HERBICIDAL COMPOUNDS

Abstract

The present invention relates to a compound of formula (I) wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and G are as defined herein; and wherein the compound of formula (I) is optionally present as an agrochemically acceptable salt thereof. These compounds are suitable for use as herbicides. The invention therefore also relates to a method of controlling weeds, especially grassy monocotyledonous weeds, in crops of useful plants, comprising applying a compound of formula (I), or a herbicidal composition comprising such a compound, to the plants or to the locus thereof.

##STR00001##

Claims

1. A compound of formula (I): ##STR00641## wherein: R.sup.1 is selected from the group consisting of methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl, ethynyl, fluorine, chlorine, bromine, methoxy, difluoromethoxy and trifluoromethoxy; and either (a): R.sup.2 is R.sup.2A and R.sup.3 is R.sup.3A; or (b): R.sup.2 is R.sup.2B and R.sup.3 is R.sup.3B; wherein: R.sup.2A is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, C.sub.1-C.sub.2fluoroalkyl, vinyl, prop-1-enyl, prop-1-ynyl, —C≡C—R.sup.2AA, halogen and (C.sub.1-C.sub.2fluoroalkyl)-methoxy-; wherein R.sup.2AA is selected from the group consisting of hydrogen, fluorine, chlorine, trifluoromethyl, ethyl and cyclopropyl; or R.sup.2A is phenyl optionally substituted by 1, 2 or 3 substituents independently selected from the group consisting of halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, methoxymethyl, vinyl, ethynyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, —S(O).sub.pmethyl, cyano or nitro, provided that either one or none (i.e. no more than one) of these optional substituents are methoxymethyl, vinyl, ethynyl, —S(O).sub.pmethyl or nitro; or R.sup.2A is a monocyclic heteroaryl optionally substituted by 1, 2 or 3 substituents independently selected from the group consisting of halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, methoxymethyl, vinyl, ethynyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, —S(O).sub.pmethyl, cyano and nitro, provided that either one or none (i.e. no more than one) of these optional substituents are methoxymethyl, vinyl, ethynyl, —S(O).sub.pmethyl or nitro; R.sup.3A is selected from the group consisting of hydrogen, methyl, fluorine and chlorine; and wherein R2B is hydrogen, methyl or fluorine; and either R.sup.3B is phenyl optionally substituted by 1, 2 or 3 substituents independently selected from the group consisting of halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, methoxymethyl, vinyl, ethynyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, —S(O).sub.pmethyl, cyano and nitro, provided that either one or none (i.e. no more than one) of these optional substituents are methoxymethyl, vinyl, ethynyl, —S(O).sub.pmethyl or nitro; or R.sup.3B is a monocyclic heteroaryl optionally substituted by 1, 2 or 3 substituents independently selected from the group consisting of halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, methoxymethyl, vinyl, ethynyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, —S(O).sub.pmethyl, cyano and nitro, provided that either one or none (i.e. no more than one) of these optional substituents are methoxymethyl, vinyl, ethynyl, —S(O).sub.pmethyl or nitro; R.sup.4 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, vinyl, ethynyl, fluorine, chlorine, bromine, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, C.sub.1-C.sub.2alkoxy-C.sub.1-C.sub.3alkoxy-, or C.sub.1fluoroalkoxy-C.sub.1-C.sub.3alkoxy-; R.sup.5, R.sup.6 and R.sup.7 are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3alkynyl, C.sub.1-C.sub.2haloalkyl and C.sub.1-C.sub.2alkoxyC.sub.1-C.sub.2alkyl; R.sup.8 and R.sup.9 are independently selected from the group consisting of hydrogen, fluorine and C.sub.1-C.sub.3alkyl; R.sup.10 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.6alkylcyano, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.6-alkenyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.6-alkynyl-, C.sub.1-C.sub.6alkenyloxyC.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl-, C.sub.1-C.sub.6alkylcarbonyl- and C.sub.1-C.sub.6alkylcarbonylC.sub.1-C.sub.6-alkyl-; R.sup.11 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.8cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.6alkylcyano, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.6-alkenyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.6-alkynyl-, C.sub.1-C.sub.6alkenyloxyC.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl-, C.sub.1-C.sub.6alkylcarbonyl-, C.sub.1-C.sub.6alkylcarbonylC.sub.1-C.sub.6-alkyl-; or R.sup.11 is —(CR′R″).sub.n—X.sup.1—R.sup.13 wherein X.sup.1 is a bond, —(CH═CH)— or —(C═O)— and wherein R′ and R″ are independently selected from hydrogen and methyl or together from a C.sub.2-C.sub.3 alkylene chain); or R.sup.10 and R.sup.11 together form a four to six membered heterocycle, the heterocycle comprising one or more heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; the heterocycle being optionally substituted by one or more independent R.sup.12; R.sup.12 is selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.6alkoxy-, nitro, —(CO)OR.sup.14, cyano, phenyl, pyridyl; R.sup.13 is a three- to ten-membered mono- or bicyclic ring system, which may be aromatic, saturated or partially saturated and can contain from 1 to 4 heteroatoms each independently selected from the group consisting of nitrogen, oxygen and sulphur the ring system being optionally substituted by one or more R.sup.12 substituents; R.sup.14 is H or C.sub.1-C.sub.6 alkyl; n=0, 1, 2, 3 or 4; p=0, 1 or 2; and G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or ammonium group; or G is —C(X.sup.a)—R.sup.a, —C(X.sup.b)—X.sup.c—R.sup.b, —C(X.sup.d)—N(R.sup.c)—R.sup.d, —SO.sub.2—R.sup.e, —P(X.sup.e)(R.sup.f)—R.sup.g, —CH.sub.2—X.sup.f—R.sup.h; or phenyl-CH.sub.2— or phenyl-CH(C.sub.1-C.sub.2alkyl)- (in each of which the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or heteroaryl-CH.sub.2— or heteroaryl-CH(C.sub.1-C.sub.2alkyl)- (in each of which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or phenyl-C(O)—CH.sub.2— (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro); or C.sub.1-C.sub.6alkoxy-C(O)—CH.sub.2—, C.sub.1-C.sub.6alkyl-C(O)—CH.sub.2—, C.sub.1-C.sub.6alkoxy-C(O)—CH═CH—, C.sub.2-C.sub.7alken-1-yl-CH.sub.2—, C.sub.2-C.sub.7alken-1-yl-CH(C.sub.1-C.sub.2alkyl)-, C.sub.2-C.sub.4fluoroalken-1-yl-CH.sub.2—, C.sub.2-C.sub.7alkyn-1-yl-CH.sub.2—, or C.sub.2-C.sub.7alkyn-1-yl-CH(C.sub.1-C.sub.2alkyl)-; wherein X.sup.a, X.sup.b, X.sup.c, X.sup.d, X.sup.e and X.sup.f are independently of each other oxygen or sulfur; and wherein R.sup.a is H, C.sub.1-C.sub.21alkyl, C.sub.2-C.sub.21alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy (C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N—(C.sub.1-C.sub.5)alkylcarbonyl-N—(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; R.sup.b is C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl, C.sub.3-C.sub.18alkynyl, C.sub.2-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.2-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N—(C.sub.1-C.sub.5)alkylcarbonyl-N—(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroarylC.sub.1-C.sub.5alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkyl-thio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.3-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; and R.sup.c and R.sup.d are each independently of each other hydrogen, C.sub.1-C.sub.10alkyl, C.sub.3-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl, C.sub.2-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N—(C.sub.1-C.sub.5)alkylcarbonyl-N—(C.sub.2-C.sub.5)alkylaminoalkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or by nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or C.sub.3-C.sub.7cycloalkylamino, di(C.sub.3-C.sub.7cycloalkyl)amino or C.sub.3-C.sub.7cycloalkoxy; or R.sup.c and R.sup.d, together with the nitrogen to which they are bonded, to form an unsubstituted 4, 5, 6 or 7 (e.g. 5 or 6) membered ring, optionally containing one heteroatom selected from O or S; and R.sup.e is C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N—(C.sub.1-C.sub.5)alkylcarbonyl-N—(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or C.sub.3-C.sub.7cycloalkylamino, di(C.sub.3-C.sub.7cycloalkyl)amino, C.sub.3-C.sub.7cycloalkoxy, C.sub.1-C.sub.10alkoxy, C.sub.1-C.sub.10fluoroalkoxy, C.sub.1-C.sub.5alkylamino or di(C.sub.1-C.sub.4alkyl)amino; R.sup.f and R.sup.g are are each independently of each other C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl, C.sub.1-C.sub.10alkoxy, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N—(C.sub.1-C.sub.5)alkylcarbonyl-N—(C.sub.2-C.sub.5)alkylaminoalkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or C.sub.3-C.sub.7cycloalkylamino, di(C.sub.3-C.sub.7cycloalkyl)amino, C.sub.3-C.sub.7cycloalkoxy, C.sub.1-C.sub.10fluoroalkoxy, C.sub.1-C.sub.5alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and phenyl groups are in turn optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; and R.sup.h is C.sub.1-C.sub.10alkyl, C.sub.3-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.2-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N—(C.sub.1-C.sub.5)alkylcarbonyl-N—(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), phenoxy(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), heteroaryloxy(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), C.sub.3-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; C.sub.1-C.sub.6alkyl-C(O)—; or phenyl-C(O)— wherein the phenyl is optionally substituted by 1 or 2 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro; wherein “heteroaryl” means an aromatic ring system containing at least one ring heteroatom and consisting either of a single ring or of two fused rings; and wherein the compound of formula (I) is optionally present as an agrochemically acceptable salt thereof.

2. The compound of claim 1, wherein G is hydrogen.

3. The compound according to claim 1, wherein R.sup.1 is selected from the group consisting of methyl, fluorine, chlorine, bromine, methoxy, difluoromethoxy and trifluoromethoxy.

4. The compound according to claim 1, wherein R.sup.2 is R.sup.2A and R.sup.3 is R.sup.3A and wherein R.sup.2A is selected from the group consisting of methyl, ethynyl and prop-1-ynyl and R.sup.3A is hydrogen or methyl.

5. The compound according to claim 1, wherein R.sup.2 is R.sup.2A and R.sup.3 is R.sup.3A wherein R.sup.3A is hydrogen or methyl, and wherein R.sup.2A is of sub-formula (2Aa): ##STR00642## in which: R.sup.15 is selected from the group consisting of hydrogen, C.sub.1-C.sub.2alkyl, fluorine and chlorine; R.sup.16 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, cyano and nitro; R.sup.17 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, cyano and nitro; and R.sup.18 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, cyano and nitro.

6. The compound according to claim 1, wherein: R.sup.2A is selected from the group consisting of (R.sup.2Ab), (R.sup.2Ac), (R.sup.2Ad), (R.sup.2Ae), (R.sup.2Af), R.sup.2Ag, R.sup.hAh, R.sup.2Ai and R.sup.2Aj: ##STR00643## wherein: R.sup.19 is selected from the group consisting of halogen, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, cyano and nitro; R.sup.20 is selected from the group consisting of hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly fluorine or chlorine), C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, cyano and nitro; and R.sup.21 is selected from the group consisting of hydrogen, halogen (in particular fluorine, chlorine or bromine, more particularly fluorine or chlorine), C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, cyano and nitro; provided that either one or none (i.e. no more than one) of R.sup.19, R.sup.20 and R.sup.21 are C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2alkoxy or nitro; and R.sup.22 is selected from the group consisting of hydrogen, halogen, methyl, C.sub.1fluoroalkyl, C.sub.1fluoroalkoxy and cyano.

7. The compound according to claim 6, wherein R.sup.2 is a monocyclic heteroaryl of sub-formula (2.sup.Ab), and wherein R.sup.19 is fluorine or chlorine, R.sup.20 is hydrogen and R.sup.21 is fluorine.

8. The compound according to claim 1, wherein R.sup.4 is selected from the group consisting of hydrogen, methyl, fluorine, chlorine, methoxy, ethoxy, C.sub.1fluoroalkyl-methoxy- and MeO—CH.sub.2—CH.sub.2—O—.

9. The compound according to claim 1, wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are hydrogen.

10. The compound according to claim 9, wherein R.sup.10 is hydrogen.

11. The compound according to claim 1, wherein R.sup.11 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6-alkyl-, C.sub.1-C.sub.6alkoxy-C.sub.2-C.sub.3-alkoxy-C.sub.2-C.sub.3-alkyl- and —(CH.sub.2).sub.n—X.sup.2—R.sup.13.

12. The compound according to claim 11, wherein R.sup.11 is is —(CH.sub.2).sub.n—X.sup.2—R.sup.13 and wherein R.sup.13 is selected from the group consisting of R.sup.13a to R.sup.13o ##STR00644## ##STR00645## wherein R.sup.12a is selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, halogen, C.sub.1-C.sub.4alkoxy, cyano and nitro; R.sup.12b is selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, halogen, C.sub.1-C.sub.4alkoxy, nitro and phenyl; R.sup.12c is selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, halogen, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy-; R.sup.12d is hydrogen or halogen; R.sup.12e is selected from the group consisting of hydrogen, halogen and C.sub.1-C.sub.2alkyl ; and R.sup.12f is hydrogen or C.sub.1-C.sub.2alkyl.

13. The compound according to claim 1, wherein R.sup.10 and R.sup.11 together form a four to six membered heterocycle, the heterocycle comprising one or more heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur; the heterocycle being optionally substituted by one or more independent R.sup.12.

14. The compound of claim 1, wherein the compound of formula (I) is a compound of formula (Ia): ##STR00646## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and G are as defined therein.

15. A herbicidal composition which comprises: (i) a compound of formula (I), as defined in claim 1, (ii) an agrochemically acceptable carrier, diluent and/or solvent; and (iii) optionally one or more further herbicides and/or optionally a safener.

16. A method of controlling grassy monocotyledonous weeds in crops of useful plants, comprising applying a compound of formula (I), as defined in claim 1, or a herbicidal composition comprising such a compound, to the weeds and/or to the plants and/or to the locus thereof.

Description

PREPARATION EXAMPLES

[0315] Those skilled in the art will appreciate that certain compounds described below are β-ketoenols (beta-ketoenols), and as such may exist as a single tautomer or as a mixture of keto-enol and diketone tautomers, as described, for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons. The compounds shown below, and in Table T1 herein, are generally drawn as an arbitrary single enol tautomer, but it should be inferred that this description covers both the diketone form and any possible enols which could arise through tautomerism. Where more than one tautomer is observed in proton NMR (.sup.1H NMR), the data shown are for the mixture of tautomers. Furthermore, some of the compounds shown below have the possibility of being present in at least two enantiomeric forms; unless drawn as single enantiomers, these compounds will usually be present as a mixture of enantiomers. Additionally, some of the compounds can exist as diastereoisomers, and it should be inferred that these can be present as a mixture of diastereoisomers or as any possible single diastereoisomer. Within the detailed experimental section the diketone tautomer is chosen for naming purposes, even if the predominant tautomer is the enol form.

[0316] Typical Abbreviations:

[0317] DCM—dichloromethane

[0318] DMF—N,N-dimethylformamide

[0319] LDA—lithium diisopropylamide

[0320] Tf—trifluoromethanesulfonate

[0321] THF—tetrahydrofuran

[0322] RT—room temperature (typically ca. 15-30° C. such as ca. 18-25° C.)

[0323] NMR—nuclear magnetic resonance

Example 1

Synthesis of 2-[2,4-dioxo-3-(2,4,6-trimethylphenyl)cyclopentyl]-N-phenethyl-acetamide (Compound A1)

Step 1: Synthesis of ethyl 2-(trifluoromethylsulfonyloxy)acetate

[0324] To a stirred solution of ethyl glycolate (7.1 g, 0.068 mol) in DCM (200 mL) at 0° C. was added pyridine (11.0 mL, 0.136 mol) followed by dropwise addition of trifluoromethane sulfonic anhydride (14.3 mL, 0.085 mol). The reaction was stirred at 0° C. for 3 hours then allowed to warm to room temperature. The reaction was quenched by addition of water (100 mL) and 2M HCl (50 mL). The phases were separated and the aqueous phase extracted with further DCM (2×50 mL). The combined organic extracts were washed with 2M HCl (50 mL), water (50 mL), saturated aqueous NaHCO.sub.3 solution (50 mL) and water (50 mL) then dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product (8.2 g) as a colourless oil which was used without further purification.

[0325] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 4.90 (s, 2H), 4.30 (q, 2H), 1.30 (t, 3H).

Step 2: Synthesis of ethyl 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetate

[0326] To a stirred solution of 3-methoxy-2-(2,4,6-trimethylphenyl)cyclopent-2-en-1-one (3.97 g, 0.0173 mol) in THF (170 mL) at −78° C. under an N.sub.2 atmosphere was added dropwise a solution of LDA (10.0 mL of a 1.8M solution in THF/heptane/ethylbenzene). The reaction was stirred at −78° C. for 1.5 hours then a solution of ethyl 2-(trifluoromethylsulfonyloxy)acetate (4.5 g, 0.019 mol) in THF (25 mL) was added portionwise over 5 minutes. The reaction was stirred at −78° C. for 30 minutes then allowed to warm to room temperature. The reaction was quenched with water (100 mL) and brine (50 mL) then was extracted with EtOAc (3×75 mL). The combined organic extracts were washed with brine (50 mL), dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a yellow oil (5.92 g). The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOAc as eluent to give the desired product (3.83 g, 73%) as a colourless oil.

[0327] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 6.85 (s, 2H), 4.15 (q, 2H), 3.75 (s, 3H), 3.05 (dd, 1H), 3.05-2.95 (m, 2H), 2.60 (dd, 1H), 2.50 (dd, 1H), 2.25 (s, 3H), 2.10 (2×s, 2×3H), 1.25 (t, 3H).

Step 3: Synthesis of 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetic acid

[0328] To a stirred solution of ethyl 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetate (1.08 g, 0.0034 mol) in THF (40 mL) and water (40 mL) was added NaOH (0.273 g, 0.0068 mol). The reaction was stirred at room temperature for 3 hours then diluted with water (40 mL). The reaction pH was adjusted to 3-4 with 2M HCl then extracted with EtOAc (3×50 mL). The combined organic extracts were dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product (0.748 g) as a white solid which was used without further purification.

[0329] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 6.85 (s, 2H), 3.75 (s, 3H), 3.10 (dd, 1H), 3.00-2.90 (m, 2H), 2.60-2.55 (m, 2H), 2.30 (s, 3H), 2.10 (2×s, 2×3H).

Step 4: Synthesis of 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]-N-phenethyl-acetamide

[0330] To a stirred solution of 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetic acid (0.35 g, 0.0012 mol) in DCM (25 mL) was added oxalyl chloride (0.213 mL, 0.0024 mol) followed by 2 drops of NMP (effervescence ensued). The reaction was stirred at room temperature for 3 hours then evaporated to dryness under reduced pressure. The residue was dissolved in DCM (25 mL) and Et.sub.3N (0.75 mL, 0.005 mol) added followed by dropwise addition of phenethylamine (0.525 mL, 0.0042 mol). The reaction was stirred at room temperature for 73 hours then diluted with water (25 mL). The phases were separated and the aqueous phase extracted with DCM (2×25 mL). The combined organic extracts were dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown oil (0.411 g). The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOAc as eluent to give the desired product (0.081 g)

[0331] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.30-7.15 (m, 5H), 6.85 (s, 2H), 6.35 (br, 1H), 3.80 (s, 3H), 3.55-3.45 (m, 1H), 3.40-3.35 (m, 1H), 3.05 (dd, 1H), 2.95-2.90 (m, 1H), 2.80-2.70 (m, 4H), 2.35 (dd, 1H), 2.25 (s, 3H), 2.10 (s, 3H), 2.05 (s, 3H).

Step 5: Synthesis of 2-[2,4-dioxo-3-(2,4,6-trimethylphenyl)cyclopentyl]-N-phenethyl-acetamide

[0332] A solution of 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]-N-phenethyl-acetamide (0.064 g, 0.00016 mol) in acetone (2 mL) and 2M HCl (2 mL) was added to a microwave vial, capped and heated at 50° C. for 10 minutes under microwave irradiation followed by further heating at 100° C. for 5 minutes under microwave irradiation. The reaction was diluted with water (20 mL) and extracted with EtOAc (3×10 mL). The combined organic extracts were washed with brine (10 mL), dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOAc as eluent to give the desired product as an off-white solid (0.034 g).

[0333] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.35-7.30 (m, 2H), 7.25 (m, 1H), 7.20 (d, 2H), 6.85 (s, 6H), 6.05 (br, 1H), 3.60 (m, 2H), 3.25 (m, 1H), 2.90-2.80 (m, 3H), 2.65 (d, 2H), 2.25 (s, 3H), 2.20 (dd, 1H), 2.10 (2×s, 2×3H).

Example 2

Synthesis of N-tert-butyl-2-[2,4-dioxo-3-(2,4,6-trimethylphenyl)cyclopentyl]-acetamide (Compound A2).

Step 1: Synthesis of N-tert-butyl-2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetamide

[0334] To a solution of 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetic acid (0.15 g, 0.00052 mol) in DMF (5 mL) were added t-butylamine (0.047 g, 0.00062 mol), 1-propane phosphonic anhydride (50 mass % solution in EtOAc) (0.50 g, 0.00078 mol) and 4-dimethylaminopyridine (0.064 g, 0.00052 mol). The reaction was stirred at room temperature for 24 hours then diluted with Et.sub.2O and washed with brine (×3). The organic phase was dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give an orange gum (161 mg). The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.087 g, 47%).

[0335] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.86(s, 2H), 6.03(br, 1H), 3.77(s, 3H), 3.10(dd, 1H), 2.99-2.91(m, 1H), 2.78(dd, 1H), 2.71(dd, 1H), 2.33-2.29(m, 1H), 2.26(s, 3H), 2.20-2.04(m, 6H), 1.33(s, 9H).

Step 2: Synthesis of N-tert-butyl-2-[2,4-dioxo-3-(2,4,6-trimethylphenyl)cyclopentyl]acetamide

[0336] A suspension of N-tert-butyl-2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]acetamide (0.087 g, 0.00025 mol) in morpholine (1 mL) was heated at 100° C. for six hours. The reaction was evaporated to dryness under reduced pressure and the residue partitioned between 2M HCl and DCM. The aqueous phase was extracted with DCM (×2) and the combined organic extracts washed with water and brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a pale yellow gum. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc to give the desired product (0.019 g, 23%) as a white powder.

[0337] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 6.87(s, 2H), 5.83(s, 1H), 3.32-3.23(m, 1H), 2.93-2.83(m, 1H), 2.72-2.58(m, 2H), 2.25(s, 3H), 2.24-2.14(m, 1H), 2.11(s, 6H), 1.38(s, 9H).

Example 3

Synthesis of 2-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-cyclopentyl]-N-isopropyl-acetamide (Compound A8)

Step 1: Synthesis of ethyl 2-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate

[0338] A microwave vial was charged with ethyl 2-[3-(4-bromo-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0.20 g, 0.0005 mol), cesium fluoride (0.159 g, 0.00105 mmol), Cu(I)I (0.02 g, 0.000105 mmol), PdCl2(dppf) (0.058 g, 0.00008 mol) and DMF (2 mL). The vial was capped, evacuated and purged with nitrogen. Tributyl(prop-1-ynyl)stannane (0.52 g, 0.0016 mol) was then added and the reaction mixture heated at 120° C. under microwave irradiation for 1 hour. The reaction mixture was diluted with water and extracted with ethyl acetate (×3). The combined organic extracts were washed with water and brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown gum. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc to give the desired product (0.168 g, 94%) as an orange gum.

[0339] 1H NMR δ ppm 7.08(s, 2H), 4.16(q, 2H), 3.72(s, 3H), 3.11-3.02(m, 1H), 3.01-2.93(m, 2H), 2.63-2.55(m, 1H), 2.54-2.43(m, 1H), 2.09(d, 6H), 2.02(s, 3H), 1.26(t, 3H).

Step 2: Synthesis of 2-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid

[0340] To a solution of ethyl 2-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0.168 g, 0.00049 mol) in THF (1.7 mL) was added a solution of lithium hydroxide monohydrate (0.041 g, 0.00099 mol) in water (1.7 mL). The reaction mixture was allowed to stir at room temperature overnight then diluted with water and the pH adjusted to ˜4 with 2M HCl. The reaction was then extracted with ethyl acetate (×3) and the combined organic extracts washed with water, then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product (0.153 g, 99%) as a brown gum which was used without further purification.

[0341] .sup.1H NMR (CDCl.sub.3) δ ppm 7.08(s, 2H), 3.74(s, 3H), 3.15-2.83(m, 3H), 2.70-2.52(m, 2H), 2.11(s, 3H), 2.07(s, 3H), 2.03(s, 3H).

Step 3: Synthesis of 2-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-2,4-dioxo-cyclopentyl]-N-isopropyl-acetamide

[0342] To a solution of 2-[3-(2,6-dimethyl-4-prop-1-ynyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid (0.153 g, 0.0004898 mol) in DMF (2 mL) was added 1-propanephosponic anhydride (50 mass % solution in EtOAc) (0.44 mL, 0.001469 mmol), isopropylamine (0.083 mL, 0.00098 mol) and 4-dimethylaminopyridine (0.06 g, 0.00049 mol). The reaction was stirred at room temperature overnight and then evaporated to dryness under reduced pressure to give a brown solid.

[0343] The crude intermediate enol ether was dissolved in morpholine (2 mL) and heated at 100° C. for 3 hrs and then evaporated to dryness under reduced pressure to give an orange syrup. The crude product was diluted with 2M HCl and extracted with EtOAc (×3). The combined organic extracts were washed with water, then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a pale yellow gum (0.25 g). The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give an off-white powder (88 mg) which was triturated with Et.sub.2O to give the desired product (0.04 g, 24%) as a white powder.

[0344] .sup.1H NMR (d4-MeOH) δ ppm 7.03(s, 2H), 3.98(m, 1H), 3.19-3.10(m, 1H), 2.87(dd, 1H), 2.71(dd, 1H), 2.47-2.34(m, 2H), 2.06(s, 6H), 1.99(s, 3H), 1.14(dd, 6H)

Example 4

Synthesis of 2-[3-(4-ethynyl-2,6-dimethyl-phenyl)-2,4-dioxo-cyclopentyl]-N-sec-butyl-acetamide (Compound A9)

Step 1: Synthesis of ethyl 2-[3-[2,6-dimethyl-4-(2-trimethylsilylethynyl)phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate

[0345] A solution of ethyl 2-[3-(4-bromo-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (2.0 g, 0.0052 mol) in degassed toluene (40 mL) was divided equally into four microwave vials. To each vial was added palladium(0) tetrakis(triphenylphosphine) (0.045 g, 0.00004 mol per vial/0.182 g, 0.0001574 mol in total). The vials were capped then evacuated and purged with nitrogen. To each vial was added tributyl(trimethylsilylethynyl)tin (0.635 g, 0.0016 mol per vial/2.54 g, 0.0065 mol in total) was added to each vial and they were each heated at 130° C. under microwave irradiation for 30 mins. The reactions were combined, poured into water and extracted with ethyl acetate (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown oil (6.0 g). The crude product was purified by flash chromatography on silica using a gradient of 5-100% ethyl acetate in isohexane as eluent to give the desired product (1.99 g, 95%) as a yellow oil.

[0346] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.17(s, 2H), 4.16(q, 2H), 3.71(s, 3H), 3.11-3.02(m, 1H), 3.02-2.92(m, 2H), 2.63-2.55(m, 1H), 2.56-2.47(m, 1H), 2.10(s, 6H), 1.28(t, 3H), 0.22(s, 9H).

Step 2: Synthesis of 2-[3-(4-ethynyl-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid

[0347] To a stirred solution of ethyl 2-[3-[2,6-dimethyl-4-(2-trimethylsilylethynyl)phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0. 50 g, 0.001254 mol) in THF (5 mL) was added a solution of lithium hydroxide monohydrate (0.105 g, 0.0025 mol) in water (5 mL). The reaction was stirred at room temperature overnight then diluted with water and then the pH adjusted to ˜4 with 2M HCl. The reaction mixture was then extracted with ethyl acetate (×3). The combined organic extracts were, washed with water, then brine, dried over MgSO4 and evaporated to dryness under reduced pressure to give the desired product (0.391 g, quant) which was used without further purification.

[0348] .sup.1H NMR (400 MHz, CDCl3) δ ppm 7.18(s, 2H), 3.76(s, 1H), 3.44(s, 3H), 3.14-2.82(m, 3H), 2.70-2.40(m, 2H), 2.12(s, 6H).

Step 3: Synthesis of 2-[3-(4-ethynyl-2,6-dimethyl-phenyl)-2,4-dioxo-cyclopentyl]-N-sec-butyl-acetamide

[0349] To a solution of 2-[3-(4-ethynyl-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid (0.391 g, 0.0013 mol) in DMF (2 mL) was added 1-propanephosponic anhydride (50 mass % solution in EtOAc) (1.17 mL, 0.0039 mmol), sec-butylamine (0.192 g, 0.00262 mol) and 4-dimethylaminopyridine (0.160 g, 0.00131 mol). The reaction was stirred at room temperature overnight then evaporated to dryness under reduced pressure. To the residue was added morpholine (2 mL) and the reaction heated to 100° C. for 3 hours. The reaction was evaporated to dryness under reduced pressure to give a brown syrup. To this residue was added 2M HCl then extracted with DCM (×3). The combined organic extracts were washed with water, then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown gum (0.506 g). The crude product was purified by flash chromatography on silica using a 5% EtOAc in isohexane to 100% EtOAc gradient as eluent followed by mass-directed HPLC to give the desired product (0.108 g, 24%) as an off white solid.

[0350] .sup.1H NMR (400 MHz, d.sub.4-MeOH) δ ppm 7.14(s, 2H), 3.81(q, 1H), 3.38(s, 1H), 3.21-3.11(m, 1H), 2.93-2.85(m, 1H), 2.78-2.69(m, 1H), 2.50-2.38(m, 2H), 2.09(s, 6H), 1.56-1.42(m, 2H), 1.22(d, 3H), 0.96-0.87(m, 3H).

Example 5

Synthesis of 2-[3-[4-(4-fluorophenyl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]-N-isopropyl-acetamide (Compound A34)

Step 1: Synthesis of ethyl 2-[3-[4-(4-fluorophenyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate

[0351] A microwave vial was charged with ethyl 2-[3-(4-bromo-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0.50 g, 0.0013 mol), cesium fluoride (0.598 g, 0.00393 mol), PdCl.sub.2(dppf) (0.096 g, 0.00013 mol), 4-fluorophenyl boronic acid (0.257 g, 0.00184 mol) and degassed 1,2-dimethoxyethane (4 mL). The vial was capped, evacuated and purged with nitrogen and then the reaction heated at 160° C. under microwave irradiation for 40 minutes. The reaction mixture was evaporated to dryness under reduced pressure and the crude product purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.38 g, 73%) as a pale orange solid.

[0352] 1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.55-7.48(m, 2H), 7.22(s, 2H), 7.12-7.05(m, 2H), 4.18(q, 2H), 3.80(s, 3H), 3.17-3.06(m, 1H), 3.06-2.95(m, 2H), 2.64(dd, 1H), 2.58-2.48(m, 1H), 2.19(s, 6H), 1.29(t, 3H).

Step 2: Synthesis of 2-[3-[4-(4-fluorophenyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid

[0353] To a stirred solution of ethyl 2-[3-[4-(4-fluorophenyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0.35 g, 0.00088 mol) in THF (3.5 mL) was added a solution of lithium hydroxide (0.085 g, 0.0035 mol). The reaction was stirred at room temperature for 2 hrs then poured into water, acidified with 2M HCl and extracted with DCM (×3). The combined organic extracts were washed with water, then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product (0.378 g, quant) as a pale yellow solid.

[0354] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.55-7.47(m, 2H), 7.22(s, 2H), 7.09(t, 2H), 3.81(s, 3H), 3.19-3.10(m, 1H), 3.10-2.94(m, 2H), 2.71-2.60(m, 2H), 2.19(d, 6H).

Step 3: Synthesis of 2-[3-[4-(4-fluorophenyl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]-N-isopropyl-acetamide

[0355] To a solution of 2-[3-[4-(4-fluorophenyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid (0.189 g, 0.000513 mol) in DMF (2 mL) was added 1-propanephosponic anhydride (50 mass % solution in EtOAc) (0.46 mL, 0.00154 mmol), isopropylamine (0.087 mL, 0.00103 mol) and 4-dimethylaminopyridine (0.063 g, 0.000513 mol). The reaction was stirred at room temperature overnight then evaporated to dryness under reduced pressure. To the residue was added morpholine (2 mL) and the reaction heated to 100° C. for 4 hours. The reaction was evaporated to dryness under reduced pressure to give a brown syrup. To this residue was added 2M HCl then extracted with EtOAc (×3). The combined organic extracts were washed with water, then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by mass-directed HPLC to give the desired product (0.077 g, 38%) as an off white solid.

[0356] .sup.1H NMR (400 MHz, d4-MeOH) δ ppm 7.62-7.57(m, 2H), 7.27(s, 2H), 7.13(t, 2H), 3.99(m, 1H), 3.22-3.12(m, 1H), 2.94-2.85(m, 1H), 2.77-2.70(m, 1H), 2.49-2.38(m, 2H), 2.17(s, 6H), 1.19-1.12(m, 6H).

Example 6

Synthesis of N-tert-butyl-2-[3-[4-(5-chloro-3-fluoro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (Compound A39)

Step 1: Synthesis of ethyl 2-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate

[0357] Two microwave vials were charged with equal portions of ethyl 2-[3-(4-bromo-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (1.20 g, 0.0031 mol), bis(pinacolato)diboron (1.20 g, 0.0047 mol), tris(dibenzylideneacetone)dipalladium(0) (0.12 g, 0.00013 mol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.21 g, 0.0005 mol), potassium acetate (0.46 g, 0.0047 mol) and 1,4-dioxane (24 mL). The vials were capped, evacuated and purged with nitrogen and heated at 150° C. under microwave irradiation for 15 minutes. The reactions were combined, evaporated to dryness under reduced pressure and the residue purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product as (1.40 g,) an orange oil.

[0358] .sup.1H NMR (400 MHz CDCl.sub.3) δ ppm 7.49(s, 2H), 4.17(q, 2H), 3.69(s, 3H), 3.12-3.02(m, 1H), 3.02-2.92(m, 2H), 2.62-2.54(m, 1H), 2.54-2.44(m, 1H), 2.13(d, 6H), 1.33(s, 12H), 1.25(t, 3H).

Step 2: Synthesis of ethyl 2-[3-[4-(5-chloro-3-fluoro-2-pyridyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate

[0359] A microwave vial was charged with ethyl 2-[3-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0.20 g, 0.00047 mol), 2-bromo-5-chloro-3-fluoro-pyridine (0.147 g, 0.0007 mol) and PdCl.sub.2(dppf) (0.068 g, 0.000093 mmol), 1,2-dimethoxyethane (degassed) (3.2 mL) and a solution of tripotassium phosphate (0.397 g, 0.00187 mol) in water (0.8 mL). The vial was capped then evacuated and purged with nitrogen and the reaction heated at 130° C. under microwave irradiation for 30 minutes. The reaction mixture was diluted with water and EtOAc and then filtered through celite. The phases of the filtrate were separated and the aqueous extracted with EtOAc (×2). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown gum. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc to give the desired product (0.131 g) as a brown gum (131 mg),

[0360] .sup.1H NMR (400 MHz, CDCl3) δ ppm 8.47(s, 1H), 7.62(s, 2H), 7.51(d, 1H), 4.18(q, 2H), 3.76(s, 3H), 3.14-2.94(m, 3H), 2.68-2.45(m, 2H), 2.22(s, 6H), 1.28(t, 3H).

Step 3: Synthesis of 2-[3-[4-(5-chloro-3-fluoro-2-pyridyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid

[0361] To a stirred solution of ethyl 2-[3-[4-(5-chloro-3-fluoro-2-pyridyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (0.131 g, 0.00033 mol) in THF (1.3 mL) and water (2.6 mL) was added lithium hydroxide (0.029 g, 0.0012 mol). The reaction was stirred at room temperature overnight then diluted with water and the pH adjusted to 5 with 2M HCl. The reaction was extracted with ethyl acetate (×3) and the combined organic extracts dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product (0.081 g) as a brown gum which was used without further purification.

[0362] .sup.1H NMR (400 MHz, d4-MeOH) δ ppm 8.39(s, 1H), 7.53(d, 1H), 7.47(s, 2H), 3.69(s, 3H), 3.16-3.04(m, 1H), 2.93-2.79(m, 1H), 2.79-2.66(m, 2H), 2.38-2.25(m, 1H), 2.16(s, 3H), 2.09(s, 3H).

Step 4: Synthesis of N-tert-butyl-2-[3-[4-(5-chloro-3-fluoro-2-pyridyl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide

[0363] To a solution of 2-[3-[4-(5-chloro-3-fluoro-2-pyridyl)-2,6-dimethyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetic acid (0.189 g, 0.000513 mol) in DMF (2 mL) was added 1-propanephosponic anhydride (50 mass % solution in EtOAc) (0.38 mL, 0.00064 mmol), t-butylamine (0.045 mL, 0.00042 mol) and 4-dimethylaminopyridine (0.027 g, 0.00021 mol). The reaction was stirred at room temperature overnight then evaporated to dryness under reduced pressure. The residue was diluted with water and the pH was adjusted to 5 with saturated aqueous sodium hydrogen carbonate solution then extracted with EtOAc (×3). The combined organic extracts were , washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown gum. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.030 g, 32%) as a brown gum.

[0364] .sup.1H NMR (400 MHz d4-MeOH) δ ppm 8.46(s, 1H), 7.85(br.s, 1H), 7.81(d, 1H), 7.59(s, 2H), 3.21-3.12(m, 1H), 2.99-2.83(m, 1H), 2.74-2.68(m, 1H), 2.50-2.39(m, 2H), 2.19(s, 6H), 1.34(s, 9H).

Example 7

Synthesis of N-tert-butyl-2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (Compound A67)

Step 1: Synthesis of ethyl 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetate

[0365] To a solution of ethyl 2-[3-(4-bromo-2,6-dimethyl-phenyl)-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetate (6.6 g, 0.017 mol) in DMF (130 mL) was added 4-chloropyrazole (3.5 g, 0.035 mol), CuI (6.6 g, 0.035 mol), dimethyl glycine (7.1 g, 0.069 mol) and potassium carbonate (6.9 g, 0.069 mol). The reaction was evacuated and purged with nitrogen three times then heated at 140° C. overnight. The reaction was allowed to cool to room temperature then diluted with water and the pH was adjusted to 4 with 2M HCl. The reaction mixture was extracted with Et.sub.2OAc (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown oil. The residue was dissolved in acetone (260 mL) and potassium carbonate (17.9 g, 0.129 mol) and methyl iodide (26.8 mL, 0.431 mol) were added. The reaction was stirred at room temperature for two hours then evaporated to dryness under reduced pressure. The residue was diluted with water and extracted with EtOAc (×3). The combined organic extracts were dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a brown solid. The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (3.12 g, 46%) as a pale orange solid.

[0366] .sup.1H NMR (400 MHz, d4-MeOH) δ ppm 8.34(s, 1H), 7.68(s, 1H), 7.46(s, 2H), 4.18(q, 2H), 3.13-3.03(m, 1H), 3.03-2.95(m, 1H), 2.92-2.81(m, 1H), 2.69-2.53(m, 2H), 2.20(s, 6H), 1.28(t, 3H)

Step 2: Synthesis of 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetic acid

[0367] To a stirred solution of 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetate (3.12 g, 0.00802 mol) in THF (31 mL) and water (31 mL) was added lithium hydroxide monohydrate (0.673 g, 0.016 mmol) and the reaction stirred at room temperature overnight. The reaction mixture pH was adjusted to ˜5 with 2M HCl then extracted with EtOAc (×3). The combined organic extracts were washed with water then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product (3.1 g, quant) as a pale yellow crushed foam which was used without further purification.

[0368] .sup.1H NMR (400 MHz, d4-MeOH) δ ppm 8.31(s, 1H), 7.64(s, 1H), 7.42(s, 2H), 3.10-3.02(m, 1H), 3.02-2.92(m, 1H), 2.89-2.80(m, 1H), 2.63-2.50(m, 2H), 2.18(s, 6H).

Step 3: Synthesis of N-tert-butyl-2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide

[0369] To a solution of 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetic acid (0.17 g, 0.00047 mol) in DMF (2 mL) was added 1-propanephosponic anhydride (50 mass % solution in EtOAc) (0.42 mL, 0.00141 mol), t-butylamine (0.10 mL, 0.00094 mol) and 4-dimethylaminopyridine (0.058 g, 0.000471 mol) and the reaction stirred at room temperature overnight. The reaction mixture was diluted with water and the pH adjusted to 5 with 2M HCl. It was then extracted with Et.sub.2O (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a yellow gum. The crude product was purified by flash chromatography on silica using a gradient of 50% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (0.098 g, 50%) as a white crushed foam.

[0370] .sup.1H NMR (400 MHz, d4-MeOH) δ 8.33(s, 1H), 7.67(s, 1H), 7.44(s, 2H), 3.23-3.12(m, 1H), 2.98-2.85(m, 1H), 2.76-2.65(m, 1H), 2.52-2.38(m, 2H), 2.20(s, 6H), 1.38(s, 9H).

Example 8

Synthesis of 2-[2,4-dioxo-3-(2,4,6-trimethylphenyl)cyclopentyl]-N-[[3-(trifluoromethyl)phenyl]methyl]acetamide (Compound A93)

Step 1: Synthesis of ethyl 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]acetate

[0371] To a stirred solution of 3-methoxy-2-(2,4,6-trimethylphenyl)cyclopent-2-en-1-one (8.31 g, 0.0361 mol) in THF (70 mL) at −78° C. under a nitrogen atmosphere was added dropwise lithium bis(trimethylsilyl)amide (1M in THF) (39.7 mL, 0.0397 mol) was added dropwise maintaining temperature at <−60° C. Once addition was complete the reaction mixture was warmed to 0° C. (ice bath) and allowed to stir at this temperature for 1.5 hrs. The reaction was then cooled to −78° C. and a solution of ethyl 2-(trifluoromethylsulfonyloxy)acetate (9.54 g, 0.0404 mmol) in THF (15 ml) was added dropwise maintaining temperature at <−60° C. Once addition was complete the reaction mixture was allowed to warm to 0° C. and stir at this temperature for 2 hrs. The reaction mixture was quenched with water. The organic solvent was removed under reduced pressure and the residue was extracted with ethyl acetate (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give an orange oil (14.5 g). The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (11.8 g, quant) as an orange oil.

[0372] .sup.1H NMR (400 MHz, CDCl3) δ ppm 6.84 (2H, s), 4.18 (2H, q), 3.52 (3H, s), 3.37-3.29 (1H, m), 2.91-2.80 (2H, m), 2.49-2.41 (1H, m), 2.33 (1H, d), 2.00(6H, s), 1.28 (3H, t).

Step 2: Synthesis of 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]acetic acid

[0373] To a solution of ethyl 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]acetate (1.0 g, 0.0032 mol) in EtOH (7.5 mL) was added a suspension of tetrabutylammonium hydroxide (2.46 g, 0.0095 mol) in water (2.5 mL). This reaction was stirred at room temperature for 2.5 hrs then diluted with water, acidified with 2M HCl and extracted with EtOAc (×3). The combined organic extracts were washed with water, then brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the desired product as an orange solid (804 mg) which was used without further purification.

[0374] .sup.1H NMR (400 MHz, d4MeOH) δ ppm 6.88 (2H, s), 3.54(3H, s), 3.39-3.27 (1H, m), 2.88-2.77 (2H, m), 2.58-2.50 (1H, m), 2.39 (1H, dd), 2.15 (3H, s), 2.09 (6H, s).

Step 3: Synthesis of (2,3,4,5,6-pentafluorophenyl) 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]acetate

[0375] To a stirred solution of 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]acetic acid (8.94 g, 0.031 mol) in DCM (110 mL) was added 2,3,4,5,6-pentafluorophenol (7.13 g, 0.039 mmol) followed by 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (7.43 g, 0.039 mmol). This reaction mixture was stirred at room temperature for 72 hours then the solvent removed under reduced pressure. The residue was diluted with water and extracted with EtOAc (×3). The combined organic extracts were washed with saturated aqueous NaHCO.sub.3, then water and brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give a dark orange oil (35 g). The crude product was purified by flash chromatography on silica using a gradient of 5% EtOAc in isohexane to 100% EtOAc as eluent to give the desired product (12.39 g) as an orange oil.

[0376] .sup.1H NMR (400 MHz, CDCl3) δ ppm 6.84 (2H, s), 3.55 (3H, s), 3.52-3.43 (1H, m), 3.18(1H, dd), 2.99-2.84 (2H, m), 2.42 (1H, dd), 2.25 (3H, s), 2.11 (6H, s).

Step 4: Synthesis of 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]-N-[[3-(trifluoromethyl)phenyl]methyl]acetamide

[0377] To a stirred solution of (2,3,4,5,6-pentafluorophenyl) 2-[2-methoxy-4-oxo-3-(2,4,6-trimethylphenyl)cyclopent-2-en-1-yl]acetate (1.00 g, 0.0022 mol) in DCM (10 mL) was added the [3-(trifluoromethyl)phenyl]methanamine (0.463 g, 0.002.64 mmol) followed by the N,N-diethylethanamine (0.767 mL, 0.0055 mol). The reaction was stirred overnight at room temperature then evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOAc to give the desired product (0.680 g).

[0378] .sup.1H NMR (400 MHz, CDCl3) δ ppm 7.60-7.45 (m, 4H), 6.85 (s, 2H), 5.95 (br, 1H), 4.55 (dd, 1H), 4.45 (dd, 1H), 3.50 (s, 3H), 3.50-3.40 (m, 1H), 2.90-2.80 (m, 2H), 2.35-2.25 (m, 2H), 2.25 (s, 3H), 2.05 (2×s, 2×3H).

Step 5: Synthesis of 2-[2,4-dioxo-3-(2,4,6-trimethylphenyl)cyclopentyl]-N-[[3-(trifluoromethyl)phenyl]methyl]acetamide

[0379] To a stirred solution of 2-[4-methoxy-2-oxo-3-(2,4,6-trimethylphenyl)cyclopent-3-en-1-yl]-N-[[3-(trifluoromethyl)phenyl]methyl]acetamide (0.680 g, 0.00153 mol,) in acetone (15 mL) was added 2M HCl (10 mL). The reaction was heated at 70° C. for 1 hour then organic solvent was removed under reduced pressure. The aqueous residue was extracted with DCM and the organic extract evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica using a gradient of 100% isohexane to 100% EtOAc as eluent to give the desired product (0.363 g) as a white solid.

[0380] .sup.1H NMR (400 MHz, d4-MeOH) δ ppm 8.70 (br, 1H), 7.55-7.45 (m, 4H), 6.85 (s, 2H), 4.45 (s, 2H), 3.20-3.10 (m, 1H), 2.90-2.75 (m, 2H), 2.50-2.35 (m, 2H), 2.25 (s, 3H), 2.05 (2×s, 2×3H).

Example 9

Synthesis of [4-[2-(tert-butylamino)-2-oxo-ethyl]-2-[4-(5-chloropyrimidin-2-yl)-2,6-dimethyl-phenyl]-3-oxo-cyclopenten-1-yl] 4-methoxybenzoate (compound P1)

Step 1: Synthesis of [4-[2-(tert-butylamino)-2-oxo-ethyl]-2-[4-(5-chloropyrimidin-2-yl)-2,6-dimethyl-phenyl]-3-oxo-cyclopenten-1-yl] 4-methoxybenzoate

[0381] To a stirred solution of N-tert-butyl-2-[3-[4-(5-chloropyrimidin-2-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (0.15 g, 0.3505 mmol) in DCM was added triethylamine (0.054 ml, 0.351 mmol) and 4-methoxybenzoyl chloride (0.066 g, 0.386 mmol). The reaction was stirred at room temperature for 2 hours then evaporated to dryness under reduced pressure. The crude material was purified by flash chromatography on silica using a gradient of 5% EtOAc/isohexane to 100% EtOAc as eluent to give the desired product (0.163 g, 83%) as a white solid.

[0382] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.70 (s, 2H), 8.09 (s, 2H), 7.83 (d, 2H), 6.86 (d, 2H), 5.91 (s, 1H), 3.80 (s, 3H), 3.53 (dd, 1H), 3.28-3.14 (m, 2H), 2.79 (dd, 1H), 2.48-2.39 (m, 1H), 2.27 (d, 6H), 1.33 (s, 9H)

Example 10

Synthesis of tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-ethynyl-6-methyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (compound B381)

Step 1: Synthesis of 2,4-dibromo-6-methyl-phenyl)-(2-furyl)methanol

[0383] To a solution of 1,5-dibromo-2-iodo-3-methyl-benzene (5.00 g, 13.30 mmol) in dry tetrahydrofuran (27 mL) under N.sub.2 at −78° C. was added dropwise a solution of isopropylmagnesium chloride lithium chloride complex (1.12 mol/L in THF 15.57 mmol) over a period of 90 mins, maintaining the temperature below −78° C. The reaction was stirred for 30 min and a solution of furan-2-carbaldehyde (15.30 mmol) in tetrahydrofuran (6 mL) was then added dropwise over 15 mins. The mixture was stirred cold for a further 30 mins, allowed to warm to room temperature and stirred for 1 hour. The mixture was added into saturated NH.sub.4Cl(aq) and this mixture was extracted with ethyl acetate. The combined ethyl acetate layers were dried (MgSO4) and concentrated under reduced pressure. The residue was purified by flash chromatography on silica using a gradient of 100% isohexane to 20% EtOAc/isohexane as eluent to give (2,4-dibromo-6-methyl-phenyl)-(2-furyl)methanol (2.838 g, 62% yield).

[0384] 1H NMR (400 MHz, CDCl.sub.3) 7.64-7.54 (m, 1H), 7.43-7.38 (m, 1H), 7.31 (d, 1H), 6.46 (d, 1H), 6.35-6.31 (m, 1H), 6.09-6.03 (m, 1H), 2.78 (d, 1H), 2.43-2.38 (m, 3H)

Step 2: Synthesis of 2-(2,4-dibromo-6-methyl-phenyl)-3-methoxy-cyclopent-2-en-1-one

[0385] (2,4-dibromo-6-methyl-phenyl)-(2-furyl)methanol (2.830 g, 6.543 mmol) was dissolved in N,N-dimethylacetamide (28 mL, 300 mmol). 4-methylbenzenesulfonic acid hydrate (3.952 mmol) was added and the mixture was heated under reflux for 4 h, then cooled to 0° C. After the addition of potassium carbonate (19.63 mmol) and methyl iodide (3.0 equiv., 19.63 mmol), the mixture was allowed to warm to room temperature and stirred overnight. The mixture was poured into 2M HCl(aq) (200 mL), then partitioned with ethyl acetate (100 mL). The phases were separated and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were washed sequentially with 2M HCl(aq) (2×100 mL) and brine (100 mL). The organic layer was dried (MgSO4) and concentrated under reduced pressure. The residue was purified by flash chromatography on silica using a gradient of 10% EtOAc/isohexane to 100% EtOAc as eluent to give 2-(2,4-dibromo-6-methyl-phenyl)-3-methoxy-cyclopent-2-en-1-one (1.462 g, 62% yield).

[0386] 1H NMR (400 MHz, CDCl.sub.3) 7.61 (d, 1H), 7.37-7.28 (m, 1H), 3.82-3.71 (m, 3H), 2.88-2.76 (m, 2H), 2.69-2.57 (m, 2H), 2.18 (s, 3H)

Step 3: Synthesis of 2-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-3-methoxy-cyclopent-2-en-1-one

[0387] To a solution of 2-(2,4-dibromo-6-methyl-phenyl)-3-methoxy-cyclopent-2-en-1-one (0.150 g, 0.417 mmol) in N,N-dimethylformamide (5 L/mol) was added tributyl-(3,5-difluoro-2-pyridyl)stannane (0.625 mmol) followed by cesium fluoride (0.833 mmol) and cuprous hydroiodide (0.0417 mmol). After degassing with nitrogen, the Palladium (dppf) dichloride (0.0208 mmol) was added and the mixture heated in the microwave for 30 mins at 130° C. The reaction was diluted with EtOAc, filtered and concentrated in vacuo. The resulting residue was purified by flash chromatography on silica using a gradient of 5% EtOAc/isohexane to 100% EtOAc/isohexane as eluent to give 2-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-3-methoxy-cyclopent-2-en-1-one (0.066 g, 40% yield)

[0388] 1H NMR (400 MHz, CDCl.sub.3) 8.46-8.39 (m, 1H), 7.75 (s, 1H), 7.35-7.30 (m, 1H), 3.82-3.78 (m, 3H), 2.85-2.76 (m, 2H), 2.69-2.58 (m, 2H), 2.32-2.25 (m, 3H)

Step 4: Synthesis of 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetonitrile

[0389] 2-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-3-methoxy-cyclopent-2-en-1-one (0.400 g, 1.01 mmol) was dissolved in tetrahydrofuran (30 mL/g) and cooled to −70° C. Lithium bis(trimethylsilyl)amide (1M in THF, 1.12 mmol) was added dropwise, and stirred for 1 hour. 2-Bromoacetonitrile (1.14 mmol) was then added dropwise and after stirring for 30 mins, the reaction mixture was allowed to warm to 0° C. and was stirred for a further 1 hr. The reaction mixture was quenched with 0.5M NH.sub.4Cl and extracted with ethyl acetate. The organic layer was combined, washed with brine, dried (MgSO4) and concentrated. The resulting residue was purified by flash chromatography on silica using a gradient of 5% EtOAc/isohexane to 100% EtOAc as eluent to give 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetonitrile (0.104 g, 24% yield) and 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetonitrile (0.230 g, 52% yield).

[0390] 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-4-methoxy-2-oxo-cyclopent-3-en-1-yl]acetonitrile: 1H NMR (400 MHz, CDCl.sub.3) 8.48-8.41 (m, 1H), 8.04 (s, 1H), 7.84-7.74 (m, 1H), 7.37-7.26 (m, 1H), 3.74-3.66 (m, 3H), 3.00-2.76 (m, 2H), 2.55-2.48 (m, 2H), 2.43-2.37 (m, 3H), 2.32-2.20 (m, 1H). 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetonitrile: 1H NMR (400 MHz, CDCl.sub.3) 8.48-8.41 (m, 1H), 8.04 (s, 1H), 7.84-7.74 (m, 1H), 7.37-7.26 (m, 1H), 3.74-3.66 (m, 3H), 3.00-2.76 (m, 2H), 2.55-2.48 (m, 2H), 2.43-2.37 (m, 3H), 2.32-2.20 (m, 1H)

Step 5: Synthesis of 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]-N-tert-butyl-acetamide

[0391] The 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetonitrile (0.500 g, 1.15 mmol) was suspended in tert-butyl acetate (5.00 mL, 37.1 mmol) and sulfuric acid (0.3 mL, 6 mmol) was added. The reaction mixture was heated at 45° C. for 5 h 30 mins, allowed to cool to room temperature then diluted with saturated sodium bicarbonate solution and extracted with EtOAc. The organic layer was dried and concentrated in vacuo and purified by flash chromatography on silica using a 5% MeOH/DCM eluant to give 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]-N-tert-butyl-acetamide (0.558 g, 95% yield)

[0392] 1H NMR (400 MHz, CDCl.sub.3) 8.46-8.40 (m, 1H), 8.06-8.00 (m, 1H), 7.76 (s, 1H), 7.37-7.27 (m, 1H), 3.66-3.61 (m, 3H), 3.51-3.41 (m, 1H), 2.92-2.76 (m, 2H), 2.33-2.26 (m, 4H), 2.22-2.14 (m, 1H), 1.40-1.35 (m, 9H).

Step 6: Synthesis of N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-(2-trimethylsilylethynyl)phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetamide

[0393] 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]-N-tert-butyl-acetamide (0.294 g, 0.579 mmol), trimethyl(2-tributylstannylethynyl)silane (0.869 mmol) and [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (0.0290 mmol) was dissolved in toluene (17 mL/mmol). The reaction was stirred at 160° C. for 2 hours under air. Upon cooling, the reaction was filtered and concentrated in vacuo and purified by flash chromatography on silica using a 5% MeOH/DCM eluant to give N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-(2-trimethylsilylethynyl)phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetamide (0.272 g, 89% yield).

[0394] 1H NMR (400 MHz, CDCl.sub.3) 8.46-8.36 (m, 1H), 7.95-7.88 (m, 1H), 7.80-7.68 (m, 1H), 7.34-7.28 (m, 1H), 3.69-3.59 (m, 3H), 3.53-3.31 (m, 1H), 2.94-2.73 (m, 2H), 2.41-2.31 (m, 1H), 2.29-2.24 (m, 3H), 2.23-2.08 (m, 1H), 1.58-1.51 (m, 9H), 0.24-0.18 (m, 9H)

Step 7: Synthesis of N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-ethynyl-6-methyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide

[0395] The N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-(2-trimethylsilylethynyl)phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetamide (0.270 g, 0.515 mmol) was suspended in acetone (5 mL/mmol) and hydrochloric acid (2M solution, 5.15 mmol) was added. The reaction mixture was heated at 60° C. for 10.5 h. The reaction mixture was concentrated in vacuo and the resulting aqueous layer was extracted with EtOAc. The organic layer was dried and concentrated in vacuo and purified by flash chromatography on silica using a 5% MeOH/DCM eluant to give N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-(2-trimethylsilylethynyl)phenyl]-2,4-dioxo-cyclopentyl]acetamide (0.113 g, 43% yield) and N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-ethynyl-6-methyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (0.043 g, 19% yield).

[0396] N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-(2-trimethylsilylethynyl)phenyl]-2,4-dioxo-cyclopentyl]acetamide: 1H NMR (400 MHz, CD.sub.3OD) 8.31-8.23 (m, 1H), 7.61 (d, 1H), 7.56 (s, 1H), 7.49-7.41 (m, 1H), 3.04-2.86 (m, 1H), 2.79-2.62 (m, 1H), 2.56-2.41 (m, 1H), 2.35-2.17 (m, 2H), 2.07-1.96 (m, 3H), 1.16 (d, 9H), 0.03 -0.05 (m, 9H)

[0397] N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-ethynyl-6-methyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide: 1H NMR (400 MHz, CD.sub.3OD) δ=8.51 (dd, 1H), 8.13-8.01 (m, 1H), 7.95 (s, 1H), 7.75-7.68 (m, 1H), 3.24-3.07 (m, 1H), 2.99-2.79 (m, 1H), 2.75-2.65 (m, 1H), 2.54 (d, 1H), 2.44 (br. s., 2H), 2.31 (s, 3H), 1.41-1.35 (m, 9H)

Example 11

Synthesis of tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-ethynyl-6-methyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (compound B382)

Step 1: Synthesis of N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-vinyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide

[0398] 2-[3-[2-bromo-4-(3,5-difluoro-2-pyridyl)-6-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]-N-tert-butyl-acetamide (0.294 g, 0.579 mmol), tributyl(vinyl)stannane (0.869 mmol) and [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (0.0290 mmol) was dissolved in toluene (17 mL/mmol) and stirred at 160° C. for 2 hours under air. The reaction was cooled to room temperature, filtered and the solvent removed in vacuo. The resulting residue was purified by flash chromatography on silica using a 10% MeOH/DCM eluant to give N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-vinyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetamide (0.201 g, 76% yield).

[0399] 1H NMR (400 MHz, CDCl.sub.3) 8.44 (d, 1H), 7.97 (s, 1H), 7.70 (br. s., 1H), 7.34-7.28 (m, 1H), 6.66 (dt, 1H), 5.81-5.71 (m, 1H), 5.31-5.26 (m, 1H), 3.56-3.50 (m, 3H), 3.43 (br. s., 1H), 2.95-2.81 (m, 1H), 2.77-2.65 (m, 1H), 2.46-2.38 (m, 2H), 2.29-2.22 (m, 3H), 1.37 (d, 9H).

Step 2: Synthesis of N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-vinyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide

[0400] The N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-phenyl]-2-methoxy-4-oxo-cyclopent-2-en-1-yl]acetamide (0.200 g, 0.467 mmol) was suspended in acetone (5.89 mL/mmol) and hydrochloric acid (2M solution) (5.89 mL/mmol, 5.50 mmol) was added. The reaction mixture was heated at 60° C. for 10.5 hour. The reaction mixture was concentrated in vacuo to remove the acetone and the resulting aqueous layer was extracted with EtOAc. The organic layers were dried (MgSO.sub.4) and concentrated in vacuo, and the resulting residue was purified by flash chromatography on silica using a 10% MeOH/DCM eluant to give N-tert-butyl-2-[3-[4-(3,5-difluoro-2-pyridyl)-2-methyl-6-vinyl-phenyl]-2,4-dioxo-cyclopentyl]acetamide (0.090 g, 44% yield).

[0401] 1H NMR (400 MHz, CD.sub.3OD) δ=8.50-8.45 (m, 1H), 7.97 (s, 1H), 7.74-7.64 (m, 2H), 6.70 (ddd, 1H), 5.73 (dd, 1H), 5.28-5.17 (m, 1H), 3.26-3.13 (m, 1H), 2.99-2.86 (m, 1H), 2.79-2.68 (m, 1H), 2.52-2.41 (m, 2H), 2.25-2.19 (m, 3H), 1.40-1.33 (m, 9H)

Example 12

Synthesis of 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]-N-propyl-acetamide (compound B314)

Step 1: Synthesis of 6-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-3a,4-dihydro-3H-cyclopenta[b]furan-2,5-dione

[0402] The 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]acetic acid (1.66 mmol, 0.600 g) was dissolved in dichloromethane (15.0 mL) and 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride (2.08 mmol, 0.399 g) was added. After 3 h, a further portion of 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-1-amine hydrochloride (0.249 mmol, 0.0478 g) was added and stirring continued for a further 1 hour. The crude reaction mixture was directly used in the next step without further processing.

Step 2: Synthesis of 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]-N-propyl-acetamide

[0403] A DCM solution of 6-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-3a,4-dihydro-3H-cyclopenta[b]furan-2,5-dione (0.415 mmol, 0.142 g) was added to propan-1-amine hydrochloride (0.498 mmol, 0.0476 g) and N,N-diethylethanamine (0.830 mmol, 0.0840 g, 0.116 mL) and stirred at room temperature overnight. The reaction mixture was washed with 2M HCl then purified by flash chromatography on silica using a 0% to 50% MeCN/DCM as eluant to give 2-[3-[4-(4-chloropyrazol-1-yl)-2,6-dimethyl-phenyl]-2,4-dioxo-cyclopentyl]-N-propyl-acetamide (82 mg).

[0404] 1H NMR (400 MHz, CDCl.sub.3) 14.16-13.45 (m, 1H), 7.87 (s, 1H), 7.59 (s, 1H), 7.31 (s, 2H), 7.15-7.01 (m, 1H), 3.36-3.03 (m, 3H), 2.85 (dd, 1H), 2.61 (d, 2H), 2.18 (d, 7H), 1.57-1.32 (m, 2H), 0.87 (t, 3H)

Example 13

Chiral HPLC or SFC Separation of Enantiomers

[0405] In one optional embodiment of the invention, any specific compound of the invention is separated into the two corresponding enantiomerically pure (or substantially enantiomerically pure) compounds using a chiral HPLC or SFC column. In one optional example, the chiral HPLC uses the following method and the following conditions.

[0406] Chiral HPLC column: a (s,s) WhelkO1−5 micron−21 mm×250 mm HPLC column, manufactured by Regis Technologies, Inc. In this column, the chiral stationary phase is (S,S) 1-(3-5-dinitrobenzamido)-1,2,3,4-tetrahydrophenanthrene.

[0407] The solvent system to be used as an eluent for the column varies depending on the racemic compound to be separated into enantiomers, but one example of a solvent system is:

[0408] a 30:70 (by volume) mixture of Solvent A and Solvent B, in which:

[0409] Solvent A is isohexane containing 0.1% v/v of trifluoroacetic acid (TFA), and

[0410] Solvent B is ethanol.

[0411] Other conditions (these are sample conditions only and may vary widely):

[0412] Flow rate through column: about 21 ml/minute. Run time: about 20 minutes.

[0413] Loading (compound loaded onto column): about 50 mg/ml of compound in ethanol.

[0414] Volume of sample (compound) injected per run=about 1800 microlitres.

[0415] Number of injections of compound=about 5.

[0416] Abbreviation:

[0417] HPLC=high performance (or high pressure) liquid chromatography.

[0418] SFC=Supercritical fluid chromatography

[0419] General Note on Chiral HPLC or SFC Separation of Enantiomers:

[0420] The above procedure using chiral HPLC is used to separate the enantiomers of other compounds of formula (I) of the present the invention. Alternative chiral columns which might be useful to achieve this are as follows:

[0421] (s,s) WhelkO1−5 micron−21 mm×250 mm HPLC column, manufactured by Regis Technologies, Inc [in this column, the chiral stationary phase is (S,S) 1-(3-5-dinitrobenzamido)-1,2,3,4-tetrahydrophenanthrene];

[0422] Kromasil® AmyCoat™ [whose chiral stationary phase is tris-(3,5-dimethylphenyl)carbamoyl amylose];

[0423] Kromasil® CelluCoat™ [whose chiral stationary phase is tris-(3,5-dimethylphenyl)carbamoyl cellulose];

[0424] Chiralpak® IA [whose chiral stationary phase is a (3,5-dimethylphenyl)carbamate derivative of amylose];

[0425] Chiralpak® IB [whose chiral stationary phase is tris-(3,5-dimethylphenyl)carbamate derivative of cellulose];

[0426] Chiralpak® IC [whose chiral stationary phase is cellulose tris(3,5-dichlorophenyl) carbamate];

[0427] Lux® Amylose-2 [whose chiral stationary phase is amylose tris(5-chloro-2-methylphenylcarbamate)]; or

[0428] Lux® Cellulose-2 [whose chiral stationary phase is Cellulose tris(3-chloro-4-methylphenylcarbamate)].

[0429] Lux® Cellulose-4 [whose chiral stationary phase is Cellulose tris(4-chloro-3-methylphenylcarbamate)]

Example 14

Chiral HPLC Separation of Enantiomers of Compound B75

[0430] Compound B75 (racemic), was separated into individual enantiomer compounds using a chiral HPLC column, by the following method and under the following conditions.

[0431] The chiral HPLC column used was a (s,s) WhelkO1−5 micron−20 mm×250 mm HPLC column, manufactured by Regis Technologies Inc. In this column, the chiral stationary phase is (S,S) 1-(3-5-dinitrobenzamido)-1,2,3,4-tetrahydrophenanthrene.

[0432] The solvent system used as an eluent for the column was a 63:37 (by volume) mixture of Solvent A and Solvent B, in which:

[0433] Solvent A is isohexane containing 1.0% v/v of ethanol and 0.2% v/v of glacial acetic acid, and Solvent B is ethanol. Other conditions were as follows:

[0434] Flow rate through column: 24 ml/minute.

[0435] Loading (compound loaded onto column): 53 mg/ml in isopropanol.

[0436] Volume of sample (compound) injected per run=0.30 to 0.35 ml

[0437] Number of injections of compound=60

[0438] Length of run=20 minutes

[0439] Chiral HPLC on a total of 150 mg of compound B75 (racemic) under the above conditions gave 41 mg of 100% enantiomeric excess (e.e.) at retention time 14.77 and 37 mg of 93% e.e at retention time 16.48.

[0440] General Note on NMR and HPLC:

[0441] NMR spectra were run in the deuterated solvent specified and on an instrument operating at the indicated frequency. [0442] HPLC retention times were acquired on Waters Aquity UPLC-MS using a Sample Organizer with Sample Manager FTN, H-class QSM, Column Manager, 2× Column Manager Aux, photodiode array, ELSD and SQD 2 equipped with a Waters HSS T3 C18 column (column length 30 mm, internal diameter of column 2.1 mm, particle size 1.8 micron). The analysis was conducted using a two minute run time, according to the following gradient table:

TABLE-US-00010 Time Solvent A Solvent B Flow (mins) (%) (%) (ml/mn) 0 95 5 0.7 1.75 0 100 0.7 1.76 0 100 0.7 2 0 5 0.7 2.01 95 5 0.7 2.11 95 5 0.7 Solvent A: H.sub.2O with 0.05% TFA Solvent B: CH.sub.3CN with 0.05% TFA

[0443] Additional compounds in Tables T1 an T2 below illustrate the present invention, and are particular embodiments of the compounds of formula (I) according to the present invention.

[0444] For the most part, these compounds can generally be prepared by methods similar to those shown in the Examples and/or in the process section hereinabove using appropriate starting materials.

TABLE-US-00011 TABLE T1 It should be noted that certain compounds of the invention may exist as a mixture of isomers, including sometimes atropisomers, e.g. as noted above, under the conditions used to obtain the .sup.1H NMR data. Where this has occurred, the characterising data are reported for all isomers present at ambient temperature in the specified solvent. Unless otherwise stated, proton (.sup.1H) NMR spectra disclosed herein were recorded at ambient temperature. .sup.1H NMR (400 MHz, Compound CDCl.sub.3) unless Number Structure stated A1 [00034] 7.35-7.30 (m, 2H), 7.25 (m, 1H), 7.20 (d, 2H), 6.85 (s, 6H), 6.05 (br, 1H), 3.60 (m, 2H), 3.25 (m, 1H), 2.90-2.80 (m, 3H), 2.65 (d, 2H), 2.25 (s, 3H), 2.20 (dd, 1H), 2.10 (2 × s, 2 × 3H). A2 [00035] 6.87 (s, 2H), 5.83 (s, 1H), 3.32-3.23 (m, 1H), 2.93-2.83 (m, 1H), 2.72- 2.58 (m, 2H), 2.25 (s, 3H), 2.24-2.14 (m, 1H), 2.11 (s, 6H), 1.38 (s, 9H). A3 [00036] 6.86 (s, 2H), 5.92 (br. s, 1H), 3.99-3.87 (m, 1H), 3.32-3.21 (m, 1H), 2.94- 2.84 (m, 1H), 2.69 (d, 2H), 2.25 (s, 3H), 2.24- 2.15 (m, 1H), 2.11 (s, 6H), 1.55-1.44 (m, 2H), 1.20-1.12 (m, 3H), 0.98- 0.88 (m, 3H) A4 [00037] 7.39-7.29 (m, 3H), 7.29- 7.23 (m, 2H), 6.86 (s, 2H), 6.70 (br. m, 1H), 4.49-4.36 (m, 2H), 3.30- 3.21 (m, 1H), 2.89-2.81 (m, 1H), 2.74-2.62 (m, 2H), 2.24 (s, 3H), 2.22- 2.12 (m, 1H), 2.09 (s, 6H) A5 [00038] 7.60 (s, 1H), 6.85 (s, 2H), 3.28-3.15 (m, 1H), 3.13-3.02 (m, 2H), 2.94- 2.72 (m, 2H), 2.72-2.61 (m, 2H), 2.25 (s, 3H), 2.10 (s, 6H), 1.87-1.74 (m, 1H), 0.92 (d, 6H) A6 [00039] 7.26 (m, 1H), 6.97 (m, 2H), 6.87 (d, 2H), 6.67 (br.s, 1H), 4.68-4.53 (m, 2H), 3.31-3.22 (m, 1H), 2.92-2.82 (m, 1H), 2.73- 2.62 (m, 2H), 2.25 (s, 3H), 2.23-2.14 (m, 1H), 2.10 (d, 6H) A7 [00040] 6.84 (s, 2H), 4.02-3.93 (m, 1H), 3.18-3.08 (m, 1H), 2.91-2.82 (m, 1H), 2.74-2.68 (m, 1H), 2.44- 2.33 (m, 2H), 2.23 (s, 3H), 2.04 (s, 6H), 1.15 (d, 6H) A8 [00041] (d.sub.4-MeOH) 7.03 (s, 2H), 3.98 (m, 1H), 3.19-3.10 (m, 1H), 2.87 (dd, 1H), 2.71 (dd, 1H), 2.47-2.34 (m, 2H), 2.06 (s, 6H), 1.99 (s, 3H), 1.14 (dd, 6H) A9 [00042] (d4-MeOH) 7.14 (s, 2H), 3.81 (q, 1H), 3.38 (s, 1H), 3.21-3.11 (m, 1H), 2.93- 2.85 (m, 1H), 2.78-2.69 (m, 1H), 2.50- 2.38 (m, 2H), 2.09 (s, 6H), 1.56-1.42 (m, 2H), 1.22 (d, 3H), 0.96-0.87 (m, 3H) A10 [00043] 12.40 (1H, br), 6.95 (t, 1H), 6.85 (2 × s, 2H), 4.10-3.95 (m, 2H), 3.30- 3.20 (m, 1H), 2.90 (dd, 1H), 2.80-2.60 (m, 2H), 2.30 (s, 1H), 2.25 (s, 3H), 2.20 (d, 1H), 2.10 (s, 6H) A11 [00044] (d4-MeOH) (resticted rotation) 6.85 (s, 2H), 3.12 (br, 1H), 2.95-2.85 (m, 1H), 2.80-2.70 (m, 1H), 2.50-2.30 (m, 2H), 2.25 (s, 3H), 2.12 (s, 1H), 2.05 (s, 6H), 1.60 (s, 3.9H), 1.35 (s, 2.1H) A12 [00045] 13.10 (br, 1H), 6.85 (2 × s, 2H), 6.50 (t, 1H), 3.30-3.15 (3H, m), 2.90 (d, 1H), 2.70-2.60 (m, 2H), 2.25 (s, 3H), 2.20 (d, 1H), 2.10 (s, 6H), 1.50-1.40 (m, 2H), 1.35- 1.30 (m, 2H), 0.90 (t, 3H) A13 [00046] 13.10 (br, 1H), 7.05 (t, 1H), 6.87 (2 × s, 2H), 4.00-3.90 (m, 2H), 3.35 (t, 2H), 3.30-3.20 (m, 1H), 3.15-3.00 (m, 2H), 2.90 (dd, 1H), 2.75 (d, 1H), 2.65-2.60 (m, 1H), 2.30 (s, 3H), 2.20 (dd, 1H), 2.10 (s, 6H), 1.75- 1.65 (m, 1H), 1.55 (d, 2H), 1.30-1.20 (m, 2H) A14 [00047] (d4-MeOH) 6.85 (2H, s), 3.20-3.10 (1H, m), 3.05 (2H, s), 2.90 (1H, dd), 2.80 (1H, dd), 2.50-2.40 (2H, m), 2.25 (3H, s), 2.05 (6H, s), 0.90 (9H, s) A15 [00048] 6.87 (s, 2H), 3.25-3.15 (m, 1H), 2.92-2.78 (m, 2H), 2.80-2.70 (m, 1H), 2.70-2.58 (m, 1H), 2.25 (s, 3H), 2.15 (d, 1H), 2.12 (s, 6H), 0.85-0.75 (m, 2H), 0.60-0.50 (m, 2H) A16 [00049] (d4-MeOH) 6.90 (2H, s), 4.14-4.10 (1H, m), 3.90- 3.80 (5H, m), 3.20-3.10 (1H, m), 2.90 (1H, dd), 2.75 (1H, dd), 2.50-2.40 (2H, m), 2.18 (3H, s), 2.10 (6H, s), 1.18 (3H, d) A17 [00050] 6.88 (s, 1H), 6.87 (s, 1H), 6.72 (br, 1H), 4.05- 3.90 (m, 3H), 3.50-3.42 (m, 2H), 3.25 (br, 1H), 2.89 (dd, 1H), 2.25 (s, 3H), 2.17 (d, 1H), 2.11 (s, 3H), 2.10 (s, 3H), 2.06-1.97 (m, 2H), 1.90- 1.80 (m, 2H), 1.55-1.40 (m, 2H) A18 [00051] 9.88 (s, 1H), 8.60 (d, 1H), 8.20 (t, 1H), 7.68- 7.60 (m, 2H), 6.85 (s, 2H), 3.25-3.15 (m, 1H), 2.92-2.78 (m, 2H), 2.70- 2.58 (m, 1H), 2.26 (d, 1H), 2.23 (s, 3H), 2.05 (s, 6H), 1.60-1.50 (m, 4H) A19 [00052] (d4MeOH) 6.87 (s, 2H), 3.20-3.10 (m, 1H), 3.08 (d, 2H), 2.90-2.82 (m, 1H), 2.78-2.72 (m, 1H), 2.50-2.38 (m, 2H), 2.23 (s, 3H), 2.05 (s, 6H), 1.02-0.90 (m, 1H), 0.55- 0.45 (m, 2H), 0.24-0.18 (m, 2H) A20 [00053] (d4MeOH) 6.86 (s, 2H), 3.22 (q, 2H), 3.18-2.18 (m, 1H), 2.92-2.82 (m, 1H), 2.76-2.70 (m, 1H), 2.50-2.38 (m, 2H), 2.24 (s, 3H), 2.00 (s, 6H), 1.12 (t, 3H) A21 [00054] (d4MeOH) 6.86 (s, 2H), 4.18-4.08 (m, 1H), 3.20- 3.10 (m, 1H), 2.90-2.80 (m, 1H), 2.74-2.64 (m, 1H), 2.45-2.35 (m, 2H), 2.23 (s, 3H), 2.05 (s, 6H), 2.00-1.88 (m, 2H), 1.75-1.65 (m, 2H), 1.65- 1.55 (m, 2H), 1.52-1.40 (m, 2H) A22 [00055] (d4MeOH) 6.85 (s, 2H), 3.65-3.45 (m, 4H), 3.20- 3.10 (m, 1H), 2.94-2.82 (m, 2H), 2.80-2.70 (m, 1H), 2.43 (d, 1H), 2.25 (s, 3H), 2.05 (s, 6H), 1.70-1.50 (m, 6H) A23 [00056] 9.80 (s, 1H), 8.45 (s, 1H), 8.10 (dd, 1H), 7.80 (d, 1H), 6.87 (s, 2H), 4.70 (s, 2H), 3.22-3.13 (m, 1H), 2.93-2.82 (m, 2H), 2.70-2.62 (1H, m), 2.52 (3H, s), 2.26 (d, 1H), 2.23 (3H, s), 2.06 (d, 6H) A24 [00057] 12.1 (s, 1H), 6.86 (d, 2H), 3.82-2.58 (m, 8H), 3.47-3.35 (m, 1H), 3.11 (d, 1H), 2.98-2.88 (m, 1H), 2.64-2.50 (m, 1H), 2.30-2.20 (m, 1H), 2.25 (s, 3H), 2.10 (d, 6H) A25 [00058] (restricted rotation) 12.70 (1H, 2 × s), 6.85 (2H, 2 × s), 3.60-3.25 (3H, m), 3.10 (1H, d), 3.05 (3H, 2 × s), 2.65- 2.50 (1H, s), 2.30-2.20 (4H, m), 2.10 (6H, 2 × s), 1.70-1.55 (2H, m), 1.00-0.90 (3H, 2 × t) A26 [00059] 12.8 (s, 1H), 6.86 (s, 2H), 6.35 (br, 1H), 3.30- 3.18 (m, 3H), 2.92-2.84 (m, 1H), 2.72-2.65 (m, 2H), 2.30 (s, 3H), 2.20 (d, 1H), 2.12 (s, 6H), 1.55 (q, 2H), 0.95 (t, 3H) A27 [00060] 12.8 (s, 1H), 6.87 (s, 2H), 5.73 (s, 1H), 3.30- 3.20 (m, 1H), 2.90-2.80 (m, 1H), 2.75-2.65 (m, 2H), 2.27 (s, 3H), 2.20 (d, 1H), 2.12 (s, 6H), 1.75 (q, 2H), 1.32 (s, 6H), 0.86 (t, 3H) A28 [00061] (d4-MeOH) 7.05 (2H, s), 3.98 (2H, s), 3.15-3.10 (1H, m), 2.90 (1H, dd), 2.75 (1H, dd), 2.60 (1H, s), 2.50-2.40 (2H, m), 2.10 (6H, s), 2.00 (3H, s) A29 [00062] 13.1 (1H, s), 7.09 (2H, s), 6.49-6.42 (1H, br), 3.30-3.20 (3H, m), 2.93- 2.83 (1H, m), 2.70-2.60 (2H, m), 2.20 (1H, d), 2.12 (6H, s), 2.01 (3H, s), 1.52-1.42 (2H, m), 1.40-1.29 (2H, m), 0.92 (3H, t) A30 [00063] 13.1 (1H, s), 7.08 (2H, s), 6.58 (br, 1H), 3.30- 3.20 (1H, m), 3.15-3.05 (2H, m), 2.93-2.83 (1H, m), 2.75-2.60 (2H, m), 2.18 (1H, d), 2.10 (6H, s), 2.02 (3H, s), 1.83- 1.70 (1H, m), 0.92 (6H, d) A31 [00064] 13.1 (1H, s), 7.08 (2H, s), 5.95 (1H, br), 3.30- 3.21 (1H, m), 2.92-2.82 (1H, m), 2.67-.60 (2H, m), 2.17 (1H, d), 2.10 (6H, s), 2.02 (3H, s), 1.36 (9H, s) A32 [00065] 13.20 (1H, br), 7.10 (2H, 2 × s), 6.90 (1H, br), 3.30-3.20 (1H, br), 2.85 (1H, dd), 2.80-2.70 (1H, m), 2.20-2.10 (8H, m), 2.05 (3H, s), 0.85-0.75 (2H, m), 0.55-0.50 (2H, m) A33 [00066] (d4-MeOH) 7.06 (s, 2H), 3.84 (m, 1H), 3.22-3.13 (m, 1H), 2.92 (dd, 1H), 2.76 (dd, 1H), 2.52-2.42 (m, 2H), 2.09 (s, 6H), 2.02 (s, 3H), 1.52 (m, 2H), 1.16 (d, 3H), 0.99- 0.91 (m, 3H) A34 [00067] (d4-MeOH) 7.62-7.57 (m, 2H), 7.27 (s, 2H), 7.13 (t, 2H), 3.99 (m, 1H), 3.22-3.12 (m, 1H), 2.94-2.85 (m, 1H), 2.77- 2.70 (m, 1H), 2.49-2.38 (m, 2H), 2.17 (s, 6H), 1.19-1.12 (m, 6H) A35 [00068] (d4-MeOH) 7.58 (d, 2H), 7.40 (d, 2H), 7.29 (s, 2H), 3.99 (m, 1H), 3.22- 3.11 (m, 1H), 2.95-2.85 (m, 1H), 2.78-2.69 (m, 1H), 2.50-2.38 (m, 2H), 2.18 (s, 6H), 1.99-1.02 (m, 6H) A36 [00069] (d4-MeOH) 7.62-7.56 (m, 2H), 7.26 (s, 2H), 7.12 (t, 2H), 3.22-3.12 (m, 1H), 2.94-2.85 (m, 1H), 2.74-2.66 (m, 1H), 2.51-2.35 (m, 2H), 2.17 (s, 6H), 1.35 (s, 9H) A37 [00070] (d4-MeOH) 7.85-7.77 (m, 4H), 7.39 (s, 2H), 4.02 (m, 1H), 3.28-3.16 (m, 1H), 3.00-2.91 (m, 1H), 2.80-2.72 (m, 1H), 2.54-2.42 (m, 2H), 2.22 (s, 6H), 1.22-1.16 (m, 6H) A38 [00071] (d4-MeOH) 7.69-7.59 (m, 3H), 7.26 (s, 2H), 3.99 (m, 1H), 3.23-3.12 (m, 1H), 2.96-2.87 (m, 1H), 2.78-2.70 (m, 1H), 2.51-2.37 (m, 2H), 2.19 (s, 6H), 1.20-1.12 (m, 6H) A39 [00072] (d4-MeOH) 8.50 (s, 1H), 7.85 (d, 1H), 7.61 (s, 2H), 3.24-3.13 (m, 1H), 2.98-2.88 (m, 1H), 2.77- 2.68 (m, 1H), 2.53-2.39 (m, 2H), 2.21 (s, 6H), 1.38 (s, 9H) A40 [00073] (d4-MeOH) 8.81 (s, 2H), 8.09 (s, 2H), 3.23-3.11 (m, 1H), 2.97-2.86 (m, 1H), 2.75-2.65 (m, 1H), 2.54-2.33 (m, 2H), 2.21 (s, 6H), 1.35 (s, 9H) A41 [00074] (d4-MeOH) 8.58 (1H, s), 7.92-7.85 (2H, m), 7.68 (2H, s), 3.25-3.12 (1H, br), 2.98-2.88 (1H, m), 2.77-2.68 (1H, m), 2.52- 2.39 (2H, br.m), 2.22 (6H, s), 1.38 (9H, s) A42 [00075] (d4-MeOH) 7.18 (s, 2H), 4.06-3.94 (m, 1H), 3.40 (s, 1H), 3.22-3.12 (m, 1H), 2.98-2.85 (m, 1H), 2.78-2.69 (m, 1H), 2.50- 2.38 (m, 2H), 2.11 (s, 6H), 1.17 (d, 6H) A43 [00076] (d4-MeOH) 7.16 (s, 2H), 3.41 (s, 1H), 3.22-3.12 (m, 1H), 2.95-2.85 (m, 1H), 2.74-2.65 (m, 1H), 2.51-2.38 (m, 2H), 2.11 (s, 6H), 1.37 (s, 9H) A44 [00077] (d4-MeOH) 8.50 (s, 1H), 7.85 (d, 1H), 7.61 (s, 2H), 3.28-3.16 (m, 1H), 3.23 (t, 2H), 3.00-2.90 (m, 1H), 2.83-2.74 (m, 1H), 2.55-2.43 (m, 2H), 2.21 (s, 6H), 1.59-1.48 (m, 2H), 1.47-1.34 (m, 2H), 0.98 (t, 3H) A45 [00078] (d4-MeOH) 8.50 (s, 1H), 7.85 (d, 1H), 7.62 (s, 2H), 3.23-3.13 (m, 1H), 3.00-2.90 (m, 1H), 2.79- 2.66 (m, 2H), 2.54-2.35 (m, 2H), 2.22 (s, 6H), 0.79-0.71 (m, 2H), 0.56- 0.49 (m, 2H) A46 [00079] (d4-MeOH) 8.49 (s, 1H), 7.82 (d, 1H), 7.61 (s, 2H), 3.23-3.13 (m, 1H), 2.98-2.89 (m, 1H), 2.79- 2.69 (m, 1H), 2.53-2.40 (m, 2H), 2.21 (s, 6H), 1.78 (q, 2H), 1.32 (s, 6H), 0.89 (t, 3H) A47 [00080] (d4-MeOH) 8.51 (s, 1H), 7.85 (d, 1H), 7.62 (s, 2H), 3.50 (t, 2H), 3.42 (t, 2H), 3.38 (s, 3H), 3.24- 3.13 (m, 1H), 2.98-2.88 (m, 1H), 2.85-2.77 (m, 1H), 2.57-2.44 (m, 2H), 2.22 (s, 6H) A48 [00081] (d4-MeOH) 7.04 (s, 2H), 3.20-3.08 (m, 1H), 2.92- 2.82 (m, 1H), 2.72-2.65 (m, 1H), 2.45-2.32 (m, 4H), 2.04 (s, 3H), 2.00 (s, 3H), 1.34 (s, 9H), 1.05 (t, 3H) A49 [00082] (d4-MeOH) 7.05 (s, 2H), 3.49-3.42 (m, 2H), 3.42- 3.35 (m, 2H), 3.34 (s, 3H), 3.19-3.09 (m, 1H), 2.93-2.83 (m, 1H), 2.79- 2.70 (m, 1H), 2.50-2.32 (m, 4H), 2.04 (s, 3H), 2.00 (s, 3H), 1.05 (t, 3H) A50 [00083] (d4-MeOH) 7.05 (s, 2H), 3.20-3.06 (m, 1H), 2.93- 2.81 (m, 1H), 2.74-2.66 (m, 1H), 2.49-2.33 (m, 4H), 2.04 (s, 3H), 2.00 (s, 3H), 1.80-1.70 (m, 2H), 1.29 (s, 6H), 1.05 (t, 3H), 0.87 (t, 3H) A51 [00084] (d4-MeOH) 7.06 (s, 2H), 3.20 (t, 2H), 3.18-3.10 (m, 1H), 2.93-2.84 (m, 1H), 2.78-2.69 (m, 1H), 2.48-2.32 (m, 4H), 2.04 (s, 3H), 2.00 (s, 3H), 1.54-1.45 (m, 2H), 1.42- 1.32 (m, 2H), 1.05 (t, 3H), 0.94 (t, 3H) A52 [00085] (d4-MeOH) 7.06 (s, 2H), 4.17-4.07 (m, 1H), 3.20- 3.08 (m, 1H), 2.92-2.81 (m, 1H), 2.74-2.67 (m, 1H), 2.49-2.33 (m, 4H), 2.03 (s, 3H), 2.00 (s, 3H), 2.00-1.87 (m, 2H), 1.78-1.65 (m, 2H), 1.65- 1.53 (m, 2H), 1.53-1.41 (m, 2H), 1.05 (t, 3H) A53 [00086] (d4-MeOH) 7.05 (s, 2H), 3.20-3.10 (m, 1H), 3.03 (s, 2H), 2.94-2.84 (m, 1H), 2.83-2.73 (m, 1H), 2.53-2.43 (m, 2H), 2.43- 2.33 (q, 2H), 2.04 (s, 3H), 2.00 (s, 3H), 1.05 (t, 3H), 0.92 (s, 9H) A54 [00087] (d4-MeOH) 7.05 (s, 2H), 4.03-3.93 (m, 1H), 3.20- 3.08 (m, 1H), 2.93-2.81 (m, 1H), 2.74-2.66 (m, 1H), 2.50-2.32 (m, 4H), 2.04 (s, 3H), 2.00 (s, 3H), 1.19-1.10 (m, 6H), 1.04 (t, 3H) A55 [00088] 12.85 (1H, br), 7.36- 7.34 (1H, m), 7.20 (1H, s), 7.10 (2H, 2 × s), 7.05 (1H, d), 6.55 (1H, br), 4.55-4.40 (1H, m), 3.35- 3.25 (1H, m), 2.90 (1H, dd), 2.75-2.70 (1H, m), 2.20 (1H, dd), 2.15-2.10 (7H, m), 2.05 (3H, s) A56 [00089] (d6-DMSO) Diagnostic peaks 7.03 (s, 2H), 2.95-2.85 (m, 1H), 2.80- 2.70 (m, 1H), 2.70-2.55 (m, 1H), 2.40-2.30 (m, 1H), 2.30-2.15 (m, 1H), 2.05-1.97 (m, 12H) A57 [00090] 12.90 (1H, br), 7.10 (2H, 2 × s), 6.00-5.95 (1H, br), 5.80-5.70 (1H, m), 5.20 (1H, s), 5.15 (1H, d), 3.45-3.40 (2H, m), 3.30-3.25 (1H, m), 2.90 (1H, dd), 2.70 (1H, d), 2.35-2.30 (2H, m), 2.25 (1H, dd), 2.15-2.10 (7H, m), 2.05 (3H, s) A58 [00091] 12.60 (1H, br), 7.10 (2H, 2 × s), 6.75 (1H, br), 3.55-3.45 (2H, m), 3.35 (1H, br), 2.90 (1H, dd), 2.75-2.65 (1H, m), 2.45- 2.30 (2H, m), 2.20 (1H, dd), 2.15-2.10 (7H, m), 2.02 (3H, s) A59 [00092] 12.55 (1H, br), 7.10 (2H, 2 × s), 6.85 (1H, br), 4.30 (2H, br), 3.30 (1H, br), 2.95-2.80 (1H, m), 2.75 (1H, dd), 2.25 (1H, dd), 2.15-2.10 (7H, m), 2.05 (3H, s), 1.20 (9H, s) A60 [00093] 13.10 (1H, br), 7.10 (2H, 2 × s), 5.65 (1H, br), 3.30-3.20 (1H, m), 2.90 (1H, dd), 2.70-2.65 (1H, m), 2.20 (1H, dd), 2.15- 2.10 (7H, m), 2.05 (3H, s), 1.75 (2H, q), 1.35 (6H, s), 0.85 (3H, t) A61 [00094] Restricted rotation 12.60 (1H, br), 7.05 (2H, 2 × s), 3.50-3.25 (2H, m), 3.10 (1H, d), 3.05 (3H, s), 2.90 (1H, dd), 2.60-2.50 (1H, m), 2.35 (1H, d), 2.10-2.05 (7H, m), 2.00 (3H, s), 1.70- 1.50 (2H, m), 0.90 (3H, t) A62 [00095] 13.15 (1H, br), 7.08 (2H, 2 × s), 6.20 (1H, br), 4.25-4.15 (1H, m), 3.25 (1H, br), 2.88 (1H, dd), 2.70-2.65 (1H, m), 2.18 (1H, dd), 2.15-2.05 (7H, m), 2.05 (3H, s), 1.80- 1.30 (8H, m) A63 [00096] 7.08 (s, 2H), 3.86 (br, 1H), 3.40-3.35 (m, 1H), 3.10 (d, 2H), 2.95-2.82 (m, 1H), 2.72-2.60 (m, 2H), 2.14-2.05 (m, 7H), 2.02 (s, 3H), 1.03- 0.94 (m, 1H), 0.58-0.50 (m, 2H), 0.25-0.20 (m, 2H) A64 [00097] 13.10 (1H, br), 7.10 (2H, 2 × s), 6.22 (1H, br), 5.95-5.80 (1H, m), 5.35- 5.20 (2H, m), 4.02 (2H, d), 3.38 (2H, s), 3.25 (1H, br), 2.90 (1H, dd), 2.70 (1H, d), 2.20 (1H, dd), 2.15-2.10 (7H, m), 2.05 (3H, s), 1.40 (6H, 2 × s) A65 [00098] 13.15 (1H, br), 7.10 (2H, 2 × s), 6.40 (1H, br), 3.30-3.20 (1H, m), 3.10- 3.00 (2H, m), 2.90 (1H, dd), 2.70-2.65 (1H, m), 2.20 (1H, dd), 2.15-2.10 (7H, m), 2.05 (3H, s), 0.90 (9H, s) A66 [00099] (d4-MeOH) 7.08 (s, 2H), 3.20-3.10 (m, 1H), 2.95- 2.85 (m, 1H), 2.76-2.68 (m, 2H), 2.50-2.32 (m, 4H), 2.07 (s, 3H), 2.02 (s, 3H), 1.06 (t, 3H), 0.79-0.72 (m, 2H), 0.55- 0.48 (m, 2H) A67 [00100] (d4-MeOH) 8.33 (s, 1H), 7.67 (s, 1H), 7.44 (s, 2H), 3.23-3.12 (m, 1H), 2.98-2.85 (m, 1H), 2.76- 2.65 (m, 1H), 2.52-2.38 (m, 2H), 2.20 (s, 6H), 1.38 (s, 9H) A68 [00101] (d4-MeOH) 7.08 (s, 2H), 4.00 (s, 2H), 3.20-3.10 (m, 1H), 2.97-2.86 (m, 1H), 2.83-2.73 (m, 1H), 2.61 (s, 1H), 2.51-2.35 (m, 4H), 2.07 (s, 3H), 2.01 (s, 3H), 1.08 (t, 3H) A69 [00102] (d4-MeOH) 8.47 (s, 1H), 7.82 (d, 1H), 7.59 (s, 2H), 3.99 (s, 2H), 3.21- 3.11 (m, 1H), 2.99-2.88 (m, 1H), 2.82-2.73 (m, 1H), 2.61 (s, 1H), 2.54- 2.41 (m, 2H), 2.18 (s, 6H) A70 [00103] (d4-MeOH) 8.21 (s, 1H), 7.53 (s, 1H), 7.32 (s, 2H), 4.08-3.99 (m, 1H), 3.11-3.02 (m, 1H), 2.84- 2.74 (m, 1H), 2.68-2.59 (m, 1H), 2.41-2.28 (m, 2H), 2.08 (s, 6H), 1.90- 1.75 (m, 2H), 1.71-1.57 (m, 2H), 1.57-1.43 (m, 2h), 1.43-1.30 (m, 2H) A71 [00104] (d4-MeOH) 8.50 (d, 1H), 8.32 (s, 1H), 7.84 (t, 1H), 7.66 (s, 1H), 7.49- 7.41 (m, 1H), 7.43 (s, 2H), 7.38-7.31 (m, 1H), 4.55 (s, 2H), 3.28-3.18 (m, 1H), 3.02-2.82 (m, 2H), 2.65-2.51 (m, 2H), 2.19 (d, 6H) A72 [00105] (d4-MeOH) 8.34 (s, 1H), 7.68 (s, 1H), 7.44 (s, 2H), 3.25-3.12 (m, 1H), 3.05 (d, 2H), 2.99-2.88 (m, 1H), 2.84-2.74 (m, 1H), 2.54-2.43 (m, 2H), 2.20 (s, 6H), 1.88-1.74 (m, 1H), 0.94 (d, 6H) A73 [00106] (d4-MeOH) 8.41 (d, 1H), 8.32 (s, 1H), 7.73 (t, 1H), 7.66 (s, 1H), 7.49 (d, 1H), 7.43 (s, 2H), 7.22-7.13 (m, 1H), 3.27- 3.18 (m, 1H), 3.03-2.53 (m, 1H), 2.90-2.81 (m, 1H), 2.63-2.52 (m, 2H), 2.19 (d, 6H), 1.64-1.56 (m, 2H), 1.34-1.26 (m, 2H) A74 [00107] (d4-MeOH) 8.33 (1H, s), 7.68 (1H, s), 7.45 (2H, s), 4.08-3.94 (1H, m), 3.25-3.12 (1H, br), 2.99- 2.88 (1H, m), 2.80-2.70 (1H, m), 2.54-2.49 (2H, br.m), 2.20 (6H, s), 1.18 (6H, d) A75 [00108] (d4-MeOH) 8.33 (1H, s), 7.68 (1H, s), 7.45 (2H, s), 3.23-3.12 (1H, br), 2.99-2.89 (1H, m), 2.79- 2.69 (1H, m), 2.54-2.49 (2H, br.m), 2.20 (6H, s), 0.79-0.72 (m, 2H), 0.57- 0.48 (m, 2H) A76 [00109] (d4-MeOH) 8.33 (1H, s), 7.66 (1H, s), 7.44 (2H, s), 5.89-5.77 (1H, m), 5.15-5.03 (2H, m), 3.35- 3.26 (2H, m), 3.22-3.12 (1H, br), 2.99-2.88 (1H, m), 2.81-2.71 (1H, m), 2.53-2.41 (2H, br.m), 2.35-2.24 (2H, m), 2.19 (6H, s) A77 [00110] (d4-MeOH) 8.33 (1H, s), 7.67 (1H, s), 7.44 (2H, s), 3.53-3.46 (2H, m), 3.46-3.38 (2H, m), 3.37 (3H, s), 3.25-3.12 (1H, br), 2.98-2.88 (1H, m), 2.82-2.73 (1H, m), 2.56- 2.44 (2H, br.m), 2.20 (6H, s) A78 [00111] (d4-MeOH) 7.05 (2H, s), 4.18 (2H, s), 3.18-3.08 (1H, br), 2.99-2.90 (1H, m), 2.86-2.78 (1H, m), 2.54-2.42 (2H, m), 2.08 (6H, s), 2.01 (3H, s) A79 [00112] (d4-MeOH) 7.05 (s, 2H), 3.41-3.32 (m, 2H), 3.23- 3.12 (m, 1H), 3.06, 2.96 (s, 3H), 2.97-2.72 (m, 2H), 2.50-2.34 (m, 4H), 2.06 (s, 3H), 2.00 (s, 3H), 1.70-1.52 (m, 2H), 1.06 (t, 3H), 0.98-0.86 (m, 3H) A80 [00113] (d4-MeOH) 8.36 (1H, s), 7.78-7.72 (1H, m), 7.56- 7.49 (1H, m), 7.51 (2H, s), 3.12-3.02 (1H, m), 2.84-2.75 (1H, m), 2.63- 2.54 (1H, m), 2.38- 2.36 (2H, m), 2.09 (6H, s), 1.24 (9H, s) A81 [00114] 12.90 (1H, s), 7.10 (2H, 2 × s), 6.05 (1H, br), 4.45-4.35 (1H, m), 3.30- 3.25 (1H, m), 2.90 (1H, dd), 2.75-2.70 (1H, m), 2.45-2.35 (2H, m), 2.20 (1H, dd), 2.15-2.10 (7H, m), 2.05 (3H, s), 2.00- 1.85 (2H, m), 1.85-1.75 (2H, m) A82 [00115] (d4-MeOH) 6.89 (2H, s), 3.16-3.07 (1H, m), 2.99- 2.89 (1H, m), 2.78-2.68 (1H, m), 2.52-2.43 (1H, m), 2.41-2.32 (1H, m), 2.27 (3H, s), 2.07 (6H, s), 1.52-1.45 (2H, m), 1.28-1.18 (2H, m) A83 [00116] (d4-MeOH) 6.88 (2H, s), 4.18 (2H, s), 3.18-3.08 (1H, m), 2.99-2.49 (1H, m), 2.87-2.78 (1H, m), 2.53-2.40 (2H, m), 2.26 (3H, s), 2.07 (6H, s) A84 [00117] (d4-MeoH) 6.87 (2H, s), 6.02 (1H, s), 4.39 (2H, s), 3.75 (2H, s), 3.19- 3.10 (1H, m), 2.95-2.85 (1H, m), 2.83-2.73 (1H, m), 2.50-2.40 (2H, m), 2.27 (3H, s), 2.18 (3H, s), 2.06 (6H, d) A85 [00118] (d4-MeOH) 8.45 (1H, s), 7.67 (1H, t), 7.56 (2H, s), 3.24 (1H, br), 2.98- 2.88 (1H, m), 2.78-2.69 (1H, m), 2.53-2.48 (2H, br. m), 2.21 (6H, s), 1.38 (9H, s) A86 [00119] (d4-MeOH) 6.89 (2H, s), 3.94 (t, 2H), 3.19-3.11 (1H, m), 2.97-2.87 (1H, m), 2.83-2.75 (1H, m), 2.67 (2H, t), 2.51-2.39 (2H, m), 2.27 (3H, s), 2.08 (6H, s) A87 [00120] (d4-MeOH) 8.62 (2H, s), 7.95 (2H, s), 3.39-3.32 (2H, m), 3.32-3.26 (2H, m), 3.25 (3H, s), 3.12- 3.03 (m, 1H), 2.87-2.78 (m, 1H), 2.72-2.62 (1H, m), 2.44-2.32 (2H, m), 2.11 (6H, s) A88 [00121] (d4-MeoH) 7.20 (1H, t), 7.15-7.05 (3H, m), 6.85 (2H, s), 4.35 (2H, s), 3.15-3.10 (1H, m), 2.90 (1H, dd), 2.80 (1H, dd), 2.50-2.40 (2H, m), 2.35 (3H, s), 2.25 (3H, s), 2.10 (6H, s) A89 [00122] (d4-MeOH) 7.60-7.45 (4H, m), 6.85 (2H, s), 4.45 (2H, s), 3.20-3.10 (1H, m), 2.90-2.80 (2H, m), 2.50-2.40 (2H, m), 2.25 (3H, s), 2.05 (6H, 2 × s) A90 [00123] (d4-MeOH) 7.25-7.15 (2H, m), 6.95-6.85 (2H, m), 6.85 (2H, s), 4.35 (2H, s), 3.80 (3H, s), 3.15-3.05 (1H, m), 2.85 (1H, dd), 2.75 (1H, dd), 2.50-2.35 (2H, m), 2.25 (3H, s), 2.05 (6H, s) A91 [00124] (d4-MeOH) 6.85 (2H, s), 5.50-5.45 (1H, m), 3.30- 3.25 (2H, m), 3.15-3.10 (1H, m), 2.85 (1H, dd), 2.75 (1H, dd), 2.45-2.35 (2H, m), 2.25 (3H, s), 2.15 (2H, t), 2.05 (6H, s), 2.00-1.90 (4H, m), 1.70-1.55 (4H, m) A92 [00125] (d4-MeoH) 7.50 (2H, d), 7.25 (2H, d), 6.85 (2H, s), 4.40 (2H, s), 3.20- 3.15 (1H, m), 2.90 (1H, dd), 2.80 (1H, dd), 2.55- 2.45 (2H, m), 2.30 (3H, s), 2.05 (6H, 2 × s) A93 [00126] (d4-MeOH) 7.35 (2H, t), 7.05 (2H, t), 6.85 (2H, s), 5.05-4.95 (1H, m), 3.15-3.05 (1H, m), 2.85 (1H, dd), 2.75 (1H, dd), 2.50-2.40 (2H, m), 2.25 (3H, s), 2.05 (6H, s), 1.40 (3H, s) A94 [00127] (d4-MeoH) 6.85 (2H, s), 5.85-5.70 (1H, m), 5.12- 5.00 (2H, m), 3.25 (2H, t), 3.15-3.10 (1H, m), 2.85 (1H, dd), 2.70 (1H, dd), 2.45-2.35 (2H, m), 2.25-2.20 (5H, m), 2.05 (6H, s) A95 [00128] (d4-MeOH) 7.45 (1H, s), 7.40 (1H, d), 7.30 (1H, d), 6.85 (1H, s), 4.45 (2H, s), 3.20-3.10 (1H, m), 2.90 (1H, dd), 2.85 (1H, dd), 2.55-2.45 (2H, m), 2.25 (3H, s), 2.07 (3H, s), 2.05 (3H, s) A96 [00129] (d4-MeoH), 7.30-7.15 (4H, m), 6.85 (2H, s), 4.30 (2H, s), 3.15-3.10 (1H, m), 2.85 (1H, dd), 2.75 (1H, dd), 2.45-2.40 (2H, m), 2.25 (3H, s), 2.05 (6H, s) A97 [00130] (d4-MeOH) 6.85 (2H, s), 6.10 (1H, d), 5.90 (1H, d), 4.30 (2H, s), 3.15- 3.10 (1H, m), 2.85 (1H, dd), 2.75 (1H, dd), 2.45- 2.40 (2H, m), 2.22 (3H, s), 2.21 (3H, s), 2.05 (6H, s) A98 [00131] (d4-MeOH) 8.65 (1H, s), 7.95 (1H, d), 7.75 (1H, d), 6.85 (2H, s), 4.47 (2H, s), 3.20-3.15 (1H, m), 2.90 (1H, dd), 2.80 (1H, dd), 2.55-2.45 (2H, m), 2.25 9(3H, s), 2.04 (3H, s), 2.02 (3H, s) A99 [00132] (d4-MeOH) 7.45 (2H, d), 6.85 (2H, s), 6.40 (1H, s), 4.20 (2H, s), 3.20- 3.10 (1H, m), 2.85 (1H, dd), 2.75 (1H, dd), 2.45- 2.35 (2H, m), 2.20 (3H, s), 2.05 (6H, s) A100 [00133] (d4-MeOH) 7.90 (2H, t), 7.45 (1H, t), 7.35 (1H, t), 6.82 (2H, s), 4.75 (2H, s), 3.20-3.10 (1H, m), 2.95-2.85 (2H, m), 2.60- 2.45 (2H, m), 2.22 (3H, s), 2.05 (6H, s) A101 [00134] (d4-MeOH) 7.22 (2H, d), 7.05 (2H, d), 6.85 (2H, 2 × s), 6.35 (1H, d), 5.82 (1H, d), 3.25-3.15 (1H, m), 2.95 (1H, dd), 2.80 (1H, dd), 2.55-2.40 (2H, m), 2.30 (3H, s), 2.25 (3H, s), 2.05 (6H, s), 1.15-1.05 (4H, m) A102 [00135] (d4-MeoH) 8.02 (1H, d), 7.65 (1H, t), 7.60 (1H, d), 7.50 (1H, t), 6.85 (2H, s), 4.65 (2H, s), 3.20-3.10 (1H, m), 2.90 (1H, dd), 2.55-2.40 (2H, m), 2.25 (3H, s), 2.03 (3H, s), 2.02 (3H, s) A103 [00136] (d4-MeOH) (diagnostic peaks) 6.85 (s, 2H), 3.15 (br, 1H), 2.92-2.83 (m, 1H), 2.80-2.70 (m, 1H), 2.48-2.35 (m, 2H), 2.25 (s, 3H), 2.05 (s, 6H), 1.95-0.85 (m, 14H) A104 [00137] (d4-MeOH) 6.85 (2H, s), 4.10 (2H, s), 3.35 (3H, s), 3.15-3.10 (1H, m), 2.90 (1H, dd), 2.75 (1H, dd), 2.45-2.35 (2H, m), 2.25 (3H, s), 2.05 (6H, s), 1.60 (6H, s) A105 [00138] (d4-MeOH) 7.35 (1H, s), 6.85 (2H, s), 4.60 (2H, s), 3.20-3.10 (1H, m), 2.95 (1H, dd), 2.85 (1H, dd), 2.50-2.45 (2H, m), 2.45 (3H, s), 2.15 (3H, s), 2.05 (6H, s) A106 [00139] (d4-MeOH) 7.30-7.15 (4H, m), 6.85 (2H, m), 5.37 (1H, t), 3.20-3.10 (1H, m), 3.00-2.70 (4H, m), 2.50-2.40 (3H, m), 2.25 (3H, s), 2.05 (6H, s), 1.90-1.80 (1H, m) A107 [00140] (d4-MeoH) 8.45 (1H, d), 7.75 (1H, d), 7.35 (1H, dd), 6.85 (2H, s), 4.62 (2H, s), 3.20-3.10 (1H, m), 2.95-2.80 (2H, m), 2.60-2.45 (2H, m), 2.25 (3H, s), 2.03 (3H, s), 2.02 (3H, s) A108 [00141] (d4-MeOH) 7.72 (d, 1H), 7.65 (dd, 1H), 7.51 (d, 1H), 7.45 (dd, 1H), 6.83 (s, 2H), 4.60 (s, 2H), 3.16 (br, 1H), 2.98-2.70 (m, 2H), 2.52-2.45 (m, 2H), 2.25 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H) A109 [00142] (d4-MeOH) 8.78 (1H, s), 8.20 (1H, s), 6.85 (2H, s), 4.65 (2H, dd), 3.20- 3.10 (1H, m), 2.95-2.85 (2H, m), 2.65-2.50 (2H, m), 2.25 (3H, s), 2.04 (3H, s), 2.02 (3H, s) A110 [00143] (d4-MeOH) 7.35 (1H, t), 7.27 (1H, dd), 7.15-7.05 (2H, m), 6.85 (2H, s), 4.40 (2H, s), 3.15-3.10 (1H, m), 2.85 (1H, dd), 2.80 (1H, dd), 2.50-2.40 (2H, m), 2.25 (3H, s), 2.05 (6H, s) A111 [00144] 13.25 (1H, br), 8.45 (1H, s), 7.62 (2H, s), 7.50 (1H, d), 6.65 (1H, br), 5.80-5.70 (1H, m), 5.15- 5.10 (2H, m), 3.40-3.20 (3H, m), 2.90 (1H, dd), 2.75-2.65 (2H, m), 2.30- 2.20 (9H, m) A112 [00145] 12.90 (1H, br), 8.45 (1H, s), 7.65 (2H, s), 7.50 (1H, d), 6.95 (1H, br), 4.10 (2H, s), 3.35 (3H, s), 3.35-3.25 (1H, m), 2.90 (1H, dd), 2.75-2.60 (2H, m), 2.30-2.20 (7H, m), 1.65 (6H, s) A113 [00146] 12.70 (1H, br), 8.72 (1H, s), 8.45 (1H, s), 8.00 (1H, s), 7.70-7.60 (3H, m), 7.50 (1H, d), 4.80- 4.75 (2H, m), 3.45-3.30 (1H, m), 3.05-2.50 (3H, m), 2.35 (1H, d), 2.23 (3H, s), 2.22 (3H, s) A114 [00147] 8.45 (3H, s), 7.90 (1H, br), 7.78 (1H, d), 7.65 (2H, s), 7.50 (1H, d), 7.35-7.30 (1H, m), 4.75- 4.70 (2H, m), 3.40-3.35 (1H, m), 3.05-2.70 (3H, m), 2.35 (1H, dd), 2.23 (3H, s), 2.22 (3H, s) A115 [00148] 13.00 (1H, br), 8.60 (1H, s), 8.45 (1H, s), 8.25 (1H, br), 7.75 (1H, br), 7.65-7.55 (3H, m), 7.50 (1H, d), 4.45-4.20 (2H, m), 3.25 (1H, br), 2.95- 2.60 (3H, m), 2.25-2.15 (7H, m) A116 [00149] 8.45 (1H, s), 8.25 (1H, s), 8.15 (1H, br), 7.60 (2H, s), 7.5-7.45 (2H, m), 7.25 (1H, d), 4.30- 4.20 (2H, m), 3.25-3.20 (1H, m), 2.90 (1H, dd), 2.70-2.60 (2H, m), 2.25 (1H, d), 2.20 (3H, s), 2.15 (3H, s) A117 [00150] 12.90 (1H, br), 8.45 (1H, s), 7.62 (2H, s), 7.50 (1H, d), 7.30 (2H, d), 7.15 (1H, br), 6.90 (1H, br), 4.50-4.30 (2H, m), 3.40-3.30 (1H, m), 2.95 (1H, dd), 2.80-2.70 (2H, m), 2.30-2.20 (7H, m) A118 [00151] 13.00 (1H, br), 8.45 (1H, s), 7.60 (2H, s), 7.50 (1H, d), 7.35-7.30 (2H, m), 7.15-7.00 (2H, m), 4.55-4.40 (2H, m), 3.30- 3.20 (1H, m), 2.90 (1H, dd), 2.75-2.65 (2H, m), 2.25-2.15 (7H, m) A119 [00152] 8.45 (1H, s), 7.62 (2H, s), 7.50 (2H, d), 7.40 (1H, br), 7.25 (1H, t), 7.10-7.00 (2H, m), 4.35 (2H, d), 3.30-3.20 (1H, m), 2.85 (1H, dd), 2.75- 2.65 (2H, m), 2.35 (3H, s), 2.25-2.15 (7H, m) A120 [00153] 13.30 (1H, br), 8.45 (1H, s), 7.90 (1H, br), 7.60 (2H, s), 7.60-7.40 (5H, m), 4.45-4.30 (2H, m), 3.25 (1H, br), 2.90 (1H, dd), 2.75-2.60 (2H, m), 2.25-2.10 (7H, m) A121 [00154] 12.60 (1H, br), 8.45 (1H, s), 7.65 (2H, s), 7.50 (1H, d), 7.35 (2H, d), 7.20 (2H, d), 6.45 (1H, br), 4.55-4.45 (2H, m), 3.35 (1H, br), 2.95 (1H, dd), 2.85-2.75 (2H, m), 2.30-2.20 (7H, m) A122 [00155] 13.30 (1H, br), 8.40 (1H, s), 8.35 (1H, br), 8.15- 8.05 (2H, m), 7.60-7.45 (5H, m), 4.40-4.30 (2H, m), 3.25 (1H, br), 2.90 (1H, dd), 2.85-2.65 (2H, m), 2.20-2.15 (7H, m) A123 [00156] (d4-MeOH) 8.50 (s, 1H), 7.85 (d, 1H), 7.60 (s, 2H), 7.37 (s, 1H), 4.61 (s, 2H), 3.20 (br, 1H), 3.00-2.90 (m, 1H), 2.87 (dd, 1H), 2.55-2.50 (m, 2H), 2.45 (s, 3H), 2.20 (s, 6H) A124 [00157] Restricted rotation 13.25 (1H, br), 8.45 (1H, s), 7.65-7.60 (3H, m), 7.50 (1H, d), 7.30-7.20 (2H, m), 7.05-6.95 (2H, m), 5.10-5.00 (1H, m), 3.25 (1H, br), 2.95-2.65 (3H, m), 2.25-2.15 (7H, m), 1.50-1.40 (3H, m) A125 [00158] 13.10 (1H, br), 8.45 (1H, s), 7.65 (2H, s), 7.50 (1H, d), 7.40 (1H, br), 7.25-7.20 (1H, m), 7.00- 6.90 (2H, m), 4.65-4.50 (2H, m), 3.30 (1H, br), 2.90 (1H, dd), 2.75-2.65 (2H, m), 2.25-2.15 (7H, m) A126 [00159] 13.20 (1H, br), 8.45 (1H, s), 7.65 (2H, s), 7.50 (1H, d), 7.35-7.25 (2H, m), 7.00-6.90 (2H, m), 6.75 (1H, br), 4.50 (2H, d), 3.90 (3H, s), 3.30 (1H, br), 2.90 (1H, dd), 2.75-2.70 (2H, m), 2.25- 2.15 (7H, m) A127 [00160] 13.00 (1H, br), 8.45 (1H, s), 7.62 (2H, s), 7.25 (1H, s), 6.95 (1H, br), 6.92 (1H, d), 4.45-4.35 (2H, m), 3.30 (1H, br), 2.90 (1H, dd), 2.65-2.60 (2H, m), 2.25-2.15 (7H, m) A128 [00161] 8.45 (1H, s), 7.95 (1H, t), 7.60 (2H, 2 × s), 7.55 (1H, d), 7.35 (1H, s), 4.40-4.30 (2H, m), 3.25 (1H, br), 2.90 (1H, dd), 2.70-2.60 (2H, m), 2.25- 2.20 (1H, m), 2.20 (3H, s), 2.15 (3H, s) A129 [00162] A130 [00163] 13.30 (1H, br), 8.40 (1H, s), 7.60 (2H, s), 7.55 (1H, br), 7.50 (1H, d), 7.30 (1H, br), 7.15 (1H, s), 7.00 (1H, d), 4.45- 4.35 (2H, m), 3.25 (1H, br), 2.90 (1H, dd), 2.80- 2.65 (2H, m), 2.25-2.10 (7H, m) A131 [00164] 13.00 (1H, br), 8.45 (1H, s), 7.65 (2H, s), 7.50 (1H, d), 7.15 (1H, br), 7.15 (1H, d), 6.70 (1H, d), 4.60-4.50 (2H, m), 3.30 (1H, br), 2.90 (1H, dd), 2.75-2.65 (2H, m), 22.5-2.15 (10H, m) A132 [00165] (d4-MeOH) 8.54 (s, 1H), 8.50 (d, 1H), 7.98-7.90 (m, 2H, 7.87 (d, 1H), 7.62 (s, 2H), 7.41-7.35 (m, 1H), 4.68 (s, 2H), 3.27-3.18 (m, 1H), 3.00- 2.82 (m, 2H), 2.68-2.52 (m, 2H), 2.19 (d, 6H) A133 [00166] (d4-MeOH) 8.95 (s, 2H), 7.64-7.50 (m, 4H), 7.39 (s, 2H), 4.48 (s, 2H), 3.26-3.14 (m, 1H), 2.94 (dd, 1H), 2.84 (dd, 1H), 2.59-2.47 (m, 2H), 2.20 (d, 6H) A134 [00167] (d4-MeOH) 8.59 (s, 1H), 7.92-7.82 (m, 2H), 7.66 (s, 2H), 7.37-7.21 (m, 4H), 4.39 (s, 2H), 3.24- 3.14 (m, 1H), 2.94 (dd, 1H), 2.83 (dd, 1H), 2.59- 2.47 (m, 2H), 2.19 (d, 6H) A135 [00168] (d4-MeOH) 8.53 (s, 1H), 8.07 (s, 1H), 7.37-7.20 (m, 6H), 4.36 (s, 2H), 3.24-3.14 (m, 1H), 2.94 (dd, 1H), 2.83 (dd, 1H), 2.56-2.44 (m, 2H), 2.18 (d, 6H) A136 [00169] (d4-MeOH) 8.75 (s, 2H), 8.67 (s, 1H), 8.08 (s, 2H), 7.99 (d, 1H), 7.78 (d, 1H), 4.52 (s, 2H), 3.25-3.16 (m, 1H), 2.98 (dd, 1H), 2.85 (dd, 1H), 2.61-2.50 (m, 2H), 2.20 (d, 6H) A137 [00170] 8.00-7.84 (m, 2H), 7.82-7.73 (m, 1H), 7.67-7.58 (m, 2H), 7.54-7.40 (m, 3H), 7.27 (d, 2H), 4.76-4.56 (m, 2H), 3.32 (br, 1H), 3.03-2.87 (m, 2H), 2.84-2.70 (m, 1H), 2.29 (d, 1H), 2.18 (d, 6H) A138 [00171] (d4-MeOH) 8.72 (s, 2H), 8.04 (s, 2H), 7.33-7.19 (m, 4H), 4.37 (s, 2H), 3.25-3.13 (m, 1H), 2.93 (dd, 1H), 2.82 (dd, 1H), 2.57-2.43 (m, 2H), 2.19 (s, 6H) A139 [00172] (d4-MeOH) 8.90 (s, 2H), 7.34 (s, 2H), 7.28 (d, 1H), 6.99 (s, 1H), 6.95- 6.91 (m, 1H), 4.54 (s, 2H), 3.22-3.13 (m, 1H), 2.92 (dd, 1H), 2.79 (dd, 1H), 2.53-2.42 (m, 2H), 2.18 (s, 6H) A140* [00173] (d4-MeOH) 8.72 (s, 2H), 8.51-8.44 (m, 1H), 8.02 (s, 2H), 7.96 (d, 1H), 7.44-7.38 (m, 1H), 4.64 (s, 2H), 3.28-3.18 (m, 1H), 3.02-2.92 (m, 1H), 2.91-2.81 (m, 1H), 2.69- 2.52 (m, 2H), 2.19 (d, 6H) A141 [00174] (d4-MeOH) 8.71 (s, 2H), 8.04 (s, 2H), 7.28 (d, 1H), 6.99 (s, 1H), 6.96- 6.91 (m, 1H), 4.55 (s, 2H), 3.22-3.12 (m, 1H), 2.92 (dd, 1H), 2.79 (dd, 1H), 2.52-2.41 (m, 2H), 2.18 (s, 6H) A142 [00175] (d-4 MeOH) 9.11 (s, 1H) 9.04 (s, 2H), 7.39 (s, 2H), 7.35-7.21 (m, 4H), 4.39 (s, 2H), 3.24- 3.16 (m, 1H), 2.95 (dd, 1H), 2.83 (dd, 1H), 2.59- 2.47 (m, 2H), 2.20 (s, 6H) A143* [00176] (d4-MeOH) 9.10 (s, 1H), 9.02 (s, 2H), 8.49 (d, 1H), 7.93 (d, 1H), 7.42- 7.35 (m, 3H), 4.68 (s, 2H), 3.28-3.19 (m, 1H), 2.98 (dd, 1H), 2.88 (dd, 1H), 2.69-2.53 (m, 2H), 2.20 (d, 6H) A144 [00177] (d4-MeoH) 8.36 (s, 2H), 6.92 (s, 2H), 4.40 (s, 2H), 3.11-3.00 (m, 1H), 2.84-2.69 (m, 2H), 2.47- 2.34 (m, 2H), 2.42 (s, 3H), 1.94 (d, 6H), 1.89 (s, 3H) A145 [00178] (d4-MeOH) 8.73 (s, 2H), 8.06 (s, 2H), 7.64-7.49 (m, 4H), 4.46 (s, 2H), 3.26-3.14 (m, 1H), 2.94 (dd, 1H), 2.84 (dd, 1H), 2.57-2.43 (m, 2H), 2.19 (d, 6H) A146 [00179] (d4-MeOH) 8.56 (s, 1H), 7.90-7.81 (m, 2H), 7.65 (s, 2H), 7.62 (s, 1H), 7.60-7.49 (m, 3H), 4.46 (s, 2H), 3.24-3.14 (m, 1H), 2.94 (dd, 1H), 2.84 (dd, 1H), 2.59-2.45 (m, 2H), 2.19 (d, 6H) A147 [00180] (d4-MeOH) 9.11 (s, 1H), 8.75 (s, 2H), 8.50 (s, 1H), 8.40 (s, 1H), 7.69- 7.58 (m, 1H), 7.18 (d, 2H), 4.65-4.52 (m, 2H), 3.47-3.26 (m, 1H), 2.99 (dd, 1H), 2.89-2.76 (m, 2H), 2.58 (s, 3H), 2.47- 2.34 (m, 1H), 2.20 (d, 6H) A148 [00181] (d4-MeOH) 8.87 (s, 1H), 8.63 (s, 1H), 7.73 (s, 2H), 7.28 (d, 1H), 6.99 (s, 1H), 6.96-6.91 (m, 1H), 4.56 (s, H), 3.33- 3.13 (m, 1H), 2.93 (dd, 1H), 2.79 (dd, 1H), 2.54- 2.42 (m, 2H), 2.19 (s, 6H) A149 [00182] (d4-MeOH) 8.90 (s, 1H), 8.66 (s, 1H), 7.76 (s, 2H), 7.63-7.50 (m, 4H), 4.48 (s, 2H), 3.27-3.14 (m, 1H), 4.95 (dd, 1H), 2.84 (dd, 1H), 2.59-2.45 (m, 2H), 2.19 (d, 6H) A150 [00183] (d4-MeOH) 8.48 (s, 1H), 7.89 (dd, 1H), 7.31 (s, 2H), 7.28 (d, 1H), 7.01- 6.98 (m, 1H), 6.95-6.91 (m, 1H), 4.56 (s, 2H), 3.22-3.14 (m, 1H), 2.92 (dd, 1H), 2.79 (dd, 1H), 2.52-2.41 (m, 2H), 2.18 (d, 6H) A151 [00184] (d4-MeOH) 8.16 (d, 1H), 7.81 (d, 1H), 7.77 (s, 2H), 7.29 (d, 1H), 7.00 (s, 1H), 6.97-6.91 (m, 1H), 4.58 (s, 2H), 3.25- 3.12 (m, 1H), 2.94 (dd, 1H), 2.81 (dd, 1H), 2.56- 2.41 (m, 2H), 2.22 (s, 6H) A152 [00185] (d4-MeOH) 8.50-8.44 (m, 3H), 7.82 (d, 1H), 7.59 (s, 2H), 4.52 (s, 2H), 3.24-3.14 (m, 1H), 2.94 (dd, 1H), 2.86 (dd, 1H), 2.60-2.49 (m, 2H), 2.52 (s, 3H), 2.18 (d, 6H) A153 [00186] (d4-MeOH) 8.89 (s, 1H), 8.12 (d, 1H), 8.03 (d, 1H), 7.78 (s, 2H), 7.64- 7.49 (m, 4H), 4.47 (s, 2H), 3.25-3.14 (m, 1H), 2.95 (dd, 1H), 2.84 (dd, 1H), 2.59-2.47 (m, 2H), 2.21 (d, 6H) A154 [00187] (d4-MeOH) 8.56 (s, 1H), 8.04 (s, 1H), 7.66-7.60 (m, 3H), 7.60-7.48 (m, 4H), 4.46 (s, 2H), 3.25- 3.14 (m, 1H), 2.95 (dd, 1H), 2.83 (dd, 1H), 2.60- 2.48 (m, 2H), 2.21 (d, 6H) A155* [00188] (d4-MeOH) 8.49 (d, 1H), 8.14 (d, 1H), 7.94 (d, 1H), 7.82 (d, 1H), 7.74 (s, 2H), 7.43-7.38 (m, 1H), 4.67 (s, 2H), 3.28- 3.18 (m, 1H), 2.98 (dd, 1H), 2.88 (dd, 1H), 2.69- 2.53 (m, 2H), 2.21 (d, 6H) A156 [00189] (d4-MeOH) 8.90 (s, 1H), 8.13 (d, 1H), 8.01 (d, 1H), 7.78 (s, 2H), 7.28 (d, 1H), 6.99 (s, 1H), 6.96-6.92 (m, 1H), 4.57 (s, 2H), 3.22-3.13 (m, 1H), 2.92 (dd, 1H), 2.80 (dd, 1H), 2.53-2.42 (m, 2H), 2.19 (s, 6H) A157 [00190] (d4-MeOH) 8.73 (s, 2H), 8.47 (d, 2H), 8.04 (s, 2H), 4.52 (s, 2H), 3.22- 3.14 (m, 1H), 2.93 (dd, 1H), 2.86 (dd, 1H), 2.59- 2.48 (m, 2H), 2.53 (s, 3H), 2.18 (d, 6H) A158 [00191] (d4-MeOH) 8.41 (s, 1H), 7.75 (s, 2H), 7.64-7.50 (m, 6H), 4.47 (s, 2H), 3.22-3.12 (m, 1H), 2.96- 2.82 (m, 2H), 2.53-2.42 (m, 2H), 2.39 (s, 3H), 2.19 (d, 6H) A159 [00192] Restricted rotation 6.86 (2H, 2 × s), 3.45-3.05 (4H, m), 3.03 and 2.99 (3H, 2 × s), 2.95-2.85 (1H, m), 2.62-2.50 (1H, m), 2.30-2.25 (1H, m), 2.24 (3H, s), 2.15-2.05 (6H, m), 0.96 (3H, t), 0.90 (3H, dd) A160 [00193] Restricted rotation 6.75 (2H, 2 × s), 3.55-3.30 (3H, m), 3.15-2.92 (2H, m), 3.04 and 3.00 (3H, 2 × s), 2.65-2.50 (1H, m), 2.35 (1H, d), 2.16 (3H, s), 2.08 (3H, s), 2.07 (3H, s), 1.25 and 1.15 (3H, 2 × t) A161 [00194] Restricted rotation 6.84 and 6.82 (2H, 2 × s), 4.95-4.80 (0.6H, m), 4.12-4.02 (0.4H, m), 3.40 (1H, br), 3.20-3.02 (1H, m), 2.97-2.90 (1H, m), 2.88 and 2.87 (3H, 2 × s), 2.60-2.45 (1H, m), 2.27 (1H, d), 2.22 (3H, s), 2.11 (3H, s), 2.10 (3H, s), 1.25 (2.4H, t), 1.14 (3.6H, t) A162 [00195] 6.79 (s, 2H), 3.61-3.45 (m, 2H), 3.45-3.40 (m, 1H), 3.05-2.95 (m, 2H), 2.70-2.60 (m, 1H), 2.35 (d, 1H), 2.19 (s, 3H), 2.12-1.95 (m, 12H) A163 [00196] 6.84 (2H, 2 × s), 4.03- 3.83 (2H, m), 3.77-3.64 (2H, m), 3.37 (1H, br), 3.07 (1H, d), 2.90 (1H, dd), 2.70-2.50 (5H, m), 2.30-2.20 (1H, m), 2.23 (3H, s), 2.10 (3H, s), 2.08 (3H, s) A164 [00197] (d4-MeOH) 8.30-8.10 (m, 1H), 6.88 (2 × s, 2H), 3.15-2.59 (m, 3H), 2.27 (s, 4H), 2.19-2.03 (m, 6H), 1.44-1.30 (m, 9H), 1.26-0.95 (m, 3H A165 [00198] (d4-MeOH) 8.68-8.48 (m, 1H), 7.39-7.20 (m, 1H), 7.07-6.83 (m, 4H), 4.71-4.41 (m, 2H), 3.42-2.62 (m, 3H), 2.52-2.35 (m, 1H), 2.27 (s, 3H), 2.14-2.02 (m, 6H), 1.32-1.00 (m, 3H) A166 [00199] (d4-MeOH) 7.75-7.41 (m, 4H), 6.88 (d, 2H), 4.60-4.28 (m, 2H), 3.41-2.38 (m, 4H), 2.26 (s, 3H), 2.07 (d, 6H), 1.33-1.04 (m, 3H) A167 [00200] (d4-MeOH) 8.46 (d, 1H), 8.05-7.88 (m, 1H), 7.75 (d, 1H), 7.26 (br. s., 1H), 6.88 (s, 2H), 4.73-4.48 (m, 2H), 3.47-2.29 (m, 4H), 2.29-1.94 (m, 9H), 1.34-1.02 (m, 3H) A168 [00201] (d4-MeOH) 8.53 (s, 1H), 8.08 (s, 1H), 7.87 (br.s, 1H), 7.34 (s, 2H), 3.22- 3.12 (m, 1H), 2.91 (dd, 1H), 2.70 (dd, 1H), 2.51- 2.37 (m, 2H), 2.18 (s, 6H), 1.35 (s, 9H) A169 [00202] (d6- DMSO) 2.35 (br.s, 1H), 8.31 (br.s, 1H), 7.98 (br.s, 1H), 7.90 (br.s, 1H), 7.32 (d, 1H), 7.18-7.10 (br.s, 2H), 7.13 (d, 1H), 4.01 (br.s, 2H), 3.25-3.14 (br.m, 1H), 3.04-2.94 (br.m, 1H), 2.67-2.54 (br.m, 1H), 2.43 (s, 3H), 2.08- 2.00 (m, 2H), 1.88 (br.d, 6H) A170 [00203] 6.83 (2H, 2 × s), 3.49- 3.40 (2H, m), 3.39-3.30 (3H, m), 3.05 (1H, d), 2.90 (1H, dd), 2.52 (1H, dd), 2.30 (1H, dd), 2.22 (3H, s), 2.11 (3H, s), 2.09 (3H, s), 1.24 (3H, t), 1.16 (3H, t) A171 [00204] Restricted rotation 6.87 and 6.86 (2H, 2 × s), 3.43 (1H, q), 3.36-3.32 (3H, m), 3.24 (1H, t), 3.15 91H, br d), 2.88 (1H, dd), 2.56 (1H, br), 2.27 (1H, d), 2.25 (3H, s), 2.12 (3H, s), 2.10 (3H, s), 1.67-1.56 (2H, m), 1.23 and 1.16 (3H, 2 × 5), 0.96 and 0.91 (3H, 2 × t) A172 [00205] Restricted rotation 6.87 and 6.85 (2H, 2 × s), 4.65-4.50 (1H, m), 3.75 (1H, d), 3.37 (1H, br), 3.20-3.05 (2H, m), 2.95- 2.85 (1H, m), 2.70-2.50 (2H, m), 2.30-2.20 (1H, m), 2.25 (3H, s), 2.15- 2.08 (6H, m), 1.80-1.55 (3H, m), 1.20-1.10 (2H, m), 0.98 (3H, dd) A173 [00206] Restricted rotation 6.88 and 6.86 (2 × s, 2H), 4.70-4.53 (m, 1H), 3.81- 3.67 (m, 1H), 3.50-3.32 (m, 1H), 3.21-3.03 (m, 1H), 2.96-2.83 (m, 1H), 2.69-2.46 (m, 2H), 2.34- 2.20 (m, 4H, 2.17-2.04 (m, 7H), 1.96-1.79 (m, 1H), 1.75-1.59 (m, 2H), 1.00-0.90 (m, 6H), 0.88- 0.75 (m, 1H) A174 [00207] 14.10-13.35 (m, 1H), 8.02 (br. s., 1H), 6.89 (d, 2H), 3.44-2.97 (m, 6H), 2.97-2.54 (m, 4H), 2.54-2.31 (m, 1H), 2.31-1.86 (m, 10H) A175 [00208] 13.50 (1H, br), 7.42 (1H, br), 6.86 (2H, s), 5.79- 5.60 (1H, m), 5.18-5.03 (2H, m), 3.72-3.60 (2H, m), 3.08 (1H, br), 2.81 (1H, dd), 2.62 (1H, d), 2.54-2.36 (1H, m), 2.23 (3H, s), 2.20-2.10 (1H, m), 2.10 (6H, s) A176 [00209] 13.60 (1H, br), 7.45 (1H, br), 6.87 (2H, s), 3.42 (2H, t), 3.35 (3H, s), 3.30-3.20 (2H, m), 3.15 (1H, br), 2.75 (1H,dd), 2.62-2.45 (2H, m), 2.25 (3H, s), 2.15 (1H, d), 2.10 (6H, s), 1.75-1.65 (2H, m) A177 [00210] 7.60 (1H, br), 6.86 (2H, s), 3.15 (1H, br), 3.05- 2.90 (1H, m), 2.90-2.75 (2H, m), 2.65 (1H, d), 2.50-2.40 (1H, m), 2.25 (3H, s), 2.12 (1H, d), 2.09 (6H, s), 1.50-1.25 (2H, m), 1.12-1.00 (1H, m), 0.90-0.80 (6H, m) A178 [00211] 7.35 (1H, br), 6.85 (2H, s), 3.20-3.10 (1H, m), 3.10-3.00 (2H, m), 2.82 (1H, dd), 2.62 (1H, d), 2.50-2.10 (1H, m), 2.25 (3H, s), 2.12 (1H, d), 2.10 (6H, s), 1.40-1.20 (10H, m), 0.88 (3H, t) A179 [00212] 13.60 (1H, br), 7.72 (1H, br), 6.87 (2H, s), 3.60- 3.50 (6H, m), 3.39 (3H, s), 3.38-3.29 (2H, m), 3.18 (1H, m), 2.75 (1H, dd), 2.68-2.47 (2H, m), 2.25 (3H, s), 2.18 (1H, d), 2.10 (6H, s), 1.79- 1.70 (2H, m) A180 [00213] 13.25 (1H, br), 8.08 (1H, br), 6.87 (2H, s), 4.69 (2H, dd), 4.51-4.41 (2H, m), 3.18 (1H, br), 2.87 (1H, dd), 2.70 (1H, d), 2.52-2.45 (1H, m), 2.28 (3H, s), 2.16 (1H, d), 2.10 (6H, s) A181 [00214] (~1:1 mixture of cis/trans) 8.20 (1H, br), 6.87 (2H, s), 5.20-5.00 (0.5H, m), 4.90-4.65 (0.5H, m), 4.48-4.35 (m, 0.5H), 3.90-3.80 (0.5H, m), 3.10 (1H, br), 2.95- 2.75 (2H, m), 2.65-2.40 (3H, m), 2.30-2.10 (5H, m), 2.10-2.05 (7H, m) A182 [00215] 8.50 (1H, br), 6.85 (2H, s), 4.85-4.70 (3H, m), 4.45-4.35 (2H m), 3.15- 3.05 (1H, m), 2.81 (1H, dd), 2.57 (1H, d), 2.45- 2.40 (1H, m), 2.25 (3H, s), 2.20 (1H, d), 2.10 (6H, s) A183 [00216] Restricted rotation and mix of diastereoisomers 6.86 (2H, s), 5.66-5.50 (1H, m), 3.32 (1H, br), 3.16-2.77 (5H, m), 2.72- 2.49 (1H, m), 2.36 (1H, s), 2.30-2.18 (4H, m), 2.15-2.03 (6H, m), 1.55- 1.33 (3H, m) A184 [00217] 7.34 (1H, br), 6.87 (2H, s), 3.20-3.00 (3H, m), 2.72 (1H, dd), 2.65 (1H, d), 2.50-2.40 (1H, m), 2.35-2.25 (1H, m), 2.25 (3H, s), 2.12 (1H, d), 2.10 (6H, s), 2.00-1.90 (2H, m), 1.85-1.75 (2H, m), 1.67-1.52 (2H, m) A185 [00218] (d4-MeOH) 6.85 (2H, s), 4.15-4.10 (1H, m), 2.95- 2.85 (3H, m), 2.75-2.65 (2H, m), 2.60-2.45 (2H, m), 2.30-2.25 (2H, m), 2.25 (3H, s), 2.10 (3H, s), 2.05 (3H, s) A186 [00219] (d4-MeOH) 7.82 (d, 1H), 7.62 (s, 2H), 7.54 (d, 1H), 3.21-3.13 (m, 1H), 2.41 (dd, 1H), 2.70 (dd, 1H), 2.50-2.39 (m, 2H), 2.19 (s, 6H), 1.35 (s, 9H) A187 [00220] (d4-MeOH) 6.87 (s, 2H), 4.60 (br, 2H), 3.20-3.12 (m, 1H), 2.92 (dd, 1H), 2.73 (dd, 1H), 2.54 (dd, 1H), 2.41 (d, 1H), 2.25 (s, 3H), 2.10 (s, 6H)

TABLE-US-00012 TABLE T2 Physical Data LCMS or Compound .sup.1H NMR (400 MHz, Number Structure CDCl.sub.3) unless stated. B1 [00221] 1H NMR (400 MHz, d6-DMSO) 10.4 (s, 1H), 7.72 (s, 4H), 6.74 (s, 2H), 3.00-2.70 (m, 3H), 2.48-2.35 (m, 2H), 2.14 (s, 3H), 1.92 (d, 6H) B2 [00222] 1H NMR (CDCl3 + 2 drops of d6- DMSO) 9.65 (br, 1H), 7.30 (s, 1H), 6.99 (d, 1H), 6.87 (d, 2H), 6.81 (d, 1H), 3.86 (2 × s, 6H), 3.40-3.22 (m, 1H), 3.06-2.75 (m, 2H), 2.26 (s, 3H), 2.20-2.02 (m, 8H) B3 [00223] 8.66 (br.s, 1H), 7.95-7.85 (m, 1H), 6.91-6.81 (m, 1H), 6.81 (s, 2H), 3.31-3.22 (m, 1H), 2.97-2.82 (m, 2H), 2.82-2.72 (m, 1H), 2.32-2.23 (m, 1H), 2.20 (s, 3H), 2.06 (s, 6H) B4 [00224] 1.83 mins m/z 394.28 [M + H]+ B5 [00225] 1H NMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.07 (s, 2H), 3.24-3.11 (m, 1H), 3.01-2.84 (m, 1H), 2.79-2.62 (m, 1H), 2.54-2.33 (m, 2H), 2.20 (s, 6H), 1.36 (s, 9H) B6 [00226] 1.20 mins, m/z = 484.14 (M + H)+ B7 [00227] 7.84-7.60 (m, 1H), 6.86 (s, 2H), 3.66-3.49 (m, 6H), 3.43-3.08 (m, 6H), 2.83 (s, 1H), 2.70-2.44 (m, 2H), 2.32-2.02 (m, 10H), 1.75 (t, 2H) B8 [00228] 1H NMR (400 MHz, CD3OD) 6.88 (s, 2H), 4.57 (br.s., 2H), 3.25-3.08 (m, 1H), 2.92 (dd, 1H), 2.74 (d, 1H), 2.63-2.35 (m, 2H), 2.26 (s, 3H), 2.09 (d, 6H) B9 [00229] 1.22 mins, m/z = 389.24 (M + H)+ B10 [00230] 1.27 mins, m/z = 422.26 (M + H)+ B11 [00231] 1.29 mins, m/z = 394.26 (M + H)+ B12 [00232] 1.36 mins, m/z = 378.26 (M + H)+ B13 [00233] 1.38 mins, m/z = 398.21 (M + H)+ B14 [00234] 1.37 mins, m/z = 378.25 (M + H)+ B15 [00235] 1.41 mins, m/z = 432.24 (M + H)+ B16 [00236] 1.30 mins, m/z = 382.21 (M + H)+ B17 [00237] 1.36 mins, m/z = 398.21 (M + H)+ B18 [00238] 1.29 mins, m/z = 394.26 (M + H)+ B19 [00239] 1.41 mins, m/z = 432.23 (M + H)+ B20 [00240] 1.27 mins, m/z = 409.25 (M + H)+ B21 [00241] 1.30 mins, m/z = 382.21 (M + H)+ B22 [00242] 1.38 mins, m/z = 442.1 (M + H)+ B23 [00243] 1.40 mins, m/z = 442.1 (M + H)+ B24 [00244] 7.60 (s, 1H), 7.52 (s, 2H), 6.42 (s, 1H), 3.28-3.19 (m, 1H), 2.84 (dd, 1H), 2.65-2.59 (m, 2H), 2.19 (d, 6H), 2.19-2.12 (m, 1H), 1.33 (s, 9H) B25 [00245] 6.87 (s, 2H), 6.76 (d, 1H), 4.09- 3.94 (m, 1H), 3.30-3.12 (m, 1H), 2.93-2.79 (m, 1H), 2.73-2.48 (m, 2H), 2.25 (s, 3H), 2.10 (s, 6H), 1.65-1.48 (m, 1H), 1.37-1.14 (m, 3H), 1.11-1.02 (m, 3H), 0.94-0.81 (m, 6H) B26 [00246] 6.78 (s, 2H), 6.66-6.53 (m, 1H), 3.93-3.80 (m, 1H), 3.30-3.16 (m, 1H), 2.96-2.81 (m, 1H), 2.75-2.55 (m, 2H), 2.25-2.18 (m, 4H), 2.07 (s, 6H), 1.09-0.98 (m, 3H), 0.90- 0.85 (m, 9H) B27 [00247] 6.78 (s, 2H), 6.27 (s, 1H), 5.81- 5.62 (m, 1H), 5.18-5.04 (m, 2H), 3.72-3.54 (m, 1H), 3.24-3.20 (m, 1H), 2.92-2.85 (m, 1H), 2.63-2.58 (m, 1H), 2.44-2.40 (m, 2H), 2.23- 2.18 (m, 4H), 2.08 (s, 3H), 2.07 (s, 3H), 1.32 (s, 6H) B28 [00248] 6.79 (s, 2H), 6.62 (d, 1H), 4.07- 3.90 (m, 1H) 3.75-3.54 (m, 1H), 3.27-3.20 (m, 1H), 2.95-2.82 (m, 1H), 2.67-2.50 (m, 2H), 2.25-2.20 (m, 4H), 2.08 (s, 6H), 1.88-1.66 (m, 3H), 1.64-1.32 (m, 5H), 1 16- 0.99 (m, 5H) B29 [00249] 7.37-7.19 (m, 5H), 7.08 (s, 1H), 6.79 (s, 2H), 3.70-3.55 (m, 1H), 3.23-3.12 (m, 1H), 2.88-2.82 (m, 1H), 2.72-2.67 (m, 1H), 2.59-2.52 (m, 1H), 2.19 (s, 3H), 2.07 (s, 3H), 2.04 (s, 3H), 1.65 (s, 3H), 1.63 (s, 3H) B30 [00250] 1H NMR (400 MHz, CD3OD) 8.44 (s, 1H), 7.69 (s, 2H), 3.22-3.13 (m, 1H), 2.92 (dd, 1H), 2.70 (dd, 1H), 2.52-2.39 (m, 2H), 2.20 (s, 6H), 1.36 (s, 9H) B31 [00251] 6.81 (s, 2H), 6.49-6.38 (m, 1H), 3.44-3.25 (m, 2H), 2.97-2.81 (m, 1H), 2.73-2.61 (m, 2H), 2.25-2.21 (m, 4H), 2.09 (s, 6H), 1.23-1.19 (m, 3H), 0.77-0.73 (m, 1H), 0.59- 0.39 (m, 2H), 0.38-0.16 (m, 2H) B32 [00252] 6.88 (s, 2H), 3.20-3.10 (m, 1H), 2.93-2.86 (m, 1H), 2.74-2.68 (m, 1H), 2.45-2.32 (m, 4H), 2.27 (s, 3H), 2.08 (s, 6H), 2.08-2.00 (m, 2H), 1.95-1.85 (m, 2H), 1.47 (s, 3H) B33 [00253] 1H NMR (400 MHz, CD3OD) 8.42 (s, 1H), 7.68-7.60 (m, 1H), 7.53 (s, 2H), 7.34-7.20 (m, 4H), 4.38 (s, 2H), 3.23-3.14 (m, 1H), 2.93 (dd, 1H), 2.83 (dd, 1H), 2.56-2.46 (m, 2H), 2.19 (d, 6H) B34 [00254] 7.42 (d, 2H), 7.27 (d, 2H), 6.84 (s, 2H), 4.37 (s, 2H), 3.44 (s, 1H), 3.19-3.10 (m, 1H), 2.88 (dd, 1H), 2.79 (dd, 1H), 2.50-2.39 (m, 2H), 2.23 (s, 3H), 2.03 (d, 6H) B35 [00255] 13.16-12.86 (m, 1H), 6.86 (d, 3H), 3.32-3.12 (m, 1H), 2.90-2.70 (m, 1H), 2.69-2.42 (m, 2H), 2.25 (s, 3H), 2.10 (s, 7H), 1.80 (s, 3H), 1.53 (d, 6H) B36 [00256] 8.00-7.63 (m, 1H), 6.88 (d, 2H), 4.11 (t, 2H), 3.83 (d, 2H), 3.29- 3.07 (m, 1H), 2.85 (dd, 1H), 2.60 (br.s., 2H), 2.31-2.03 (m, 10H) B37 [00257] 7.71-7.43 (m, 1H), 6.88 (d, 2H), 3.29-3.06 (m, 3H), 2.83 (dd, 1H), 2.73-2.39 (m, 2H), 2.34-1.94 (m, 13H) B38 [00258] 6.86 (d, 2H), 4 40-3.95 (m, 2H), 3.42-3.26 (m, 1H), 3.18-2.95 (m, 4H), 2.88 (dd, 1H), 2.77-2.53 (m, 1H), 2.44-2.19 (m, 5H), 2.10 (d, 6H) B39 [00259] 1HNMR (400 MHz, CD3OD) 6.86 (s, 2H), 4.00-3.80 (m, 2H), 3.16- 3.04 (m, 1H), 2.87 (dd, 1H), 2.74 (dd, 1H), 2.49-2.32 (m, 2H), 2.25 (s, 3H), 2.06 (s, 6H), 1.39 (d, 6H) B40 [00260] 1H NMR (400 MHz, CD3OD) 6.91-6.80 (m, 2H), 3.56-3.39 (m, 1H), 3.28-3.11 (m, 2H), 2.95-2.76 (m, 2H), 2.50-2.41 (m, 2H), 2.28- 2.21 (m, 3H), 2.11-2.01 (m, 6H), 1.99-1.86 (m, 1H), 1.66 (dd, 1H), 1.31 (t, 1H) B41 [00261] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 3.13 (dq, 1H), 2.86 (dd, 1H), 2.72-2.64 (m, 1H), 2.45-2.33 (m, 2H), 2.25 (s, 3H), 2.07-1.98 (m, 8H), 1.79-1.57 (m, 6H), 1.44- 1.36 (m, 3H) B42 [00262] 10.63-10.36 (m, 1H), 6.85 (d, 2H), 3.24 (d, 3H), 2.66 (br.s., 3H), 2.24 (s, 4H), 2.06 (d, 6H), 1.40 (d, 6H) B43 [00263] 8.16 (s, 1H), 6.87 (d, 2H), 3.30- 3.11 (m, 1H), 2.95-2.44 (m, 3H), 2.26 (s, 4H), 2.07 (s, 6H), 1.49 (d, 6H) B44 [00264] 13.94-13.14 (m, 1H), 7.72-7.37 (m, 1H), 6.86 (s, 2H), 4.91-4.58 (m, 2H), 3.69-3.37 (m, 2H), 3.26- 3.03 (m, 1H), 2.81 (dd, 3H), 2.31- 2.00 (m, 10H), 1.67 (s, 3H) B45 [00265] 6.86 (d, 2H), 4 44-4.14 (m, 4H), 3.45-2.95 (m, 2H), 2.89 (dd, 1H), 2.81-2.64 (m, 1H), 2.40 (s, 1H), 2.34-2.19 (m, 5H), 2.09 (d, 6H) B46 [00266] 13.68-13.20 (m, 1H), 7.98-7.53 (m, 1H), 6.88 (d, 2H), 6.05 (d, 1H), 5.82-5.57 (m, 1H), 3.93-3.36 (m, 2H), 3.23-3.01 (m, 1H), 2.92-2.72 (m, 1H), 2.70-2.35 (m, 2H), 2.34- 2.02 (m, 10H) B47 [00267] 13.69-13.30 (m, 1H), 7.22-7.00 (m, 1H), 6.86 (s, 2H), 5.68-5.19 (m, 2H), 3.66 (d, 2H), 3.32-3.02 (m, 1H), 2.79 (d, 1H), 2.67-2.38 (m, 2H), 2.33-1.95 (m, 10H), 1.75- 1.55 (m, 3H) B48 [00268] 1H NMR (400 MHz, CD3OD) 8.83 (s, 1H), 8.37 (s, 1H), 7.59 (s, 2H), 3.22-3.13 (m, 1H), 2.91 (dd, 1H), 2.72 (dd, 1H), 2.50-2.39 (m, 2H), 2.22 (s, 6H), 1.36 (s, 9H) B49 [00269] 1HNMR (400 MHz, CD3OD) 8.78 (s, 2H), 8.06 (s, 2H), 7.87 (br, 1H), 3.22-3.13 (m, 1H), 2.92 (dd, 1H), 2.70 (dd, 1H), 2.50-2.38 (m, 2H), 2.20 (s, 6H), 1.34 (s, 9H) B50 [00270] 1HNMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.04 (s, 2H), 7.88 (br, 1H), 3.22-3.13 (m, 1H), 2.91 (dd, 1H), 2.69 (dd, 1H), 2.51-2.38 (m, 2H), 2.20 (s, 6H), 1.34 (s, 9H) B51 [00271] 1HNMR (400 MHz, d4MeOH, 14ba357) 8.41 (s, 1H), 7.88 (br, 1H), 7.62 (t, 1H), 7.53 (s, 2H), 3.22-3.13 (m, 1H), 2.91 (dd, 1H), 2.70 (dd, 1H), 2.50-2.38 (m, 2H), 2.19 (s, 6H), 1.34 (s, 9H) B52 [00272] 1HNMR (400 MHz, CD3OD) 8.41 (s, 1H), 7.78 (br, 1H), 7.52 (t, 1H), 7.42 (s, 2H), 3.11-3.02 (m, 1H), 2.80 (dd, 1H), 2.59 (dd, 1H), 2.39- 2.28 (m, 2H), 2.08 (s, 6H), 1.24 (s, 9H) B53 [00273] 8.48 (s, 1H), 7.81 (d, 1H), 7.58 (s, 2H), 3.21-3.12 (m, 1H), 2.93 (dd, 1H), 2.79 (dd, 1H), 2.56-2.43 (m, 2H), 2.19 (s, 6H) B54 [00274] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 8.4, 1H), 7.55 (s, 2H), 3.24-3.12 (m, 1H), 2.95 (dd, 1H), 2.80 (m, 1H), 2.51 (t, 2H), 2.23-2.13 (m, 6H) B55 [00275] 7.20-7.03 (m, 1H), 6.86 (d, 2H), 3.64-3.30 (m, 5H), 3.27-3.14 (m, 1H), 2.93-2.74 (m, 1H), 2.74-2.47 (m, 2H), 2.40 (d, 1H), 2.32-1.89 (m, 10H), 1.58 (s, 3H) B56 [00276] 7.76-7.47 (m, 1H), 6.87 (s, 2H), 4.82-4.48 (m, 1H), 3.23-3.03 (m, 1H), 2.89-2.70 (m, 1H), 2.65-2.34 (m, 2H), 2.31-2.03 (m, 11H), 1.37 (d, 3H) B57 [00277] 1H NMR (400 MHz, CD3OD) 6.85 (s, 2H), 6.09-5.71 (m, 1H), 3.64- 3.50 (m, 2H), 3.15-3.04 (m, 1H), 2.93-2.76 (m, 2H), 2.46-2.36 (m, 2H), 2.24 (s, 3H), 2.08-2.01 (m, 6H) B58 [00278] 1H NMR (400 MHz, CD3OD) 6.89-6.81 (m, 2H), 4.44 (dd, 1H), 3.12 (br.s., 1H), 2.99-2.75 (m, 2H), 2.54-2.36 (m, 2H), 2.28-2.21 (m, 3H), 2.06 (d, 6H), 1.36-1.28 (m, 1H), 0.78-0.62 (m, 2H), 0.57- 0.43 (m, 2H) B59 [00279] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 3.97-3.84 (m, 2H), 3.17- 3.04 (m, 1H), 2.94-2.79 (m, 2H), 2.49-2.36 (m, 2H), 2.26-2.19 (m, 3H), 2.05 (s, 6H) B60 [00280] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 5.84-5.53 (m, 1H), 3.40 (d, 2H), 3.13 (dd, 1H), 2.95-2.72 (m, 2H), 2.49-2.36 (m, 2H), 2.27- 2.19 (m, 3H), 2.09-2.01 (m, 6H), 0.83-0.66 (m, 4H) B61 [00281] 1H NMR (400 MHz, CD3OD) 6.89-6.80 (m, 2H), 4.56-4.35 (m, 2H), 3.58-3.41 (m, 2H), 3.19-3.07 (m, 1H), 2.94-2.71 (m, 2H), 2.49- 2.40 (m, 2H), 2.24 (s, 3H), 2.09- 2.03 (m, 6H) B62 [00282] 7.88-7.67 (m, 1H), 6.87 (d, 2H), 5.44-4.89 (m, 3H), 3.26-3.04 (m, 1H), 2.87 (d, 1H), 2.74-2.48 (m, 2H), 2.25 (s, 4H), 2.15-2.02 (m, 6H), 1.21-0.79 (m, 4H) B63 [00283] 1H NMR (400 MHz, CD3OD) 6.92-6.76 (m, 2H), 4.65 (dtd, 1H), 3.13 (d, 1H), 2.94-2.76 (m, 2H), 2.51-2.33 (m, 2H), 2.25 (s, 3H), 2.05 (s, 6H), 1.36-1.28 (m, 3H) B64 [00284] 1H NMR (400 MHz, CD3OD) 8.31-8.23 (m, 1H), 8.09 (d, 1H), 7.77 (ddd, 1H), 7.16-7.02 (m, 1H), 6.91-6.80 (m, 2H), 3.20 (dtd, 1H), 3.05-2.88 (m, 2H), 2.67 (dd, 1H), 2.56 (dd, 1H), 2.28-2.19 (m, 3H), 2.07 (d, 6H) B65 [00285] 1H NMR (400 MHz, CD3OD) 6.85 (s, 2H), 3.13 (d, 1H), 2.86 (dd, 1H), 2.70 (dd, 1H), 2.48-2.31 (m, 2H), 2.24 (s, 3H), 2.06 (s, 6H), 1.36-1.28 (m, 1H), 1.25 (d, 6H), 0.46-0.30 (m, 4H) B66 [00286] 1H NMR (400 MHz, CD3OD) 8.30 (d, 1H), 7.27 (s, 1H), 7.17 (d, 1H), 6.84 (s, 2H), 4 48 (s, 2H), 3.19- 3.10 (m, 1H), 2.93-2.80 (m, 2H), 2.57-2.42 (m, 2H), 2.36 (s, 3H), 2.23 (s, 3H), 2.03 (d, 6H) B67 [00287] 1H NMR (400 MHz, CD3OD) 8.32 (d, 1H), 7.67 (d, 1H), 7.30-7.23 (m, 1H), 6.82 (s, 2H), 4.53 (s, 2H), 3.20-3.11 (m, 1H), 2.91-2.76 (m, 2H), 2.57-2.49 (m, 1H), 2.49-2.40 (m, 1H), 2.35 (s, 3H), 2.12 (s, 3H), 2.03 (d, 6H) B68 [00288] 1H NMR (400 MHz, CD3OD) 7.69 (t, 1H), 7.24-7.14 (m, 2H), 6.83 (s, 2H), 4 47 (s, 2H), 3.19-3.10 (m, 1H), 2.92-2.78 (m, 2H), 2.55-2.42 (m, 2H), 2.52 (s, 3H), 2.23 (s, 3H), 2.04 (d, 6H) B69 [00289] 1H NMR (400 MHz, CD3OD) 7.64 (d, 2H), 7 44 (d, 2H), 6.84 (s, 2H), 4.42 (s, 2H), 3.18-3.10 (m, 1H), 2.89 (dd, 1H), 2.80 (dd, 1H), 2.52- 2.41 (m, 2H), 2.23 (s, 3H), 2.03 (d, 6H) B70 [00290] 1H NMR (400 MHz, CD3OD) 8.41 (s, 1H), 7.67-7.59 (m, 1H), 7.52 (s, 2H), 7.36-7.28 (m, 1H), 7.11 (d, 1H), 7.03 (d, 1H), 7.11-6.93 (m, 1H), 4.39 (s, 2H), 3.23-3.14 (m, 1H), 2.93 (dd, 1H), 2.83 (dd, 1H), 2.57-2.46 (m, 2H), 2.18 (s, 6H) B71 [00291] 1H NMR (400 MHz, CD3OD) 8.42 (s, 1H), 7.67-7.59 (m, 1H), 7.52 (s, 2H), 6.95-6.88 (m, 2H), 6.87-6.78 (m, 1H), 4.38 (s, 2H), 3.22-3.14 (m, 1H), 2.94 (dd, 1H), 2.85 (dd, 1H), 2.57-2.48 (m, 2H), 2.18 (s, 6H) B72 [00292] 1H NMR (400 MHz, CD3OD) 8.42 (s, 1H), 7.68-7.59 (m, 1H), 7.53 (s, 2H), 7.36-7.28 (m, 2H), 7.08-7.00 (m, 2H), 4.37 (s, 2H), 3.23-3.14 (m, 1H), 2.92 (dd, 1H), 2.81 (dd, 1H), 2.56-2.44 (m, 2H), 2.19 (s, 6H) B73 [00293] 1H NMR (400 MHz, CD3OD) 8.42 (s, 1H), 7.69-7.62 (m, 1H), 7 54 (s, 2H), 7.27-7.15 (m, 2H), 7.15-7.08 (m, 1H), 4.36 (s, 2H), 3.23-3.14 (m, 1H), 2.93 (dd, 1H), 2.82 (dd, 1H), 2.54-2.44 (m, 2H), 2.19 (s, 6H) B74 [00294] 8.51 (d, 1H), 7.97 (d, 1H), 7.89- 7.83 (m, 1H), 7.31 (s, 2H), 3.22- 3.13 (m, 1H), 2.91 (dd, 1H), 2.71 (dd, 1H), 2.49-2.39 (m, 2H), 2.19 (s, 6H), 1.34 (s, 9H) B75 [00295] 1H NMR (400 MHz, CD3OD) 8.99-8.79 (m, 1H), 8.18-8.01 (m, 1H), 7.99-7.86 (m, 1H), 7.74 (s, 2H), 7.64-7.51 (m, 1H), 3.30-3.13 (m, 1H), 3.04-2.86 (m, 1H), 2.78- 2.51 (m, 2H), 2.48-2.33 (m, 1H), 2.25 (d, 6H), 1.38 (s, 9H) B76 [00296] 1H NMR (400 MHz, CD3OD) 6.91-6.79 (m, 2H), 4.60-4.39 (m, 4H), 3.36-3.32 (m, 2H), 3.14 (d, 1H), 2.93-2.71 (m, 2H), 2.49-2.39 (m, 2H), 2.36-2.27 (m, 1H), 2.27- 2.21 (m, 3H), 2.10-2.00 (m, 6H) B77 [00297] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 3.56-3.43 (m, 1H), 3.28-3.21 (m, 1H), 3.24-3.11 (m, 1H), 2.99- 2.90 (m, 1H), 2.85-2.75 (m, 1H), 2.57-2.45 (m, 2H), 2.22-2.14 (m, 6H), 2.00-1.87 (m, 1H), 1.68 (dd, 1H), 1.35-1.26 (m, 1H) B78 [00298] 1HNMR (400 MHz, CD3OD) 6.88-6.79 (m, 2H), 3.12 (dd, 1H), 2.87 (dd, 1H), 2.74-2.62 (m, 1H), 2.45-2.29 (m, 2H), 2.27-2.19 (m, 3H), 2.09-1.97 (m, 6H), 1.42-1.28 (m, 1H), 0.72-0.57 (m, 4H), 0.44- 0.35 (m, 2H), 0.23-0.12 (m, 2H) B79 [00299] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 3.48-3.36 (m, 2H), 3.37- 3.27 (m, 1H), 3.25-3.10 (m, 1H), 2.98-2.86 (m, 2H), 2.80 (br.s., 1H), 2.42 (d, 1H), 2.27-2.20 (m, 3H), 2.10-2.01 (m, 6H), 1.74-1.57 (m, 2H), 1.12-0.99 (m, 1H), 0.93 (td, 3H), 0.53-0.45 (m, 1H), 0.63- 0.44 (m, 2H), 0.34-0.23 (m, 2H) B80 [00300] 1H NMR (400 MHz, CD3OD) 6.90-6.80 (m, 2H), 3.16 (br.s., 1H), 3.01-2.99 (m, 3H), 2.97-2.83 (m, 1H), 2.41-2.21 (m, 5H), 2.13- 2.08 (m, 1H), 2.09-1.98 (m, 6H), 1.46-1.43 (m, 9H) B81 [00301] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 4.74-4.50 (m, 1H), 3.21- 3.05 (m, 1H), 2.94-2.68 (m, 3H), 2.51-2.35 (m, 2H), 2.25 (s, 3H), 2.05 (s, 6H), 1.18-1.04 (m, 1H), 0.99-0.84 (m, 1H) B82 [00302] 1H NMR (400 MHz, CD3OD) 6.90-6.78 (m, 2H), 3.74-3.64 (m, 1H), 3.26 (s, 1H), 3.15 (d, 1H), 2.93-2.75 (m, 2H), 2.57-2.37 (m, 2H), 2.26-2.18 (m, 3H), 2.10-2.01 (m, 6H), 1.54-1.47 (m, 1H), 1.41- 1.36 (m, 3H), 1.34-1.25 (m, 1H) B83 [00303] 1H NMR (400 MHz, CD3OD) 8.84 (s, 1H), 8.36 (s, 1H), 7.42 (s, 2H), 3.22-3.14 (m, 1H), 2.92 (dd, 1H), 2.70 (dd, 1H), 2.51-2.39 (m, 2H), 2.19 (s, 6H), 1.34 (s, 9H) B84 [00304] 1H NMR (400 MHz, CD3OD) 8.47 (d, 1H), 7.78 (t, 1H), 7.52 (s, 2H), 7.51-7.44 (m, 1H), 3.22-3.14 (m, 1H), 2.91 (dd, 1H), 2.71 (dd, 1H), 2.52-2.39 (m, 2H), 2.19 (s, 6H), 1.34 (s, 9H) B85 [00305] 8.77 (s, 1H), 8.14 (dd, 1H), 7.53 (s, 2H), 3.23-3.14 (m, 1H), 2.92 (dd, 1H), 2.71 (dd, 1H), 2.51-2.39 (m, 2H), 2.21 (s, 6H), 1.35 (s, 9H) B86 [00306] 7.42-7.26 (m, 4H), 6.84 (s, 2H), 4.33 (s, 2H), 3.48 (s, 1H), 3.19- 3.09 (m, 1H), 2.88 (dd, 1H), 2.79 (dd, 1H), 2.50-2.38 (m, 2H), 2.23 (s, 3H), 2.04 (s, 6H) B87 [00307] 8.78 (s, 1H), 8.15 (dd, 1H), 7.54 (s, 2H), 3.23-3.14 (m, 1H), 2.92 (dd, 1H), 2.71 (dd, 1H), 2.51-2.40 (m, 2H), 2.21 (s, 6H), 1.35 (s, 9H) B88 [00308] 1H NMR (400 MHz, CD3OD) 8.43 (s, 1H), 7.69-7.49 (m, 7H), 4.48 (s, 2H), 3.25-3.17 (m, 1H), 2.95 (dd, 1H), 2.87 (dd, 1H), 2.59-2.49 (m, 2H), 2.20 (d, 6H) B89 [00309] 1H NMR (400 MHz, CD3OD) 8.45 (s, 1H), 7.71-7.60 (m, 3H), 7.57 (s, 2H), 7.51 (d, 2H), 4.49 (s, 2H), 3.27-3.18 (m, 1H), 2.97 (dd, 1H), 2.87 (dd, 1H), 2.60-2.51 (m, 2H), 2.20 (d, 6H) B90 [00310] 1H NMR (400 MHz, CD3OD) 8.44 (s, 1H), 7.70-7.62 (m, 1H), 7.56 (s, 2H), 7.50 (s, 1H), 7.42 (d, 1H), 7.33-7.22 (m, 2H), 4.39 (s, 2H), 3.25-3.17 (m, 1H), 2.96 (dd, 1H), 2.85 (dd, 1H), 2.58-2.48 (m, 2H), 2.20 (s, 6H) B91 [00311] 1H NMR (400 MHz, CD3OD) 8.42 (s, 1H), 7.66-7.58 (m, 1H), 7.53 (s, 2H), 7.21 (d, 2H), 6.86 (d, 2H), 4.32 (s, 2H), 3.73 (s, 3H), 3.23- 3.14 (m, 1H), 2.91 (dd, 1H), 2.79 (dd, 1H), 2.53-2.43 (m, 2H), 2.18 (d, 6H) B92 [00312] 1H NMR (400 MHz, CD3OD) 6.89-6.79 (m, 2H), 4.71-4.46 (m, 2H), 3.94 (d, 2H), 3.19-3.05 (m, 1H), 2.94-2.75 (m, 2H), 2.50-2.38 (m, 2H), 2.28-2.21 (m, 3H), 2.05 (s, 6H) B93 [00313] 1NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.88-7.78 (m, 1H), 7.60 (s, 2H), 3.75-3.51 (m, 8H), 3.25- 3.11 (m, 1H), 3.07-2.86 (m, 2H), 2.83-2.44 (m, 2H), 2.21 (d, 6H) B94 [00314] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.89-7.78 (m, 1H), 7.60 (s, 2H), 4.87-4.81 (m, 2H), 3.78 (s, 2H), 3.24-3.13 (m, 1H), 3.00-2.78 (m, 2H), 2.56-2.40 (m, 2H), 2.20 (s, 6H), 1.78-1.71 (m, 3H) B95 [00315] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.90-7.77 (m, 1H), 7.60 (s, 2H), 4.57-4.37 (m, 2H), 3.57- 3.43 (m, 2H), 3.24-3.12 (m, 1H), 2.94 (dd, 1H), 2.81 (dd, 1H), 2.53- 2.42 (m, 2H), 2.23-2.14 (m, 6H) B96 [00316] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 3.72-3.66 (m, 3H), 3.17- 3.05 (m, 1H), 2.89 (dd, 1H), 2.68- 2.44? (m, 2H), 2.29-2.19 (m, 4H), 2.09-1.98 (m, 6H) B97 [00317] 1H NMR (500 MHz, CD3OD) 6.91-6.78 (m, 2H), 3.26-3.23 (m, 1H), 2.93-2.81 (m, 1H), 2.76-2.67 (m, 1H), 2.82-2.65 (m, 1H), 2.46- 2.30 (m, 2H), 2.28-2.21 (m, 3H), 2.07-2.00 (m, 6H), 1.34-1.20 (m, 2H), 1.14-0.99 (m, 1H) B98 [00318] 1H NMR (500 MHz, CD3OD) 6.91-6.82 (m, 2H), 3.34-3.22 (m, 1H), 3.18-3.00 (m, 1H), 2.95-2.86 (m, 1H), 2.78 (ddd, 1H), 2.50-2.34 (m, 2H), 2.28-2.20 (m, 3H), 2.09- 1.97 (m, 6H), 1.85-1.73 (m, 1H), 1.48-1.33 (m, 1H) B99 [00319] 1H NMR (400 MHz, CD3OD) 8.78 (s, 1H), 8.26 (d, 1H), 7.73 (s, 2H), 3.22-3.14 (m, 1H), 2.92 (dd, 1H), 2.70 (dd, 1H), 2.51-2.39 (m, 2H), 2.20 (s, 6H), 1.36 (s, 9H) B100 [00320] 1H NMR (400 MHz, CD3OD) 8.41 (s, 1H), 7.67-7.58 (m, 1H), 7.53 (s, 2H), 7.44 (d, 2H), 7.21 (d, 2H), 4.33 (s, 2H), 3.22-3.14 (m, 1H), 2.92 (dd, 1H), 2.81 (dd, 1H), 2.54- 2.45 (m, 2H), 2.18 (d, 6H) B101 [00321] 1H NMR (400 MHz, CD3OD) 8.48-8.35 (m, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 3.74-3.52 (m, 8H), 3.25-3.11 (m, 1H), 3.03-2.90 (m, 2H), 2.84-2.71 (m, 1H), 2.51 (dd, 1H), 2.23-2.13 (m, 6H) B102 [00322] 1H NMR (400 MHz, CD3OD) 6.93-6.76 (m, 2H), 5.88-5.78 (m, 1H), 5.59-5.44 (m, 1H), 4.10-4.01 (m, 2H), 3.20-3.08 (m, 1H), 2.98- 2.76 (m, 2H), 2.55-2.37 (m, 2H), 2.27-2.21 (m, 3H), 2.09-1.97 (m, 6H) B103 [00323] 1H NMR (400 MHz, CD3OD) 8.49 (d, 1H), 7.88-7.79 (m, 1H), 7.60 (s, 2H), 3.28-3.13 (m, 3H), 2.93 (dd, 1H), 2.81-2.69 (m, 1H), 2.54- 2.37 (m, 2H), 2.24-2.16 (m, 6H), 1.19-1.10 (m, 3H) B104 [00324] 7.58 (s, 1H), 7.14 (s, 2H), 3.28- 3.12 (m, 1H), 2.98-2.88 (m, 1H), 2.74-2.67 (m, 1H), 2.53-2.37 (m, 2H), 2.30 (s, 3H), 2.18 (s, 6H), 1.35 (s, 9H) B105 [00325] 8.22 (s, 1H), 7.38 (s, 2H), 3.22- 3.12 (m, 1H), 2.89 (dd, 1H), 2.69 (dd, 1H), 2.50-2.38 (m, 2H), 2.28 (s, 3H), 2.16 (s, 6H), 1.35 (s, 9H) B106 [00326] 8.62 (s, 2H), 8.13-8.00 (m, 2H), 7.46-7.32 (m, 1H), 3.46-3.35 (m, 2H), 3.31 (s, 6H), 2.95-2.75 (m, 1H), 2.69-2.54 (m, 2H), 2.23 (d, 7H), 1.78-1.60 (m, 2H) B107 [00327] 8.72 (s, 2H), 8.04 (s, 2H), 3.24- 3.09 (m, 1H), 3.01-2.86 (m, 1H), 2.85-2.70 (m, 1H), 2.58-2.40 (m, 2H), 2.20 (s, 6H) B108 [00328] 8.62 (s, 2H), 8.05 (d, 2H), 7.48- 7.30 (m, 1H), 5.81-5.58 (m, 1H), 5.20-5.01 (m, 2H), 3.83-3.59 (m, 2H), 3.28-3.07 (m, 1H), 2.95-2.77 (m, 1H), 2.72-2.44 (m, 2H), 2.20 (d, 7H) B109 [00329] 8.63 (s, 2H), 8.11-8.00 (m, 2H), 7.65-7.47 (m, 1H), 3.30-3.13 (m, 1H), 3.08-2.98 (m, 2H), 2.96-2.85 (m, 1H), 2.76-2.60 (m, 2H), 2.42- 2.27 (m, 1H), 2.23 (d, 6H), 0.89 (s, 9H) B110 [00330] 8.61 (s, 2H), 8.03 (d, 2H), 4.44- 4.17 (m, 4H), 3.48-3.27 (m, 1H), 2.92 (s, 3H), 2.50-2.12 (m, 9H) B111 [00331] 14.14-13.60 (m, 1H), 8.62 (s, 2H), 8.07 (d, 2H), 3.08 (d, 3H), 2.95- 2.78 (m, 1H), 2.72-2.44 (m, 2H), 2.22 (d, 7H), 1 46-1.14 (m, 4H), 0.85 (t, 3H) B112 [00332] 14.07-13.16 (m, 1H), 8.62 (s, 2H), 8.07 (d, 2H), 7.21-7.03 (m, 1H), 3.34-3.14 (m, 1H), 3.07-2.80 (m, 3H), 2.63 (s, 2H), 2.23 (d, 7H), 1.66 (s, 1H), 0.83 (dd, 6H) B113 [00333] 1H NMR (400 MHz, CD3OD) 8.74 (s, 2H), 8.07 (s, 2H), 3.24-3.08 (m, 1H), 3.00-2.84 (m, 1H), 2.80-2.69 (m, 1H), 2.62 (s, 1H), 2.56-2.33 (m, 2H), 2.21 (s, 6H), 1.60 (s, 6H) B114 [00334] 1H NMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.14-7.88 (m, 2H), 4.27- 3.91 (m, 1H), 3.26-3.07 (m, 1H), 2.99-2.83 (m, 1H), 2.80-2.67 (m, 1H), 2.55-2.35 (m, 2H), 2.20 (s, 6H), 1.99-1.87 (m, 2H), 1.84-1.40 (m, 6H) B115 [00335] 1HNMR (400 MHz, CD3OD) 6.93-6.78 (m, 2H), 6.47-6.35 (m, 1H), 6.27-6.15 (m, 1H), 4.01-3.70 (m, 2H), 3.17-3.09 (m, 1H), 2.93- 2.85 (m, 1H), 2.76 (dd, 1H), 2.51- 2.37 (m, 2H), 2.27-2.20 (m, 3H), 2.10-2.01 (m, 6H) B116 [00336] 1H NMR (400 MHz, CD3OD) 8.53-8.42 (m, 1H), 7.84 (dd, 1H), 7.60? (s, 2H), 5.86 (tdd, 1H), 5.29- 5.07 (m, 2H), 3.84 (d, 2H), 3.24- 3.13 (m, 1H), 2.94 (dd, 1H), 2.81 (dd, 1H), 2.55-2.43 (m, 2H), 2.21- 2.17 (m, 6H) B117 [00337] 1H NMR (400 MHz, Methanol) Shift = 7.25-7.08 (m, 2H), 5.85 (tdd, J = 5.4, 10.5, 17.2 Hz, 1H), 5.25-5.06 (m, 2H), 3.89-3.77 (m, 2H), 3.15 (d, J = 6.0 Hz, 1H), 2.91 (dd, J = 7.0, 17.9 Hz, 1H), 2.80-2.66 (m, 1H), 2.52-2.37 (m, 2H), 2.14-2.00 (m, 6H) B118 [00338] 1H NMR (400 MHz, CD3OD) 8.55-8.40 (m, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 4.00 (quin, 1H), 3.19 (d, 1H), 2.92 (dd, 1H), 2.74 (dd, 1H), 2.52-2.39 (m, 2H), 2.24-2.17 (m, 6H), 1.18-1.13 (m, 6H) B119 [00339] 1H NMR (400 MHz, CD3OD) 8.55-8.45 (m, 1H), 7.84 (dd, 1H), 7.60? (s, 2H), 3.90-3.69 (m, 1H), 3.24-3.12 (m, 1H), 2.93 (dd, 1H), 2.77 (ddd, 1H), 2.53-2.33 (m, 2H), 2.23-2.17 (m, 6H), 1.56-1.40 (m, 2H), 1.14 (dd, 3H), 0.93 (dt, 3H) B120 [00340] 1HNMR (400 MHz, CD3OD) 7.29-7.11 (m, 2H), 3.81 (sxt, 1H), 3.21-3.03 (m, 1H), 2.89 (ddd, 1H), 2.74 (ddd, 1H), 2.50-2.33 (m, 2H), 2.13-1.98 (m, 6H), 1.56-1.41 (m, 2H), 1.18-1.06 (m, 3H), 0.92 (dt, 3H) B121 [00341] 1H NMR (400 MHz, CD3OD) 8.52-8.40 (m, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 4.18-3.96 (m, 1H), 3.41-3.34 (m, 5H), 3.23-3.12 (m, 1H), 2.92 (dd, 1H), 2.82-2.65 (m, 1H), 2.54-2.37 (m, 2H), 2.24-2.17 (m, 6H), 1.15 (dd, 3H) B122 [00342] 1HNMR (400 MHz, CD3OD) 7.25- 7.13 (m, 2H), 3.26-3.12 (m, 1H), 3.07 (d, 2H), 2.90 (dd, 1H), 2.75 (dd, 1H), 2.55-2.38 (m, 2H), 2.09 (s, 6H), 1.05-0.89 (m, 1H), 0.54- 0.45 (m, 2H), 0.26-0.11 (m, 2H) B123 [00343] 1H NMR (400 MHz, CD3OD) 8.52-8.43 (m, 1H), 7.88-7.72 (m, 1H), 7.63-7.45 (m, 2H), 3.24-3.14 (m, 1H), 3.10-3.02 (m, 2H), 2.93 (dd, 1H), 2.78 (dd, 1H), 2.55-2.41 (m, 2H), 2.23-2.18 (m, 6H), 1.07- 0.90 (m, 1H), 0.58-0.46 (m, 2H), 0.29-0.16 (m, 2H) B124 [00344] 1H NMR (400 MHz, CD3OD) 8.54-8.36 (m, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 3.25-3.12 (m, 1H), 3.04 (d, 2H), 2.93 (dd, 1H), 2.79 (dd, 1H), 2.55-2.41 (m, 2H), 2.20 (s, 6H), 1.80 (quind, 1H), 0.94 (d, 6H) B125 [00345] 1H NMR (400 MHz, CD3OD) 8.49 (d, 1H), 7.84 (dd, 1H), 7.65-7.45 (m, 2H), 4.22-4.05 (m, 1H), 3.24- 3.08 (m, 1H), 2.92 (dd, 1H), 2.74 (dd, 1H), 2.46 (d, 2H), 2.24-2.17 (m, 6H), 2.04-1 87 (m, 2H), 1 78- 1.67 (m, 2H), 1.66-1.58 (m, 2H), 1.49 (td, 2H) B126 [00346] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7 84 (dd, 1H), 7.60 (s, 2H), 3.21-3.08 (m, 1H), 2.94 (dd, 1H), 2.75 (dd, 1H), 2.65 (s, 1H), 2.52-2.38 (m, 2H), 2.21-2.17 (m, 6H), 1.62-1.52 (m, 6H) B127 [00347] 1H NMR (400 MHz, CD3OD) 7.26-7.03 (m, 2H), 3.14 (d, 1H), 2.91 (dd, 1H), 2.72 (dd, 1H), 2.66- 2.60 (m, 1H), 2.53-2.33 (m, 2H), 2.12-2.03 (m, 6H), 1.63-1.53 (m, 6H) B128 [00348] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 3.44 (t, 2H), 3.33 (s, 3H), 3.29-3.26 (m, 2H), 3.24-3.10 (m, 1H), 2.93 (dd, 1H), 2.77 (dd, 1H), 2.54-2.39 (m, 2H), 2.21-2.16 (m, 6H), 1.78 (quin, 2H) B129 [00349] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.84 (dd, 1H), 7.65-7.54 (m, 2H), 7.34 (dt, 1H), 7.13 (d, 1H), 7.08-6.92 (m, 2H), 4.41 (s, 2H), 3.26-3.13 (m, 1H), 3.00-2.78 (m, 2H), 2.56-2.46 (m, 2H), 2.19 (d, 6H) B130 [00350] 1HNMR (400 MHz, CD3OD) 7.39-7.27 (m, 1H), 7.21 (s, 2H), 7.11 (d, 1H), 7.05 (dd, 1H), 6.98 (dt. 1H), 4.45-4.33 (m, 2H), 3.26- 3.11 (m, 1H), 2.91 (dd, 1H), 2.81 (dd, 1H), 2.57-2.43 (m, 2H), 2.13- 2.07 (m, 6H) B131 [00351] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 7.23 (t, 1H), 6.90-6.85 (m, 2H), 6.82 (dd, 1H), 4.41-4.33 (m, 2H), 3.80-3.75 (m, 3H), 3.26-3.10 (m, 1H), 2.94 (dd, 1H), 2.83 (dd, 1H), 2.51 (d, 2H), 2.19 (d, 6H) B132 [00352] 1HNMR (400 MHz, CD3OD) 7.25-7.17 (m, 4H), 6.91-6.85 (m, 2H), 4.41-4.29 (m, 2H), 3.80-3.73 (m, 3H), 3.17 (d, 1H), 2.91 (dd, 1H), 2.80 (dd, 1H), 2.55-2.41 (m, 2H), 2.08 (d, 6H) B133 [00353] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 5.45-5.27 (m, 2H), 4.01 (s, 2H), 3.13 (br.s., 1H), 2.93-2.76 (m, 2H), 2.50-2.40 (m, 2H), 2.28- 2.19 (m, 3H), 2.09-2.02 (m, 6H) B134 [00354] 1H NMR (400 MHz, CD3OD15bn227h1) 7.25-7.09 (m, 2H), 4.14-3.97 (m, 1H), 3.41-3.32 (m, 5H), 3.20-3.06 (m, 1H), 2.89 (dd, 1H), 2.80-2.66 (m, 1H), 2.52- 2.37 (m, 2H), 2.13-2.02 (m, 6H), 1.18-1.04 (m, 3H) B135 [00355] 13.92-13.60 (m, 1H), 7.89 (s, 1H), 7.61 (s, 1H), 7.40-7.29 (m, 2H), 6.87-6.69 (m, 1H), 3.37-3.13 (m, 1H), 2.96-2.40 (m, 5H), 2.18 (d, 4H), 1.39-1.27 (m, 9H), 1.14 (dt, 3H) B136 [00356] 13.77-13.36 (m, 1H), 7.12-6.92 (m, 2H), 6.83-6.58 (m, 1H), 6.45- 6.05 (m, 2H), 3.30-3.02 (m, 1H), 2.42 (d, 5H), 2.11 (s, 4H), 1.85 (dd, 3H), 1.34-1.19 (m, 9H), 1.10 (d, 3H) B137 [00357] 12.50-12.02 (m, 1H), 7.03 (dd, 2H), 6.41-6.04 (m, 2H), 3.95-3.44 (m, 8H), 3.40-3.25 (m, 1H), 3.19- 2.81 (m, 2H), 2.42 (d, 3H), 2.32- 2.07 (m, 4H), 1 85 (dd, 3H), 1.10 (dt, 3H) B138 [00358] 1H NMR (400 MHz, CD3OD) 8.94-8.81 (m, 1H), 6.86 (s, 2H), 3.19-3.02 (m, 1H), 2.98-2.83 (m, 1H), 2.73 (s, 1H), 2.53-2.30 (m, 2H), 2.25 (s, 3H), 2.05 (s, 6H), 1.27 (s, 2H), 1.10 (s, 2H) B139 [00359] 6.65 (s, 2H), 6.52-6.33 (m, 1H), 4.31 (d, 2H), 3.33-3.12 (m, 1H), 2.93-2.76 (m, 1H), 2.73-2.49 (m, 2H), 2.13 (d, 7H), 1.32 (s, 9H) B140 [00360] 1HNMR (400 MHz, CD3OD) 7.25-7.11 (m, 2H), 4.03-3.90 (m, 1H), 3.19-3.09 (m, 1H), 2.89 (dd, 1H), 2.73-2.65 (m, 1H), 2.49-2.36 (m, 2H), 2.09 (s, 6H), 1.19-1.11 (m, 6H) B141 [00361] 1H NMR (400 MHz, CD3OD) 7.24-7.14 (m, 2H), 3.51 (td, 1H), 3.29-3.21 (m, 1H), 3.15 (br.s., 1H), 2.92 (ddd, 1H), 2.78 (ddd, 1H), 2.57-2.42 (m, 2H), 2.09 (d, 6H), 2.00-1.89 (m, 1H), 1.67 (dd, 10.5 Hz, 1H), 1.38-1.21 (m, 1H) B142 [00362] 1H NMR (400 MHz, CD3OD) 7.25-7.05 (m, 2H), 5.85-5.48 (m, 1H), 3.45-3.34 (m, 2H), 3.13 (d, 1H), 2.90 (dd, 1H), 2.82-2.68 (m, 1H), 2.52-2.35 (m, 2H), 2.14-2.07 (m, 6H), 0.83-0.64 (m, 4H) B143 [00363] 1H NMR (400 MHz, CD3OD) 8.54-8.40 (m, 1H), 7.81 (dd, 1H), 7.61-7.51 (m, 2H), 5.92-5.47 (m, 1H), 3.45-3.36 (m, 2H), 3.23-3.12 (m, 1H), 3.00-2.87 (m, 1H), 2.85- 2.73 (m, 1H), 2.53-2.35 (m, 2H), 2.22-2.12 (m, 6H), 0.81-0.66 (m, 4H) B144 [00364] 1H NMR (400 MHz, CD3OD) 8.49-8.34 (m, 1H), 7.89-7.71 (m, 1H), 7.66-7.45 (m, 2H), 3.23-3.08 (m, 3H), 2.99-2.85 (m, 1H), 2.77 (dd, 1H), 2.53-2.44 (m, 2H), 2.24- 2.10 (m, 6H), 1.59-1.47 (m, 2H), 1.01-0.85 (m, 3H) B145 [00365] 1HNMR (400 MHz, CD3OD) 7.2S-7.15 (m, 2H), 3.22-3.03 (m, 3H), 2.90 (dd, 1H), 2.74 (dd, 1H), 2.52-2.37 (m, 2H), 2.09 (s, 6H), 1.54 (sxt, 2H), 0.98-0.87 (m, 3H) B146 [00366] 6.64 (s, 2H), 4.39-4.20 (m, 2H), 3.85-3.43 (m, 8H), 3.39-3.24 (m, 1H), 2.87 (s, 2H), 2.68-2.49 (m, 1H), 2.29-2.18 (m, 1H), 2.12 (d, 6H) B147 [00367] 13.69-13.21 (m, 1H), 7.46-7.27 (m, 1H), 6.64 (s, 2H), 4.93-4.62 (m, 2H), 4.30 (d, 2H), 3.82-3.51 (m, 2H), 3.31-3.07 (m, 1H), 2.95- 2.43 (m, 3H), 2.11 (s, 7H), 1.69 (s, 3H) B148 [00368] 7.21-6.99 (m, 3H), 3.80-3.24 (m, 9H), 2.89 (dd, 2H), 2.45 (t, 3H), 2.32-2.07 (m, 4H), 1.10 (dt, 3H) B149 [00369] 7.28-6.99 (m, 4H), 3.24-3.09 (m, 1H), 2.85 (d, 1H), 2.57 (d, 2H), 2.49-2.38 (m, 2H), 2.35-2.22 (m, 1H), 2.12 (d, 3H), 1.34 (d, 9H), 1.10? (t, 3H) B150 [00370] 14.19-13.47 (m, 1H), 7.67-7.39 (m, 1H), 7.22-6.92 (m, 3H), 2.98 (s, 4H), 2.44 (dd, 4H), 2.13 (d, 4H), 1.47-1.31 (m, 2H), 1.10 (q, 3H), 0.84 (t, 3H) B151 [00371] 13.61-13.02 (m, 1H), 8.11-7.64 (m, 1H), 7.24-6.97 (m, 3H), 3.87- 3.58 (m, 2H), 3.28-3.04 (m, 1H), 2.97-2.73 (m, 1H), 2.68-2.50 (m, 1H), 2.50-2.03 (m, 8H), 1.10 (dt, 3H) B152 [00372] 13.89-13.46 (m, 1H), 7.89-7.53 (m, 1H), 7.21-6.99 (m, 3H), 4.90- 4.63 (m, 2H), 3.57 (d, 2H), 3.23- 3.03 (m, 1H), 2.91-2.74 (m, 1H), 2.69-2.55 (m, 1H), 2.55-2.30 (m, 3H), 2.11 (d, 4H), 1.67 (s, 3H), 1.10 (td, 3H) B153 [00373] 7.05 (s, 2H), 6.33 (d, 2H), 3.23- 3.05 (m, 1H), 2.74 (d, 2H), 2.54- 2.33 (m, 4H), 2.07 (s, 3H), 1.92- 1.76 (m, 3H), 1.07 (t, 3H) B154 [00374] 1H NMR (400 MHz, CD3OD) 6.71 (s, 2H), 4.46 (d, 2H), 3.21-2.36 (m, 5H), 2.09 (s, 6H) B155 [00375] 7.07 (d, 2H), 3.81-3.20 (m, 9H), 2.86 (dd, 2H), 2.71-2.43 (m, 1H), 2.31-1.98 (m, 10H) B156 [00376] 7.52-7.31 (m, 1H), 7.08 (s, 2H), 3.42 (t, 2H), 3.36-3.11 (m, 6H), 2.90-2.76 (m, 1H), 2.62-2.44 (m, 2H), 2.23-1.95 (m, 10H), 1.71 (s, 2H) B157 [00377] 7.48-7.30 (m, 1H), 7.08 (s, 2H), 5.80-5.51 (m, 1H), 5.20-5.04 (m, 2H), 3.71 (s, 2H), 3.24-3.04 (m, 1H), 2.91-2.74 (m, 1H), 2.67-2.38 (m, 2H), 2.22-1.95 (m, 10H) B158 [00378] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 3.45-3.37 (m, 1H), 3.23 (dd, 1H), 3.13 (d, 1H), 2.88 (dd, 1H), 2.77 (dd, 1H), 2.50-2.35 (m, 2H), 2.28-2.20 (m, 3H), 2.06 (s, 6H), 1.96-1.83 (m, 1H), 1.49 (ddt, 1H), 1.23-1.10 (m, 1H) B159 [00379] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 6.04 (t, 1H), 3.93 (d, 2H), 3.13 (br.s., 1H), 2.93-2.87 (m, 1H), 2.81-2.68 (m, 1H), 2.48-2.34 (m, 2H), 2.27-2.20 (m, 3H), 2.08- 2.00 (m, 6H) B160 [00380] 1H NMR (400 MHz, CD3OD) 8.48 (s, 1H), 7.83 (dd, 1H), 7.60 (s, 2H), 3.51 (td, 1H), 3.31-3.24 (m, 1H), 3.19 (d, 1H), 2.95 (dd, 1H), 2.81 (ddd, 1H), 2.58-2.37 (m, 2H), 2.25-2.14 (m, 6H), 2.02-1.90 (m, 1H), 1.72-1.60 (m, 1H), 1.36-1.18 (m, 1H) B161 [00381] 1H NMR (400 MHz, CD3OD) 8.56-8.37 (m, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 5.74-5.59 (m, 1H), 5.55-5.36 (m, 1H), 3.91-3.72 (m, 2H), 3.23-3.11 (m, 1H), 2.93 (dd, 1H), 2.77 (dd, 1H), 2.52-2.39 (m, 2H), 2.19 (s, 6H), 1.74-1.64 (m, 3H) B162 [00382] 1H NMR (400 MHz, CD3OD) 8.49 (d, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 6.33 (d, 1H), 6.04-5.77 (m, 1H), 3.83 (d, 2H), 3.15 (d, 1H), 2.94 (dd, 1H), 2.78 (dd, 1H), 2.57- 2.41 (m, 2H), 2.23-2.18 (m, 6H) B163 [00383] 1H NMR (400 MHz, CD3OD) 6.90-6.71 (m, 2H), 5.27-5.14 (m, 1H), 3.79 (d, 2H), 3.23-3.03 (m, 1H), 2.87 (dd, 1H), 2.78-2.66 (m, 1H), 2.48-2.34 (m, 2H), 2.26-2.19 (m, 3H), 2.08-1.97 (m, 6H), 1.77- 1.65 (m, 6H) B164 [00384] 12.71-12.00 (m, 1H), 6.75-6.55 (m, 2H), 4.32 (q, 2H), 3.90-3.45 (m, 8H), 3.36 (br.s., 1H), 2.90 (dd, 2H), 2.43 (quin, 3H), 2.24 (d, 1H), 2.12 (d, 3H), 1.10 (dt, 3H) B165 [00385] 13.85-13.21 (m, 1H), 6.81-6.56 (m, 3H), 4.32 (q, 2H), 3.34-3.12 (m, 1H), 2.43 (dd, 5H), 2.11 (d, 4H), 1.37-1.25 (m, 9H), 1.10 (dt, 3H) B166 [00386] 13.49-12.77 (m, 1H), 7.96-7.55 (m, 1H), 6.82-6.51 (m, 2H), 4.33 (q, 2H), 3.98-3.73 (m, 2H), 3.29- 3.07 (m, 1H), 2.92-2.32 (m, 5H), 2.29-2.04 (m, 5H), 1.09 (dt, 3H) B167 [00387] 1H NMR (400 MHz, CD3OD) 6.72 (s, 2H), 4.48 (d, 2H), 3.24-3.02 (m, 1H), 2.99-2.66 (m, 2H), 2.58- 2.31 (m, 4H), 2.08 (s, 3H), 1.07 (t, 3H) B168 [00388] 1H NMR (400 MHz, CD3OD) 7.05 (s, 2H), 3.21-3.05 (m, 1H), 2.98- 2.66 (m, 2H), 2.46 (s, 2H), 2.06 (s, 6H), 2.02-1.93 (m, 3H) B169 [00389] 6.89 (t, 2H), 3.85-3.44 (m, 8H), 3.42-3.25 (m, 1H), 2.90 (dd, 2H), 2.68-2.34 (m, 3H), 2.27-2.20 (m, 4H), 2.09 (d, 3H), 1.09 (dt, 3H) B170 [00390] 6.94-6.79 (m, 2H), 6.69-6.55 (m, 1H), 3.30-3.08 (m, 1H), 2.90-2.75 (m, 1H), 2.41 (d, 4H), 2.27 (s, 3H), 2.09 (s, 4H), 1.29 (d, 9H), 1.09 (dt, 3H) B171 [00391] 1H NMR (400 MHz. CD3OD) 6.88 (br.s., 2H), 3.11 (br.s., 1H), 2.88 (dd, 1H), 2.75 (dd, 1H), 2.52-2.32 (m, 4H), 2.26 (s, 3H), 2.05 (s, 3H), 1.05 (t, 3H) B172 [00392] 12.55-11.92 (m, 1H), 7.01 (d, 2H), 6.47-6.06 (m, 2H), 3.90-3.26 (m, 9H), 3.2-2.89 (dd, 2H), 2.66-2.45 (m, 1H), 2.38-2.03 (m, 7H), 1.85 (dd, 3H) B173 [00393] 7.09-6.93 (m, 2H), 6.74-6.53 (m, 1H), 6.40-5.96 (m, 2H), 3.32-3.05 (m, 1H), 2.93-2.71 (m, 1H), 2.69- 2.40 (m, 2H), 2.12 (d, 7H), 1.84 (dd, 3H), 1.29 (s, 9H) B174 [00394] 7.74-7.54 (m, 1H), 7.02 (d, 2H), 6.34-6.09 (m, 2H), 3.93-3.71 (m, 2H), 3.22-3.05 (m, 1H), 2.93-2.73 (m, 1H), 2.68-2.39 (m, 2H), 2.25- 2.02 (m, 8H), 1.84 (dd, 3H) B175 [00395] 1H NMR (400 MHz, CD3OD) 7.02 (s, 2H), 6.39-6.10 (m, 2H), 3.21- 3.04 (m, 1H), 2.99-2.84 (m, 1H), 2.80-2.66 (m, 1H), 2.51-2.35 (m, 2H), 2.08 (s, 6H), 1.84 (dd, 3H) B176 [00396] 1H NMR (400 MHz, CD3OD) 7.25-7.13 (m, 2H), 6.31 (td, 1H), 5.50-5.59 (m, 1H), 3.82 (dd, 2H), 3.14 (d, 1H), 2.91 (dd, 1H), 2.81- 2.66 (m, 1H), 2.51-2.38 (m, 2H), 2.09 (s, 6H) B177 [00397] 1H NMR (400 MHz, CD3OD) 7.26-7.12 (m, 2H), 5.73-5.59 (m, 1H), 5.54-5.39 (m, 1H), 3.91-3.70 (m, 2H), 3.22-3.09 (m, 1H), 2.95- 2.80 (m, 1H), 2.74 (dd, 1H), 2.51- 2.39 (m, 2H), 2.09 (s, 6H), 1.73- 1.52 (m, 3H) B178 [00398] 1H NMR (400 MHz, CD3OD) 8.52-8.39 (m, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 3.24-3.11 (m, 1H), 3.07-3.01 (m, 2H), 2.97-2.91 (m, 1H), 2.82 (dd, 1H), 2.58-2.42 (m, 2H), 2.23-2.16 (m, 6H), 0.99-0.87 (m, 9H) B179 [00399] 1H NMR (400 MHz, CD3OD) 6.86 (s, 2H), 5.85 (dddd, 1H), 5.21-5.12 (m, 1H), 5.09-5.04 (m, 1H), 4.47 (t, 1H), 3.13 (d, 1H), 2.88 (dd, 1H), 2.77 (dd, 1H), 2.42 (d, 2H), 2.25 (s, 3H), 2.06 (s, 6H), 1.26-1.18 (m, 3H) B180 [00400] 1H NMR (400 MHz, CD3OD) 6.91-6.76 (m, 2H), 3.53-3.44 (m, 2H), 3.35 (s, 3H), 3.20-3.03 (m, 1H), 2.86 (dd, 1H), 2.70 (dd, 1H), 2.50-2.34 (m, 2H), 2.29-2.19 (m, 3H), 2.06 (s, 6H), 1.35-1.27 (m, 6H) B181 [00401] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 7.36-7.21 (m, 5H), 4.41 (s, 2H), 3.20 (br.s., 1H), 2.94 (dd, 1H), 2.84 (dd, 1H), 2.58-2.45 (m, 2H), 2.23-2.14 (m, 6H) B182 [00402] 7.91-7.57 (m, 1H), 7.29-7.20 (m, 2H), 7.16 (s, 1H), 7.10-6.95 (m, 3H), 4.28-4.03 (m, 2H), 3.27-3.09 (m, 1H), 2.91-2.72 (m, 1H), 2.69- 2.42 (m, 2H), 2.27-1.91 (m, 10H) B183 [00403] 13.90-13.26 (m, 1H), 8.07-7.66 (m, 1H), 7.35-7.18 (m, 1H), 7.11- 6.77 (m, 5H), 4.19 (d, 2H), 3.22- 3.04 (m, 1H), 2.79 (d, 1H), 2.69- 2.33 (m, 2H), 2.22-1.89 (m, 9H) B184 [00404] 7.78-7.51 (m, 1H), 7.19-7.01 (m, 4H), 6.83 (d, 2H), 4.20 (d, 2H), 3.77 (s, 3H), 3.24-3.05 (m, 1H), 2.74 (d, 1H), 2.47 (s, 2H), 2.14- 1.93 (m, 10H) B185 [00405] 13.93-13.42 (m, 1H), 7.87-7.57 (m, 1H), 7.42-6.98 (m, 7H), 4.24 (d, 2H), 3.32-2.95 (m, 1H), 2.86- 2.62 (m, 1H), 2.60-2.33 (m, 2H), 2.14-1.91 (m, 10H) B186 [00406] 1H NMR (400 MHz, CD3OD) 7.67 (d, 2H), 7.46 (d, 2H), 7.04 (s, 2H), 4.44 (s, 2H), 3.23-3.09 (m, 1H), 2.99-2.72 (m, 2H), 2.59-2.41 (m, 2H), 2.13-1.94 (m, 9H) B187 [00407] 13.81-12.98 (m, 1H), 7.97 (br.s., 1H), 7.41-7.08 (m, 3H), 7.06-6.89 (m, 3H), 6.43-5.96 (m, 2H), 4.19- 3.86 (m, 2H), 3.30-2.96 (m, 1H), 2.88-2.61 (m, 2H), 2.36 (d, 3H), 2.21-1.92 (m, 4H), 1.85 (dd, 3H), 1.05 (td, 3H) B188 [00408] 7.79-7.56 (m, 1H), 7.33-7.19 (m, 1H), 7.08-6.79 (m, 5H), 6.39-6.07 (m, 2H), 4.28-4.01 (m, 2H), 3.33- 3.11 (m, 1H), 2.94-2.65 (m, 2H), 2.55 (s, 1H), 2.45-2.27 (m, 2H), 2.05 (d, 4H), 1.85 (dd, 3H), 1.06 (td, 3H) B189 [00409] 7.67-7.43 (m, 1H), 7.09 (d, 2H), 7.06-6.97 (m, 2H), 6.88-6.74 (m, 2H), 6.38-6.10 (m, 2H), 4.16 (s, 2H), 3.77 (s, 3H), 3.20-3.03 (m, 1H), 2.83-2.67 (m, 1H), 2.37 (d, 4H), 2.06 (s, 4H), 1.84 (dd, 3H), 1.07 (dt, 3H) B190 [00410] 13.80-13.02 (m, 1H), 7.92-7.58 (m, 1H), 7.40-7.08 (m, 5H), 7 00 (d, 2H), 6.42-5.89 (m, 2H), 4.19 (s, 2H), 3.28-2.99 (m, 1H), 2.84- 2.26 (m, 5H), 2.16-1.75 (m, 7H), 1.06 (dt, 3H) B191 [00411] 13.76-12.91 (m, 1H), 8.60-8.25 (m, 1H), 7.53 (d, 2H), 7.16 (d, 2H), 7.03-6.87 (m, 2H), 6.39-6.07 (m, 2H), 4.19-3.81 (m, 2H), 3.31-3.11 (m, 1H), 2.96-2.76 (m, 2H), 2.63- 2.45 (m, 1H), 2.45-2.11 (m, 3H), 2.02 (d, 3H), 1.86 (dd, 3H), 1.03 (td, 3H) B192 [00412] 14.12-13.30 (m, 1H), 7.20-6.94 (m, 3H), 6.47-5.98 (m, 2H), 4.13- 3.82 (m, 1H), 3.16 (br.s., 1H), 2.81 (dd, 1H), 2.67-2.34 (m, 4H), 2.23- 2.01 (m, 4H), 1.85 (dd, 3H), 1.20- 0.97 (m, 9H) B193 [00413] 13.83-12.88 (m, 1H), 7.63-7.34 (m, 1H), 7.11-6.90 (m, 2H), 6.47- 6.05 (m, 2H), 5.79-5.55 (m, 1H), 5.19-4.97 (m, 2H), 3.65 (br.s., 2H), 3.28-3.03 (m, 1H), 2.93-2.72 (m, 1H), 2.40 (d, 4H), 2.09 (s, 4H), 1.85 (dd, 3H), 1.08 (dt, 3H) B194 [00414] 12.84 (br.s., 1H), 7.09-6.93 (m, 2H), 6.46-6.05 (m, 2H), 3.63-3.20 (m, 3H), 3.16-2.66 (m, 5H), 2.61- 1.96 (m, 7H), 1.85 (dd, 3H), 1.32- 0.97 (m, 6H) B195 [00415] 12.50-11.80 (m, 1H), 7.14-6.89 (m, 2H), 6.44-6.00 (m, 2H), 4.19 (d, 2H), 3.47-2.78 (m, 5H), 2.73- 1.76 (m, 12H), 1.23-0.96 (m, 3H) B196 [00416] 13.85-13.09 (m, 1H), 7.47-7.19 (m, 1H), 7.00-6.82 (m, 2H), 6.31- 5.97 (m, 2H), 3.15-2.96 (m, 1H), 2.89-2.62 (m, 3H), 2.30 (q, 4H), 2.12-1.92 (m, 4H), 1.73 (dd, 3H), 0.97 (dt, 3H), 0.70 (br.s., 1H), 0.42-0.24 (m, 2H), 0.12-0.07 (m, 2H) B197 [00417] 1H NMR (400 MHz, CD3OD) 8.47 (dd, 1H), 7.82 (dd, 1H), 7.59 (s, 2H), 3.47-3.36 (m, 1H), 3.28-3.13 (m, 2H), 3.01-2.88 (m, 1H), 2.79 (dd, 1H), 2.51-2.42 (m, 2H), 2.19 (s, 6H), 1.94-1.84 (m, 1H), 1.58- 1.43 (m, 1H), 1.27-1.10 (m, 1H) B198 [00418] 1H NMR (400 MHz, CD3OD) 7.28-7.13 (m, 2H), 3.45-3.35 (m, 1H), 3.25-3.12 (m, 2H), 2.97-2.88 (m, 1H), 2.76 (dd, 1H), 2.53-2.45 (m, 2H), 2.09 (s, 6H), 1.98-1.76 (m, 1H), 1.49 (ddt, 1H), 1.23-1.03 (m, 1H) B199 [00419] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.72-7.62 (m, 3H), 7.55 (br.s., 2H), 7.49 (d, 2H), 4.48 (s, 2H), 3.24-3.15 (m, 1H), 2.99-2.81 (m, 2H), 2.57-2.48 (m, 2H), 2.21- 2.14 (m, 6H) B200 [00420] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.67-7.60 (m, 1H), 7.55 (s, 2H), 4.95-4.88 (m, 2H), 3.78 (s, 2H), 3.18 (br.s., 1H), 2.94 (dd, 1H), 2.86-2.78 (m, 1H), 2.50 (d, 2H), 2.20 (s, 6H), 1.78-1.72 (m, 3H) B201 [00421] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 3.28-3.22 (m, 2H), 3.20-3.10 (m, 1H), 2.92 (dd, 1H), 2.76 (dd, 1H), 2.47 (d, 2H), 2.21-2.08 (m, 6H), 1.20-1.10 (m, 3H) B202 [00422] 1H NMR (400 MHz, CD3OD) 8.85 (s, 1H), 8.44 (d, 1H), 8.12 (dd, 1H), 7.69-7.61 (m, 1H), 7.60-7.52 (m, 3H), 4.59 (s, 2H), 3.18-3.08 (m, 1H), 2.95-2.84 (m, 2H), 2.61- 2.45 (m, 2H), 2.19 (d, 6H) B203 [00423] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 4.05-3.92 (m, 1H), 3.26-3.11 (m, 1H), 2.91 (dd, 1H), 2.74 (dd, 1H), 2.52-2.35 (m, 2H), 2.24-2.13 (m, 6H), 1.16 (dd, 6H) B204 [00424] 1.43 mins, m/z = 482.14 (M + H)+ B205 [00425] 1.35 mins, m/z = 466.18 (M + H)+ B206 [00426] 1.34 mins, m/z = 478.20 (M + H)+ B207 [00427] 1.27 mins, m/z = 473.17 (M + H)+ B208 [00428] 1.26 mins, m/z = 400.18 (M + H)+ B209 [00429] 1.21 mins, m/z = 398.17 (M + H)+ B210 [00430] 1.28 mins, m/z = 412.18 (M + H)+ B211 [00431] 1.26 mins, m/z = 400.18 (M + H)+ B212 [00432] 1.46 mins, m/z = 428.21 (M + H)+ B213 [00433] 1.23 mins, m/z = 410.17 (M + H)+ B214 [00434] 1.40 mins, m/z = 480.220 (M + H)+ B215 [00435] 1.38 mins, m/z = 492.21 (M + H)+ B216 [00436] 1.32 mins, m/z = 487.20 (M + H)+ B217 [00437] 1.31 mins, m/z = 414.20 (M + H)+ B218 [00438] 1.26 mins, m/z = 412.18 (M + H)+ B219 [00439] 1.33 mins, m/z = 426.20 (M + H)+ B220 [00440] 1.32 mins, m/z = 414.20 (M + H)+ B221 [00441] 1.51 mins, m/z = 442.22 (M + H)+ B222 [00442] 1.28 mins, m/z = 424.18 (M + H)+ B223 [00443] 1.36 mins, m/z = 468.15 (M + H)+ B224 [00444] 1.35 mins, m/z = 480.18 (M + H)+ B225 [00445] 1.27 mins, m/z = 475.17 (M + H)+ B226 [00446] 1.21 mins, m/z = 400.16 (M + H)+ B227 [00447] 1.28 mins, m/z = 414.17 (M + H)+ B228 [00448] 1.26 mins, m/z = 402.16 (M + H)+ B229 [00449] 1.48 mins, m/z = 430.20 (M + H)+ B230 [00450] 1.23 mins, m/z = 412.14 (M + H)+ B231 [00451] 1.47 mins, m/z = 498.14 (M + H)+ B232 [00452] 1.40 mins, m/z = 482.18 (M + H)+ B233 [00453] 1.39 mins, m/z = 494.19 (M + H)+ B234 [00454] 1.32 mins, m/z = 489.18 (M + H)+ B235 [00455] 1.32 mins, m/z = 416.17 (M + H)+ B236 [00456] 1.26 mins, m/z = 414.16 (M + H)+ B237 [00457] 1.34 mins, m/z = 428.18 (M + H)+ B238 [00458] 1.32 mins, m/z = 416.19 (M + H)+ B239 [00459] 1.52 mins, m/z = 444.21 (M + H)+ B240 [00460] 1.28 mins, m/z = 426.17 (M + H)+ B241 [00461] 1.47 mins, m/z = 424.19 (M + H)+ B242 [00462] 1.41 mins, m/z = 408.21 (M + H)+ B243 [00463] 1.39 mins, m/z = 420.24 (M + H)+ B244 [00464] 1.32 mins, m/z = 415.21 (M + H)+ B245 [00465] 1.31 mins, m/z = 342.22 (M + H)+ B246 [00466] 1.26 mins, m/z = 340.22 (M + H)+ B247 [00467] 1.33 mins, m/z = 354.21 (M + H)+ B248 [00468] 1.32 mins, m/z = 342.23 (M + H)+ B249 [00469] 1.53 mins, m/z = 370.24 (M + H)+ B250 [00470] 1.28 mins, m/z = 352.20 (M + H)+ B251 [00471] 1.43 mins, m/z = 412.18 (M + H)+ B252 [00472] 1.35 mins, m/z = 396.20 (M + H)+ B253 [00473] 1.35 mins, m/z = 408.23 (M + H)+ B254 [00474] 1.27 mins, m/z = 403.21 (M + H)+ B255 [00475] 1.25 mins, m/z = 330.23 (M + H)+ B256 [00476] 1.19 mins, m/z = 328.21 (M + H)+ B257 [00477] 1.27 mins, m/z = 342.23 (M + H)+ B258 [00478] 1.25 mins, m/z = 330.23 (M + H)+ B259 [00479] 1.48 mins, m/z = 358.23 (M + H)+ B260 [00480] 1.21 mins, m/z = 340.21 (M + H)+ B261 [00481] 1.46 mins, m/z = 496.16 (M + H)+ B262 [00482] 484.13 mins, m/z = 1.38 (M + H)+ B263 [00483] 13.76-13.08 (m, 1H), 8.60 (s, 2H), 8.04 (s, 2H), 7 47-7.11 (m, 6H), 4.32 (d, 2H), 3.38-3.09 (m, 1H), 2.95-2.73 (m, 1H), 2.62 (br.s., 2H), 2.19 (d, 7H) B264 [00484] 8.60 (s, 2H), 8.02 (s, 2H), 7.73- 7.54 (m, 1H), 7.33-7.18 (m, 1H), 7.02-6.79 (m, 3H), 4.23 (dd, 2H), 3.31-3.11 (m, 1H), 2.85 (dd, 1H), 2.77-2.49 (m, 2H), 2.28-2.09 (m, 7H) B265 [00485] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.72-7.63 (m, 1H), 7.58- 7.52 (m, 2H), 3.26-3.13 (m, 1H), 3.12-3.07 (m, 3H), 2.99 (s, 4H), 2.97-2.86 (m, 2H), 2.48 (d, 1H), 2.25-2.16 (m, 6H) B266 [00486] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.59-7.49 (m, 2H), 3.65-3.52 (m, 8H), 3.38- 3.34 (m, 6H), 3.25-3.12 (m, 1H), 2.99-2.84 (m, 3H), 2.51-2.34 (m, 1H), 2.20 (d, 6H) B267 [00487] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.69-7.60 (m, 1H), 7.58- 7.52 (m, 2H), 3.48-3.36 (m, 1H), 3.25-3.12 (m, 1H), 3.02-2.96 (m, 3H), 2.99-2.82 (m, 2H), 2.48-2.31 (m, 1H), 2.24-2.14 (m, 6H), 1.49- 1 43 (m, 9H) B268 [00488] 1H NMR (400 MHz, CD3OD) 8.96-8.81 (m, 2H), 8.10 (s, 2H), 3.20-3.09 (m, 1H), 2.90 (dd, 1H), 2.71 (dd, 1H), 2.49-2.34 (m, 2H), 2.21 (s, 6H), 1.36 (s, 9H) B269 [00489] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 3.22-3.11 (m, 1H), 2.92 (dd, 1H), 2.80-2.71 (m, 4H), 2.47 (d, 2H), 2.19 (s, 6H) B270 [00490] 1H NMR (400 MHz, CD3OD) 9.11-9.03 (m, 2H), 8.15 (s, 2H), 3.25-3.14 (m, 1H), 2.99-2.85 (m, 1H), 2.78-2.64 (m, 1H), 2.54-2.38 (m, 2H), 2.26-2.18 (m, 6H), 1.38- 1.31 (m, 9H) B271 [00491] 8.60 (s, 2H), 8.14-7.95 (m, 2H), 7.23-7.08 (m, 3H), 6.92-6.71 (m, 2H), 4.37-4.20 (m, 2H), 3.78 (s, 3H), 3.35-3.09 (m, 1H), 2.93-2.75 (m, 1H), 2.72-2.50 (m, 2H), 2.20 (d, 7H) B272 [00492] 8.62 (s, 2H), 8.39-8.17 (m, 1H), 7.99 (s, 2H), 7.50 (d, 2H), 7.24- 7.08 (m, 2H), 4.30-3.98 (m, 2H), 3.30-3.12 (m, 1H), 2.95-2.70 (m, 2H), 2.67-2.51 (m, 1H), 2.15 (s, 7H), B273 [00493] 12.87-12.10 (m, 1H), 8.62 (s, 2H), 8.07 (d, 2H), 7.44-6.77 (m, 4H), 4.56 (s, 2H), 3.57-3.35 (m, 1H), 3.28-2.79 (m, 5H), 2.77-2.54 (m, 1H), 2.41-2.14 (m, 7H) B274 [00494] 12.75-12.43 (m, 1H), 7.10-6.93 (m, 2H), 6.43-5.99 (m, 2H), 3.51- 3.30 (m, 1H), 2.99 (d, 5H), 2.69- 2.20 (m, 4H), 2.12 (d, 3H), 1.85 (dd, 3H), 1.45 (s, 9H), 1.11 (t, 3H) B275 [00495] 13.60-12.87 (m, 1H), 8.63 (s, 2H), 8.07 (d, 2H), 6.35-5.93 (m, 1H), 4.30-3.94 (m, 1H), 3.45-3.11 (m, 1H), 2.90 (s, 1H), 2.67 (d, 2H), 2.25 (d, 7H), 1.18 (dd, 6H) B276 [00496] 12.74-11.76 (m, 1H), 8.63 (s, 2H), 8.07 (d, 2H), 3.99-3.27 (m, 9H), 2.94 (m, 2H), 2.70-2.49 (m, 1H), 2.25 (d, 6H) B277 [00497] 13.63-13.02 (m, 1H), 8.63 (s, 2H), 8.07 (br.s., 2H), 6.75-6.45 (m, 1H), 3.26 (d, 3H), 2.98-2.79 (m, 1H), 2.66 (br.s., 2H), 2.24 (d, 7H), 1.12 (t, 3H) B278 [00498] 13.53-13.03 (m, 1H), 8.62 (s, 2H), 8.06 (br.s., 2H), 7.07-6.78 (m, 1H), 4.95-4.65 (m, 2H), 3.88-3.53 (m, 2H), 3.41-3.14 (m, 1H), 3.03- 2.51 (m, 3H), 2.22 (d, 7H), 1.69 (s, 3H) B279 [00499] 13.05-12.46 (m, 1H), 8.63 (s, 2H), 8.06 (d, 2H), 3.52-3.26 (m, 1H), 3.05 (d, 8H), 2.68-2.51 (m, 1H), 2.25 (d, 7H) B280 [00500] 8.63 (s, 2H), 8.05 (d, 2H), 7.19- 7.03 (m, 1H), 3.35-3.10 (m, 1H), 3.02-2.81 (m, 1H), 2.75-2.46 (m, 5H), 2.22 (d, 7H) B281 [00501] 13.03-12.28 (m, 1H), 8.62 (s, 2H), 8.20-7.84 (m, 2H), 3.77-3.45 (m, 8H), 3.33 (d, 8H), 3.00-2.83 (m, 1H), 2.76-2.51 (m, 1H), 2.26 (d, 7H) B282 [00502] 1H NMR (400 MHz, Methanol) Shift = 8.90 (s, 2H), 8.18-8.02 (m, 2H), 3.27-3.22 (m, 2H), 3.18 (br. s., 1H), 2.92 (dd, J = 7.1, 18.0 Hz, 1H), 2.76 (dd, J = 6.5, 15.1 Hz, 1H), 2.47 (d, J = 16.0 Hz, 2H), 2.20 (s, 6H), 1.14 (t, J = 7.3 Hz, 3H) B283 [00503] 1H NMR (400 MHz, CD3OD) 8.90 (s, 2H), 8.10 (s, 2H), 4.86-4.77 (m, 2H), 3.78 (s, 2H), 3.23-3.13 (m, 1H), 2.94 (dd, 1H), 2.83 (dd, 1H), 2.50 (d, 2H), 2.20 (s, 6H), 1.75 (s, 3H) B284 [00504] 1H NMR (400 MHz, CD3OD) 9.14 (s, 2H), 8.21 (s, 2H), 7.36-7.21 (m, 4H), 4.39 (s, 2H), 3.26-3.15 (m, 1H), 2.99-2.78 (m, 2H), 2.59-2.45 (m, 2H), 2.26-2.17 (m, 6H) B285 [00505] 1H NMR (400 MHz, CD3OD) 8.97-8.80 (m, 2H), 8.17-7.85 (m, 2H), 3.78-3.49 (m, 8H), 3.24-3.12 (m, 1H), 3.05-2.89 (m, 2H), 2.82- 2.72 (m, 1H), 2.61-2.31 (m, 1H), 2.26-2.16 (m, 6H) B286 [00506] 1H NMR (400 MHz, CD3OD) 9.14 (s, 2H), 8.21 (br.s., 2H), 3.24 (d, 3H), 2.99-2.88 (m, 1H), 2.80-2.68 (m, 1H), 2.51-2.37 (m, 2H), 2.22 (s, 6H), 1.15(1, 3H) B287 [00507] 1H NMR (400 MHz, CD3OD) 9.14 (s, 2H), 8.21 (s, 2H), 4.85 (br.s., 2H), 3.84-3.70 (m, 2H), 3.20 (br.s., 1H), 3.01-2.92 (m, 1H), 2.87-2.76 (m, 1H), 2.51 (d, 2H), 2.24-2.14 (m, 6H), 1.80-1.66 (m, 3H) B288 [00508] 1H NMR (400 MHz, CD3OD) 9.18-9.05 (m, 2H), 8.20 (s, 2H), 3.72-3.50 (m, 6H), 3.20 (d, 1H), 3.05-2.74 (m, 5H), 2.59-2.41 (m, 1H), 2.27-2.17 (m, 6H) B289 [00509] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 4.77-4.50 (m, 1H), 3.22-3.07 (m, 1H), 2.98-2.70 (m, 3H), 2.56- 2.38 (m, 2H), 2.20 (s, 6H), 1.16- 1.05 (m, 1H), 1.00-0.86 (m, 1H) B290 [00510] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 6.33 (td, 1H), 6.01-5.89 (m, 1H), 3.87-3.75 (m, 2H), 3.23-3.08 (m, 1H), 3.00-2.88 (m, 1H), 2.84- 2.66 (m, 1H), 2.56-2.37 (m, 2H), 2.23-2.17 (m, 6H) B291 [00511] 1H NMR (400 MHz, CD3OD) 12.43-12.31 (m, 1H), 11.64-11.55 (m, 1H), 11.54-11.47 (m, 2H), 9.71-9.54 (m, 1H), 9.50-9.37 (m, 1H), 7.87-7.67 (m, 2H), 7.20-7.06 (m, 1H), 6.94-6.66 (m, 2H), 6.50- 6.36 (m, 2H), 6.17-6.09 (m, 6H), 5.69-5.56 (m, 3H) B292 [00512] 1H NMR (400 MHz, Methanol) Shift = 8.75 (s, 2H), 8.16-7.98 (m, 2H), 3.38-3.32 (m, 1H), 3.23- 3.07 (m, 1H), 2.95 (ddd, J = 3.9, 7.1, 17.9 Hz, 1H), 2.82 (dd, J = 5.0, 15.3 Hz, 1H), 2.56-2.39 (m, 2H), 2.20 (s, 6H), 1.88-1.73 (m, 1H), 1.51-1.37 (m, 1H) B293 [00513] 1H NMR (400 MHz, CD3OD) 8.80-8.62 (m, 2H), 8.08 (s, 2H), 4.79-4.51 (m, 1H), 3.24-3.08 (m, 1H), 2.98-2.72 (m, 3H), 2.58-2.40 (m, 2H), 2.24-2.10 (m, 6H), 1.18- 1.06 (m, 1H), 1.01-0.82 (m, 1H) B294 [00514] 1H NMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.08 (s, 2H), 4.69-4.46 (m, 2H), 3.95 (d, 2H), 3.23-3.11 (m, 1H), 2.95 (dd, 1H), 2.84-2.72 (m, 1H), 2.58-2.42 (m, 2H), 2.23-2.15 (m, 6H) B295 [00515] 8.86 (d, 1H), 7.94 (dd, 1H), 7.77 (d, 1H), 7.67 (s, 3H), 7.26-7.02 (m, 4H), 4.28 (dd, 2H), 3.36-3.14 (m, 1H), 2.95-2.54 (m, 3H), 2.18 (d, 7H) B296 [00516] 8.75-8.58 (m, 1H), 7.99-7.80 (m, 1H), 7.61 (s, 3H), 4.14-3.93 (m, 1H), 3.28-3.10 (m, 1H), 2.93 (br.s., 4H), 2.76-2.28 (m, 3H), 2.22 (d, 6H), 1.25-1.11 (m, 6H) B297 [00517] 12.54-12.26 (m, 1H), 8.78-8.56 (m, 1H), 7.91-7.77 (m, 1H), 7 64 (s, 3H), 6.27-5.90 (m, 1H), 3.49- 3.24 (m, 1H), 3.06-2.85 (m, 1H), 2.79-2.61 (m, 2H), 2.42 (s, 1H), 2.24 (d, 7H), 1.69 (d, 6H) B298 [00518] 8.79-8.58 (m, 1H), 7.89-7.78 (m, 1H), 7.64 (s, 3H), 6.19-5.90 (m, 1H), 5.00-4.77 (m, 2H), 4.00-3.70 (m, 2H), 3.41-3.25 (m, 1H), 3.03- 2.84 (m, 1H), 2.83-2.70 (m, 2H), 2.24 (d, 7H), 1.77 (s, 3H) B299 [00519] 12.45-12.14 (m, 1H), 8.78-8.54 (m, 1H), 7.91-7.76 (m, 1H), 7.70- 7.53 (m, 3H), 3.89-3.34 (m, 8H), 3.21-3.05 (m, 1H), 3.02-2.81 (m, 1H), 2.69-2.49 (m, 1H), 2.24 (d, 7H) B300 [00520] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.84 (dd, 1H), 7.64-7.45 (m, 2H), 5.89-5.76 (m, 1H), 5.23- 5.15 (m, 1H), 5.07 (qd, 1H), 4.49 (quin, 1H), 3.24-3.11 (m, 1H), 2.94 (dd, 1H), 2.79 (dd, 1H), 2.57-2.42 (m, 2H), 2.23-2.12 (m, 6H), 1.31- 1.16 (m, 3H) B301 [00521] 1HNMR (400 MHz, CD3OD) 7.25-7.04 (m, 2H), 5.94-5.68 (m, 1H), 5.23-5.12 (m, 1H), 5.07 (qd, 1H), 4.53-4.39 (m, 1H), 3.20-3.08 (m, 1H), 2.90 (dd, 1H), 2.76 (ddd, 1H), 2.56-2.34 (m, 2H), 2.14-2.01 (m, 6H), 1.28-1.03 (m, 3H) B302 [00522] 1H NMR (400 MHz, CD3OD) 8.82-8.68 (m, 2H), 8.14-7.99 (m, 2H), 6.32 (td, 1H), 6.01-5.86 (m, 1H), 3.83 (dd, 2H), 3.24-3.10 (m, 1H), 2.94 (dd, 1H), 2.78 (dd, 1H), 2.56-2.38 (m, 2H), 2.24-2.16 (m, 6H) B303 [00523] 1H NMR (400 MHz, Methanol) Shift = 8.77-8.70 (m, 2H), 8.07 (s, 2H), 5.73-5.61 (m, 1H), 5.53- 5.41 (m, 1H), 3.76 (d, J = 5.9 Hz, 2H), 3.22 - 3.09 (m, 1H), 2.91 (dd, J = 7.2, 18,0 Hz, 1H), 2.78 (dd, J = 6.2, 14.9 Hz, 1H), 2.53-2.38 (m, 2H), 2.20 (s, 6H), 1.71-1.61 (m, 3H) B304 [00524] 1H NMR (400 MHz, CD3OD) 8.48-8.34 (m, 1H), 7.69-7.60 (m, 1H), 7.55 (s, 2H), 4.70-4.46 (m, 2H), 4.00-3.89 (m, 2H), 3.22-3.09 (m, 1H), 2.94 (dd, 1H), 2.86-2.75 (m, 1H), 2.56-2.41 (m, 2H), 2.22- 2.16 (m, 6H) B305 [00525] 14.28-13.63 (m, 1H), 8.70 (s, 2H), 8.08 (d, 2H), 7.46-7.30 (m, 1H), 3.14 (dd, 3H), 2.94-2.78 (m, 1H), 2.69-2.40 (m, 2H), 2.22 (d, 7H), 1.03 (t, 3H) B306 [00526] 14.19-13.13 (m, 1H), 8.57 (d, 1H), 7.85-7.51 (m, 4H), 7.41-7.26 (m, 1H), 3.18 (quin, 3H), 2.83 (dd, 1H), 2.53 (d, 2H), 2.32-2.06 (m, 7H), 1.06 (t, 3H) B307 [00527] 13.90 (br.s., 1H), 7.88 (s, 1H), 7.59 (s, 1H), 7.38-7.18 (m, 2H), 3.32-3.09 (m, 3H), 2.96-2.74 (m, 1H), 2.69-2.45 (m, 2H), 2.18 (d, 7H), 1.07 (t, 3H) B308 [00528] 13.73-12.98 (m, 1H), 7.87 (s, 1H), 7.59 (s, 2H), 7.36-7.26 (m, 2H), 6.12 (d, 1H), 5.88-5.61 (m, 1H), 3.96 (s, 1H), 3.72 (br.s., 1H), 3.34- 3.07 (m, 1H), 2.81 (s, 1H), 2.57 (br.s., 2H), 2.16 (d, 7H) B309 [00529] 13.49 (br.s., 1H), 7.87 (s, 1H), 7.60 (s, 1H), 7.43-7.22 (m, 2H), 7.06-6.74 (m, 1H), 4.34-3.98 (m, 1H), 3.52-3.13 (m, 6H), 2.68 (br.s., 3H), 2.20 (d, 7H), 1.34-1.08 (m, 3H) B310 [00530] 13.93-12.81 (m, 1H), 7.88 (s, 1H), 7.60 (s, 1H), 7.38-7.25 (m, 2H), 7.15-6.98 (m, 1H), 4.28-3.98 (m, 1H), 3.46-3.12 (m, 6H), 3.02-2.78 (m, 1H), 2.76-2.52 (m, 2H), 2.18 (d, 7H), 1 16 (dd, 3H) B311 [00531] 7.86 (s, 1H), 7.59 (s, 1H), 7.35- 7.17 (m, 3H), 4.90-4.72 (m, 2H), 3.73 (d, 2H), 3.33-3.14 (m, 1H), 2.85 (dd, 1H), 2.65 (d, 2H), 2.28- 2.08 (m, 7H), 1.74-1.64 (m, 3H) B312 [00532] 13.82-13.18 (m, 1H), 7.82 (s, 2H), 7.56 (s, 1H), 7.44-7.02 (m, 6H), 4.24 (t, 2H), 3.33-3.09 (m, 1H), 2.92-2.45 (m, 3H), 2.13 (d, 7H) B313 [00533] 7.87 (s, 1H), 7.59 (s, 1H), 7.42 (s, 1H), 7.34-7.24 (m, 2H), 3.34-3.11 (m, 1H), 2.82 (dd, 1H), 2.58 (d, 2H), 2.36 (s, 1H), 2.26-2.06 (m, 7H), 1.66-1.48 (m, 6H) B314 [00534] 14.16-13.45 (m, 1H), 7.87 (s, 1H), 7.59 (s, 1H), 7.31 (s, 2H), 7.15- 7.01 (m, 1H), 3.36-3.03 (m, 3H), 2.85 (dd, 1H), 2.61 (d, 2H), 2.18 (d, 7H), 1.57-1.32 (m, 2H), 0.87 (t, 3H) B315 [00535] 14.33-13.55 (m, 1H), 7.87 (s, 1H), 7.59 (s, 1H), 7.37-7.24 (m, 2H), 7.08 (br.s., 1H), 3.84 (s, 1H), 3.35- 3.10 (m, 1H), 3.02-2.75 (m, 1H), 2.70-2.49 (m, 2H), 2.18 (d, 7H), 1.51-1.31 (m, 2H), 1.08 (dd, 3H), 0.85 (td, 3H) B316 [00536] 7.87 (s, 1H), 7.58 (s, 2H), 7.33- 7.23 (m, 2H), 5.87-5.64 (m, 1H), 5.23-5.00 (m, 2H), 4.59-4.36 (m, 1H), 3.32-3.10 (m, 1H), 2.94-2.77 (m, 1H), 2.75-2.47 (m, 2H), 2.16 (d, 7H), 1.20 (dd, 3H) B317 [00537] 13.36-12.89 (m, 1H), 7.86 (s, 1H), 7.60 (s, 2H), 7.28 (d, 2H), 3.94 (br.s., 2H), 3.38-3.11 (m, 1H), 2.94-2.76 (m, 1H), 2.74-2.44 (m, 2H), 2.33-2.03 (m, 8H) B318 [00538] 1H NMR (400 MHz, CD3OD) 8.95-8.84 (m, 1H), 8.19-8.07 (m, 1H), 8.00 (s, 1H), 7.76 (s, 2H), 3.23 (s, 3H), 3.04-2.83 (m, 1H), 2.82-2.69 (m, 1H), 2.56-2.41 (m, 2H), 2.21 (s, 6H), 1 14 (t, 3H) B319 [00539] 8.90 (dd, 1H), 7.99 (dd, 1H), 7.84 (dd, 1H), 7.71 (s, 2H), 4.94-4.77 (m, 2H), 3.81 (s, 2H), 3.34-3.17 (m, 1H), 3.04-2.86 (m, 2H), 2.78- 2.65 (m, 2H), 2.47-2.30 (m, 1H), 2.24 (d, 6H), 1.75 (s, 3H) B320 [00540] 8.90 (dd, 1H), 8.06-7.95 (m, 1H), 7.85 (d, 1H), 7.71 (s, 2H), 4.12- 3.93 (m, 1H), 3.32-3.13 (m, 1H), 3.03-2.79 (m, 1H), 2.73-2.57 (m, 2H), 2.45-2.30 (m, 1H), 2.24 (d, 6H), 1.17 (t, 6H) B321 [00541] 1H NMR (400 MHz, CD3OD) 8.91 (d, 1H), 8.20-8.06 (m, 1H), 7.97 (s, 1H), 7.75 (s, 2H), 3.72 (d, 8H), 3.29-3.16 (m, 1H), 3.11-2.86 (m, 2H), 2.84-2.59 (m, 1H), 2.57-2.43 (m, 1H), 2.25 (s, 6H) B322 [00542] 13.20-12.79 (m, 1H), 8.83-8.56 (m, 1H), 7.91-7.72 (m, 1H), 7.64 (s, 3H), 5.97-5.48 (m, 1H), 3.39- 3.24 (m, 1H), 3.08-2.82 (m, 1H), 2.79-2.57 (m, 2H), 2.24 (d, 7H), 1.40 (s, 9H) B323 [00543] 13.14-12.73 (m, 1H), 8.83-8.57 (m, 1H), 7.92-7.75 (m, 1H), 7.64 (s, 3H), 6.15-5.79 (m, 1H), 3.57- 3.20 (m, 5H), 3.00-2.84 (m, 1H), 2.24 (d, 7H), 1.35-1.06 (m, 3H) B324 [00544] 8.82 (dd, 1H), 7.98-7.87 (m, 1H), 7.83-7.71 (m, 1H), 7.67 (s, 2H), 7.48-7.33 (m, 1H), 7.15 (d, 2H), 6.83 (d, 2H), 4.37-4.19 (m, 2H), 3.77 (s, 3H), 3.29-3.09 (m, 1H), 2.89-2.72 (m, 1H), 2.70-2.48 (m, 2H), 2.19 (d, 7H) B325 [00545] 1H NMR (400 MHz, CD3OD) 8.49 (dd, 1H), 7.84 (dd, 1H), 7.60 (s, 2H), 3.53-3.43 (m, 2H), 3.36 (s, 3H), 3.21-3.09 (m, 1H), 2.90 (dd, 1H), 2.73 (dd, 1H), 2.45 (d, 2H), 2.23-2.13 (m, 6H), 1.32 (d, 6H) B326 [00546] 1HNMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.80-8.71 (m, 2H), 8.80- 8.71 (m, 2H), 8.08 (s, 2H), 6.43 (td, 1H), 6.27-6.17 (m, 1H), 3.98 (dd, 2H), 3.22-3.12 (m, 1H), 2.94 (dd, 1H), 2.79 (dd, 1H), 2.54-2.41 (m, 2H), 2.20 (s, 6H) B327 [00547] 1H NMR (400 MHz, Methanol) Shift = 8.75 (s, 2H), 8,08 (s, 2H), 3.63-3.54 (m, 1H), 3.52-3.42 (m, 3H), 3.35-3.33 (m, 1H), 3.27- 3.11 (m, 2H), 2.90 (dd, J = 7.0, 17.9 Hz, 1H), 2.73 (dd, J = 6.5, 15.0 Hz, 1H), 2.53-2.35 (m, 2H), 2.21 (s, 6H), 1.32 (d, J = 1.3 Hz, 6H) B328 [00548] 1H NMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.13-7.94 (m, 2H), 5.86 (dddd, 1H), 5.24-5.13 (m, 1H), 5.07 (dd, 1H), 4.56-4.41 (m, 1H), 3.17 (br.s., 1H), 2.93 (dd, 1H), 2.79 (dd, 1H), 2.48 (d, 2H), 2.21 (s, 6H), 1.27-1.19 (m, 3H) B329 [00549] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.67-7.60 (m, 1H), 7.55 (s, 2H), 3.51-3.44 (m, 2H), 3.37 (s, 3H), 3.21-3.06 (m, 1H), 2.90 (dd, 1H), 2.73 (dd, 1H), 2.44 (d, 2H), 2.20 (s, 6H), 1.32 (d, 6H) B330 [00550] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 5.86 (dddd, 1H), 5.17 (qd, 1H), 5.07 (qd, 1H), 4.49 (t, 1H), 3.25-3.13 (m, 1H), 2.93 (dd, 1H), 2.79 (dd, 1H), 2.57-2.39 (m, 2H), 2.20 (s, 6H), 1.30-1.22 (m, 3H) B331 [00551] 1H NMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.08 (s, 2H), 3.26-3.13 (m, 1H), 3.01 (s, 3H), 2.99-2.87 (m, 2H), 2.82 (d, 1H), 2.42 (d, 1H), 2.25-2.09 (m, 6H), 1.50-1.39 (m, 9H) B332 [00552] 1H NMR (400 MHz, CD3OD) 8.75 (s, 2H), 8.08 (s, 2H), 4.20-4.04 (m, 1H), 3.40-3.32 (m, 5H), 3.27-3.10 (m, 1H), 2.92 (dd, 1H), 2.77 (dd, 1H), 2.53-2.36 (m, 2H), 2.25-2.08 (m, 6H), 1.15 (dd, 3H) B333 [00553] 1H NMR (400 MHz, CD3OD) 8.79-8.68 (m, 2H), 8.11-8.01 (m, 2H), 4.03-3.95 (m, 2H), 3.23-3.09 (m, 1H), 2.94 (dd, 1H), 2.79 (dd, 1H), 2.63-2.59 (m, 1H), 2.58-2.39 (m, 2H), 2.22-2.18 (m, 6H) B334 [00554] 1H NMR (400 MHz, Methanol) Shift = 8.75 (s, 2H), 8.08 (s, 2H), 4.27-4.20 (m, 2H), 3.23-3.09 (m, 3H), 3.06-2.93 (m, 3H), 2.83 (s, 1H), 2.66 (t, J = 2.5 Hz, 1H), 2.50 (d, J = 16.1 Hz, 1H), 2.21 (d, J = 4.3 Hz, 6H) B335 [00555] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 4.18-4.04 (m, 1H), 3.39-3.33 (m, 5H), 3.24-3.12 (m, 1H), 2.92 (dd, 1H), 2.82-2.71 (m, 1H), 2.46 (d, 2H), 2.20 (s, 6H), 1.17-1.10 (m, 3H) B336 [00556] 1H NMR (400 MHz, CD3OD) 8.44 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 3.99 (d, 2H), 3.22-3.08 (m, 1H), 2.93 (dd, 1H), 2.86-2.72 (m, 1H), 2.61 (t, 1H), 2.54-2.38 (m, 2H), 2.24-2.17 (m, 6H) B337 [00557] 1.38 mins, m/z = 480.22 (M + H)+ B338 [00558] 1.45 mins, m/z = 494.24 (M + H)+ B339 [00559] 1.47 mins, m/z = 542.13 (M + H)+ B340 [00560] 1.27 mins, m/z = 414.23 (M + H)+ B341 [00561] 1.29 mins, m/z = 426.21 (M + H)+ B342 [00562] 1.29 mins, m/z = 426.22 (M + H)+ B343 [00563] 1.28 mins, m/z = 438.22 (M + H)+ B344 [00564] 1.35 mins, m/z = 458.26 (M + H)+ B345 [00565] 1.29 mins, m/z = 426.21 (M + H)+ B346 [00566] 1.21 mins, m/z = 444.23 (M + H)+ B347 [00567] 1.28 mins, m/z = 414.23 (M + H)+ B348 [00568] 1.51 mins, m/z = 442.25 (M + H)+ B349 [00569] 1.24 mins, m/z = 424.20 (M + H)+ B350 [00570] 1.21 mins, m/z = 412.21 (M + H)+ B351 [00571] 1.36 mins, m/z = 428.23 (M + H)+ B352 [00572] 1.29 mins, m/z = 446.17 (M + H)+ B353 [00573] 1.32 mins, m/z = 468.20 (M + H)+ B354 [00574] 1.44 mins, m/z = 496.20 (M + H)+ B355 [00575] 1.45 mins, m/z = 476.25 (M + H)+ B356 [00576] 1.36 mins, m/z = 492.25 (M + H)+ B357* [00577] 1.36 mins, m/z = 479.24 (M + H)+ B358* [00578] 1.43 mins, m/z = 493.24 (M + H)+ B359* [00579] 1.45 mins, m/z = 541.13 (M + H)+ B360* [00580] 1.26 mins, m/z = 413.24 (M + H)+ B361* [00581] 1.27 mins, m/z = 425.24 (M + H)+ B362* [00582] 1.28 mins, m/z = 425.23 (M + H)+ B363* [00583] 1.27 mins, m/z = 437.23 (M + H)+ B364* [00584] 1.33 mins, m/z = 457.27 (M + H)+ B365* [00585] 1.28 mins, m/z = 425.23 (M + H)+ B366* [00586] 1.18 mins, m/z = 443.24 (M + H)+ B367* [00587] 1.26 mins, m/z = 413.23 (M + H)+ B368* [00588] 1.48 mins, m/z = 441.26 (M + H)+ B369* [00589] 1.22 mins, m/z = 423.23 (M + H)+ B370* [00590] 1.20 mins, m/z = 411.22 (M + H)+ B371* [00591] 1.34 mins, m/z = 427.24 (M + H)+ B372* [00592] 1.27 mins, m/z = 445.17 (M + H)+ B373* [00593] 1.31 mins, m/z = 467.19 (M + H)+ B374* [00594] 1.44 mins, m/z = 495.20 (M + H)+ B375* [00595] 1.43 mins, m/z = 475.25 (M + H)+ B376 [00596] 1HNMR (400 MHz, CD3OD) 9.05- 8.99 (m, 1H), 8.71-8.63 (m, 1H), 8.44-8.36 (m, 1H), 8.08-7.99 (m, 1H), 7.77-7.71 (m, 1H), 6.78-6.61 (m, 1H), 5.88 (d, 1H), 5.33 (dd, 1H), 3.27-3.17 (m, 1H), 3.02-2.89 (m, 1H), 2.79-2.67 (m, 1H), 2.64- 2.47 (m, 2H), 2.28 (d, 3H), 1.40- 1.33 (m, 9H) B377 [00597] 12.71 (br. s., 1H), 7.94 (br. s., 1H), 7.51 (dd, J = 8.5, 5.4 Hz, 2H), 7.24 (s, 2H), 7.03-7.17 (m, 2H), 3.34 (br. s., 1H), 2.96 (d, J = 11.1 Hz, 2H), 2.52-2.76 (m, 1H), 2.34 (br. s., 1H), 2.18 (s, 6H), 1.53 (d, J = 7.1 Hz, 6H). B378 [00598] 8.33 (s, 1H), 7.48 (d, J = 8.3 Hz, 2H), 7.36 (d, J = 8.3 Hz, 2H), 7.23 (br. s., 2H), 3.20 (br. s., 1H), 2.89- 3.08 (m, 1H), 2.69 (br. s., 2H), 2.35 (br. s., 1H), 2.19 (d, J = 4.6 Hz, 6H), 1.65 (s, 6H). B379 [00599] 12.25-13.40 (br.s., 1H), 8.05 (br. s., 1H), 6.95-7.19 (m, 2H), 3.29 (br. s., 1H), 2.88 (d, J = 11.0 Hz, 2H), 2.59 (br. s., 1H), 2.12-2.25 (m, 1H), 1.96-2.12 (m, 9H), 1.51 (d, J = 9.9 Hz, 6H). B380* [00600] 1.35 mins, m/z = 491.25 (M + H)+ B381* [00601] 1HNMR (400 MHz, CD3OD) 8.52-8.46 (m, 1H), 7.88 (s, 1H), 7.80 (s, 1H), 7.74-7.66 (m, 1H), 3.15 (d, 1H), 2.92 (ddd, 1H), 2.74 (ddd, 1H), 2.60-2.50 (m, 1H), 2.53-2.34 (m, 2H), 2.26 (d, 3H), 1.42-1.34 (m, 9H) B382 [00602] 1HNMR (400 MHz, CD3OD) 8.50- 8.45 (m, 1H), 7.97 (s, 1H), 7.74- 7.64 (m, 2H), 6.70 (ddd, 1H), 5.73 (dd, 1H), 5.28-5.17 (m, 1H), 3.26- 3.13 (m, 1H), 2.99-2.86 (m, 1H), 2.79-2.68 (m, 1H), 2.52-2.41 (m, 2H), 2.25-2.19 (m, 3H), 1.40-1.33 (m, 9H) B383* [00603] 1.27 mins, m/z = 463.24 (M + H)+ B384* [00604] 1.34 mins, m/z = 523.14/525.12 (M + H)+ B385* [00605] 1.13 mins, m/z = 397.24 (M + H)+ B386* [00606] 1.16 mins, m/z = 409.23 (M + H)+ B387* [00607] 1.01 mins, m/z = 393.21 (M + H)+ B388* [00608] 1.15 mins, m/z = 421.23 (M + H)+ B389* [00609] 1.21 mins, m/z = 441.25 (M + H)+ B390* [00610] 1.16 mins, m/z = 409.24 (M + H)+ B391* [00611] 1.06 mins, m/z = 427.26 (M + H)+ B392* [00612] 1.13 mins, m/z = 397.24 (M + H)+ B393* [00613] 1.36 mins, m/z = 425.28 (M + H)+ B394* [00614] 1.10 mins, m/z = 407.21 (M + H)+ B395* [00615] 1.07 mins, m/z = 395.23 (M + H)+ B396* [00616] 1.21 mins, m/z = 411.26 (M + H)+ B397* [00617] 1.19 mins, m/z = 451.19 (M + H)+ B398* [00618] 1.31 mins, m/z = 459.27 (M + H)+ B399* [00619] 1.23 mins, m/z = 475.25 (M + H)+ B400* [00620] 1.16 mins, m/z = 429.18 (M + H)+ B401* [00621] 1.32 mins, m/z = 479.20 (M + H)+ B402 [00622] 1HNMR (400 MHz, DMSO-d6) 7.76 (s, 1H), 7.04-6.94 (m, 1H), 6.82 (s, 2H), 6.74-6.57 (m, 5H), 4.13 (s, 2H), 2.33 (br.s., 1H), 2.21- 2.06 (m, 1H), 1.93-1.87 (m, 1H), 1.85-1.76 (m, 1H), 1.71 (br.s., 1H), 1.53-1.45 (m, 1H), 1.44 (s, 6H) B403 [00623] 1HNMR (400 MHz, CD3OD) 8.43 (d, 1H), 7.65 (ddd, 1H), 7.55 (s, 2H), 3.13 (br.s., 1H), 2.89 (dd, 1H), 2.71 (dd, 1H), 2.47 (d, 1H), 2.31-2.24 (m, 1H), 2.22-2.16 (m, 6H) B404 [00624] 1HNMR (400 MHz, CD3OD) 8.82- 8.74 (m, 2H), 8.49 (s, 1H), 8.21- 8.10 (m, 1H), 6.67 (ddd, 1H), 5.83-5.70 (m, 1H), 5.27-5.12 (m, 1H), 3.24-3.13 (m, 1H), 2.93 (ddd, 1H), 2.72 (ddd, 1H), 2.51-2.38 (m, 2H), 2.25-2.17 (m, 3H), 1.40-1.31 (m, 9H) B405 [00625] 1HNMR (400 MHz, CD3OD) 8.82- 8.71 (m, 2H), 8.27 (s, 1H), 8.27- 8.13 (m, 1H), 3.20 (dtd, 1H), 2.93 (dd, 1H), 2.75-2.66 (m, 1H), 2.54- 2.38 (m, 2H), 2.30-2.16 (m, 3H), 1.39-1.31 (m, 9H) *Trifluoroacetyl (TFA) salt.

TABLE-US-00013 Compound Number Structure .sup.1H NMR (400 MHz, CDCl.sub.3) unless stated P1 [00626] 8.70 (s, 2H), 8.09 (s, 2H), 7.83 (d, 2H), 6.86 (d, 2H), 5.91 (s, 1H), 3.80 (s, 3H), 3.53 (dd, 1H), 3.28-3.14 (m, 2H), 2.79 (dd, 1H), 2.48-2.39 (m, 1H), 2.27 (d, 6H), 1.33 (s, 9H) P2 [00627] (400 MHz, d4-MeOH) 8.69 (s, 2H), 8.02 (s, 2H), 7.95-7.88 (m, 2H), 7.64 (s, 1H), 7.11 (t, 2H), 3.47 (dd, 1H), 3.23-3.12 (m, 2H), 2.77 (dd, 1H), 2.56-2.48 (m, 1H), 2.26 (d, 6H), 1.36 (s, 9H) P3 [00628] (400 MHz, d4-MeOH) 8.82 (s, 2H), 8.11 (s, 2H), 3.24 (dd, 1H), 3.17-3.09 (m, 1H), 2.92 (dd, 1H), 2.71 (dd, 1H), 2.42 (dd, 1H), 2.21 (s, 6H), 1.34 (s, 9H), 1.09 (s, 9H) P4 [00629] (400 MHz, d4-MeOH) 8.75 (s, 2H), 8.04 (s, 2H), 7.61 (s, 1H), 4.18 (q, 2H), 3.36 (dd, 1H), 31.5- 3.08 (m, 1H), 3.03 (dd, 1H), 2.70 (dd, 1H), 2.43 (dd, 1H), 2.19 (d, 6H), 1.33 (s, 9H), 1.20 (t, 3H) P5 [00630] (400 MHz, d4-MeOH) 8.74 (s, 2H), 8.04 (s, 2H), 7.59 (s, 1H), 3.33 (dd, 1H), 3.14-3.06 (m, 1H), 3.01 (dd, 1H), 2.80 (q, 2H), 2.70 (dd, 1H), 2.44 (dd, 1H), 2.19 (d, 6H), 1.33 (s, 9H), 1.27 (t, 3H) P6 [00631] 8.72 (s, 2H), 8.09 (s, 2H), 6.12 (s, 1H), 5.13 (dd, 2H), 3.68-3.56 (m, 2H), 3.27 (dd, 1H), 3.07-3.00 (m, 1H), 2.89 (dd, 1H), 2.74 (dd, 1H), 2.36-2.28 (m, 1H), 2.21 (d, 6H), 1.32 (s, 9H), 1.18 (t, 3H) P7 [00632] 8.72 (s, 2H), 8.07 (s, 2H), 5.48 (s, 1H), 3.97- 3.88 (m, 1H), 3.32-3.21 (m, 4H), 3.01 (dd, 1H), 2.71 (dd, 1H), 2.52 (d, 1H), 2.28-2.21 (m, 1H), 2.23 (d, 6H), 1.87-1.72 (m, 4H), 1.35 (s, 9H) P8 [00633] 8.72 (s, 2H), 8.08 (s, 2H), 5.81 (s, 1H), 3.50 (dd, 1H), 3.40-3.32 (m, 2H), 3.23-3.07 (m, 4H), 2.74 (dd, 1H), 2.40-2.32 (m, 1H), 2.22 (d, 6H), 1.88- 1.77 (m, 4H), 1.33 (s, 9H) P9 [00634] 6.83 (s, 2H), 3.75-3.61 (m, 2H), 3.45-3.33 (m, 2H), 3.30 (s, 4H), 3.17-3.03 (m, 2H), 2.91-2.72 (m, 2H), 2.25 (s, 3H), 2.08 (d, 6H), 1.89-1.77 (m, 2H), 1.31 (s, 9H), 1.08 (s, 9H) P10 [00635] 6.84 (s, 2H), 6.38-6.21 (m, 1H), 3.53-3.19 (m, 8H), 3.16-3.04 (m, 1H), 3.01-2.89 (m, 1H), 2.86- 2.69 (m, 1H), 2.50-2.31 (m, 1H), 2.25 (s, 3H), 2.06 (d, 6H), 1.85-1.70 (m, 2H), 1.08 (s, 9H) P11 [00636] 6.84 (s, 2H), 6.33-6.21 (m, 1H), 5.94-5.82 (m, 1H), 3.31-3.17 (m, 1H), 3.12-3.01 (m, 1H), 2.99- 2.86 (m, 1H), 2.85-2.69 (m, 1H), 2.54-2.40 (m, 1H), 2.25 (s, 3H), 2.05 (d, 6H), 1.08 (s, 9H) P12 [00637] 6.84 (s, 2H), 5.01-4.83 (m, 1H), 4.83-4.54 (m, 3H), 3.33-3.17 (m, 1H), 3.14-3.01 (m, 1H), 2.93- 2.73 (m, 2H), 2.59-2.43 (m, 1H), 2.25 (s, 3H), 2.07 (d, 6H), 1.35-0.98 (m, 19H) P13 [00638] 7.26-7.11 (m, 1H), 6.90-6.77 (m, 2H), 5.05-4.90 (m, 1H), 4.86-4.75 (m, 2H), 4.40 (s, 2H), 3.34- 3.19 (m, 1H), 3.17-3.04 (m, 1H), 2.99-2.88 (m, 1H), 2.85-2.72 (m, 1H), 2.53-2.39 (m, 1H), 2.25 (s, 3H), 2.13-1.99 (m, 6H), 1.09 (s, 9H) P14 [00639] 6.84 (s, 2H), 4.75-1.7 (m, 18H), 1.35-0.98 (m, 21H) P15 [00640] 7.15-7.00 (s, 1H), 6.90-6.77 (m, 2H), 4.75-4.60 (m, 2H), 4.30-4.40 (m, 2H), 3.33-3.25 (m, 1H), 3.17-3.04 (m, 1H), 2.99-2.88 (m, 1H), 2.85-2.72 (m, 1H), 2.45-2.35 (m, 1H), 2.25 (s, 3H), 2.13- 1.99 (m, 6H), 1.09-1.00 (m, 12H)

BIOLOGICAL EXAMPLES

Biological Example 1

[0445] Test—Glasshouse Assay for Herbicidal Activity

[0446] Seeds of a variety of monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. The plants are cultivated for one day (for pre-emergence (PRE)) or for about 12 days (for post-emergence (POST)) under controlled conditions in a glasshouse (warm climate species at 24/18° C., cool climate species at 20/16° C., both at day/night; 16 hours light; 65% humidity).

[0447] The test plants are then grown on, in a glasshouse (greenhouse) under controlled conditions (warm climate species at 24/18° C., cool climate species at 20/16° C., both at day/night; 16 hours light; 65% humidity) and are watered twice daily. 15 days after application of the test herbicide (15 DAA) (for post-emergence), and 20 days after application of the test herbicide (20 DAA) (for pre-emergence), the test plants are evaluated visually, and an assessed percentage phytotoxicity score is given for each herbicidal application on each plant species (with 100%=total damage to plant; 0%=no damage to plant).

[0448] The plant species tested are as follows: Alopecurus myosuroides (ALOMY), Avena fatua (AVEFA), Lolium perenne (LOLPE), Echinochloa crus-galli (ECHCG).

TABLE-US-00014 TABLE B1 Pre-/Post-emergence herbicidal activity (percentage phytotoxicity) LOLPE ALOMY ECHCG AVEFA Compound Rate g/ha PRE POST PRE POST PRE POST PRE POST A1 250 100 80 60 60 90 80 60 60 A2 250 80 80 80 80 70 50 10 70 A3 250 100 90 100 90 100 90 90 90 A4 250 80 90 50 50 70 80 30 80 A5 250 100 80 100 90 100 80 70 80 A6 250 100 90 90 90 100 90 60 90 A7 250 100 100 80 90 90 100 60 90 A8 250 100 100 100 100 100 100 100 100 A9 250 90 80 90 80 100 90 90 100 A10 250 90 90 70 80 90 90 70 60 A11 250 70 70 70 80 70 80 50 70 A12 250 100 90 90 100 100 80 70 80 A13 250 70 80 50 80 100 80 40 70 A14 250 80 80 90 80 100 80 70 70 A15 250 100 100 80 80 100 100 50 80 A16 250 80 80 90 90 100 100 90 90 A17 250 70 80 70 80 70 80 40 70 A18 250 60 80 60 70 60 70 20 50 A19 250 90 90 90 90 90 80 70 80 A20 250 100 100 70 80 100 100 70 80 A21 250 80 80 70 80 80 80 50 70 A22 250 70 80 60 80 100 90 30 60 A23 250 70 80 80 80 100 90 60 70 A24 250 90 100 80 90 100 100 90 90 A25 250 90 90 70 70 80 90 70 70 A26 250 100 90 80 80 80 80 70 80 A27 250 80 80 70 80 80 80 70 80 A28 250 90 100 100 100 90 100 100 100 A29 250 100 100 100 100 100 100 90 100 A30 250 100 100 100 100 100 100 100 100 A31 250 100 100 100 100 100 100 90 100 A32 250 90 100 70 100 100 100 80 100 A33 250 100 100 100 100 100 100 100 100 A34 250 100 100 100 100 100 100 100 100 A35 250 100 100 90 90 100 100 100 100 A36 250 100 90 100 90 100 100 100 100 A37 250 100 80 90 80 100 90 90 100 A38 250 90 80 80 80 100 90 90 100 A39 250 100 100 100 100 100 100 100 100 A40 250 100 100 100 100 100 100 90 100 A41 250 100 100 100 100 100 100 70 100 A42 250 100 90 100 100 100 80 100 100 A43 250 100 90 100 100 100 90 100 90 A44 250 100 100 100 100 100 100 100 100 A45 250 100 100 100 100 100 100 100 100 A46 250 90 100 100 100 100 100 90 100 A47 250 100 100 100 100 100 100 100 100 A48 250 100 100 100 100 100 100 90 100 A49 250 100 100 100 100 100 100 100 100 A50 250 100 100 100 100 90 100 100 100 A51 250 100 100 100 100 100 100 100 100 A52 250 90 90 100 100 90 100 90 100 A53 250 90 90 90 100 100 100 80 90 A54 250 100 100 100 100 100 100 100 100 A55 250 90 90 90 90 100 100 80 100 A56 250 90 90 100 100 100 100 90 100 A57 250 100 100 100 100 100 100 90 100 A58 250 90 90 100 100 100 100 100 100 A59 250 70 70 100 90 90 90 70 90 A60 250 100 90 100 100 100 100 100 100 A61 250 100 90 100 100 100 100 90 100 A62 250 100 60 100 90 100 100 90 90 A63 250 100 90 100 100 100 100 90 100 A64 250 80 70 70 90 100 100 70 90 A65 250 90 80 100 90 100 100 70 90 A66 250 100 100 100 90 100 100 100 100 A67 250 90 70 100 80 90 100 90 80 A68 250 100 100 70 90 100 100 100 100 A69 250 100 100 100 100 100 100 100 100 A70 250 70 70 70 90 100 90 70 70 A71 250 60 70 80 100 90 100 80 90 A72 250 90 80 90 90 100 90 90 90 A73 250 30 40 70 70 90 90 10 80 A74 250 90 90 100 100 100 100 90 100 A75 250 90 90 100 100 100 100 90 100 A76 250 90 80 90 100 100 100 90 90 A77 250 80 80 80 90 100 100 80 90 A78 250 20 30 10 80 60 100 30 40 A79 250 100 100 100 100 100 100 100 100 A80 250 100 100 100 100 100 100 90 100 A81 250 100 90 100 90 100 100 100 100 A82 250 — 30 — 10 — 30 — 10 A83 250 — 30 — 50 — 70 — 10 A84 250 10 20 40 60 0 70 0 20 A85 250 100 90 100 100 90 100 80 100 A86 250 10 50 0 30 20 80 0 40 A87 250 80 80 80 100 90 100 90 100 A88 250 100 100 90 70 70 80 0 10 A89 250 90 100 90 90 100 100 60 90 A90 250 60 70 0 0 40 80 0 0 A91 250 70 70 30 10 20 0 30 0 A92 250 90 40 70 60 80 80 60 70 A93 250 90 80 90 100 60 70 20 40 A94 250 90 90 90 80 60 80 20 70 A94 250 — 60 — 0 — 80 — 0 A96 250 100 100 100 80 100 80 70 80 A97 250 90 70 30 70 0 0 0 20 A98 250 80 80 100 90 80 60 20 90 A99 250 20 70 20 60 0 0 0 30 A100 250 80 70 90 70 20 20 0 0 A101 250 — 40 — 10 — 20 — 0 A102 250 60 70 20 70 50 10 0 70 A103 250 — 20 — 60 — 20 — 10 A104 250 80 60 90 90 80 70 0 70 A105 250 70 70 80 80 70 60 20 0 A106 250 70 70 0 30 20 20 0 0 A107 250 90 80 80 80 80 70 10 90 A108 250 80 60 0 0 30 20 0 60 A109 250 90 80 90 90 80 80 50 80 A110 250 100 80 70 60 90 80 50 70 A111 250 100 100 90 100 100 100 90 100 A112 250 100 100 80 90 100 100 90 100 A113 250 90 100 80 100 100 100 90 100 A114 250 90 100 90 100 100 100 90 100 A115 250 90 100 90 100 90 100 90 100 A116 250 80 100 80 90 100 100 90 100 A117 250 90 100 70 90 100 100 70 100 A118 250 90 100 80 90 100 100 100 100 A119 250 70 90 40 60 100 100 60 90 A120 250 80 100 80 100 100 100 90 100 A121 250 80 100 90 100 90 100 90 100 A122 250 20 70 70 90 90 100 0 100 A123 250 80 90 60 80 90 100 70 80 A124 250 90 100 70 90 90 100 80 100 A125 250 90 100 70 90 100 100 80 100 A126 250 80 80 30 30 100 100 50 90 A127 250 60 90 0 70 60 100 20 70 A128 250 90 100 80 100 100 100 80 100 A129 250 — 20 — 50 — 90 — 70 A130 250 90 100 70 90 100 100 90 100 A131 250 70 100 40 90 100 100 50 100 A132 250 90 100 90 100 100 100 90 100 A133 250 80 80 30 90 90 100 90 100 A134 250 80 100 70 90 90 100 90 90 A135 250 70 90 20 90 60 100 30 100 A136 250 80 90 80 100 90 100 90 100 A137 250 70 60 60 40 70 90 60 70 A138 250 100 100 90 90 100 100 100 100 A139 250 0 10 0 10 90 20 0 30 A140 250 100 90 90 100 100 100 100 100 A141 250 100 90 90 90 100 100 90 100 A142 250 20 20 0 — 30 60 0 — A143 250 10 20 0 — 10 40 0 — A144 250 90 90 80 80 100 100 90 100 A145 250 100 90 100 100 100 100 100 100 A146 250 90 100 80 100 90 100 90 100 A147 250 — 0 — 20 — 60 — 20 A148 250 80 90 70 70 100 100 80 100 A149 250 90 100 80 100 100 100 100 100 A150 250 80 70 70 70 90 90 50 90 A151 250 80 40 40 40 100 70 70 50 A152 250 90 100 70 90 100 90 100 100 A153 250 60 70 30 90 90 90 70 90 A154 250 80 70 50 80 80 100 60 90 A155 250 70 70 40 50 70 90 100 70 A156 250 80 80 60 70 100 100 70 80 A157 250 70 90 60 80 90 100 70 90 A158 250 60 80 20 70 80 90 20 70 A159 250 90 90 60 70 90 80 20 50 A160 250 100 100 70 70 100 90 80 90 A161 250 100 90 20 70 100 80 30 30 A162 250 100 100 70 90 100 90 70 90 A163 250 60 60 10 30 70 70 30 30 A164 250 60 60 70 70 70 70 10 70 A165 250 70 80 60 60 100 90 0 80 A166 250 70 70 40 40 70 90 20 70 A167 250 80 60 20 20 80 80 10 70 A168 250 80 100 80 90 80 100 20 90 A171 250 70 80 60 70 80 70 20 70 A172 250 90 60 80 80 80 70 40 70 A173 250 80 60 50 20 10 30 10 30 A174 250 — 0 — 40 — 10 — 0 A175 250 100 90 80 80 90 90 70 90 A176 250 100 100 90 90 100 100 90 90 A177 250 100 80 100 80 90 90 60 80 A178 250 80 70 20 70 80 40 0 70 A179 250 90 80 100 100 80 100 90 100 A180 250 0 30 40 70 20 70 0 70 A181 250 100 100 90 90 90 80 90 90 A182 250 70 40 70 70 0 80 20 70 A183 250 90 70 50 70 80 80 0 70 A184 250 90 80 90 90 90 90 0 70 A185 250 70 70 80 80 70 70 60 80 A186 250 60 60 40 40 70 80 0 30 A187 250 100 90 80 80 90 100 90 100 P1 250 100 100 100 100 100 100 100 100 P2 250 100 100 90 100 100 100 90 100 P3 250 100 100 100 100 100 100 80 90 P4 250 100 100 90 90 100 100 90 100 P5 250 100 100 100 100 100 100 90 100 Note: a hyphen (—) in the table above indicates that no measurement was made.

TABLE-US-00015 TABLE B2 Pre-/Post-emergence herbicidal activity (percentage phytotoxicity) Rate LOLPE ALOMY ECHCG AVEFA Compound g/ha PRE POST PRE POST PRE POST PRE POST B1 250 20 20 20 0 70 60 0 0 B2 250 80 30 40 40 80 10 60 30 B3 250 90 80 60 0 90 70 50 10 B5 250 100 90 100 100 100 100 90 100 B6 250 0 20 0 50 0 90 0 70 B7 250 90 80 100 100 80 100 90 100 B8 250 100 90 80 80 90 100 90 100 B9 250 90 70 70 70 100 70 70 70 B10 250 0 30 0 30 0 70 0 70 B11 250 90 80 70 70 90 70 70 70 B12 250 90 90 70 60 100 90 30 60 B13 250 90 90 50 50 90 80 40 70 B14 250 90 90 70 70 70 90 70 80 B15 250 100 90 80 70 90 90 80 90 B16 250 90 90 80 70 90 90 30 70 B17 250 90 70 20 40 90 70 0 50 B18 250 100 100 70 80 90 90 80 90 B19 250 80 70 10 50 90 70 20 50 B20 250 70 40 80 70 90 90 90 80 B21 250 100 90 80 80 100 90 50 90 B22 250 90 80 30 30 90 80 100 20 B23 250 100 90 70 60 90 90 60 70 B24 250 100 90 80 90 100 100 80 80 B25 250 90 80 90 80 90 90 70 80 B26 250 70 60 60 70 70 60 20 60 B27 250 60 70 30 70 60 40 20 70 B28 250 80 50 50 50 60 70 50 60 B29 250 80 70 30 70 80 70 10 60 B30 250 70 30 60 70 70 80 70 90 B31 250 90 80 100 80 90 80 70 80 B32 250 90 50 90 70 80 80 0 40 B33 250 100 90 100 90 100 100 100 100 B34 250 90 80 70 60 100 100 80 90 B35 250 80 70 90 80 80 70 0 70 B36 250 80 50 50 30 0 20 0 40 B37 250 100 80 70 70 90 90 90 100 B38 250 100 90 70 70 100 90 60 90 B39 250 60 60 30 80 0 50 30 70 B40 250 90 80 90 80 90 90 70 90 B41 250 70 60 70 80 60 60 30 70 B42 250 0 40 0 60 0 0 0 60 B43 250 60 80 70 80 40 60 30 80 B44 250 100 90 90 90 90 90 60 90 B45 250 80 80 70 80 60 80 10 80 B46 250 100 90 90 90 90 90 60 90 B47 250 100 90 90 90 90 90 60 80 B48 250 80 90 90 80 90 100 30 80 B49 250 100 100 100 100 100 100 90 100 B50 250 100 100 90 100 100 100 70 90 B51 250 100 100 90 100 100 100 80 100 B52 250 100 100 90 100 90 100 70 90 B53 250 90 100 90 90 90 100 100 100 B54 250 80 100 80 100 80 100 80 100 B55 250 70 70 80 80 50 60 30 60 B56 250 80 90 80 90 90 90 70 90 B57 250 80 80 70 70 90 80 20 80 B58 250 20 50 10 50 20 20 40 70 B59 250 90 80 70 70 90 80 30 70 B60 250 80 80 90 80 90 90 60 80 B61 250 90 90 70 80 90 90 70 90 B62 250 90 90 80 70 90 70 40 70 B63 250 80 70 80 70 80 70 50 70 B64 250 70 80 80 80 80 70 50 70 B65 250 80 70 80 70 90 70 60 50 B66 250 90 90 90 90 90 80 0 80 B67 250 90 70 90 90 90 80 10 80 B68 250 80 70 80 90 80 70 10 80 B69 250 90 80 50 40 90 80 80 100 B70 250 90 100 80 100 100 100 80 100 B71 250 90 100 90 100 100 100 90 100 B72 250 100 100 100 100 100 100 70 100 B73 250 90 100 90 100 100 100 90 100 B74 250 30 50 10 60 10 60 0 60 B75 250 90 100 100 100 100 100 90 100 B76 250 90 80 90 80 90 80 70 80 B77 250 100 100 90 100 100 100 90 100 B78 250 90 80 80 80 90 90 40 80 B79 250 80 80 60 60 80 60 0 10 B80 250 100 90 90 80 90 90 0 60 B81 250 90 90 70 80 90 80 0 90 B82 250 80 70 70 70 90 50 40 60 B83 250 80 80 80 70 90 90 30 80 B84 250 100 100 90 100 100 100 80 100 B85 250 70 80 70 70 20 100 10 50 B86 250 90 100 70 70 80 90 60 100 B87 250 70 80 40 70 20 80 10 30 B88 250 90 100 90 100 90 100 70 100 B89 250 90 100 90 100 100 100 60 100 B90 250 100 100 90 100 100 100 70 100 B91 250 90 100 80 100 80 100 70 100 B92 250 100 90 90 90 90 80 30 80 B93 250 90 100 80 100 100 100 70 100 B94 250 100 100 100 100 100 100 90 100 B95 250 100 100 100 100 100 100 100 100 B96 250 80 80 0 20 30 90 0 60 B97 250 80 70 80 70 90 80 0 50 B98 250 90 80 60 60 80 60 0 20 B99 250 80 80 70 70 70 80 30 20 B100 250 90 100 80 100 100 100 60 100 B101 250 100 100 90 90 100 100 70 90 B102 250 100 90 60 60 80 60 0 60 B103 250 100 100 100 100 100 100 90 100 B104 250 10 70 40 80 20 70 10 80 B105 250 70 60 70 70 100 100 20 60 B106 250 90 100 80 100 100 100 70 100 B107 250 20 80 60 80 60 80 10 90 B108 250 90 100 100 100 100 100 90 100 B109 63 60 70 70 20 80 90 100 80 B110 250 80 90 90 100 100 100 80 100 B111 250 100 100 70 100 100 100 90 100 B112 250 100 100 100 100 100 100 100 100 B113 250 90 100 90 100 100 100 90 100 B114 250 90 90 90 90 100 100 60 90 B115 250 100 100 80 80 100 90 50 80 B116 250 100 100 100 100 100 100 90 100 B117 250 70 70 70 80 70 70 20 70 B118 250 100 100 100 100 100 100 90 100 B119 250 100 100 100 100 100 100 90 100 B120 250 90 90 80 80 80 80 70 90 B121 250 100 100 100 100 100 100 90 100 B122 250 90 100 80 100 70 100 80 100 B123 250 100 100 100 100 100 100 90 100 B124 250 100 100 90 100 100 100 100 100 B125 250 100 100 80 90 100 100 40 100 B126 250 100 100 100 100 100 100 90 100 B127 250 70 90 90 90 70 100 80 100 B128 250 100 100 100 100 100 100 100 100 B129 250 90 100 90 100 70 100 50 100 B130 250 80 100 80 90 70 90 40 90 B131 250 80 90 80 90 90 100 30 100 B132 250 80 70 80 60 20 80 30 20 B133 250 100 90 80 50 80 50 0 60 B134 250 80 80 90 90 70 80 70 90 B135 250 100 100 100 100 100 100 90 100 B136 16 90 100 90 60 100 90 100 100 B137 250 50 100 20 100 60 90 50 100 B138 250 70 80 80 90 90 80 0 70 B139 250 90 80 60 90 100 100 50 90 B140 250 90 90 90 90 70 80 80 90 B141 250 80 80 90 80 70 80 60 90 B142 250 70 90 90 90 0 80 70 90 B143 250 100 100 90 100 100 100 90 100 B144 250 100 100 100 100 100 100 100 100 B145 250 90 90 70 80 80 80 60 90 B146 250 90 90 90 80 100 100 50 90 B147 250 90 60 90 80 100 90 50 90 B148 250 80 90 70 90 100 100 70 100 B149 250 90 80 90 90 100 90 80 90 B150 250 100 100 100 100 100 100 90 100 B151 250 90 90 100 100 100 100 90 100 B152 250 100 90 100 100 100 100 50 90 B153 250 80 100 90 100 90 100 70 100 B154 250 70 70 90 70 80 90 50 70 B155 250 100 100 90 100 100 100 100 100 B156 250 100 100 100 100 100 100 100 100 B157 250 100 100 100 100 100 100 90 100 B158 250 100 90 90 90 100 80 90 80 B159 250 90 90 80 70 90 80 0 90 B160 250 90 100 90 100 100 100 80 100 B161 250 100 100 90 100 90 100 80 100 B162 250 100 100 100 100 100 100 90 100 B163 250 100 80 90 80 90 90 50 80 B164 250 100 100 100 100 100 100 100 90 B165 250 100 100 100 100 100 100 100 100 B166 250 100 100 100 100 100 100 100 100 B167 250 100 90 100 100 100 100 90 100 B168 250 100 100 100 100 100 100 100 100 B169 250 100 100 100 100 100 100 100 100 B170 250 100 100 100 100 100 100 90 90 B171 250 100 90 100 100 100 100 100 100 B172 250 100 90 80 90 100 100 80 90 B173 250 90 80 90 90 90 90 60 80 B174 250 100 90 100 100 90 100 70 90 B175 250 100 80 100 90 100 90 90 100 B176 250 90 80 90 80 80 80 60 80 B177 250 90 80 90 80 90 90 30 80 B178 250 100 100 100 100 100 100 90 90 B179 250 100 90 90 90 100 100 70 80 B180 250 90 80 90 90 90 90 60 90 B181 250 100 100 70 100 100 100 70 100 B182 250 100 100 100 100 100 100 90 100 B183 250 100 90 100 100 100 100 90 100 B184 250 100 90 90 90 100 100 90 90 B185 250 70 100 80 100 100 100 60 100 B186 250 90 90 90 90 100 100 100 90 B187 250 80 90 70 70 80 100 10 70 B188 250 80 90 60 80 80 100 40 100 B189 250 80 90 60 90 80 100 40 90 B190 250 70 80 60 70 80 100 40 90 B191 250 70 90 60 50 80 100 40 90 B192 250 100 100 100 100 100 100 90 100 B193 250 100 100 100 100 100 100 90 100 B194 250 100 100 100 100 90 100 80 100 B195 250 100 100 90 100 100 100 80 100 B196 250 100 100 100 100 100 100 80 100 B197 250 90 100 100 100 100 100 90 100 B198 250 70 100 90 100 80 100 60 100 B199 250 70 90 80 100 50 100 60 100 B200 250 100 100 100 100 100 100 90 100 B201 250 100 100 100 100 100 100 100 100 B202 250 60 70 80 90 70 90 70 80 B203 250 100 100 100 100 100 100 100 100 B204 250 90 90 90 100 90 100 80 100 B205 250 90 90 100 100 90 90 80 90 B206 250 80 90 80 90 90 90 70 90 B207 250 10 60 40 80 40 90 0 50 B208 250 80 90 90 90 100 100 80 90 B209 250 90 80 100 90 100 100 80 80 B210 250 100 90 100 100 100 100 80 90 B211 250 NC 90 90 90 100 100 80 90 B212 250 90 70 60 90 100 90 60 60 B213 250 70 90 80 90 90 100 50 90 B214 250 90 100 100 100 100 100 90 100 B215 250 90 100 90 100 90 100 80 100 B216 250 70 90 80 100 90 100 70 90 B217 250 100 100 100 100 100 100 100 100 B218 250 100 100 100 100 100 100 90 100 B219 250 100 100 100 100 90 100 90 100 B220 250 100 100 100 100 100 100 90 100 B221 250 100 100 100 100 100 100 100 100 B222 250 100 100 100 100 100 100 90 100 B223 250 80 80 90 90 90 100 70 100 B224 250 70 80 80 80 70 90 50 80 B225 250 0 60 0 60 0 70 0 70 B226 250 80 90 100 100 100 100 90 90 B227 250 80 90 80 100 80 100 80 100 B228 250 100 100 100 100 90 100 90 100 B229 250 90 70 90 80 100 100 90 80 B230 250 90 90 90 100 100 100 90 100 B231 250 80 90 50 90 80 90 20 100 B232 250 90 100 90 100 90 100 70 100 B233 250 70 70 70 60 70 100 60 70 B234 250 70 80 60 90 70 90 80 100 B235 250 100 100 100 100 100 100 100 100 B236 250 90 100 90 100 90 100 90 100 B237 250 90 100 100 100 90 100 90 100 B238 250 100 100 100 100 100 100 100 100 B239 250 100 100 100 90 100 100 90 100 B240 250 90 100 100 100 90 100 90 100 B241 250 80 90 60 80 70 100 50 100 B242 250 0 100 0 90 0 100 0 90 B243 250 0 70 0 80 0 90 0 50 B244 250 0 60 0 0 0 90 0 80 B245 250 90 100 100 100 90 100 90 100 B246 250 90 100 60 100 70 100 50 100 B247 250 80 100 90 100 60 100 80 100 B248 250 80 100 50 100 60 100 50 100 B249 250 70 60 80 70 80 80 30 70 B250 250 80 100 50 100 90 100 50 90 B251 250 90 100 90 100 90 100 60 90 B252 250 100 100 100 100 100 100 70 90 B253 250 90 100 100 100 90 100 80 100 B254 250 90 100 90 100 100 100 90 100 B255 250 100 100 100 100 100 100 80 100 B256 250 100 100 100 100 100 100 100 100 B257 250 100 100 100 100 100 100 90 100 B258 250 100 100 100 100 100 100 90 100 B259 250 100 100 100 100 100 100 90 100 B260 250 100 100 90 100 100 100 80 100 B261 250 90 100 80 100 90 100 80 100 B262 250 60 70 60 70 80 100 40 90 B263 250 80 100 90 100 100 100 80 100 B264 250 90 100 100 100 100 100 80 100 B265 250 100 100 100 100 100 100 100 100 B266 250 90 80 100 100 100 100 40 100 B267 250 100 100 100 100 100 100 80 100 B268 250 100 100 100 90 100 100 90 100 B269 250 100 100 100 100 100 100 100 100 B270 250 100 90 100 100 100 100 90 100 B271 250 80 90 80 100 100 100 80 100 B272 250 50 80 80 100 90 100 80 100 B273 250 100 100 90 100 100 100 90 100 B274 250 70 90 70 100 70 100 50 100 B275 250 100 100 100 100 100 100 100 100 B276 250 90 100 100 90 100 100 80 90 B277 250 100 100 100 100 100 100 100 100 B278 250 100 90 100 100 100 100 100 100 B279 250 100 100 100 100 100 100 100 100 B280 250 100 100 100 100 100 100 100 100 B281 250 80 90 80 100 100 100 80 100 B282 250 100 100 100 100 100 100 100 100 B283 250 100 100 100 100 100 100 90 100 B284 250 90 100 100 100 100 100 70 100 B285 250 100 100 90 100 100 100 90 100 B286 250 90 100 100 100 100 100 90 100 B287 250 90 90 90 90 100 100 90 100 B288 250 90 90 80 100 90 100 80 90 B289 250 100 100 100 100 100 100 100 100 B290 250 100 100 100 100 100 100 100 100 B291 250 100 90 100 90 100 100 90 100 B292 250 70 90 100 100 100 100 90 100 B293 250 90 90 90 100 90 100 60 100 B294 250 100 100 90 100 100 100 100 100 B295 250 90 90 80 90 90 100 60 100 B296 250 90 100 90 100 100 100 90 100 B297 250 90 100 90 100 100 100 90 100 B298 250 90 90 90 100 100 100 90 100 B299 250 100 100 90 90 100 100 90 90 B300 250 100 100 100 100 100 100 100 100 B301 250 70 50 80 70 60 70 50 70 B302 250 100 100 100 100 100 100 100 100 B303 250 80 100 90 100 100 100 80 100 B304 250 100 100 100 100 90 100 100 100 B305 250 100 100 100 100 100 100 100 100 B306 250 100 100 100 100 100 100 100 100 B307 250 100 90 100 90 100 100 100 100 B308 250 80 60 90 90 80 100 80 100 B309 250 80 60 90 100 100 100 80 100 B310 250 90 70 90 90 90 100 80 100 B311 250 90 70 80 80 90 100 80 90 B312 250 70 80 10 90 70 100 10 100 B313 250 90 70 90 90 100 90 80 70 B314 250 90 90 100 100 100 80 90 100 B315 250 70 80 80 90 100 100 80 100 B316 250 80 90 90 90 90 100 80 100 B317 250 90 90 90 100 100 100 90 100 B318 250 100 90 90 90 90 100 90 100 B319 250 0 60 0 70 0 100 0 80 B320 250 100 100 100 100 100 100 100 100 B321 250 90 90 70 90 100 100 80 100 B322 250 90 100 90 100 90 100 70 100 B323 250 100 100 100 100 100 100 90 100 B324 250 60 80 30 70 30 100 0 90 B325 250 100 100 100 100 100 100 70 100 B326 250 100 100 100 100 100 100 80 100 B327 250 100 90 100 100 100 100 80 100 B328 250 100 100 100 100 100 100 100 100 B329 250 100 100 100 100 100 100 80 100 B330 250 100 100 100 100 100 100 100 100 B331 250 100 100 100 90 100 100 90 100 B332 250 100 100 100 100 100 100 100 100 B333 250 100 90 100 100 100 100 100 40 B334 250 100 90 100 100 100 100 100 100 B335 250 100 100 100 100 90 100 100 100 B336 250 100 100 100 100 100 100 100 100 B337 250 90 100 90 100 90 100 90 100 B338 250 100 90 100 100 100 100 80 100 B339 250 90 100 40 100 100 100 70 100 B340 250 100 100 100 100 100 100 100 100 B341 250 80 100 100 100 100 100 80 100 B342 250 100 100 100 100 100 100 90 100 B343 250 100 100 100 100 100 100 90 100 B344 250 80 90 90 100 100 100 80 100 B345 250 100 100 100 100 100 100 90 100 B346 250 100 100 100 100 100 100 90 100 B347 250 100 100 100 100 100 100 100 100 B348 250 90 100 80 100 100 100 80 100 B349 250 90 100 100 100 90 100 90 100 B350 250 100 100 100 100 100 100 90 100 B351 250 100 100 100 100 100 100 90 100 B352 250 90 100 100 100 100 100 90 90 B353 250 90 100 80 90 100 100 90 100 B354 250 80 90 70 90 90 100 80 100 B355 250 70 100 50 80 90 100 70 90 B356 250 80 100 60 90 100 100 60 100 B357 250 100 90 80 90 100 100 90 100 B358 250 90 90 90 100 100 100 100 100 B359 250 90 90 90 90 80 100 70 100 B360 250 100 100 100 100 100 100 100 100 B361 250 90 90 90 100 100 100 100 100 B362 250 100 90 100 90 100 100 100 100 B363 250 100 90 100 90 100 100 90 100 B364 250 90 90 100 100 90 90 80 90 B365 250 100 90 100 90 100 100 90 90 B366 250 100 90 100 90 100 100 100 100 B367 250 100 100 90 90 100 100 100 100 B368 250 100 100 90 90 100 100 90 100 B369 250 100 90 100 90 100 100 100 100 B370 250 100 100 100 90 100 100 100 100 B371 250 100 100 90 100 100 100 90 100 B372 250 100 90 90 90 100 100 100 100 B373 250 100 80 70 80 100 100 80 100 B374 250 90 90 70 90 90 100 90 100 B375 250 80 80 60 40 90 100 70 70 B376 250 60 100 30 90 60 100 80 90 B377 250 80 30 90 90 100 90 90 100 B378 250 80 70 70 80 90 100 90 100 B379 250 70 60 90 90 70 90 70 90 B380 250 80 90 70 70 90 100 80 90 B381 250 90 100 70 100 70 100 70 100 B382 250 60 100 60 100 60 100 40 100 B383 250 100 90 90 100 100 90 90 100 B384 250 80 90 80 90 90 40 80 100 B385 250 100 100 100 100 100 100 100 100 B386 250 100 90 100 100 100 40 100 100 B387 250 90 90 90 90 100 90 100 100 B388 250 90 90 90 90 100 100 90 100 B389 250 100 90 90 100 100 100 90 100 B390 250 100 90 100 100 100 90 100 100 B391 250 100 90 90 90 100 100 100 100 B392 250 100 90 100 90 100 100 100 100 B393 250 100 90 100 90 100 100 90 100 B394 250 100 90 100 100 100 100 100 100 B395 250 100 90 100 100 100 100 100 100 B396 250 100 90 100 90 100 100 100 100 B397 250 70 90 70 90 100 100 80 90 B398 250 70 90 50 80 70 100 40 80 B399 250 70 90 60 90 70 100 40 100 B400 250 100 90 100 100 100 100 100 100 B401 250 90 90 80 90 80 100 70 100 B402 250 80 90 60 90 80 100 70 100 B403 250 20 80 60 90 0 100 50 100 B404 250 80 100 80 90 90 100 70 100 B405 250 100 100 90 100 100 100 90 100 P6 250 100 100 100 100 100 100 100 90 P7 250 30 40 0 70 50 80 10 60 P8 250 50 70 30 70 70 90 10 80 P9 250 90 80 90 80 90 80 60 80 P10 250 90 90 90 90 90 90 60 90 P11 250 80 90 70 80 90 90 30 90 P12 250 60 80 20 80 70 60 0 60 P13 250 10 70 50 80 20 80 10 70 P14 250 70 80 70 80 70 70 10 80 P15 250 80 80 70 90 100 80 40 80 Note: a hyphen (—) in the table above indicates that no measurement was made.

Biological Example 2

[0449] Test—Glasshouse Assay for Crop Safety.

[0450] Seeds of the Winter Wheat variety ‘Hereward’ were seed treated with a wettable powder formulation of the cereal herbicide safener, cloquintocet mexyl, at a rate of 0.5 grams per kilogram of dry seed prior to the initiation of glasshouse testing. Three seeds were sown per 1.5 inch plastic pot into a sandy loam soil at a depth of 1cm, 8 days prior to application of the test compounds and was watered and grown under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity). The plants were sprayed Post-emergence with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone/water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5).

[0451] The test plants were then grown in a glasshouse under controlled conditions (at 24/16° C., day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days for pre and post-emergence, the test was evaluated (100=total damage to plant; 0=no damage to plant).

TABLE-US-00016 TABLE 3 Post-emergence herbicidal activity against cereal crops (wheat) +/− safener (cloquintocet-mexyl (CQC) - Results (percentage phytotoxicity) Post-emergence Crop Selectivity Compound Rate (g/ha) Wheat − CQC +CQC A1 250 60 0 A2 250 10 10 A3 250 60 10 A4 250 60 10 A5 250 80 10 A6 250 70 10 A7 250 30 20 A12 250 70 0 A14 250 60 10 A15 250 20 20 A16 250 80 30 A18 250 70 20 A19 250 80 40 A20 250 40 20 A21 250 60 0 A22 250 60 50 A25 250 40 0 A26 250 70 40 A27 250 30 20 A39 250 80 50 A43 250 90 50 A59 250 80 50 A67 250 70 0 A70 250 70 20 A73 250 80 20 A80 250 70 20 A85 250 80 10 A138 250 70 40 A142 250 70 50 A145 250 60 30 A146 250 80 50