7.97 (d, J= 586 156.5- ESIMS m/z 427 8.2 Hz, 1H), 7.76 158.0 ([M+H]+) (s, 1H), 7.43 (dd, J = 8.3, 4.8 Hz, 1H), 6.68 (s, 1H), 3.95 3.70 (m, 2H), 2.48 (s, 3H), 1.23 (t, J = 7.1 Hz, 3H). IH NMR (400 MHz, CDC13) 6 8.90 (d, J= 2.6 Hz, 1H), 8.61 (dd, J= 4.8, 1.4 Hz, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.5 Hz, 587 132.0- ESIMS m/z 346 1H), 7.67 (s, 1H), 134.0 ([M+H]+) 7.45 (dd, J= 8.3, 4.7 Hz, 1H), 7.36 (d, J= 1.6 Hz, 1H), 5.99 (s, 1H), 4.34 (t, J= 6.6 Hz, 2H), 3.21 (s, 3H), 2.78 (t, J= 6.6 Hz, 2H), 2.31 (s, 3H). 515 'H NMR (400 MHz, CDC3) 6 8.92 (d, J= 2.3 Hz, 1H), 8.63 (d, J = 4.1 Hz, 1H), 8.42 (d, J= 4.4 Hz, 1H), 8.02 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.92 ESIMS m/z 357 (s, 1H), 7.55 (td, J 588 (IR thin film) 1657 ([M+H]+) = '7.7, 1.8 Hz, 1H), 7.46 (dd, J= 8.4, 4.7 Hz, 1H), 7.13 (d, J= 7.8 Hz, 1H), 7.03 (dd, J= 7.0, 5.2 Hz, 1H), 3.22 (s, 3H), 2.78 (t, J= 7.4 Hz, 2H), 2.25 (t, J= 7.4 Hz, 2H), 2.07 (p, J= 7.3 Hz, 2H). H NMR (400 MHz, CDC3) 6 8.98 (d, J= 2.5 Hz, 1H), 8.64 (dd, J= 4.7, 1.3 Hz, 1H), 8.07 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 8.01 (s, 1H), ESIMS m/z 328 7.47 (ddd, J= 8.3, 589 72-75 ([M+H] ) 4.8, 0.6 Hz, 1H), 4.57 (m, 1H), 3.73 (qd, J= 13.4, 6.7 Hz, 2H), 2.70 (dd, J= 15.8, 8.0 Hz, 1H), 2.48 (dd, J= 15.8, 5.5 Hz, 1H), 1.53 (d, J= 6.6 Hz, 3H), 1.17 (t, J = 7.2 Hz, 3H). 516 "C NMR (101 1H NMR (400 MHz, CDC1 3 ) MHz, CDCl3) 6 198.64, 8.96 (s, 1H), 8.62 155.98, (d, J= 3.3 Hz, 153.41, ESIMS m/z 277 1H), 8.10 (s, 1H), 148.56, 590 ([M-t-Bu]*). 8.07 - 7.92 (m, 126.30, 1H), 7.44 (dd, J 124.04, 8.2, 4.7 Hz, 1H)' 122.20, 4.51 (s, 2H), 1.46 115.78, 81.30, (s, 9H). 77.34, 76.70, 28.02. 1H NMR (400 MHz, CDC13) 6 9.06 - 8.94 (d, J= 2.5 Hz, 1H), 8.69 8.59 (dd, J= 4.8, 135- ESIMS m/z 304 1.5 Hz, 1H), 8.25 591 136 ([M+H]) 8.11 (s, 1H), 8.11 7.96 (m, 1H), 7.53 - 7.42 (m, 1H), 4.70 (bs, 2H), 2.70 - 2.50 (m, 1H), 1.15 - 1.07 (d, J= 6.8 Hz, 7H). IH NMR (400 MHz, CDC13) 6 9.00 (d, J= 2.6 Hz, 1H), 8.66 (dd, J= 4.9, 1.4 Hz, 1H), 8.29 (s, 1H), 8.05 (ddd, J= 8.3, ESIMS ~z 351 2.7, 1.4 Hz, I1H), 592 (IR thin film) 1679 ESIMS m/z 351 7.48 (ddd, J= 8.3, 4.8, 0.4 Hz, 1H), 5.48 - 3.75 (m, 2H), 2.87 - 2.72 (m, 2H), 2.51 (dd, J= 12.1, 4.3 Hz, 1H), 2.04 (s, 3H), 1.19 (d, J= 6.6 Hz, 3H). 517 'H NMR (400 MHz, CDC3) 6 8.90 (d, J= 2.6 Hz, 1H), 8.62 (dd, J= 4.7, 1.3 Hz, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.72 (s, 1H), 593 (IR thin film) 1666 ESIMS m/z 332 7.45 (dd, J= 8.2, ([M+H]+) 4.5 Hz, 1H), 7.26 7.24 (m, 1H), 6.28 (dd, J= 3.1, 1.9 Hz, 1H), 6.01 (d, J = 3.1 Hz, 1H), 3.24 (s, 3H), 2.99 (t, J= 7.4 Hz, 2H), 2.51 (t, J= 7.5 Hz, 2H). 'H NMR (400 MHz, CDC3) 6 8.60 - 8.53 (m, 2H), 8.01 (s, 1H), 7.69 (ddd, J= 8.3, 2.6, 1.4 Hz, 1H), 7.43 (d, J= 7.9 594 69 ESIMS m/z 381 Hz, 1H), 7.40 ([M+H]+) 7.34 (m, 2H), 7.13 (t, J= 7.2 Hz, 1H), 7.02 - 6.94 (m, 2H), 6.84 (s, 1H), 3.17 (s, 3H), 3.13 (t, J= 7.0 Hz, 2H), 2.56 (t, J= 7.1 Hz, 2H). 518 'H NMR (400 MHz, CDC1 3 ) 6 9.12 - 8.86 (m, 1H), 8.55 (dd, J= 4.7, 1.4 Hz, 1H), 8.04 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 595 8.01 (d, J= 0.5 Hz, 1H), 7.84 7.65 (m, 1H), 7.41 (ddd, J= 8.3, 4.8, 0.7 Hz, 1H), 1.51 (s, 18H). 519 Table 3: GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA) Rating Table % Control (or Mortality) Rating 80-100 A More than 0 - Less than 80 B Not Tested C No activity noticed in this bioassay D Table 4. Biological Data for GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA) Compound MYZUPE BEMITA 18 D B % Ctrl @ % Ctrl @ No. 200 ppm 200 ppm 19 B A 1 B A 20 B A 2 A A 21 D D 3 B A 22 A A 4 A A 23 A A 5 A A 24 D D 6 B A 25 D D 7 B A 26 B B 8 B A 27 B A 9 B B 28 A B 10 B B 29 B A 12 D C 30 B A 520 31 D A 49 B B 32 A A 50 B B 33 C C 51 A B 34 C C 52 A B 35 C C 53 A B 36 C C 54 A B 37 C C 55 A A 38 C C 56 B B 39 B B 57 A A 40 C C 58 A A 41 B D 59 A A 42 A C 60 A A 43 A C 61 A B 44 A B 62 D D 45 A C 63 A B 46 B C 64 A A 47 B C 65 A B 48 B C 66 B D 521 67 A A 85 A B 68 C A 86 A A 69 C C 87 C A 70 A A 88 C B 71 C C 89 B B 72 A B 90 A A 73 A A 91 B B 74 A A 92 C B 75 A A 93 C A 76 A A 94 C A 77 A B 95 A A 78 A B 96 C A 79 A A 97 A A 80 A A 98 A A 81 B B 99 D B 82 B D 100 B B 83 A B 101 A A 84 B D 102 A A 522 103 A A 121 A A 104 A B 122 A A 105 A A 123 A A 106 C C 124 A A 107 B D 125 A A 108 C C 126 D B 109 D B 127 B D 110 D B 128 B A 111 A A 129 B B 112 C C 130 B D 113 D B 131 D B 114 C C 132 B A 115 A A 133 A A 116 A B 134 A A 117 B D 135 B A 118 D D 136 A A 119 B B 137 A A 120 D B 138 B A 523 139 B D 157 A A 140 D B 158 A A 141 A A 159 A A 142 A A 160 A A 143 A A 161 A A 144 A A 162 A A 145 A B 163 A A 146 C C 164 A A 147 B A 165 A A 148 A B 166 A A 149 A B 167 A B 150 A A 168 A A 151 A B 169 A B 152 A B 170 A B 153 A A 171 A B 154 A A 172 A A 155 A A 173 A A 156 A B 174 A A 524 175 A A 193 A A 176 A A 194 A A 177 A A 195 A A 178 B A 196 A A 179 A A 197 B B 180 A B 198 B B 181 A A 199 A A 182 A A 200 A A 183 A A 201 B A 184 B A 202 A A 185 A A 203 A A 186 A A 204 A A 187 A A 205 A A 188 A A 206 A A 189 A A 207 A A 190 A A 208 A A 191 A A 209 A A 192 A A 210 A A 525 211 A A 229 A A 212 A A 230 A B 213 A A 231 B A 214 A A 232 A A 215 A A 233 A A 216 A B 234 A A 217 A A 235 A A 218 A A 236 A A 219 A A 237 A A 220 B A 238 A A 221 A A 239 A A 222 A A 240 B A 223 A A 241 A A 224 A A 242 A A 225 A A 243 A A 226 B A 244 A A 227 A A 245 B A 228 B A 246 A A 526 247 A A 265 B B 248 A A 266 B A 249 A A 267 A A 250 A B 268 B B 251 B A 269 A A 252 B A 270 A A 253 A A 271 B A 254 B A 272 A A 255 A B 273 B A 256 A B 274 B A 257 A D 275 A A 258 A A 276 B A 259 A A 277 A A 260 A A 278 A A 261 A A 279 B A 262 A A 280 B A 263 A A 281 B D 264 B A 282 A A 527 283 A A 301 A A 284 A A 302 A A 285 B A 303 A A 286 A A 304 A A 287 A A 305 A A 288 B A 306 A A 289 B A 307 A A 290 B A 308 A B 291 B A 309 B B 292 A A 310 A A 293 B A 311 A A 294 B A 312 A B 295 B A 313 A A 296 B A 314 A A 297 A B 315 A A 298 A D 316 B A 299 A B 317 A A 300 A A 318 A B 528 319 A B 337 A A 320 A A 338 A A 321 A A 339 A A 322 A A 340 B A 323 A A 341 A A 324 A A 342 A A 325 A A 343 B A 326 A A 344 A A 327 B B 345 A A 328 C A 346 A A 329 A A 347 B A 330 A A 348 A B 331 A A 349 B B 332 A A 350 A A 333 A A 351 A A 334 A A 352 B B 335 A A 353 A A 336 A A 354 B B 529 355 B B 373 B A 356 B B 374 B A 357 B B 375 A B 358 B A 376 A B 359 B A 377 A B 360 B A 378 A A 361 A A 379 A A 362 A A 380 B A 363 A A 381 B A 364 A A 382 A A 365 A A 383 A A 366 A A 384 B A 367 B A 385 A A 368 B A 386 A A 369 D A 387 B A 370 B A 388 B A 371 A A 389 A A 372 A A 390 C A 530 391 C A 409 B A 392 A A 410 C A 393 A A 411 B A 394 A A 412 A A 395 B A 413 A A 396 C A 414 B A 397 A A 415 C A 398 C A 416 B A 399 A B 417 A B 400 B A 418 D A 401 B B 419 B B 402 B B 420 B B 403 B A 421 A A 404 B B 422 A A 405 C A 423 B A 406 A A 424 B B 407 A A 425 A A 408 B A 426 A A 531 427 A A 445 A A 428 A A 446 A A 429 A A 447 A A 430 A A 448 B A 431 B A 449 A A 432 A A 450 A A 433 A A 451 A A 434 B A 452 A A 435 D A 453 A A 436 B A 454 A A 437 A A 455 A A 438 C A 456 A B 439 A A 457 A A 440 C A 458 A A 441 A B 459 A A 442 B A 460 A A 443 B A 461 A A 444 A A 462 C A 532 463 A A 481 B A 464 A A 482 A A 465 A A 483 B A 466 A A 484 B B 467 A A 485 C A 468 C A 486 A A 469 A A 487 C A 470 C A 488 C A 471 A A 489 C A 472 A A 490 A A 473 C A 491 A A 474 C A 492 A A 475 C A 493 A A 476 C A 494 A A 477 C A 495 A A 478 A A 496 A A 479 A A 497 A A 480 A A 498 A A 533 499 C A 517 A B 500 C A 518 B D 501 C A 519 A A 502 C A 520 C A 503 C A 521 A B 504 C A 522 A A 505 A A 523 D B 506 A A 524 C C 507 A A 525 A B 508 A A 526 A B 509 C A 527 B D 510 A A 528 B B 511 A A 529 B D 512 C A 530 A A 513 A B 531 A A 514 C A 532 A B 515 C A 533 A A 516 C C 534 A A 534 535 A B 553 A A 536 A A 554 A A 537 A A 555 A A 538 A A 556 C A 539 C A 557 C B 540 A A 558 B A 541 A A 559 B A 542 B A 560 D A 543 B A 561 D B 544 A A 562 C A 545 A B 563 C D 546 C C 564 C A 547 A B 565 C A 548 A B 566 C B 549 A A 567 C A 550 A A 568 C A 551 A A 569 C A 552 A A 570 C C 535 571 C C 584 C C 572 C C 585 C C 573 C C 586 C C 574 C C 587 C C 575 C C 588 C C 576 C C 589 C C 577 C C 590 A A 578 C C 591 A A 579 C C 592 A A 580 C C 593 C C 581 C C 594 C C 582 C C 595 C C 583 C C 536 00858040_4.docx As used herein, except where the context requires otherwise, the term "comprise" and variations of the term, such as "comprising", "comprises" and "comprised", are not intended to exclude other additives, components, integers or steps. 5 Reference to any prior art in the specification is not, and should not be taken as, an acknowledgment, or any form of suggestion, that this prior art forms part of the common general knowledge in Australia or any other jurisdiction or that this prior art could reasonably be expected to be ascertained, understood and regarded as relevant by a person skilled in the art. 0 536A
Claims (20)
1. A composition comprising a molecule according to "Formula One" R7 sN )R8 R6 5 wherein (a) A is R4 R2 1N-- x attachment bond R5 R 1 N R 3 Al 0 (b) R1 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -C 10 cycloalkyl, substituted or unsubstituted C 3 -C 10 cycloalkenyl, substituted or unsubstituted C 6 -C 20 aryl, 15 substituted or unsubstituted C 1 -C 20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)IIOR9, S(O)nN(R9) 2 , or R9S(O), 1 R9, wherein each said R1, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 1 o cycloalkyl, C 3 -C 1 o 20 cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)IOR9, C 6 -C 2 0 aryl, or C 1 -C 20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); (c) R2 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C1-C 6 alkyl, 25 substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, 537 01064210 1.docx substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6 -C 2 0 aryl, substituted or unsubstituted C 1 -C 2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O) 1 1 OR9, or R9S(O), 1 R9, 5 wherein each said R2, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C1-C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O) 11 OR9, C 6 -C 2 0 aryl, or C 1 -C 20 heterocyclyl, (each of which that can be substituted, may optionally be substituted 0 with R9); (d) R3 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C1-C 6 alkoxy, substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, 5 substituted or unsubstituted C 3 -C 1 o cycloalkenyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)IIOR9, or R9S(O), 1 R9, wherein each said R3, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 2 -C 6 .0 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 1 o cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)OR9, C 6 -C 2 0 aryl, or C 1 -C 20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); 25 (e) Al is either (1) All R4 N-N attachment bond attachment bond to carbon R5 to nitrogen All where R4 is H, NO 2 , substituted or unsubstituted C 1 -C 6 538 01064210 1.docx alkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 20 heterocyclyl, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, S(O) 1 OR9, 5 or R9S(O), 1 R9, wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)IOR9, C 6 -C 2 0 aryl, 0 or C1-C 2 0 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9), or (2) A12 R4 \1 attachment bond attachment bond to carbon R5 to mtrogen A12 5 where R4 is a C 1 -C 6 alkyl, (f) R5 is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, 20 substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6 -C 2 0 aryl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O) 1 1 OR9, or R9S(O), 1 R9, wherein each said R5, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C1-C 6 haloalkyl, C 2 -C 6 25 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 1 o cycloalkyl, C 3 -C 1 o cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)OR9, or C 6 -C 2 0 aryl, (each of which that can be substituted, may optionally be substituted with R9); 539 01064210 1.docx (g) R6 is substituted or unsubstituted CI-C 6 alkyl, substituted or unsubstituted C 2 C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 C 10 cycloalkenyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 20 5 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O)IIOR9, R9S(O), 1 R9, C1-C 6 alkyl C 6 -C 2 0 aryl (wherein the alkyl and aryl can independently be substituted or unsubstituted), C(=X2)R9, C(=X1)X2R9, R9X2C(=X1)R9, R9X2R9, C(=0)(C1-C6 alkyl)S(O)n(C1-C6 alkyl), C(=0)(C1-C6 alkyl)C(=0)O(C1-C6 alkyl), (C 1 -C 6 alkyl)OC(=O)(C 6 -C 2 0 aryl), (C 1 -C 6 alkyl)OC(=O)(C1-C 6 alkyl), C1-C 6 alkyl-(C 3 -Cio 0 cyclohaloalkyl), or (C 1 -C 6 alkenyl)C(=O)O(C1-C 6 alkyl), or R9X2C(=X1)X2R9, wherein each said R6, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C1-C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 1 o cycloalkyl, C 3 -C 1 o cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O) 1 OR9, C 6 -C 2 0 aryl, 5 or C 1 -C 20 heterocyclyl, R9aryl, (each of which that can be substituted, may optionally be substituted with R9), optionally R6 and R8 can be connected in a cyclic arrangement, where optionally such arrangement can have one or more heteroatoms selected from 0, S, or, N, in the cyclic structure connecting R6 and R8; 0 (h) R7 is 0, S, NR9, or NOR9; (i) R8 is substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 2 C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, substituted or unsubstituted C 2 -C 6 25 alkenyloxy, substituted or unsubstituted C 3 -C 1 o cycloalkyl, substituted or unsubstituted C 3 C 10 cycloalkenyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 1 -C 20 heterocyclyl OR9, OR9S(O), 1 R9, C(=X1)R9, C(=X1)OR9, R9C(=X1)OR9, R9X2C(=X1)R9X2R9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)(R9S(O), 1 R9), N(R9)C(=X1)R9, SR9, S(O)IIOR9, R9S(O), 1 R9, or R9S(O),(NZ)R9, 30 wherein each said R8, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 1 o cycloalkyl, C 3 -C 1 o cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, N(R9)S(O) 1 R9, oxo, OR9, S(O)IIOR9, R9S(O), 1 R9, S(O), 1 R9, C 6 -C 2 0 aryl, or C 1 -C 2 0 heterocyclyl, (each of which that can 540 01064210 1.docx be substituted, may optionally be substituted with R9); (j) R9 is (each independently) H, CN, substituted or unsubstituted C 1 -C 6 alkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C 1 -C 6 alkoxy, 5 substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -Cio cycloalkyl, substituted or unsubstituted C 3 -Cio cycloalkenyl, substituted or unsubstituted C 6 -C 2 0 aryl, substituted or unsubstituted C 1 -C 20 heterocyclyl, S(O),C 1 -C 6 alkyl, N(C 1 -C 6 alkyl) 2 , wherein each said R9, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C1-C 6 haloalkyl, C 2 -C 6 0 haloalkenyl, C 1 -C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -C 1 o cycloalkyl, C 3 -C 1 o cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OC1-C 6 alkyl, OC 1 -C 6 haloalkyl, S (O)C 1 -C 6 alkyl, S (O)nOC 1 -C 6 alkyl, C 6 -C 20 aryl, or C 1 -C 20 heterocyclyl; (k) n is 0, 1, or 2; 5 (1) X is N or CR 1 i where R,,i is H, F, Cl, Br, I, CN, NO 2 , substituted or unsubstituted C1-C 6 alkyl, substituted or unsubstituted C 2 -C 6 alkenyl, substituted or unsubstituted C1-C 6 alkoxy, substituted or unsubstituted C 2 -C 6 alkenyloxy, substituted or unsubstituted C 3 -C 1 o cycloalkyl, substituted or unsubstituted C 3 -C 1 o cycloalkenyl, substituted .0 or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C1-C 2 0 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9) 2 , N(R9) 2 , N(R9)C(=X1)R9, SR9, S(O), 1 R9, S(O)IIOR9, or R9S(O), 1 R9, wherein each said R,,i which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 2 -C 6 25 haloalkenyl, C1-C 6 haloalkyloxy, C 2 -C 6 haloalkenyloxy, C 3 -Cio cycloalkyl, C 3 -Cio cycloalkenyl, C 3 -Cio halocycloalkyl, C 3 -Cio halocycloalkenyl, OR9, S(O)OR9, C 6 -C 2 0 aryl, or C 1 -C 20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9); 30 (m) X1 is (each independently) 0 or S; (n) X2 is (each independently) 0, S, =NR9, or =NOR9; and (o) Z is CN, NO 2 , C 1 -C 6 alkyl(R9), C(=X1)N(R9) 2 ; and 541 01064210 1.docx (p) with the following provisos (1) that R6 and R8 cannot both be C(=O)CH 3 , (2) that when Al is All then R6 and R8 together do not form fused ring 5 systems, (3) that R6 and R8 are not linked in a cyclic arrangement with only -CH 2 -.
2. A composition according to claim 1 wherein R1 is H, R2 is H, and R3 is selected from H or CH 3 . 0
3. A composition according to any one of the preceding claims wherein Al is All, and R4 is selected from H, CH 3 , CH(CH 3 ) 2 , or phenyl.
4. A composition according to claims 1 or 2 wherein Al is A12, and R4 is CH 3 . 5
5. A composition according to any one of the preceding claims wherein R5 is selected from H, OCH 2 CH 3 , F, Cl, Br, or CH 3 .
6. A composition according to any one of the preceding claims wherein R6 is H, CH 3 , .O CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 ) 2 , CH 2 phenyl, CH 2 CH(CH 3 ) 2 , CH 2 cyclopropyl, C(=O)CH 2 CH 2 SCH 3 , C(=O)OC(CH 3 ) 3 , CH 2 CH=CH 2 , C(=O)OCH 2 CH 3 , C(=O)CH(CH 3 )CH 2 SCH 3 , cyclopropyl, CD 3 , CH 2 0C(=O)phenyl, C(=O)CH 3 , C(=O)CH(CH 3 ) 2 , CH 2 0C(=O)CH(CH 3 ) 2 , CH 2 0C(=O)CH 3 , C(=O)phenyl, CH 2 0CH 3 , CH 2 0C(=O)CH 2 0CH 2 CH 3 , CH 2 CH 2 0CH 3 , CH 2 0C(=O)OCH(CH 3 ) 2 , CH 2 CH 2 0CH 2 0CH 3 , 25 CH 2 CH 2 0CH 3 , CH 2 CH 2 0C(=O)CH 3 , CH 2 CN.
7. A composition according to any one of the preceding claims wherein R7 is 0 or S.
8. A composition according to any one of the preceding claims wherein R8 is 30 CH(CH 3 )CH 2 SCH 3 , CH(CH 3 ) 2 , C(CH 3 ) 2 CH 2 SCH 3 , CH 2 CH 2 SCH 3 , CH 2 CF 3 , CH 2 CH 2 C(=O)OCH 3 , N(H)(CH 2 CH 2 SCH 3 ), OCH 2 CH 2 SCH 3 , CH(CH 2 SCH 3 )(CH 2 phenyl), thiazolyl, oxazolyl, isothiazolyl, substituted-furanyl, CH 3 , C(CH 3 ) 3 , phenyl, CH 2 CH 2 0CH 3 , pyridyl, CH 2 CH(CH 3 )SCH 3 , OC(CH 3 ) 3 , C(CH 3 ) 2 CH 2 SCH 3 , CH(CH 3 )CH(CH 3 )SCH 3 , CH(CH 3 )CF 3 , CH 2 CH 2 -thienyl, CH(CH 3 )SCF 3 ,CH 2 CH 2 Cl, CH 2 CH 2 CH 2 CF 3 , 542 01064210 1.docx CH 2 CH 2 S(=O)CH 3 , CH(CH 3 )CH 2 S(=O)CH 3 , CH 2 CH 2 S(=0) 2 CH 3 , CH(CH 3 )CH 2 S(=0) 2 CH 3 , NCH 2 CH 3 , N(H)(CH 2 CH 2 CH 3 ), C(CH 3 )=C(H)(CH 3 ), N(H)(CH 2 CH=CH 2 ), CH 2 CH(CF 3 )SCH 3 , CH(CF 3 )CH 2 SCH 3 , thietanyl, CH 2 CH(CF 3 ) 2 , CH 2 CH 2 CF(OCF 3 )CF 3 , CH 2 CH 2 CF(CF 3 )CF 3 , CF(CH 3 ) 2 , CH(CH 3 )phenyl-Cl, CH(CH 3 )phenyl-F, CH(CH 3 )phenyl 5 OCF 3 , CH 2 N(CH 3 )(S(=0) 2 N(CH 3 ) 2 , CH(CH 3 )OCH 2 CH 2 SCH 3 , CH(CH 3 )OCH 2 CH 2 0CH 3 , OCH 3 , CH(CH 3 )SCH 3 , CH 2 SCH 3 , N(H)CH 3 , CH(Br)CH 2 Br, or CH(CH 3 )CH 2 SCD 3 .
9. A composition according to claim 1 wherein X is CR 1 i where R,,i is H or halo. 0
10. A composition according to any one of the preceding claims wherein said molecule said X1 or X2 or both are 0.
11. A composition according to claim 1 wherein said molecule has one of the following structures 5 Com pound Structure No. CH 3 N-N/ 543 01064210 _.docx CH 3 2 C CH3 CH / 0 N-N CH 3 3s N C N-N 3HCH CH 3 N-N N- / CH 3 H CH / 0H N-N CCH 3 F N-N NN F 544 01064210 _.docx CH 3 0 / 0 CO CH3 CH 3 6 N N-N CH 3 CH3 / 0 7N H 7 CH3 NN N CH3 _ 8 N ~ CH 3 CH N-N CH 3 CH3 CH 3 9 N c CH 545 01064210 _.docx CH 3 N-N/ 3 CH3 NN 10 Nsr H IN / X CH3 0 CH 3 12 CH3 N Br HCN-N O CH 3 18 s 19 CH 3 546 01064210 1.docx H3C \ O 20 C CH3 H 3 C N-N OCH 3 1 3 N\ 3 CH 3 22CCH3 C30 CH3 NN C H 3 O C H 3 22 HC CH 3 CHCH0 CH 3 23 N CH 3 4 H3C 547 01064210 _.docx 0 H 3 C O CH 0 24 CH3 N H3C CN, 25 H3C 0 H 3 C' H 3 C CH3 NN 26 H3 N H, C H3C N-N 0 27 H1 3 N .... 26 H 3 C N 3 C 548 01064210 _.docx 28 H 3 C H 3 C NN 29 N H 3 C N 0 0 N 30 H3C'S H3C .- N H 3 C CH 3 I 0 0l NN-S 31 N 549 01064210 _.docx CHC3 O N-N CH 3 477 CH 3 CH3 0 CH3 N N CH 3 487 CH 3 C GH3i0 N--N 509 CH 3 CH 3 N H3C O CH3 N-.N 520 CH CH3 55 3 N 550 01064210 _.docx H 3 C O 556 S CH 3 CH 3 N H 3 C CH 3 N--N CH 3 557 N CH 3 -0/ CH 3 H 3 C CH 3 N--N CH 3 562 N CH 3 0 CH 3 563 N--N 53C CH3 N 551 01064210 _.docx CH3 0 N'N 564 N H 3 CH3 (N CH3 CH 3 0 s/ 565 N CH3 C H 3 N 566 N H3 N GH3 0 NN CH3 567 FC 3 CH3 55 3 N 552 01064210 1.docx CH 3 0 F N g 568 CH 3 CH 3 N
12. A composition according to any one of the preceding claims further comprising: (a) one or more compounds having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, or virucidal 5 properties; or (b) one or more compounds that are antifeedants, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammal repellents, mating disrupters, plant activators, plant growth regulators, or synergists; or (c) both (a) and (b). 0
13. A composition according to any one of the preceding claims further comprising one or more compounds selected from: (3-ethoxypropyl)mercury bromide, 1,2-dichloropropane, 1,3-dichloropropene, 1-methylcyclopropene, 1-naphthol, 2-(octylthio)ethanol, 2,3,5-tri iodobenzoic acid, 2,3,6-TBA, 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6 5 TBA-potassium, 2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5 T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl, 2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T sodium, 2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D, 2,4-D-2-butoxypropyl, 2,4-D 2-ethylhexyl, 2,4-D-3-butoxypropyl, 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB 20 dimethylammonium, 2,4-DB-isoctyl, 2,4-DB -potassium, 2,4-DB-sodium, 2,4-D-butotyl, 2,4 D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D 25 sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2 hydroxypropyl)ammonium, 2,4-D-trolamine, 2iP, 2-methoxyethylmercury chloride, 2 553 01064210 _.docx phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPA sodium, 4-CPB, 4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate, 8 phenylmercurioxyquinoline, abamectin, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetophos, acetoprole, acibenzolar, acibenzolar-S-methyl, 5 acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrep, acrinathrin, acrolein, acrylonitrile, acypetacs, acypetacs-copper, acypetacs-zinc, alachlor, alanycarb, albendazole, aldicarb, aldimorph, aldoxycarb, aldrin, allethrin, allicin, allidochlor, allosamidin, alloxydim, alloxydim-sodium, allyl alcohol, allyxycarb, alorac, alpha-cypermethrin, alpha-endosulfan, ametoctradin, ametridione, ametryn, amibuzin, amicarbazone, amicarthiazol, amidithion, 0 amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium, aminopyralid-tris(2 hydroxypropyl)ammonium, amiprofos-methyl, amiprophos, amisulbrom, amiton, amiton oxalate, amitraz, amitrole, ammonium sulfamate, ammonium a-naphthaleneacetate, amobam, ampropylfos, anabasine, ancymidol, anilazine, anilofos, anisuron, anthraquinone, antu, 5 apholate, aramite, arsenous oxide, asomate, aspirin, asulam, asulam-potassium, asulam sodium, athidathion, atraton, atrazine, aureofungin, aviglycine, aviglycine hydrochloride, azaconazole, azadirachtin, azafenidin, azamethiphos, azimsulfuron, azinphos-ethyl, azinphos methyl, aziprotryne, azithiram, azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban, barium hexafluorosilicate, barium polysulfide, barthrin, BCPC, .0 beflubutamid, benalaxyl, benalaxyl-M, benazolin, benazolin-dimethylammonium, benazolin ethyl, benazolin-potassium, bencarbazone, benclothiaz, bendiocarb, benfluralin, benfuracarb, benfuresate, benodanil, benomyl, benoxacor, benoxafos, benquinox, bensulfuron, bensulfuron-methyl, bensulide, bensultap, bentaluron, bentazone, bentazone-sodium, benthiavalicarb, benthiavalicarb-isopropyl, benthiazole, bentranil, benzadox, benzadox 25 ammonium, benzalkonium chloride, benzamacril, benzamacril-isobutyl, benzamorf, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzohydroxamic acid, benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, benzyladenine, berberine, berberine chloride, beta-cyfluthrin, beta-cypermethrin, bethoxazin, bicyclopyrone, bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos, bilanafos-sodium, 30 binapacryl, bingqingxiao, bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bisazir, bismerthiazol, bispyribac, bispyribac-sodium, bistrifluron, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid, brassinolide, brassinolide-ethyl, brevicomin, brodifacoum, brofenvalerate, brofluthrinate, bromacil, bromacil-lithium, bromacil-sodium, bromadiolone, bromethalin, bromethrin, bromfenvinfos, 554 01064210 1.docx bromoacetamide, bromobonil, bromobutide, bromocyclen, bromo-DDT, bromofenoxim, bromophos, bromophos-ethyl, bromopropylate, bromothalonil, bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, bromuconazole, bronopol, bucarpolate, bufencarb, buminafos, bupirimate, 5 buprofezin, Burgundy mixture, busulfan, butacarb, butachlor, butafenacil, butamifos, butathiofos, butenachlor, butethrin, buthidazole, buthiobate, buthiuron, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butroxydim, buturon, butylamine, butylate, cacodylic acid, cadusafos, cafenstrole, calcium arsenate, calcium chlorate, calcium cyanamide, calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor, 0 captafol, captan, carbamorph, carbanolate, carbaryl, carbasulam, carbendazim, carbendazim benzenesulfonate, carbendazim sulfite, carbetamide, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, carboxazole, carboxide, carboxin, carfentrazone, carfentrazone-ethyl, carpropamid, cartap, cartap hydrochloride, carvacrol, carvone, CDEA, cellocidin, CEPC, ceralure, Cheshunt mixture, chinomethionat, chitosan, chlobenthiazone, 5 chlomethoxyfen, chloralose, chloramben, chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium, chloramben-sodium, chloramine phosphorus, chloramphenicol, chloraniformethan, chloranil, chloranocryl, chlorantraniliprole, chlorazifop, chlorazifop-propargyl, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chlordimeform .0 hydrochloride, chlorempenthrin, chlorethoxyfos, chloreturon, chlorfenac, chlorfenac ammonium, chlorfenac-sodium, chlorfenapyr, chlorfenazole, chlorfenethol, chlorfenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfluazuron, chlorflurazole, chlorfluren, chlorfluren-methyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlormephos, chlormequat, chlormequat chloride, chlornidine, 25 chlornitrofen, chlorobenzilate, chlorodinitronaphthalenes, chloroform, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophacinone-sodium, chloropicrin, chloropon, chloropropylate, chlorothalonil, chlorotoluron, chloroxuron, chloroxynil, chlorphonium, chlorphonium chloride, chlorphoxim, chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal, 30 chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, chlorthiophos, chlozolinate, choline chloride, chromafenozide, cinerin I, cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, ciobutide, cisanilide, cismethrin, clethodim, climbazole, cliodinate, clodinafop, clodinafop-propargyl, cloethocarb, clofencet, clofencet-potassium, clofentezine, clofibric acid, clofop, clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, 555 01064210 1.docx clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(2 hydroxypropyl)ammonium, cloquintocet, cloquintocet-mexyl, cloransulam, cloransulam methyl, closantel, clothianidin, clotrimazole, cloxyfonac, cloxyfonac-sodium, CMA, codlelure, colophonate, copper acetate, copper acetoarsenite, copper arsenate, copper 5 carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, coumachlor, coumafuryl, coumaphos, coumatetralyl, coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, crimidine, crotamiton, crotoxyphos, crufomate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam, cuprous oxide, curcumenol, cyanamide, cyanatryn, cyanazine, cyanofenphos, 0 cyanophos, cyanthoate, cyantraniliprole, cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalofop, cyhalofop-butyl, cyhalothrin, cyhexatin, cymiazole, cymiazole hydrochloride, cymoxanil, cyometrinil, cypendazole, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin, cyprazine, 5 cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid, cyprosulfamide, cyromazine, cythioate, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, daminozide, dayoutong, dazomet, dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT, debacarb, decafentin, decarbofuran, dehydroacetic acid, delachlor, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O .0 methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, desmedipham, desmetryn, d-fanshiluquebingjuzhi, diafenthiuron, dialifos, di-allate, diamidafos, diatomaceous earth, diazinon, dibutyl phthalate, dibutyl succinate, dicamba, dicamba diglycolamine, dicamba-dimethylammonium, dicamba-diolamine, dicamba isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba 25 sodium, dicamba-trolamine, dicapthon, dichlobenil, dichlofenthion, dichlofluanid, dichlone, dichloralurea, dichlorbenzuron, dichlorflurenol, dichlorflurenol-methyl, dichlormate, dichlormid, dichlorophen, dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P, dichlorprop-P-2-ethylhexyl, dichlorprop-P 30 dimethylammonium, dichlorprop-potassium, dichlorprop- sodium, dichlorvos, dichlozoline, diclobutrazol, diclocymet, diclofop, diclofop-methyl, diclomezine, diclomezine-sodium, dicloran, diclosulam, dicofol, dicoumarol, dicresyl, dicrotophos, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat, diethamquat dichloride, diethatyl, diethatyl-ethyl, diethofencarb, dietholate, diethyl pyrocarbonate, diethyltoluamide, difenacoum, 556 01064210 1.docx difenoconazole, difenopenten, difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate, difethialone, diflovidazin, diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr- sodium, diflumetorim, dikegulac, dikegulac- sodium, dilor, dimatif, dimefluthrin, dimefox, dimefuron, dimepiperate, dimetachlone, dimetan, dimethacarb, 5 dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate, dimethyl phthalate, dimethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin, dinex, dinex-diclexine, dingjunezuo, diniconazole, diniconazole-M, dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinoseb acetate, 0 dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium, dinoseb-trolamine, dinosulfon, dinotefuran, dinoterb, dinoterb acetate, dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion, diphacinone, diphacinone-sodium, diphenamid, diphenyl sulfone, diphenylamine, dipropalin, dipropetryn, dipyrithione, diquat, diquat dibromide, disparlure, disul, disulfiram, disulfoton, disul-sodium, ditalimfos, dithianon, dithicrofos, dithioether, dithiopyr, diuron, d 5 limonene, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin hydrochloride, dodicin-sodium, dodine, dofenapyn, dominicalure, doramectin, drazoxolon, DSMA, dufulin, EBEP, EBP, ecdysterone, edifenphos, eglinazine, eglinazine-ethyl, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothal, endothal-diammonium, endothal .0 dipotassium, endothal-disodium, endothion, endrin, enestroburin, EPN, epocholeone, epofenonane, epoxiconazole, eprinomectin, epronaz, EPTC, erbon, ergocalciferol, erlujixiancaoan, esd6pall6thrine, esfenvalerate, esprocarb, etacelasil, etaconazole, etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethaprochlor, ethephon, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, 25 ethirimol, ethoate-methyl, ethofumesate, ethohexadiol, ethoprophos, ethoxyfen, ethoxyfen ethyl, ethoxyquin, ethoxysulfuron, ethychlozate, ethyl formate, ethyl a-naphthaleneacetate, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, ethylicin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etinofen, etnipromid, etobenzanid, 30 etofenprox, etoxazole, etridiazole, etrimfos, eugenol, EXD, famoxadone, famphur, fenamidone, fenaminosulf, fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorazole-ethyl, fenchlorphos, fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitropan, fenitrothion, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypropyl, fenoprop 557 01064210 _.docx butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop potassium, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenoxycarb, fenpiclonil, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate, fenridazon, fenridazon 5 potassium, fenridazon-propyl, fenson, fensulfothion, fenteracol, fenthiaprop, fenthiaprop ethyl, fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride, fentin hydroxide, fentrazamide, fentrifanil, fenuron, fenuron TCA, fenvalerate, ferbam, ferimzone, ferrous sulfate, fipronil, flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl, flamprop-M isopropyl, flamprop-M-methyl, flazasulfuron, flocoumafen, flometoquin, flonicamid, 0 florasulam, fluacrypyrim, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop P-butyl, fluazinam, fluazolate, fluazuron, flubendiamide, flubenzimine, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerim, flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr-ethyl, flufiprole, flumethrin, flumetover, flumetralin, 5 flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, flumorph, fluometuron, fluopicolide, fluopyram, fluorbenside, fluoridamid, fluoroacetamide, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluotrimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate, flupropanate-sodium, flupyradifurone, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron .0 methyl-sodium, fluquinconazole, flurazole, flurenol, flurenol-butyl, flurenol-methyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide, fluthiacet, fluthiacet-methyl, flutianil, flutolanil, flutriafol, fluvalinate, fluxapyroxad, fluxofenim, folpet, fomesafen, fomesafen-sodium, fonofos, foramsulfuron, forchlorfenuron, formaldehyde, formetanate, 25 formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosamine, fosamine-ammonium, fosetyl, fosetyl-aluminium, fosmethilan, fospirate, fosthiazate, fosthietan, frontalin, fuberidazole, fucaojing, fucaomi, funaihecaoling, fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr, furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin, furfural, furilazole, furmecyclox, furophanate, furyloxyfen, 30 gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellins, gliftor, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyodin, glyoxime, glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-monoammonium, glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium, glyphosine, gossyplure, grandlure, 558 01064210 1.docx griseofulvin, guazatine, guazatine acetates, halacrinate, halfenprox, halofenozide, halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop methyl, haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium, HCH, hemel, hempa, HEOD, heptachlor, heptenophos, heptopargil, heterophos, hexachloroacetone, 5 hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumuron, hexaflurate, hexalure, hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf, huancaiwo, huangcaoling, huanjunzuo, hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanide, hydroprene, hymexazol, hyquincarb, IAA, IBA, icaridin, imazalil, imazalil nitrate, imazalil sulfate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox 0 ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium, imazosulfuron, imibenconazole, imicyafos, imidacloprid, imidaclothiz, iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate, imiprothrin, inabenfide, indanofan, indaziflam, indoxacarb, inezin, iodobonil, iodocarb, iodomethane, 5 iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl- sodium, iofensulfuron, iofensulfuron-sodium, ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarbazone, iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, isamidofos, isazofos, isobenzan, isocarbamid, isocarbophos, isocil, isodrin, isofenphos, isofenphos-methyl, isolan, isomethiozin, isonoruron, isopolinate, isoprocarb, .0 isopropalin, isoprothiolane, isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen-ethyl, isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izopamfos, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan, jiecaoxi, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kadethrin, 25 karbutilate, karetazan, karetazan-potassium, kasugamycin, kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox, ketospiradox-potassium, kinetin, kinoprene, kresoxim methyl, kuicaoxi, lactofen, lambda-cyhalothrin, latilure, lead arsenate, lenacil, lepimectin, leptophos, lindane, lineatin, linuron, lirimfos, litlure, looplure, lufenuron, lvdingjunzhi, lvxiancaolin, lythidathion, MAA, malathion, maleic hydrazide, malonoben, maltodextrin, 30 MAMA, mancopper, mancozeb, mandipropamid, maneb, matrine, mazidox, MCPA, MCPA 2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mebenil, mecarbam, mecarbinzid, mecarphon, 559 01064210 1.docx mecoprop, mecoprop-2-ethylhexyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-2 ethylhexyl, mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medimeform, medinoterb, 5 medinoterb acetate, medlure, mefenacet, mefenpyr, mefenpyr-diethyl, mefluidide, mefluidide-diolamine, mefluidide-potassium, megatomoic acid, menazon, mepanipyrim, meperfluthrin, mephenate, mephosfolan, mepiquat, mepiquat chloride, mepiquat pentaborate, mepronil, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, merphos, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, mesulfen, mesulfenfos, o metaflumizone, metalaxyl, metalaxyl-M, metaldehyde, metam, metam-ammonium, metamifop, metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron, metazoxolon, metconazole, metepa, metflurazon, methabenzthiazuron, methacrifos, methalpropalin, methamidophos, methasulfocarb, methazole, methfuroxam, methidathion, methiobencarb, methiocarb, methiopyrisulfuron, methiotepa, methiozolin, methiuron, 5 methocrotophos, methometon, methomyl, methoprene, methoprotryne, methoquin-butyl, methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methyl apholate, methyl bromide, methyl eugenol, methyl iodide, methyl isothiocyanate, methylacetophos, methylchloroform, methyldymron, methylene chloride, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, .0 methylneodecanamide, metiram, metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb, metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone, metribuzin, metsulfovax, metsulfuron, metsulfuron-methyl, mevinphos, mexacarbate, mieshuan, milbemectin, milbemycin oxime, milneb, mipafox, mirex, MNAF, moguchun, molinate, molosultap, monalide, monisouron, monochloroacetic acid, monocrotophos, 25 monolinuron, monosulfuron, monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquat dichloride, moroxydine, moroxydine hydrochloride, morphothion, morzid, moxidectin, MSMA, muscalure, myclobutanil, myclozolin, N-(ethylmercury)-p toluenesulphonanilide, nabam, naftalofos, naled, naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthoxyacetic acids, naproanilide, napropamide, naptalam, 30 naptalam-sodium, natamycin, neburon, niclosamide, niclosamide-olamine, nicosulfuron, nicotine, nifluridide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl, norbormide, norflurazon, nornicotine, noruron, novaluron, noviflumuron, nuarimol, OCH, octachlorodipropyl ether, octhilinone, ofurace, omethoate, orbencarb, orfralure, ortho-dichlorobenzene, 560 01064210 1.docx orthosulfamuron, oryctalure, orysastrobin, oryzalin, osthol, ostramone, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxine-copper, oxolinic acid, oxpoconazole, oxpoconazole fumarate, oxycarboxin, oxydemeton-methyl, oxydeprofos, 5 oxydisulfoton, oxyfluorfen, oxymatrine, oxytetracycline, oxytetracycline hydrochloride, paclobutrazol, paichongding, para-dichlorobenzene, parafluron, paraquat, paraquat dichloride, paraquat dimetilsulfate, parathion, parathion-methyl, parinol, pebulate, pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin, penflufen, penfluron, penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad, pentmethrin, pentoxazone, 0 perfluidone, permethrin, pethoxamid, phenamacril, phenazine oxide, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenothrin, phenproxide, phenthoate, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phorate, phosacetim, phosalone, phosdiphen, phosfolan, phosfolan-methyl, phosglycin, 5 phosmet, phosnichlor, phosphamidon, phosphine, phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide, picloram, picloram-2-ethylhexyl, picloram-isoctyl, picloram methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram-tris(2 hydroxypropyl)ammonium, picolinafen, picoxystrobin, pindone, pindone-sodium, pinoxaden, piperalin, piperonyl butoxide, piperonyl cyclonene, piperophos, piproctanyl, piproctanyl .0 bromide, piprotal, pirimetaphos, pirimicarb, pirimioxyphos, pirimiphos-ethyl, pirimiphos methyl, plifenate, polycarbamate, polyoxins, polyoxorim, polyoxorim-zinc, polythialan, potassium arsenite, potassium azide, potassium cyanate, potassium gibberellate, potassium naphthenate, potassium polysulfide, potassium thiocyanate, potassium a-naphthaleneacetate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, pretilachlor, primidophos, 25 primisulfuron, primisulfuron-methyl, probenazole, prochloraz, prochloraz-manganese, proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol, profluralin, profluthrin, profoxydim, proglinazine, proglinazine-ethyl, prohexadione, prohexadione calcium, prohydrojasmon, promacyl, promecarb, prometon, prometryn, promurit, propachlor, propamidine, propamidine dihydrochloride, propamocarb, propamocarb hydrochloride, 30 propanil, propaphos, propaquizafop, propargite, proparthrin, propazine, propetamphos, propham, propiconazole, propineb, propisochlor, propoxur, propoxycarbazone, propoxycarbazone-sodium, propyl isome, propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin, prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothiocarb hydrochloride, prothioconazole, prothiofos, prothoate, protrifenbute, proxan, proxan-sodium, 561 01064210 _.docx prynachlor, pydanon, pymetrozine, pyracarbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyraflufen-ethyl, pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotole, pyrazolynate, pyrazophos, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyribambenz-isopropyl, 5 pyribambenz-propyl, pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol, pyridalyl, pyridaphenthion, pyridate, pyridinitril, pyrifenox, pyrifluquinazon, pyriftalid, pyrimethanil, pyrimidifen, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxyfen, pyrithiobac, pyrithiobac sodium, pyrolan, pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur, quassia, 0 quinacetol, quinacetol sulfate, quinalphos, quinalphos-methyl, quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine, quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P tefuryl, quwenzhi, quyingding, rabenzazole, rafoxanide, rebemide, resmethrin, rhodethanil, rhodojaponin-IJI, ribavirin, rimsulfuron, rotenone, ryania, saflufenacil, saijunmao, saisentong, 5 salicylanilide, sanguinarine, santonin, schradan, scilliroside, sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz, semiamitraz chloride, sesamex, sesamolin, sethoxydim, shuangjiaancaolin, siduron, siglure, silafluofen, silatrane, silica gel, silthiofam, simazine, simeconazole, simeton, simetryn, sintofen, SMA, S-metolachlor, sodium arsenite, sodium azide, sodium chlorate, sodium fluoride, sodium fluoroacetate, sodium hexafluorosilicate, .0 sodium naphthenate, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, sodium thiocyanate, sodium a-naphthaleneacetate, sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine, streptomycin, streptomycin sesquisulfate, strychnine, sulcatol, sulcofuron, sulcofuron-sodium, sulcotrione, sulfallate, sulfentrazone, sulfiram, sulfluramid, sulfometuron, sulfometuron-methyl, sulfosulfuron, 25 sulfotep, sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglycapin, sulprofos, sultropen, swep, tau-fluvalinate, tavron, tazimcarb, TCA, TCA-ammonium, TCA calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium, TDE, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tecoram, teflubenzuron, tefluthrin, tefuryltrione, tembotrione, temephos, tepa, TEPP, 30 tepraloxydim, terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuthylazine, terbutryn, tetcyclacis, tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, tetrafluron, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetrasul, thallium sulfate, thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid, thiadifluor, thiamethoxam, thiapronil, thiazafluron, thiazopyr, thicrofos, thicyofen, thidiazimin, 562 01064210 _.docx thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, thiocyclam, thiocyclam hydrochloride, thiocyclam oxalate, thiodiazole-copper, thiodicarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon, thionazin, thiophanate, thiophanate-methyl, thioquinox, 5 thiosemicarbazide, thiosultap, thiosultap-diammonium, thiosultap-disodium, thiosultap monosodium, thiotepa, thiram, thuringiensin, tiadinil, tiaojiean, tiocarbazil, tioclorim, tioxymid, tirpate, tolclofos-methyl, tolfenpyrad, tolylfluanid, tolylmercury acetate, topramezone, tralkoxydim, tralocythrin, tralomethrin, tralopyril, transfluthrin, transpermethrin, tretamine, triacontanol, triadimefon, triadimenol, triafamone, tri-allate, 0 triamiphos, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, triazbutil, triaziflam, triazophos, triazoxide, tribenuron, tribenuron-methyl, tribufos, tributyltin oxide, tricamba, trichlamide, trichlorfon, trichlormetaphos-3, trichloronat, triclopyr, triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium, tricyclazole, tridemorph, tridiphane, trietazine, trifenmorph, trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium, 5 triflumizole, triflumuron, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, trifop methyl, trifopsime, triforine, trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac, trinexapac-ethyl, triprene, tripropindan, triptolide, tritac, triticonazole, tritosulfuron, trunc-call, uniconazole, uniconazole-P, urbacide, uredepa, valerate, validamycin, valifenalate, valone, vamidothion, vangard, vaniliprole, vernolate, vinclozolin, .0 warfarin, warfarin-potassium, warfarin-sodium, xiaochongliulin, xinjunan, xiwojunan, XMC, xylachlor, xylenols, xylylcarb, yishijing, zarilamid, zeatin, zengxiaoan, zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zineb, ziram, zolaprofos, zoxamide, zuomihuanglong, a-chlorohydrin, a-ecdysone, a-multistriatin, and a-naphthaleneacetic acid. 25
14. A composition according to any one of the preceding claims further comprising one or more of the following compounds: (a) 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2 one; 30 (b) 3-(4'-chloro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa-1 azaspiro[4,5]dec-3-en-2-one; (c) 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone; 563 01064210 1.docx (d) 4- [[(6-chloro-3-pyridinyl)methyl]cyclopropylamino] -2(5H)-furanone; (e) 3-chloro-N2- [(1 S)- 1 -methyl-2-(methylsulfonyl)ethyl] -Ni -[2-methyl-4 1,2,2,2-tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl] -1,2-benzenedicarboxamide; 5 (f) 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide; (g) 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; 0 (h) 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide; (i) 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide; (j) 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide; 5 (k) 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide; (1) 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide; .0 (m) 3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl] -1-methyl-1H-pyrazole-4 carboxamide; (n) N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-a,a,a-trifluoro-p-tolyl) hydrazone; 25 (o) N-ethyl-2,2-dichloro- 1 -methylcyclopropane-carboxamide-2-(2,6-dichloro a,a,a-trifluoro-p-tolyl) hydrazone nicotine; (p) O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]I S 30 methyl thiocarbonate; (q) (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine; 564 01064210 1.docx (r) 1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro- 1,2,3,5,6,7-hexahydro imidazo[ 1,2-a]pyridin-5-ol; (s) 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate; and 5 (t) N-Ethyl-2,2-dichloro- 1 -methylcyclopropanecarboxamide-2-(2,6-dichloro alpha,alpha,alpha-trifluoro-p-tolyl)hydrazone.
15. A composition according to any one of the preceding claims further comprising a 0 compound having one or more of the following modes of action: acetylcholinesterase inhibitor; sodium channel modulator; chitin biosynthesis inhibitor; GABA and glutamate gated chloride channel antagonist; GABA and glutamate-gated chloride channel agonist; acetylcholine receptor agonist; acetylcholine receptor antagonist; MET I inhibitor; Mg stimulated ATPase inhibitor; nicotinic acetylcholine receptor; Midgut membrane disrupter; 5 oxidative phosphorylation disrupter, and ryanodine receptor (RyRs).
16. A composition according to any one of the preceding claims further comprising a seed. .0
17. A composition according to any one of claims 1 to 15 wherein said composition is encapsulated inside, or placed on the surface of, a capsule, wherein said capsule has a diameter of about 100-900 nanometers or about 10-900 microns.
18. A process comprising applying a composition according to any one of claims 1 to 15, 25 to an area to control a pest, in an amount sufficient to control such pest; wherein said amount is from about 0.01 grams per hectare to about 5000 grams per hectare; and wherein said area is an area where apples, corn, cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, 30 crucifers, pears, tobacco, almonds, sugar beets, or beans, are growing, or the seeds thereof are going to be planted.
19. A process according to claim 18 further comprising applying said composition to a genetically modified plant that has been genetically modified to express one or more 565 01064210 _.docx specialized traits, or to a plant to enhance the plant's health, yield, vigor, quality, or tolerance, at a time when pest activity is low.
20. A process comprising: orally administering; or topically applying; a composition 5 according to any one of claims 1 to 15, to a non-human animal, to control endoparasites, ectoparasites, or both. 566
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