BICYCLIC COMPOUNDS AS PEST CONTROL AGENTS

Abstract

The present application relates to novel bicyclic compounds, to their use for controlling animal pests and to processes and intermediates for their preparation.

Claims

1. Compound of formula (I) ##STR00317## in which A is an A radical from the group of (A-b) to (A-f) ##STR00318## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I) and B.sup.2 is a radical from the group of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and in each case optionally substituted cycloalkyl and cycloalkenyl, Q is oxygen or sulphur, R.sup.1 is a radical from the group of hydrogen, alkyl, alkoxy and cyano, R.sup.2 a) is a B radical from the group of ##STR00319## ##STR00320## ##STR00321## ##STR00322## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 b) is a radical from the group of (D-1) to (D-3) ##STR00323## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 c) is a radical of the formula ##STR00324## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 d) is a radical of the formula ##STR00325## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 e) is an F radical from the group of (F-1) to (F-11) ##STR00326## ##STR00327## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 f) is a radical of the formula ##STR00328## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 g) is optionally substituted phenyl, in which G.sup.2 is hydrogen or a radical from the group of halogen, nitro, amino, cyano, alkylamino, haloalkylamino, dialkylamino, alkyl, haloalkyl, saturated or unsaturated cycloalkyl which is optionally substituted and optionally interrupted by one or more heteroatoms, cycloalkylalkyl, alkoxy, haloalkoxy, alkoxyalkyl, halogenated alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, bis(alkoxy)alkyl, bis(haloalkoxy)alkyl, alkoxy(alkylsulphanyl)alkyl, alkoxy(alkylsulphinyl)alkyl, alkoxy(alkylsulphonyl)alkyl, bis(alkylsulphanyl)alkyl, bis(haloalkylsulphanyl)alkyl, bis(hydroxyalkylsulphanyl)alkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alpha-hydroxyiminoalkoxycarbonylalkyl, alpha-alkoxyiminoalkoxycarbonylalkyl, C(X.sup.2)NR.sup.3R.sup.4, NR.sup.6R.sup.7, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylthio, haloalkylsulphinyl, haloalkylsulphonyl, the heterocyclyl radicals dioxanyl, dioxolanyl, dioxepanyl, dioxocanyl, oxathianyl, oxathiolanyl, oxathiepanyl, oxathiocanyl, dithianyl, dithiolanyl, dithiepanyl, dithiocanyl, oxathianyl oxide, oxathiolanyl oxide, oxathiepanyl oxide, oxathiocanyl oxide, oxathianyl dioxide, oxathiolanyl dioxide, oxathiepanyl dioxide, oxathiocanyl dioxide, morpholinyl, triazolinonyl, oxazolinyl, dihydrooxadiazinyl, dihydrodioxazinyl, dihydrooxazolyl, dihydrooxazinyl and pyrazolinonyl (which for their part may in turn be substituted by alkyl, haloalkyl, alkoxy and alkoxyalkyl), phenyl (which for its part may in turn be substituted by halogen, cyano, nitro, alkyl and haloalkyl), the heteroaryl radicals pyridyl, pyridyl N-oxide, pyrimidyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, furanyl, thienyl, triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, triazinyl, tetrazinyl and isoquinolinyl (which for their part may in turn be substituted by halogen, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl and cycloalkyl) and the heteroarylalkyl radicals triazolylalkyl, pyridylalkyl, pyrimidylalkyl and oxadiazolylalkyl (which for their part may in turn be substituted by halogen and alkyl), or G.sup.2 is a C radical from the group of (C-1) to (C-9) ##STR00329## ##STR00330## in which the broken line denotes the bond to the B radicals, X is oxygen or sulphur, X.sup.1 is a radical from the group of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy and haloalkoxy, X.sup.2 is oxygen, sulphur, NR.sup.5 or NOH, L is oxygen or sulphur, V—Z is R.sup.24CH—CHR.sup.25 or R.sup.24C═CR.sup.25, n is 1 or 2, m is 1, 2, 3 or 4, R is NR.sup.18R.sup.19, or is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxyalkyl, alkyl-S-alkyl, alkyl-S(O)-alkyl, alkyl-S(O).sub.2-alkyl, R.sup.18—CO-alkyl, NR.sup.18R.sup.19—CO-alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, heterocyclyl, heterocyclylalkyl, phenyl, phenylalkyl, hetaryl and hetarylalkyl, R.sup.3 is hydrogen or alkyl, R.sup.4 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, aryl, arylalkyl and hetarylalkyl, R.sup.5 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, aryl, arylalkyl and hetarylalkyl, or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are bonded form a ring which may contain one or more further heteroatoms from the group of nitrogen, oxygen and sulphur, or R.sup.3 and R.sup.5 together with the nitrogen atoms to which they are bonded form a ring, R.sup.6 is hydrogen or alkyl, R.sup.7 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, aryl, arylalkyl and hetarylalkyl, or R.sup.6 and R.sup.7 together with the nitrogen atom to which they are bonded form a ring which may contain one or more further heteroatoms from the group of nitrogen, oxygen and sulphur, R.sup.8 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulphonyl, optionally halogen-substituted alkoxycarbonyl, and optionally halogen-, alkyl-, alkoxy-, haloalkyl- and cyano-substituted cycloalkylcarbonyl, or a cation, or an optionally alkyl- or arylalkyl-substituted ammonium ion, R.sup.9 is a radical from the group of in each case optionally substituted alkyl, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.9 in the (C-1) and (F-1) radicals, together with the N—S(O)n group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.10 is hydrogen or alkyl, R.sup.8 and R.sup.10 in the (C-2) and (F-2) radicals, together with the nitrogen atoms to which they are bonded, may also be a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain at least one further heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.9 and R.sup.10 in the (C-2) and (F-2) radicals, together with the N—S(O)n group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.11 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, heteroarylalkoxy and heteroarylalkylthio, R.sup.12 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, heteroarylalkoxy and heteroarylalkylthio, R.sup.11 and R.sup.12 in the (C-3) and (F-3) radicals, together with the phosphorus atom to which they are bonded, may also form a saturated or unsaturated and optionally substituted 5- to 7-membered ring which may contain one or two heteroatoms from the group of oxygen (where oxygen atoms must not be directly adjacent to one another) and sulphur, R.sup.13 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.14 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.15 is a radical from the group of in each case optionally substituted alkyl, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.15 in the (C-6) and (F-6) radicals, together with the N—S(O)n group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.16 is a radical from the group of hydrogen, in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.16 in the (C-7) and (F-7) radicals, together with the nitrogen atom to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.17 is a radical from the group of in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.17 in the (C-8) and (F-8) radicals, together with the N—C(X) group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.18 is a radical from the group of hydrogen, hydroxy, in each case optionally substituted alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, arylalkyl, heteroaryl and heteroarylalkyl and an optionally substituted amino group, R.sup.19 is a radical from the group of hydrogen, is an alkali metal or alkaline earth metal ion or is an ammonium ion which is optionally mono- to tetrasubstituted by C.sub.1-C.sub.4-alkyl or is an in each case optionally halogen- or cyano-substituted radical from the group of alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl and alkylsulphonylalkyl, Y.sup.1 and Y.sup.2 are independently C═O or S(O).sub.2, Y.sup.3 is a radical from the group of hydrogen, halogen, cyano, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy and NR.sup.20R.sup.21, W is a radical from the group of O, S, SO and SO.sub.2, R.sup.22 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, optionally halogen-substituted alkoxyalkyl, optionally halogen-substituted bis(alkoxy)alkyl, optionally halogen-substituted alkylsulphanylalkyl, optionally halogen-substituted alkylcarbonylalkyl, optionally halogen-substituted alkylsulphinylalkyl, optionally halogen-substituted alkylsulphonylalkyl, dialkylaminosulphanylalkyl, dialkylaminosulphinylalkyl, dialkylaminosulphonylalkyl, optionally halogen-substituted alkoxycarbonyl, optionally halogen-substituted alkoxycarbonylalkyl, optionally halogen-substituted alkynyloxy, optionally halogen-substituted alkynyloxycarbonyl, dialkylaminocarbonyl, N-alkyl-N-cycloalkylaminocarbonyl, dialkylaminocarbonylalkyl, N-alkyl-N-cycloalkylaminocarbonylalkyl, heterocyclylcarbonylalkyl, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkyl optionally substituted by halogen, cyano, nitro, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, haloalkoxycarbonyl or hetaryl (which for its part may optionally be substituted by alkyl or halogen), cycloalkylcarbonyl optionally substituted by halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, haloalkoxycarbonyl or hetaryl (which for its part may optionally be substituted by alkyl or halogen), cycloalkylalkyl optionally substituted by halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, haloalkoxycarbonyl or hetaryl (which for its part may optionally be substituted by alkyl or halogen), optionally substituted heterocyclyl, heterocyclylalkyl optionally substituted by halogen, cyano (including in the alkyl moiety), nitro, hydroxyl, alkyl, haloalkyl, cycloalkyl (which is optionally substituted), alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylsulphinyl, haloalkylsulphonyl, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, cycloalkylalkyl, alkylcarbonyl, alkoxycarbonyl or aminocarbonyl, aryl optionally substituted by halogen, cyano, nitro, hydroxyl, amino, alkyl, haloalkyl, cycloalkyl (which is optionally substituted), alkoxy or haloalkoxy, arylalkyl optionally substituted by halogen, cyano (including in the alkyl moiety), nitro, hydroxyl, amino, alkyl, cycloalkyl (which is optionally substituted), haloalkyl, alkoxy or haloalkoxy, hetarylalkyl optionally substituted by halogen, cyano (including in the alkyl moiety), nitro, hydroxyl, alkyl, haloalkyl, cycloalkyl (which is optionally substituted), alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylsulphinyl, haloalkylsulphonyl, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, cycloalkylalkyl, alkylcarbonyl, alkoxycarbonyl or aminocarbonyl, or R.sup.22 is a D radical from the group of (D-1) to (D-3) ##STR00331## is an E radical from the group of (E-1) to (E-11) ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## or in the case R.sup.2=d), R.sup.22 is also an E radical from the group of E-12 to E-17 ##STR00337## R.sup.20 is a radical from the group of hydrogen, halogen, cyano, nitro, amino, hydroxy and in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, alkoxycarbonyloxy, alkylsulphonyloxy, alkylamino, alkenylamino, alkynylamino, cycloalkylamino, alkylthio, haloalkylthio, alkenylthio, alkynylthio, cycloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylcarbonyl, alkoxyiminoalkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminosulphonyl, alkylsulphonylamino, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, cycloalkylcarbonylamino, alkoxycarbonylamino, alkylthiocarbonylamino, bicycloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy, where the substituents are independently of one another selected from halogen, cyano, nitro, hydroxy, amino, alkyl and haloalkyl, R.sup.21 is a radical from the group of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulphonyl and haloalkylsulphonyl, R.sup.23 is a radical from the group of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl and alkoxyalkyl, or, when R.sup.2=c) or f), R.sup.22 and R.sup.23 together with the nitrogen atom to which they are bonded form a ring which may contain one or more further heteroatoms from the group of nitrogen, oxygen and sulphur, and R.sup.24 is hydrogen or an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl and R.sup.25 is hydrogen or an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.27 is hydrogen or alkyl and R.sup.26 is a radical from the group of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl and cyanoalkyl and compounds of the formula (I) in which A is the A radical ##STR00338## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I) and G.sup.1 is N or C—B.sup.1, B.sup.1 is a radical from the group of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and in each case optionally substituted cycloalkyl and cycloalkenyl, B.sup.2 is a radical from the group of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and in each case optionally substituted cycloalkyl and cycloalkenyl, T is oxygen or an electron pair, Q is oxygen or sulphur, R.sup.1 is a radical from the group of hydrogen, alkyl, alkoxy and cyano, R.sup.2 a) is a B radical from the group of ##STR00339## ##STR00340## ##STR00341## ##STR00342## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 c) is a radical of the formula ##STR00343## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 d) is a radical of the formula ##STR00344## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 e) is an F radical from the group of ##STR00345## ##STR00346## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 f) is a radical of the formula ##STR00347## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), in which G.sup.2 is hydrogen or a radical from the group of halogen, nitro, amino, cyano, alkylamino, haloalkylamino, dialkylamino, alkyl, haloalkyl, saturated or unsaturated cycloalkyl which is optionally substituted and optionally interrupted by one or more heteroatoms, cycloalkylalkyl, alkoxy, haloalkoxy, alkoxyalkyl, halogenated alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, bis(alkoxy)alkyl, bis(haloalkoxy)alkyl, alkoxy(alkylsulphanyl)alkyl, alkoxy(alkylsulphinyl)alkyl, alkoxy(alkylsulphonyl)alkyl, bis(alkylsulphanyl)alkyl, bis(haloalkylsulphanyl)alkyl, bis(hydroxyalkylsulphanyl)alkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alpha-hydroxyiminoalkoxycarbonylalkyl, alpha-alkoxyiminoalkoxycarbonylalkyl, C(X.sup.2)NR.sup.3R.sup.4, NR.sup.6R.sup.7, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylthio, haloalkylsulphinyl, haloalkylsulphonyl, the heterocyclyl radicals dioxanyl, dioxolanyl, dioxepanyl, dioxocanyl, oxathianyl, oxathiolanyl, oxathiepanyl, oxathiocanyl, dithianyl, dithiolanyl, dithiepanyl, dithiocanyl, oxathianyl oxide, oxathiolanyl oxide, oxathiepanyl oxide, oxathiocanyl oxide, oxathianyl dioxide, oxathiolanyl dioxide, oxathiepanyl dioxide, oxathiocanyl dioxide, morpholinyl, triazolinonyl, oxazolinyl, dihydrooxadiazinyl, dihydrodioxazinyl, dihydrooxazolyl, dihydrooxazinyl and pyrazolinonyl (which for their part may in turn be substituted by alkyl, haloalkyl, alkoxy and alkoxyalkyl), phenyl (which for its part may in turn be substituted by halogen, cyano, nitro, alkyl and haloalkyl), the heteroaryl radicals pyridyl, pyridyl N-oxide, pyrimidyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, furanyl, thienyl, triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, triazinyl, tetrazinyl and isoquinolinyl (which for their part may in turn be substituted by halogen, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl and cycloalkyl) and the heteroarylalkyl radicals triazolylalkyl, pyridylalkyl, pyrimidylalkyl and oxadiazolylalkyl (which for their part may in turn be substituted by halogen and alkyl), or G.sup.2 is a C radical from the group of (C-1) to (C-9) ##STR00348## in which the broken line denotes the bond to the B radicals, X is oxygen or sulphur, X.sup.1 is a radical from the group of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy and haloalkoxy, X.sup.2 is oxygen, sulphur, NR.sup.5 or NOH, L is oxygen or sulphur, V—Z is R.sup.24CH—CHR.sup.25 or R.sup.24C═CR.sup.25, n is 1 or 2, m is 1, 2, 3 or 4, R is NR.sup.18R.sup.19, or is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxyalkyl, alkyl-S-alkyl, alkyl-S(O)-alkyl, alkyl-S(O).sub.2-alkyl, R.sup.18—CO-alkyl, NR.sup.18R.sup.19—CO-alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, heterocyclyl, heterocyclylalkyl, phenyl, phenylalkyl, hetaryl and hetarylalkyl, R.sup.3 is hydrogen or alkyl, R.sup.4 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, aryl, arylalkyl and hetarylalkyl, R.sup.5 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, aryl, arylalkyl and hetarylalkyl, or R.sup.3 and R.sup.4 together with the nitrogen atom to which they are bonded form a ring which may contain one or more further heteroatoms from the group of nitrogen, oxygen and sulphur, or R.sup.3 and R.sup.5 together with the nitrogen atoms to which they are bonded form a ring, R.sup.6 is hydrogen or alkyl, R.sup.7 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, haloalkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, aryl, arylalkyl and hetarylalkyl, or R.sup.6 and R.sup.7 together with the nitrogen atom to which they are bonded form a ring which may contain one or more further heteroatoms from the group of nitrogen, oxygen and sulphur, R.sup.8 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulphonyl, optionally halogen-substituted alkoxycarbonyl, and optionally halogen-, alkyl-, alkoxy-, haloalkyl- and cyano-substituted cycloalkylcarbonyl, or a cation, or an optionally alkyl- or arylalkyl-substituted ammonium ion, R.sup.9 is a radical from the group of in each case optionally substituted alkyl, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.9 in the (C-1) radical, together with the N—S(O)n group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.10 is hydrogen or alkyl, R.sup.8 and R.sup.10 in the (C-2) and (F-2) radicals, together with the nitrogen atoms to which they are bonded, may also be a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain at least one further heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.9 and R.sup.10 in the (C-2) and (F-2) radicals, together with the N—S(O)n group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.11 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, heteroarylalkoxy and heteroarylalkylthio, R.sup.12 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, heteroarylalkoxy and heteroarylalkylthio, R.sup.11 and R.sup.12 in the (C-3) and (F-3) radicals, together with the phosphorus atom to which they are bonded, may also form a saturated or unsaturated and optionally substituted 5- to 7-membered ring which may contain one or two heteroatoms from the group of oxygen (where oxygen atoms must not be directly adjacent to one another) and sulphur, R.sup.13 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.14 is an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.15 is a radical from the group of in each case optionally substituted alkyl, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.15 in the (C-6) and (F-6) radicals, together with the N—S(O)n group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.16 is a radical from the group of hydrogen, in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.16 in the (C-7) and (F-7) radicals, together with the nitrogen atom to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.17 is a radical from the group of in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R.sup.8 and R.sup.17 in the (C-8) and (F-8) radicals, together with the N—C(X) group to which they are bonded, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, R.sup.18 is a radical from the group of hydrogen, hydroxy, in each case optionally substituted alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkylcarbonyl, alkoxycarbonyl, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl, in which the rings may contain at least one heteroatom from the group of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen, in each case optionally substituted aryl, arylalkyl, heteroaryl and heteroarylalkyl and an optionally substituted amino group, R.sup.19 is a radical from the group of hydrogen, is an alkali metal or alkaline earth metal ion or is an ammonium ion which is optionally mono- to tetrasubstituted by C.sub.1-C.sub.4-alkyl or is an in each case optionally halogen- or cyano-substituted radical from the group of alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl and alkylsulphonylalkyl, Y.sup.1 and Y.sup.2 are independently C═O or S(O).sub.2, Y.sup.3 is a radical from the group of hydrogen, halogen, cyano, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy and NR.sup.20R.sup.21, W is a radical from the group of S, SO and SO.sub.2, and in the case that R.sup.2 is f) R.sup.22 is a radical from the group of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, optionally halogen-substituted alkoxyalkyl, optionally halogen-substituted bis(alkoxy)alkyl, optionally halogen-substituted alkylsulphanylalkyl, optionally halogen-substituted alkylcarbonylalkyl, optionally halogen-substituted alkylsulphinylalkyl, optionally halogen-substituted alkylsulphonylalkyl, dialkylaminosulphanylalkyl, dialkylaminosulphinylalkyl, dialkylaminosulphonylalkyl, optionally halogen-substituted alkoxycarbonylalkyl, optionally halogen-substituted alkynyloxy, dialkylaminocarbonylalkyl, N-alkyl-N-cycloalkylaminocarbonylalkyl, heterocyclylcarbonylalkyl, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cycloalkyl optionally substituted by halogen, cyano, nitro, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, haloalkoxycarbonyl or hetaryl (which for its part may optionally be substituted by alkyl or halogen), cycloalkylalkyl optionally substituted by halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, haloalkoxycarbonyl or hetaryl (which for its part may optionally be substituted by alkyl or halogen), optionally substituted heterocyclyl, heterocyclylalkyl optionally substituted by halogen, cyano (including in the alkyl moiety), nitro, hydroxyl, alkyl, haloalkyl, cycloalkyl (which is optionally substituted), alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylsulphinyl, haloalkylsulphonyl, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, cycloalkylalkyl, alkylcarbonyl, alkoxycarbonyl or aminocarbonyl, aryl optionally substituted by halogen, cyano, nitro, hydroxyl, amino, alkyl, haloalkyl, cycloalkyl (which is optionally substituted), alkoxy or haloalkoxy, arylalkyl optionally substituted by halogen, cyano (including in the alkyl moiety), nitro, hydroxyl, amino, alkyl, cycloalkyl (which is optionally substituted), haloalkyl, alkoxy or haloalkoxy, hetarylalkyl optionally substituted by halogen, cyano (including in the alkyl moiety), nitro, hydroxyl, alkyl, haloalkyl, cycloalkyl (which is optionally substituted), alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylsulphinyl, haloalkylsulphonyl, amino, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, cycloalkylalkyl, alkylcarbonyl, alkoxycarbonyl or aminocarbonyl, and in the case that R.sup.2 is c), d) or f) R.sup.22 is a D radical from the group of (D-1) to (D-3) ##STR00349## is an E radical from the group of (E-1) to (E-11) ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## or in the case R.sup.2=d), R.sup.22 is also an E radical from the group of E-12 to E-17 ##STR00355## R.sup.20 is a radical from the group of hydrogen, halogen, cyano, nitro, amino, hydroxy and in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, alkoxycarbonyloxy, alkylsulphonyloxy, alkylamino, alkenylamino, alkynylamino, cycloalkylamino, alkylthio, haloalkylthio, alkenylthio, alkynylthio, cycloalkylthio, alkylsulphinyl, alkylsulphonyl, alkylcarbonyl, alkoxyiminoalkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminosulphonyl, alkylsulphonylamino, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, cycloalkylcarbonylamino, alkoxycarbonylamino, alkylthiocarbonylamino, bicycloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy, where the substituents are independently of one another selected from halogen, cyano, nitro, hydroxy, amino, alkyl and haloalkyl, R.sup.21 is a radical from the group of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulphonyl and haloalkylsulphonyl, R.sup.23 is a radical from the group of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl and alkoxyalkyl, or when R.sup.2=f) R.sup.22 and R.sup.23 together with the nitrogen atom to which they are bonded form a ring which may contain one or more further heteroatoms from the group of nitrogen, oxygen and sulphur, and R.sup.24 is hydrogen or an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl and R.sup.25 is hydrogen or an in each case optionally substituted radical from the group of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.27 is hydrogen or alkyl and R.sup.26 is a radical from the group of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl and cyanoalkyl.

2. Compound of formula (I) according to claim 1 in which A is the (A-a) radical ##STR00356## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), G.sup.1 is C—B.sup.1, B.sup.1 is hydrogen or fluorine, B.sup.2 is hydrogen, T is an electron pair or oxygen, Q is sulphur, R.sup.1 is hydrogen, R.sup.2 a) is one of the following B radicals: ##STR00357## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 c) is a radical of the formula ##STR00358## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 f) is a radical of the formula ##STR00359## in which the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), in which G.sup.2 is a radical from the group of hydrogen, C.sub.1-C.sub.4-alkyl, halo-C.sub.1-C.sub.4-alkyl C.sub.1-C.sub.4-alkoxy, halo-C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio and C.sub.1-C.sub.4-haloalkylthio, and in the case that R.sup.2 is c) R.sup.22 is the D radical ##STR00360## in which R is optionally mono-, di-, tri-, tetra- or penta-fluorine- or -chlorine-substituted C.sub.1-C.sub.4-alkyl, W is a radical from the group of S, SO and SO.sub.2, and in the case that R.sup.2 is f) R.sup.22 is optionally fluorine-, chlorine- or bromine-substituted phenyl and R.sup.23 is hydrogen or C.sub.1-C.sub.6-alkyl.

3. Composition, comprising a content of at least one compound of formula (I) according to claim 1 and one or more customary extenders and/or surfactants.

4. Compound of formula (I) according to claim 1 or a composition thereof for controlling pests.

5. Compound of the formula ##STR00361##

Description

DESCRIPTION OF THE PROCESSES AND INTERMEDIATES

[0795] The preparation and use examples which follow illustrate the invention without limiting it. The products were characterized by .sup.1H NMR spectroscopy and/or LC-MS (Liquid Chromatography Mass Spectrometry).

[0796] The log P values were determined in accordance with OECD Guideline 117 (EC Directive 92/69/EEC) by HPLC (high-performance liquid chromatography) using reversed-phase (RP) columns (C18), by the following methods:

[a] The LC-MS determination in the acidic range is carried out at pH 2.7 with 0.1% aqueous formic acid and acetonitrile (contains 0.1% formic acid) as eluents; linear gradient from 10% acetonitrile to 95% acetonitrile.
[b] LC-MS determination in the neutral range is effected at pH 7.8 with 0.001 molar aqueous ammonium hydrogencarbonate solution and acetonitrile as eluents; linear gradient from 10% acetonitrile to 95% acetonitrile.

[0797] Calibration is carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known log P values (log P values determined on the basis of the retention times by linear interpolation between two successive alkanones).

[0798] The NMR spectra were determined using a Bruker Avance 400 fitted with a flow probe head (60 μl volume). In individual cases, the NMR spectra were measured with a Bruker Avance II 600.

[0799] The 1H-NMR data of selected examples are noted in the form of 1H-NMR peak lists. For each signal peak, first the δ value in ppm and then the signal intensity in round brackets are listed. The pairs of δ value-signal intensity numbers for different signal peaks are listed with separation from one another by semicolons.

[0800] The peak list for one example therefore has the form:

δ.sub.1 (intensity.sub.1); δ.sub.2 (intensity.sub.2); . . . ; δ.sub.i (intensity.sub.i); . . . ; δ.sub.n (intensity.sub.n)

[0801] The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and the relative intensity thereof may be shown in comparison to the most intense signal in the spectrum.

[0802] Calibration of the chemical shift of 1H NMR spectra is accomplished using tetramethylsilane and/or the chemical shift of the solvent, particularly in the case of spectra which are measured in DMSO. Therefore, the tetramethylsilane peak may but need not occur in NMR peak lists.

[0803] The lists of the 1H-NMR peaks are similar to the classic 1H-NMR prints and thus usually comprise all peaks listed in a classic NMR interpretation.

[0804] In addition, like classic 1H-NMR prints, they may show solvent signals, signals of stereoisomers of the target compounds, which are likewise the subject matter of the invention, and/or peaks of impurities.

[0805] When stating compound signals in the delta range of solvents and/or water, in our lists of 1H NMR peaks, the usual solvent peaks, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water are shown, which usually have on average a high intensity.

[0806] The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for example with a purity of >90%).

[0807] Such stereoisomers and/or impurities may be typical of the particular preparation process. Their peaks can thus help in this case to identify the reproduction of our preparation process with reference to “by-product fingerprints”.

[0808] An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can, if required, isolate the peaks of the target compounds, optionally using additional intensity filters. This isolation would be similar to the relevant peak picking in classic 1H-NMR interpretation.

[0809] Further details of 1H NMR peak lists can be found in the Research Disclosure Database Number 564025.

Synthesis of Benzothiazoles of the Formula (I) by Method A

6-Bromo-2-(pyridin-3-yl)-1,3-benzothiazole (I-a-1)

Step 1: N-(3,5-Dibromopyridin-2-yl)nicotinamide (A-III-1)

[0810] ##STR00161##

[0811] 25.0 g (99.2 mmol) of 3,5-dibromopyridin-2-amine were dissolved in 200 ml of pyridine and cooled in an ice bath, and 19.0 g (106.7 mmol) of 3-(chlorocarbonyl)pyridinium chloride were added in portions. The mixture was warmed to room temperature, rotated on a rotary evaporator in a lukewarm water bath for 20 minutes and then concentrated under reduced pressure. The residue obtained was admixed with water and aqueous ammonia solution, and the precipitated solids were filtered off with suction. The solids were recrystallized from fluorobenzene/methyl-THF/ethanol, by briefly boiling with activated carbon and filtering while hot. The solids formed were washed with aqueous ammonia solution, water and petroleum ether and dried. In this way, 11.4 g (100% purity, 29.9% of theory) of the title compound (A-III-1) were obtained.

[0812] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=11.050 (9.9); 9.136 (8.3); 9.134 (9.2); 9.130 (8.9); 9.128 (8.6); 8.809 (6.9); 8.805 (7.4); 8.797 (7.3); 8.793 (7.2); 8.674 (13.9); 8.669 (15.7); 8.593 (16.0); 8.588 (14.1); 8.333 (3.9); 8.327 (5.3); 8.323 (3.9); 8.313 (4.3); 8.307 (5.7); 8.303 (4.0); 7.610 (4.7); 7.609 (4.9); 7.598 (4.6); 7.597 (4.8); 7.591 (4.6); 7.589 (4.7); 7.578 (4.4); 7.577 (4.5); 3.327 (53.4); 2.676 (0.3); 2.672 (0.5); 2.667 (0.3); 2.525 (1.4); 2.512 (26.9); 2.507 (54.1); 2.503 (71.3); 2.498 (51.3); 2.494 (24.4); 2.334 (0.3); 2.330 (0.5); 2.325 (0.3); 0.146 (0.5); 0.008 (4.4); 0.000 (110.7); −0.009 (3.9); −0.150 (0.5)

Steps 2&3: 6-Bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1)

[0813] ##STR00162##

[0814] 14.7 g (41.2 mmol) of N-(3,5-dibromopyridin-2-yl)nicotinamide (A-III-1) and 10.0 g (61.8 mmol) of 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulphide (Lawesson's reagent) were dissolved in a minimum amount of anisole and stirred at 120° C. for 2 hours. Subsequently, the mixture was concentrated and cooled. The residue was taken up in ethyl acetate and aqueous potassium carbonate solution. The aqueous phase was extracted repeatedly with ethyl acetate. The combined organic phases were dried over magnesium sulfate, filtered and concentrated.

[0815] The residue was taken up directly in 400 ml of DMF, admixed with 24.0 g (173.7 mmol) of potassium carbonate and stirred at 120° C. for 2 hours. Subsequently, the mixture was concentrated, and water and petroleum ether were added. The solids which precipitate were filtered off, washed with aqueous ammonia solution and dried. In this way, 9.6 g (100% purity, 79.8% of theory) of the title compound (I-a-1) were obtained.

[0816] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.339 (8.2); 9.337 (8.7); 9.333 (8.6); 9.332 (8.2); 9.046 (15.3); 9.040 (16.0); 8.842 (15.8); 8.836 (15.1); 8.830 (7.6); 8.827 (7.8); 8.818 (7.7); 8.814 (7.5); 8.548 (4.4); 8.544 (5.4); 8.543 (5.3); 8.538 (4.3); 8.528 (4.7); 8.524 (5.4); 8.523 (5.8); 8.518 (4.4); 8.318 (0.4); 7.679 (5.3); 7.677 (5.4); 7.667 (5.2); 7.665 (5.3); 7.659 (5.2); 7.657 (5.1); 7.647 (5.0); 7.645 (5.0); 3.757 (1.1); 3.329 (112.8); 2.678 (0.5); 2.674 (0.7); 2.669 (0.5); 2.527 (1.9); 2.514 (39.9); 2.509 (80.5); 2.505 (105.7); 2.500 (75.9); 2.496 (35.9); 2.336 (0.5); 2.331 (0.7); 2.327 (0.5); 0.146 (0.7); 0.008 (5.9); 0.000 (157.7); −0.009 (5.5); −0.150 (0.7)

Synthesis of Compounds of the Formula (I) by Method B and I

6-(2-Methylphenyl)-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (2)

[0817] ##STR00163##

[0818] Under argon, 150.0 mg (0.51 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 76.8 mg (0.56 mmol) of (2-methylphenyl)boric acid, 17.8 mg (0.01 mmol) of tetrakis(triphenylphosphine)palladium(0) and 108.8 mg (1.03 mmol) of sodium carbonate were weighed together into a microwave reaction vessel, and 3.8 ml of a 4:1 mixture of degassed dioxane and water were added. The vessel was flooded again with argon, sealed and heated in a Biotage Initiator microwave at 130° C. for 30 minutes. The cooled mixture was diluted with water and extracted repeatedly with dichloromethane. The combined organic phases were filtered through a silica gel cartridge and washed through with dichloromethane, and the filtrate was concentrated under reduced pressure. The residue was stirred with acetonitrile, filtered and dried. This gave 53.0 mg (97.5% purity, 33.2% of theory) of the title compound (2).

[0819] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.366 (2.3); 9.361 (2.3); 8.833 (1.7); 8.829 (1.9); 8.821 (1.8); 8.817 (1.9); 8.753 (2.7); 8.748 (4.7); 8.735 (4.4); 8.730 (2.6); 8.573 (1.0); 8.569 (1.5); 8.564 (1.0); 8.553 (1.1); 8.549 (1.5); 8.544 (1.0); 7.693 (1.4); 7.681 (1.4); 7.673 (1.3); 7.661 (1.3); 7.404 (0.5); 7.393 (2.4); 7.390 (2.7); 7.383 (3.6); 7.376 (3.2); 7.369 (3.3); 7.362 (4.8); 7.355 (1.5); 7.349 (1.1); 7.340 (0.4); 3.329 (15.8); 2.526 (0.8); 2.508 (33.3); 2.504 (44.1); 2.500 (33.0); 2.383 (0.4); 2.331 (0.4); 2.315 (16.0); 0.008 (1.8); 0.000 (50.9); −0.009 (2.0)

6-(3-Chlorophenyl)-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (7)

[0820] ##STR00164##

[0821] Under argon, 150 mg (0.51 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 88.3 mg (0.57 mmol) of (3-chlorophenyl)boric acid, 17.8 mg (0.01 mmol) of tetrakis(triphenylphosphine)palladium(0) and 108.8 mg (1.03 mmol) of sodium carbonate were weighed together into a microwave reaction vessel, and 3.8 ml of a 4:1 mixture of degassed dioxane and water were added. The vessel was flooded again with argon, sealed and heated in a Biotage Initiator microwave at 130° C. for 30 minutes. The cooled mixture was diluted with water and extracted repeatedly with dichloromethane. The combined organic phases were filtered through a silica gel cartridge and washed through with dichloromethane, and the filtrate was concentrated under reduced pressure. The residue was stirred with acetonitrile, filtered and dried. Purification was by chromatography by MPLC (eluent: water/acetonitrile). This gave 14.0 mg (100.0% purity, 8.4% of theory) of the title compound (7).

[0822] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.374 (8.4); 9.368 (8.3); 9.117 (11.3); 9.111 (15.3); 9.084 (16.0); 9.078 (11.2); 8.834 (6.6); 8.830 (6.7); 8.822 (6.8); 8.818 (6.5); 8.582 (3.8); 8.577 (5.3); 8.572 (3.6); 8.562 (4.1); 8.557 (5.5); 8.552 (3.5); 8.317 (1.9); 7.969 (6.9); 7.964 (12.0); 7.960 (6.7); 7.857 (5.8); 7.838 (6.5); 7.811 (0.4); 7.693 (5.3); 7.681 (5.2); 7.673 (5.1); 7.661 (4.9); 7.611 (4.5); 7.591 (10.7); 7.572 (7.8); 7.547 (7.4); 7.530 (2.8); 7.527 (3.2); 7.289 (0.4); 6.937 (0.5); 6.925 (0.4); 6.914 (0.4); 5.757 (0.7); 3.744 (3.2); 3.327 (467.3); 2.676 (4.1); 2.671 (5.6); 2.667 (4.1); 2.602 (0.5); 2.524 (15.1); 2.507 (606.6); 2.502 (788.2); 2.498 (575.0); 2.333 (3.8); 2.329 (5.2); 2.325 (3.7); 2.170 (0.5); 1.355 (0.5); 1.277 (0.4); 1.259 (0.5); 1.232 (5.8); 1.154 (0.4); 1.136 (0.6); 1.118 (0.4); 0.853 (0.7); 0.836 (0.4); 0.146 (2.7); 0.082 (0.4); 0.073 (6.2); 0.008 (20.0); 0.000 (579.1); −0.009 (21.1); −0.150 (2.8)

6-[2-(Ethylsulphanyl)phenyl]-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (14)

[0823] ##STR00165##

[0824] Under argon, 200.0 mg (0.68 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 137.1 mg (0.75 mmol) of [4-(ethylsulphanyl)phenyl]boric acid, 23.7 mg (0.02 mmol) of tetrakis(triphenylphosphine)palladium(0) and 145.1 mg (1.4 mmol) of sodium carbonate were weighed together into a reaction vessel, and 2 ml of a 1:1 mixture of degassed dioxane and water were added. The vessel was flooded again with argon, sealed and heated in a Biotage Initiator microwave at 130° C. for 30 minutes. The cooled mixture was diluted with water and extracted repeatedly with dichloromethane. The combined organic phases were filtered through a silica gel cartridge and washed through with dichloromethane, and the filtrate was concentrated under reduced pressure. Purification was by chromatography by MPLC (eluent: cyclohexane/ethyl acetate). This gave 240.0 mg (81.3% purity, 81.6% of theory) of the title compound (14).

[0825] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.364 (3.7); 9.359 (3.7); 8.834 (2.8); 8.831 (3.0); 8.823 (3.0); 8.819 (2.9); 8.742 (4.8); 8.736 (6.6); 8.713 (6.5); 8.707 (4.7); 8.572 (1.6); 8.568 (2.3); 8.563 (1.6); 8.553 (1.8); 8.548 (2.4); 8.543 (1.6); 8.317 (0.4); 8.070 (6.5); 7.695 (2.2); 7.683 (2.2); 7.675 (2.1); 7.663 (2.0); 7.540 (2.1); 7.522 (3.9); 7.520 (3.9); 7.493 (1.8); 7.488 (1.9); 7.475 (2.3); 7.471 (2.7); 7.455 (1.1); 7.451 (1.4); 7.414 (1.8); 7.410 (2.1); 7.395 (4.0); 7.391 (3.4); 7.365 (3.2); 7.362 (3.2); 7.345 (4.2); 7.328 (2.3); 7.325 (2.4); 7.315 (0.8); 7.311 (0.7); 7.297 (0.9); 7.294 (0.9); 7.278 (0.4); 7.274 (0.4); 7.177 (0.6); 7.174 (0.7); 7.159 (1.0); 7.156 (1.0); 7.141 (0.4); 7.138 (0.4); 4.038 (0.5); 4.020 (0.6); 3.568 (0.4); 3.328 (165.3); 2.936 (2.2); 2.918 (7.2); 2.904 (3.7); 2.900 (7.5); 2.886 (3.1); 2.882 (2.7); 2.868 (0.9); 2.676 (1.1); 2.671 (1.5); 2.667 (1.1); 2.524 (4.1); 2.507 (166.9); 2.502 (217.8); 2.498 (164.7); 2.334 (1.1); 2.329 (1.5); 2.325 (1.1); 1.989 (2.2); 1.242 (0.4); 1.234 (0.3); 1.212 (2.8); 1.194 (6.2); 1.186 (7.9); 1.175 (4.5); 1.167 (16.0); 1.157 (1.3); 1.149 (7.4); 0.000 (0.5)

6-[2-(Ethylsulphinyl)phenyl]-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (15)

[0826] ##STR00166##

[0827] To an initial charge of 100.0 mg (0.28 mmol) of 6-[2-(ethylsulphanyl)phenyl]-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (14) in 10 ml of dichloromethane were added 118.8 mg (0.68 mmol) of m-chloroperbenzoic acid. The mixture was stirred at room temperature overnight. Subsequently, the mixture was admixed with one drop of aqueous sodium hydrogensulphite, washed with aqueous sodium carbonate solution, dried and concentrated. Purification was by chromatography by MPLC (eluent: water/acetonitrile). This gave 26.0 mg (100.0% purity, 24.9% of theory) of the title compound (15).

[0828] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.374 (4.2); 9.370 (4.3); 8.866 (6.3); 8.860 (7.5); 8.843 (3.2); 8.839 (3.5); 8.831 (3.4); 8.827 (3.5); 8.805 (7.3); 8.800 (6.2); 8.585 (1.8); 8.580 (2.5); 8.575 (1.9); 8.565 (2.0); 8.559 (2.7); 8.555 (1.9); 8.318 (0.3); 8.006 (2.9); 8.003 (3.1); 7.987 (3.4); 7.984 (3.5); 7.799 (1.4); 7.795 (1.5); 7.780 (3.2); 7.777 (3.2); 7.761 (2.2); 7.757 (2.2); 7.740 (2.0); 7.736 (2.1); 7.721 (3.3); 7.718 (3.4); 7.701 (3.5); 7.699 (3.7); 7.688 (2.4); 7.681 (2.3); 7.669 (2.2); 7.667 (2.2); 7.571 (3.6); 7.569 (3.6); 7.553 (3.0); 7.550 (2.9); 5.758 (1.5); 3.332 (197.0); 2.783 (0.5); 2.764 (1.8); 2.746 (2.1); 2.731 (2.4); 2.712 (2.2); 2.694 (0.7); 2.677 (0.8); 2.672 (1.0); 2.668 (0.8); 2.542 (0.6); 2.525 (2.5); 2.508 (116.7); 2.503 (153.0); 2.499 (113.2); 2.444 (0.7); 2.426 (2.1); 2.408 (2.4); 2.392 (2.1); 2.374 (1.8); 2.355 (0.6); 2.334 (0.7); 2.330 (1.0); 2.325 (0.8); 0.905 (7.4); 0.887 (16.0); 0.869 (7.1); 0.000 (6.3)

6-[2-(Ethylsulphinyl)phenyl]-2-(1-oxidopyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (16)

[0829] ##STR00167##

[0830] In the course of the preparation of compound (15), compound (16) was isolated as a by-product. This gave 16.7 mg (92.8% purity, 14.2% of theory) of the title compound (16).

[0831] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.371 (4.2); 9.365 (4.1); 8.840 (3.2); 8.836 (3.3); 8.828 (3.3); 8.824 (3.3); 8.764 (5.8); 8.759 (7.2); 8.719 (7.0); 8.713 (5.7); 8.580 (1.8); 8.575 (2.5); 8.571 (1.9); 8.561 (1.9); 8.555 (2.6); 8.551 (1.8); 8.318 (1.8); 8.132 (3.1); 8.115 (3.4); 8.112 (3.4); 7.889 (1.6); 7.873 (3.3); 7.870 (3.3); 7.854 (2.3); 7.851 (2.2); 7.815 (2.1); 7.812 (2.5); 7.795 (3.0); 7.792 (3.1); 7.776 (1.3); 7.773 (1.3); 7.699 (2.5); 7.686 (2.5); 7.679 (2.5); 7.666 (2.4); 7.627 (0.5); 7.601 (3.6); 7.598 (3.7); 7.583 (3.2); 7.580 (3.1); 5.757 (1.7); 4.040 (0.5); 4.022 (0.5); 3.376 (0.5); 3.327 (653.5); 3.012 (2.1); 2.993 (7.0); 2.975 (7.2); 2.957 (2.2); 2.675 (4.7); 2.671 (6.3); 2.667 (4.8); 2.623 (0.3); 2.524 (17.2); 2.510 (380.2); 2.506 (748.3); 2.502 (973.4); 2.497 (719.5); 2.372 (0.3); 2.333 (4.7); 2.328 (6.4); 2.324 (4.8); 2.299 (0.4); 2.206 (0.3); 1.355 (0.3); 1.234 (1.4); 1.165 (1.7); 1.026 (7.4); 1.008 (16.0); 0.989 (7.2); 0.146 (17.1); 0.096 (0.3); 0.086 (0.7); 0.070 (0.7); 0.058 (1.2); 0.047 (1.5); 0.007 (153.7); 0.000 (3211.2); −0.009 (157.6); −0.068 (0.9); −0.075 (0.9); −0.095 (0.6); −0.121 (0.4); −0.150 (16.9)

6-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (19)

[0832] ##STR00168##

[0833] 200.0 mg (0.68 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 198.9 mg (0.75 mmol) of {2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}boric acid and 23.7 mg (0.02 mmol) of tetrakis(triphenylphosphine)palladium(0) were initially charged under argon, and then 9.4 ml of degassed acetonitrile and 1.4 ml of two molar sodium carbonate solution were added. The mixture was stirred under argon at 80° C. overnight. Subsequently, the cooled mixture was concentrated, admixed with dichloromethane and washed with a little water. The organic phase was dried, filtered and concentrated. Purification was by chromatography by MPLC (eluent: water/acetonitrile). This gave 92.0 mg (97.8% purity, 30.5% of theory) of the title compound (19).

[0834] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.370 (2.7); 9.366 (2.7); 9.365 (2.7); 8.834 (2.3); 8.830 (2.5); 8.822 (2.4); 8.818 (2.5); 8.759 (2.5); 8.753 (8.0); 8.749 (7.8); 8.744 (2.3); 8.578 (1.3); 8.574 (1.7); 8.568 (1.3); 8.558 (1.4); 8.553 (1.8); 8.548 (1.3); 8.318 (0.3); 7.694 (1.6); 7.693 (1.6); 7.682 (1.6); 7.681 (1.6); 7.674 (1.6); 7.673 (1.6); 7.662 (1.5); 7.661 (1.5); 7.536 (5.9); 7.297 (4.6); 4.035 (1.2); 4.009 (3.8); 3.982 (4.0); 3.956 (1.4); 3.328 (100.9); 2.676 (0.7); 2.672 (0.9); 2.667 (0.7); 2.525 (2.7); 2.520 (3.9); 2.512 (49.4); 2.507 (100.6); 2.503 (133.6); 2.498 (97.4); 2.494 (47.0); 2.418 (14.4); 2.334 (0.6); 2.329 (0.9); 2.325 (0.6); 2.275 (16.0); 1.233 (0.4); 0.146 (0.8); 0.019 (0.4); 0.008 (6.1); 0.000 (176.8); −0.009 (6.0); −0.150 (0.8)

6-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (20)

[0835] ##STR00169##

[0836] To an initial charge of 60.0 mg (0.14 mmol) of 6-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (19) in 10 ml of dichloromethane were added 34.3 mg (0.15 mmol) of m-chloroperbenzoic acid. The mixture was stirred at room temperature overnight. Subsequently, the mixture was admixed with one drop of aqueous sodium hydrogensulphite, washed with aqueous sodium carbonate solution, dried and concentrated. Purification was by chromatography by MPLC (eluent: water/acetonitrile). This gave 28 mg (90.0% purity, 40.5% of theory) of the title compound (20).

[0837] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.379 (3.2); 9.374 (3.0); 8.830 (7.8); 8.825 (9.1); 8.586 (1.4); 8.581 (1.9); 8.577 (1.3); 8.566 (1.5); 8.561 (2.0); 8.557 (1.3); 8.317 (0.5); 8.145 (0.6); 7.820 (6.5); 7.697 (1.8); 7.685 (1.8); 7.676 (1.8); 7.664 (1.7); 7.400 (4.8); 5.758 (2.3); 4.197 (1.1); 4.170 (3.3); 4.142 (3.5); 4.115 (1.2); 3.366 (0.8); 3.329 (136.7); 2.891 (0.7); 2.731 (0.6); 2.695 (0.4); 2.676 (1.3); 2.671 (1.7); 2.667 (1.3); 2.539 (1.9); 2.507 (193.1); 2.502 (244.6); 2.498 (184.8); 2.431 (15.1); 2.398 (0.8); 2.378 (16.0); 2.334 (1.3); 2.329 (1.7); 2.325 (1.3); 1.234 (1.0); 1.165 (1.0); 1.150 (0.6); 0.000 (6.2)

6-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (21)

[0838] ##STR00170##

[0839] In the course of the preparation of compound (20), compound (21) was isolated as a by-product. This gave 21 mg (90.0% purity, 29.3% of theory) of the title compound (21).

[0840] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=8.927 (4.0); 8.861 (2.0); 8.854 (9.9); 8.848 (2.3); 8.841 (0.8); 8.830 (0.4); 8.814 (0.3); 8.690 (0.3); 8.466 (2.0); 8.448 (2.1); 8.317 (1.3); 8.148 (0.5); 8.104 (2.1); 8.084 (2.3); 7.846 (0.5); 7.818 (7.0); 7.680 (2.2); 7.663 (2.3); 7.660 (2.3); 7.643 (1.9); 7.555 (0.4); 7.401 (4.8); 7.383 (0.3); 5.757 (2.2); 4.194 (1.1); 4.167 (3.4); 4.140 (3.6); 4.113 (1.2); 4.037 (0.4); 4.020 (0.4); 3.428 (0.3); 3.416 (0.4); 3.402 (0.5); 3.368 (1.5); 3.330 (615.1); 3.294 (2.0); 2.891 (1.5); 2.731 (1.3); 2.695 (1.2); 2.676 (2.8); 2.671 (3.9); 2.667 (3.0); 2.545 (2.0); 2.540 (2.2); 2.524 (10.1); 2.507 (425.8); 2.502 (566.6); 2.498 (425.9); 2.430 (14.9); 2.392 (2.1); 2.372 (16.0); 2.333 (2.6); 2.329 (3.6); 2.324 (2.8); 1.234 (2.2); 1.165 (1.4); 1.149 (0.8); 0.853 (0.4); 0.008 (0.5); 0.000 (15.0); −0.008 (0.7)

6-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (22)

[0841] ##STR00171##

[0842] 150.0 mg (0.51 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 151.4 mg (0.56 mmol) of {2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}boric acid, 17.8 mg (0.01 mmol) of tetrakis(triphenylphosphine)palladium(0) and 108.8 mg (1.0 mmol) of sodium carbonate were weighed into a reaction vessel under argon, and 4.8 ml of a 5:1 mixture of degassed dioxane and water were added.

[0843] The vessel was flooded again with argon, sealed and heated in a Biotage Initiator microwave at 130° C. for 30 minutes. The cooled mixture was diluted with water and extracted repeatedly with dichloromethane. The combined organic phases were filtered through a silica gel cartridge and washed with dichloromethane, then the filtrate was concentrated under reduced pressure. The residue was stirred with acetonitrile, filtered and dried. This gave 75.0 mg (96.2% purity, 32.3% of theory) of the title compound (22).

[0844] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.375 (3.0); 9.370 (3.0); 8.953 (9.2); 8.950 (9.1); 8.836 (2.4); 8.833 (2.6); 8.824 (2.6); 8.821 (2.7); 8.583 (1.3); 8.578 (1.8); 8.573 (1.4); 8.563 (1.5); 8.558 (2.0); 8.553 (1.4); 7.902 (3.1); 7.882 (3.1); 7.693 (1.8); 7.681 (1.8); 7.673 (1.8); 7.663 (1.7); 7.661 (1.8); 7.422 (2.7); 7.393 (2.7); 5.758 (0.6); 4.114 (1.3); 4.088 (4.0); 4.062 (4.2); 4.036 (1.5); 3.328 (42.3); 2.677 (0.5); 2.673 (0.6); 2.668 (0.5); 2.526 (1.6); 2.521 (2.5); 2.512 (35.8); 2.508 (72.9); 2.503 (97.3); 2.499 (72.8); 2.495 (36.8); 2.468 (16.0); 2.403 (0.5); 2.335 (0.5); 2.330 (0.7); 2.326 (0.5); 2.076 (1.5); 0.146 (0.5); 0.008 (3.9); 0.000 (116.1); −0.009 (4.6); −0.150 (0.5)

6-{2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (23)

[0845] ##STR00172##

[0846] To an initial charge of 155.0 mg (0.35 mmol) of 6-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (22) in 25 ml of dichloromethane were added 87.7 mg (0.39 mmol) of m-chloroperbenzoic acid. The mixture was stirred at room temperature overnight. Subsequently, the mixture was admixed with one drop of aqueous sodium hydrogensulphite, washed with aqueous sodium carbonate solution, dried and concentrated. Purification was by chromatography by MPLC. This gave 43.2 mg (98.3% purity, 26.4% of theory) of the title compound (23).

[0847] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.383 (12.6); 9.378 (12.3); 9.036 (15.7); 9.033 (14.8); 9.022 (12.3); 9.018 (16.0); 9.013 (7.6); 8.841 (9.7); 8.837 (10.6); 8.829 (10.1); 8.825 (10.6); 8.590 (5.6); 8.586 (7.4); 8.581 (5.7); 8.570 (6.1); 8.565 (8.1); 8.560 (5.8); 8.317 (1.4); 8.159 (13.2); 8.139 (13.3); 7.697 (7.3); 7.685 (7.1); 7.679 (6.9); 7.677 (7.0); 7.667 (6.7); 7.665 (6.9); 7.644 (0.6); 7.627 (0.8); 7.624 (0.8); 7.615 (0.7); 7.597 (0.8); 7.575 (0.6); 7.567 (0.7); 7.538 (10.5); 7.509 (10.2); 5.758 (3.5); 4.329 (0.4); 4.302 (1.4); 4.293 (2.2); 4.276 (2.8); 4.266 (7.1); 4.253 (6.9); 4.239 (7.4); 4.225 (7.4); 4.212 (2.8); 4.198 (2.7); 4.189 (1.6); 4.161 (0.5); 4.056 (1.0); 4.038 (2.9); 4.020 (3.0); 4.002 (1.0); 3.827 (0.4); 3.812 (0.5); 3.640 (0.6); 3.407 (0.3); 3.392 (0.7); 3.334 (1093.5); 3.268 (0.5); 3.175 (0.4); 3.162 (0.4); 2.677 (2.9); 2.672 (4.1); 2.668 (2.9); 2.645 (0.3); 2.525 (11.2); 2.512 (231.5); 2.508 (469.6); 2.503 (621.0); 2.499 (458.4); 2.494 (229.3); 2.485 (73.3); 2.434 (0.9); 2.410 (0.6); 2.388 (0.5); 2.372 (0.6); 2.334 (3.1); 2.330 (4.2); 2.325 (3.3); 1.990 (12.4); 1.909 (1.8); 1.298 (1.4); 1.259 (2.1); 1.233 (5.3); 1.193 (3.5); 1.175 (6.8); 1.157 (3.4); 0.853 (0.8); 0.836 (0.4); 0.146 (0.7); 0.008 (6.1); 0.000 (167.9); −0.008 (6.2); −0.150 (0.8)

Synthesis of Compounds of the Formula (I) by Method D

N-(3-Chlorophenyl)-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-amine (25)

[0848] ##STR00173##

[0849] 150 mg (0.51 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 78.6 mg (0.61 mmol) of 3-chloroaniline, 18.4 mg (0.08 mmol) of palladium(II) acetate, 57.5 mg (0.09 mmol) of rac-BINAP and 301.1 mg (0.92 mmol) of caesium carbonate were initially charged under argon, and then 5 ml of degassed toluene were added. The vessel was flooded again with argon, sealed and heated in a Biotage Initiator microwave at 140° C. for 60 minutes. The cooled mixture was diluted with water and extracted repeatedly with dichloromethane and ethyl acetate. The combined organic phases were filtered and concentrated under reduced pressure. Purification was by chromatography by MPLC (eluent: water/acetonitrile). This gave 44.0 mg (96.9% purity, 24.5% of theory) of the title compound (25).

[0850] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.269 (6.7); 9.264 (6.8); 8.962 (11.3); 8.772 (5.4); 8.768 (5.9); 8.760 (5.8); 8.756 (5.9); 8.483 (9.8); 8.476 (13.1); 8.465 (3.5); 8.461 (4.5); 8.456 (3.4); 8.445 (3.7); 8.440 (5.6); 8.436 (16.0); 8.429 (10.0); 8.317 (1.2); 7.647 (4.3); 7.646 (4.3); 7.635 (4.1); 7.627 (4.1); 7.626 (4.1); 7.615 (4.0); 7.614 (3.9); 7.356 (0.3); 7.339 (4.5); 7.319 (9.7); 7.299 (6.0); 7.189 (4.3); 7.184 (10.1); 7.179 (7.2); 7.170 (5.9); 7.150 (4.0); 7.146 (3.3); 6.967 (4.5); 6.964 (4.4); 6.947 (3.9); 6.944 (4.1); 5.757 (0.5); 3.326 (236.5); 2.891 (1.4); 2.732 (1.2); 2.680 (1.3); 2.676 (2.6); 2.671 (3.6); 2.667 (2.7); 2.662 (1.3); 2.525 (8.9); 2.520 (13.4); 2.511 (186.4); 2.507 (384.3); 2.502 (519.2); 2.498 (389.2); 2.493 (195.6); 2.338 (1.2); 2.333 (2.5); 2.329 (3.5); 2.325 (2.6); 2.086 (4.0); 2.075 (1.1); 0.146 (2.0); 0.008 (14.5); 0.000 (450.0); −0.009 (17.3); −0.150 (2.0)

Synthesis of Compounds of the Formula (I) by Method E

6-(1H-Pyrazol-1-yl)-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (26)

[0851] ##STR00174##

[0852] Under argon, 400.0 mg (1.4 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 1.0 g (14.7 mmol) of 1H-pyrazole, 21 mg (0.1 mmol) of copper(I) iodide, 568.0 mg (4.1 mmol) of potassium carbonate and 40 mg (0.14 mmol) of trans-1,2-bis(2′-pyridylidenamino)cyclohexane (racemic) [preparable according to Chem. Eur. J. 2005, 2483] were weighed into a reaction vessel, and 19.0 g of DMF were added. The mixture was heated under argon at 120° C. overnight. The cooled mixture was concentrated under reduced pressure, and the residue was admixed with water and extracted repeatedly with ethyl acetate. The combined organic phases were dried, filtered and concentrated. Purification was by chromatography by MPLC. This gave 20.0 mg (100% purity, 5.2% of theory) of the title compound (26).

[0853] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=11.160 (0.7); 10.721 (0.7); 9.345 (14.2); 9.294 (15.7); 9.162 (14.9); 8.822 (10.6); 8.814 (10.8); 8.761 (0.5); 8.697 (15.8); 8.551 (8.4); 8.531 (8.8); 8.475 (0.5); 8.429 (0.4); 7.894 (16.0); 7.799 (0.4); 7.684 (7.1); 7.667 (8.7); 7.654 (6.8); 7.235 (0.5); 7.220 (0.4); 7.216 (0.4); 6.673 (14.6); 5.935 (0.7); 4.134 (0.5); 3.391 (0.6); 3.326 (63.2); 2.671 (2.1); 2.503 (265.8); 2.329 (2.3); 2.283 (0.7); 2.265 (0.6); 2.244 (0.5); 2.234 (0.5); 2.209 (0.4); 2.205 (0.4); 2.178 (0.4); 2.160 (0.4); 2.155 (0.4); 2.141 (0.4); 2.087 (4.1); 2.058 (0.6); 2.044 (0.4); 1.983 (0.7); 1.926 (0.4); 1.907 (0.5); 1.886 (0.4); 1.870 (0.4); 1.852 (0.4); 1.821 (0.4); 1.743 (1.2); 1.678 (0.5); 1.671 (0.5); 1.625 (1.4); 1.532 (0.7); 1.511 (0.7); 1.463 (0.6); 1.453 (0.6); 1.433 (0.6); 1.416 (0.6); 1.367 (0.9); 1.349 (1.1); 1.297 (3.4); 1.257 (4.8); 1.230 (8.0); 1.171 (2.8); 1.146 (4.1); 1.136 (4.0); 1.088 (1.2); 1.065 (1.0); 1.042 (0.9); 1.036 (0.9); 0.981 (0.6); 0.943 (0.6); 0.928 (0.7); 0.863 (3.1); 0.755 (0.5); 0.724 (0.4); 0.701 (0.4); 0.145 (0.9); 0.123 (0.4); 0.105 (0.5); 0.095 (0.6); −0.001 (131.7); −0.150 (1.2); −0.190 (0.4); −0.201 (0.4)

6-(1H-Pyrazol-1-yl)-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (27)

[0854] ##STR00175##

[0855] Under argon, 300.0 mg (1.0 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 1.4 g (10.3 mmol) of 3-(trifluoromethyl)-1H-pyrazole and 147 mg (1.0 mmol) of copper(I) oxide were weighed into a reaction vessel, and 15.0 g of pyridine were added. The mixture was heated under argon at 90° C. overnight. Subsequently, a further 300 mg (1.0 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (II-1) and 440 mg (3.0 mmol) of copper(I) oxide were added and the mixture was heated at 115° C. for a further 7 hours. The cooled mixture was then concentrated under reduced pressure. Purification was by chromatography by MPLC (at first water/acetonitrile eluent gradient; then for enriched fraction separation by petroleum ether/acetone eluent gradient). This gave 20.0 mg (82% purity, 4.6% of theory) of the title compound (27).

[0856] 1H-NMR (601.6 MHz, CD3CN): δ=9.373 (4.7); 9.355 (0.8); 9.156 (8.3); 9.151 (8.5); 8.877 (8.9); 8.873 (8.7); 8.789 (3.3); 8.782 (3.4); 8.734 (0.6); 8.729 (0.6); 8.511 (2.6); 8.508 (3.8); 8.505 (2.6); 8.498 (3.3); 8.495 (3.9); 8.492 (3.0); 8.488 (1.3); 8.485 (1.1); 8.476 (0.6); 8.385 (5.8); 8.383 (5.8); 7.585 (3.2); 7.577 (3.3); 7.572 (3.3); 7.564 (3.3); 7.545 (0.5); 7.466 (0.6); 7.452 (1.5); 7.446 (0.9); 7.441 (0.7); 7.433 (0.7); 7.238 (0.5); 7.234 (0.4); 7.224 (0.4); 7.220 (0.4); 6.953 (6.6); 6.949 (6.5); 5.448 (0.7); 2.828 (1.2); 2.748 (0.6); 2.575 (2.2); 2.563 (2.3); 2.501 (0.5); 2.172 (9.1); 2.107 (5.6); 2.087 (3.1); 2.076 (2.7); 2.059 (3.2); 2.055 (4.1); 2.051 (5.1); 2.047 (3.9); 2.043 (2.7); 1.965 (67.2); 1.957 (37.4); 1.952 (51.3); 1.949 (253.4); 1.945 (433.6); 1.940 (624.6); 1.936 (441.3); 1.932 (228.3); 1.916 (4.5); 1.883 (1.7); 1.850 (1.1); 1.842 (1.1); 1.834 (2.0); 1.830 (3.1); 1.826 (4.2); 1.822 (3.0); 1.818 (1.8); 1.567 (0.5); 1.434 (0.5); 1.340 (13.1); 1.319 (2.0); 1.308 (2.5); 1.298 (2.3); 1.285 (16.0); 1.269 (9.4); 1.248 (1.2); 1.227 (1.0); 1.217 (1.0); 1.206 (1.0); 1.184 (1.3); 1.173 (1.2); 1.153 (0.8); 1.134 (0.8); 1.112 (0.7); 1.083 (0.8); 1.071 (0.7); 1.048 (0.6); 1.038 (0.6); 1.022 (4.4); 1.010 (8.3); 0.999 (4.3); 0.914 (0.7); 0.893 (1.2); 0.882 (2.1); 0.870 (1.5); 0.844 (1.3); 0.000 (2.8)

4,5-Dimethyl-2-[2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]-2,4-dihydro-3H-1,2,4-triazol-3-one (30)

[0857] ##STR00176##

[0858] Under argon, 250 mg (0.86 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 136 mg (1.20 mmol) of 4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 16 mg (0.09 mmol) of copper(I) iodide, 355 mg (2.57 mmol) of potassium carbonate and 43 mg (0.26 mmol) of potassium iodide were initially charged in 5 ml of dioxane and the vessel was flooded with argon. Subsequently, 24 mg (0.17 mmol) of trans-N,N′-dimethylcyclohexane-1,2-diamine (racemic) were added, and the reaction vessel was sealed and stirred at 130° C. overnight. The cooled mixture was then diluted with 5 ml of ethyl acetate and filtered through Celite, and the filtrate was concentrated under reduced pressure. Purification was by chromatography by means of MPLC (eluent: water/acetonitrile). This gave 6.0 mg (90.0% purity, 1.95% of theory) of the title compound (30).

[0859] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.336 (0.6); 9.317 (2.7); 9.310 (3.0); 9.307 (3.9); 9.300 (3.8); 9.119 (3.3); 9.113 (3.3); 8.808 (2.1); 8.800 (2.2); 8.796 (2.0); 8.712 (0.4); 8.543 (0.4); 8.522 (1.4); 8.518 (1.8); 8.512 (1.4); 8.502 (1.4); 8.497 (1.6); 8.493 (1.2); 7.673 (1.3); 7.661 (1.6); 7.655 (1.5); 7.643 (1.3); 3.556 (0.4); 3.322 (46.2); 3.255 (17.4); 3.177 (1.4); 3.141 (0.4); 3.127 (0.6); 3.122 (0.5); 3.076 (0.3); 3.060 (2.0); 2.755 (0.3); 2.736 (0.4); 2.728 (0.5); 2.670 (2.4); 2.666 (2.1); 2.505 (269.8); 2.501 (349.1); 2.497 (274.9); 2.356 (0.9); 2.338 (16.0); 2.250 (1.0); 2.227 (0.7); 2.119 (1.8); 1.234 (0.5); 0.883 (0.4); 0.000 (50.2)

4,5-Dimethyl-2-[2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione (31)

[0860] ##STR00177##

[0861] Under argon, 250 mg (0.86 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 155 mg (1.20 mmol) of 4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-thione, 16 mg (0.09 mmol) of copper(I) iodide, 355 mg (2.57 mmol) of potassium carbonate and 43 mg (0.26 mmol) of potassium iodide were initially charged in 5 ml of dioxane and the vessel was flooded with argon. Subsequently, 24 mg (0.17 mmol) of trans-N,N′-dimethylcyclohexane-1,2-diamine (racemic) were added, and the reaction vessel was sealed and stirred at 130° C. overnight. The cooled mixture was then diluted with 5 ml of ethyl acetate and filtered through Celite, and the filtrate was concentrated under reduced pressure. Purification was by chromatography by means of MPLC (eluent: water/acetonitrile). This gave 4.0 mg (90.0% purity, 1.24% of theory) of the title compound (31).

[0862] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.318 (0.6); 8.816 (0.4); 8.806 (0.4); 8.701 (0.7); 8.695 (1.0); 8.668 (0.9); 8.662 (0.8); 8.524 (0.4); 8.504 (0.4); 7.669 (0.4); 7.657 (0.4); 7.649 (0.4); 3.557 (4.4); 3.387 (0.7); 3.319 (4.7); 2.506 (37.0); 2.501 (51.1); 2.497 (42.5); 2.406 (4.4); 2.328 (0.3); 2.291 (0.5); 1.158 (2.3); 1.069 (16.0); 0.000 (7.1); −0.002 (4.9)

4-Methyl-2-[2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]-1,2,4-triazine-3,5(2H,4H)-dione (39)

[0863] ##STR00178##

[0864] Under argon, 200 mg (0.69 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1), 122 mg (0.96 mmol) of 4-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 13 mg (0.07 mmol) of copper(I) iodide, 284 mg (2.05 mmol) of potassium carbonate and 34 mg (0.21 mmol) of potassium iodide were initially charged in 5 ml of dioxane and the vessel was flooded with argon. Subsequently, 19 mg (0.14 mmol) of trans-N,N′-dimethylcyclohexane-1,2-diamine (racemic) were added, and the reaction vessel was sealed and stirred at 130° C. overnight. The cooled mixture was diluted with 5 ml of ethyl acetate and filtered through Celite, and the filtrate was concentrated under reduced pressure. Purification was by chromatography by means of MPLC (eluent: water/acetonitrile). This gave 8.0 mg (88.0% purity, 3.04% of theory) of the title compound (39).

[0865] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.356 (8.6); 8.902 (8.8); 8.897 (11.6); 8.877 (11.6); 8.871 (8.2); 8.834 (6.1); 8.823 (6.3); 8.763 (1.1); 8.755 (1.0); 8.731 (0.9); 8.711 (0.9); 8.561 (5.1); 8.542 (5.7); 8.313 (0.5); 8.177 (0.4); 7.953 (1.0); 7.879 (16.0); 7.692 (4.3); 7.681 (5.2); 7.673 (4.7); 7.661 (4.5); 7.647 (0.9); 7.550 (0.8); 7.539 (0.7); 7.529 (0.7); 7.517 (0.6); 5.308 (0.4); 3.432 (0.6); 3.320 (260.1); 3.256 (48.0); 3.190 (0.5); 3.153 (0.4); 3.076 (0.3); 2.995 (3.2); 2.891 (4.8); 2.732 (4.6); 2.711 (1.2); 2.671 (2.4); 2.645 (0.4); 2.630 (0.5); 2.541 (215.4); 2.502 (389.5); 2.368 (2.0); 2.329 (3.0); 2.295 (0.8); 2.277 (0.7); 2.243 (0.6); 2.220 (0.7); 2.200 (0.6); 2.189 (1.2); 2.173 (0.6); 2.131 (0.6); 2.117 (0.9); 2.105 (0.7); 2.086 (0.6); 2.073 (0.6); 2.036 (0.6); 2.005 (0.5); 1.997 (0.5); 1.990 (0.5); 1.980 (0.5); 1.942 (0.5); 1.909 (5.1); 1.840 (0.9); 1.816 (0.4); 1.809 (0.4); 1.762 (0.4); 1.754 (0.4); 1.722 (0.3); 1.704 (0.4); 1.673 (0.3); 1.621 (0.3); 1.610 (0.4); 1.605 (0.4); 1.603 (0.4); 1.585 (0.4); 1.574 (0.4); 1.536 (0.5); 1.514 (0.6); 1.507 (0.6); 1.500 (0.6); 1.490 (0.6); 1.466 (0.7); 1.458 (0.6); 1.386 (1.4); 1.380 (1.4); 1.347 (1.8); 1.335 (1.8); 1.298 (1.7); 1.259 (1.7); 1.234 (2.6); 1.201 (1.3); 1.141 (1.4); 1.085 (0.5); 1.070 (0.6); 1.054 (0.5); 1.045 (0.5); 1.035 (0.5); 0.988 (0.5); 0.968 (0.4); 0.922 (0.3); 0.892 (0.4); 0.864 (0.6); 0.852 (0.9); 0.830 (1.3); 0.756 (0.5); 0.726 (0.3); 0.000 (43.1)

Synthesis of Compounds of the Formula (I) by Method G

Methyl 2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxylate (I-j-1)

[0866] ##STR00179##

[0867] To a mixture of 10.8 g (36.97 mmol) of 6-bromo-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-a-1) in 200 ml of THF, 100 ml of DMF and 100 ml of methanol were added 11.22 g (110.91 mmol) of triethylamine and 5.41 g (7.39 mmol) of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II). Carbon monoxide was introduced into the solution and the mixture was stirred at 70° C. and 45 psi CO pressure for 16 hours. Subsequently, the mixture was filtered and concentrated under reduced pressure. Purification was by chromatography by means of MPLC (eluent gradient: petroleum ether/ethyl acetate). This gave 7.50 g of the target compound (I-j-1), which was converted further to amides without further purification. For this purpose, a purity of 100% was assumed.

[0868] LC-MS: m/z 272 [M+H.sup.+]

Methyl 2-(5-fluoropyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxylate (I-j-2)

[0869] ##STR00180##

[0870] The preparation was effected in analogy to the synthesis of (I-j-1), except proceeding from 3-(chlorocarbonyl)-5-fluoropyridinium chloride in Method A, Step 1.

[0871] LC-MS: m/z 290 [M+H.sup.+]

N-[2-(Methylsulphanyl)ethyl]-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxamide (52)

[0872] ##STR00181##

[0873] To a solution of 300 mg (1.11 mmol, assumed purity 100%) of methyl 2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxylate (I-j-1) in 8 ml of THF were added 1.2 molar equivalents (eq.) of potassium trimethylsilanolate. The mixture was stirred at 30° C. for another 16 hours and then concentrated under reduced pressure. The residue was taken up in 5 ml of DMF, and 1.2 molar equivalents (eq.) of 2-(7-aza-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU) and 3 molar equivalents (eq.) of diisopropylethylamine were added. The mixture was stirred at 30° C. for 30 minutes. Subsequently, 121.4 mg (1.33 mmol, 1.2 eq.) of 2-(methylsulphanyl)ethanamine were added and the mixture was stirred at 30° C. for another 16 hours. Thereafter, the reaction mixture was concentrated under reduced pressure. Purification was by chromatography by means of MPLC. This gave 49.2 mg (95.4% purity, 12.8% of theory) of the title compound (52).

[0874] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.365 (1.2); 9.153 (2.3); 9.148 (2.8); 9.101 (2.7); 9.096 (2.4); 8.981 (0.5); 8.967 (1.0); 8.953 (0.5); 8.843 (0.9); 8.831 (0.8); 8.574 (0.7); 8.568 (1.0); 8.564 (0.7); 8.554 (0.7); 8.548 (1.0); 8.544 (0.8); 7.695 (0.8); 7.683 (0.8); 7.676 (0.8); 7.664 (0.8); 3.902 (4.0); 3.556 (0.8); 3.540 (1.6); 3.522 (1.6); 3.507 (0.9); 3.356 (130.8); 3.349 (200.4); 2.724 (1.7); 2.706 (2.5); 2.689 (1.6); 2.678 (0.4); 2.673 (0.5); 2.669 (0.3); 2.526 (1.2); 2.513 (24.8); 2.509 (53.4); 2.504 (76.2); 2.500 (58.4); 2.495 (28.7); 2.331 (0.4); 2.326 (0.3); 2.128 (16.0); 0.000 (2.5)

N-[2-(Methylsulphonyl)ethyl]-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxamide (54)

[0875] ##STR00182##

[0876] To a solution of 300 mg (1.11 mmol, assumed purity 100%) of methyl 2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxylate (I-j-1) in 8 ml of THF were added 1.2 molar equivalents (eq.) of potassium trimethylsilanolate. The mixture was stirred at 30° C. for another 16 hours and then concentrated under reduced pressure. The residue was taken up in 5 ml of DMF, and 1.2 molar equivalents (eq.) of 2-(7-aza-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU) and 3 molar equivalents (eq.) of diisopropylethylamine were added. The mixture was stirred at 30° C. for 30 minutes. Subsequently, 163.8 mg (1.33 mmol, 1.2 eq.) of 2-(methylsulphonyl)ethanamine were added and the mixture was stirred at 30° C. for another 16 hours. Thereafter, the reaction mixture was concentrated under reduced pressure. Purification was by chromatography by means of MPLC. This gave 74.3 mg (97.6% purity, 18.0% of theory) of the title compound (54).

[0877] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.372 (1.9); 9.152 (3.4); 9.147 (4.5); 9.125 (1.7); 9.115 (4.8); 9.109 (4.2); 8.849 (1.3); 8.838 (1.3); 8.576 (1.0); 8.571 (1.4); 8.567 (1.1); 8.556 (1.1); 8.551 (1.5); 8.547 (1.1); 7.698 (1.2); 7.686 (1.2); 7.678 (1.2); 7.666 (1.1); 3.955 (0.6); 3.902 (8.0); 3.777 (0.9); 3.760 (2.4); 3.745 (2.5); 3.729 (1.2); 3.455 (2.2); 3.438 (4.0); 3.421 (1.9); 3.344 (186.2); 3.336 (242.0); 3.176 (0.6); 3.162 (0.6); 3.075 (16.0); 2.677 (0.6); 2.672 (0.8); 2.668 (0.6); 2.543 (0.6); 2.526 (2.1); 2.512 (47.9); 2.508 (101.9); 2.503 (144.1); 2.499 (111.8); 2.334 (0.6); 2.330 (0.8); 2.325 (0.6); 0.000 (3.8)

2-(5-Fluoropyridin-3-yl)-N-{3-[(trifluoromethyl)sulphanyl]phenyl}[1,3]thiazolo[4,5-b]pyridine-6-carboxamide (57)

[0878] ##STR00183##

[0879] To a solution of 300 mg (1.11 mmol, assumed purity 100%) of methyl 2-(5-fluoropyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine-6-carboxylate (I-j-2) in 8 ml of THF were added 1.2 molar equivalents (eq.) of potassium trimethylsilanolate. The mixture was stirred at 30° C. for another 16 hours and then concentrated under reduced pressure. The residue was taken up in 5 ml of DMF, and 1.2 molar equivalents (eq.) of 2-(7-aza-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU) and 3 molar equivalents (eq.) of diisopropylethylamine were added. The mixture was stirred at 30° C. for 30 minutes. Subsequently, 256.9 mg (1.33 mmol, 1.2 eq.) of 3-[(trifluoromethyl)sulphanyl]aniline were added and the mixture was stirred at 30° C. for another 16 hours. Thereafter, the reaction mixture was concentrated under reduced pressure. Purification was by chromatography by means of MPLC. This gave 41.3 mg (99.5% purity, 8.2% of theory) of the title compound (57).

[0880] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=10.872 (8.7); 9.298 (6.5); 9.293 (10.8); 9.277 (16.0); 8.887 (6.9); 8.880 (7.1); 8.555 (2.2); 8.549 (3.3); 8.544 (2.4); 8.532 (2.3); 8.525 (3.3); 8.521 (2.3); 8.308 (0.3); 8.273 (7.1); 8.025 (3.4); 8.004 (3.7); 7.605 (3.2); 7.585 (7.0); 7.565 (4.6); 7.509 (5.1); 7.490 (3.2); 3.902 (15.3); 3.705 (0.4); 3.657 (0.4); 3.603 (0.6); 3.508 (1.4); 3.361 (1440.1); 3.174 (0.6); 2.678 (1.6); 2.674 (2.2); 2.670 (1.6); 2.582 (0.4); 2.544 (1.6); 2.509 (266.9); 2.505 (367.0); 2.500 (281.7); 2.336 (1.5); 2.331 (2.0); 1.233 (0.6); 0.000 (7.6)

2-(5-Fluoropyridin-3-yl)-N-{3-[(trifluoromethyl)sulphinyl]phenyl}[1,3]thiazolo[4,5-b]pyridine-6-carboxamide (58)

[0881] ##STR00184##

[0882] To a solution of 300 mg (0.67 mmol) of 2-(5-fluoropyridin-3-yl)-N-{3-[(trifluoromethyl)sulphanyl]phenyl}[1,3]thiazolo[4,5-b]pyridine-6-carboxamide (57) in 10 ml of dichloromethane were added 2 molar equivalents (222.5 mg, 1.3 mmol) of meta-chloroperbenzoic acid at 0° C. The reaction mixture was stirred at 20° C. for another 16 hours and then concentrated under reduced pressure. Purification was by chromatography by means of MPLC. This gave 17.4 mg (95.5% purity, 5.3% of theory) of the title compound (58).

[0883] 1H-NMR (601.6 MHz, d.sub.6-DMSO): δ=11.037 (1.3); 9.317 (7.8); 9.313 (14.4); 9.306 (16.0); 9.302 (8.6); 9.278 (8.6); 8.887 (8.8); 8.883 (10.4); 8.833 (0.9); 8.829 (0.8); 8.825 (0.9); 8.554 (2.8); 8.551 (3.7); 8.547 (2.8); 8.539 (3.0); 8.536 (3.8); 8.532 (2.6); 8.452 (8.0); 8.270 (1.6); 8.189 (0.8); 8.176 (0.9); 8.160 (4.1); 8.147 (4.3); 8.145 (4.3); 8.022 (0.8); 8.007 (0.8); 7.760 (4.0); 7.746 (8.2); 7.733 (4.8); 7.646 (5.2); 7.634 (4.1); 7.596 (0.7); 7.583 (1.5); 7.569 (0.9); 7.505 (1.0); 7.493 (0.8); 3.322 (411.9); 2.614 (2.3); 2.611 (1.7); 2.541 (1.0); 2.523 (4.5); 2.520 (5.8); 2.517 (6.8); 2.505 (256.7); 2.502 (334.0); 2.499 (250.5); 2.386 (2.0); 1.231 (0.6); 0.000 (7.3)

Synthesis of Compounds of the Formula (I) by Method H

2-(Pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-amine (I-s-1)

[0884] ##STR00185##

[0885] To a stirred solution of 8.0 g (31 mmol) of 6-nitro-2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridine (I-r-1) (prepared analogously to the synthesis for compound (I-a-1), proceeding from 3-bromo-5-nitropyridin-2-amine in Method A, Step 1) in 300 ml of THF were added 1.6 g of Pd/C (10 wt %) under nitrogen at 30° C. The mixture was stirred at 50° C. under hydrogen (50 psi) for 48 hours. Subsequently, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. This gave 5.0 g of 2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-amine (I-s-1) as a crude product, which was converted further to amides without further purification. For this purpose, a purity of 100% was assumed.

[0886] LC-MS: m/z 229 [M+H.sup.+]

2-(5-Fluoropyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-amine (I-s-2)

[0887] ##STR00186##

[0888] The preparation was effected in analogy to the synthesis of (I-s-1), except proceeding from 3-(chlorocarbonyl)-5-fluoropyridinium chloride in Method A, Step 1.

[0889] LC-MS: m/z 247 [M+H.sup.+]

N-Methyl-N-[2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]propanamide (59)

Step 1: N-[2-(Pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]propanamide

[0890] ##STR00187##

[0891] To a mixture of 300 mg (1.31 mmol) of 2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-amine (I-s-2) and 398 mg (3.93 mmol) of triethylamine in 5 ml of dichloromethane were added 121.6 mg (1.31 mmol) of propanoyl chloride. The mixture was stirred at 30° C. for 16 hours and then concentrated under reduced pressure. Purification was by chromatography by means of MPLC (eluent gradient: petroleum ether/ethyl acetate). This gave 300 mg (80.5% of theory, assumed purity 100%) of the title compound N-[2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]propanamide, which was converted further directly.

Step 2: N-Methyl-N-[2-(pyridin-3-yl)[1,3]thiazolo[4,5-b]pyridin-6-yl]propanamide (59)

[0892] ##STR00188##

[0893] 172 mg (0.605 mmol) of N-[2-(pyridin-3-yl)-1,3-benzothiazol-6-yl]propanamide (Example 59, Step 1) were dissolved in 5 ml of THF and cooled to 0° C. Subsequently, 24.2 mg (0.605 mmol) of sodium hydride (60% suspension in paraffin) were added at 0° C. The mixture was stirred at this temperature for another 30 minutes and then 85.9 mg (0.605 mmol) of methyl iodide were added. The mixture was stirred at 30° C. for another 16 hours and then 1 ml of aqueous ammonium chloride solution was added at 0° C. After the mixture had been concentrated under reduced pressure, the residue was purified by chromatography by means of preparative HPLC. This gave 34.8 mg (99.9% purity, 19.3% of theory) of the title compound (59).

[0894] 1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.231 (6.6); 8.861 (5.8); 8.854 (6.1); 8.761 (8.3); 8.508 (1.9); 8.503 (2.6); 8.485 (1.9); 8.480 (2.6); 8.475 (1.8); 3.902 (16.0); 3.508 (0.4); 3.342 (396.2); 3.338 (410.6); 3.176 (0.7); 3.164 (0.7); 2.677 (1.1); 2.672 (1.5); 2.668 (1.2); 2.548 (0.6); 2.525 (4.3); 2.512 (90.4); 2.508 (185.6); 2.503 (257.8); 2.499 (197.1); 2.335 (1.2); 2.330 (1.5); 2.325 (1.2); 2.199 (0.5); 2.143 (0.6); 2.130 (0.6); 2.112 (0.6); 2.074 (0.4); 1.249 (0.3); 1.235 (0.3); 0.969 (4.6); 0.008 (0.4); 0.000 (10.5)

[0895] Compounds of the formula (I) and also those not embraced by formula (I) are listed in the table below. The compounds not covered by the formula (I) also form part of the subject-matter of the invention.

[0896] The compounds I-a-1, I-j-1, I-j-2, I-s-1 and I-s-2 listed in the table also form part of the subject-matter of the invention.

TABLE-US-00001 TABLE 1 Compounds of the formula [00189] Preparation Example method No. A Q R.sup.1 R.sup.2 B  1 [00190] S H [00191] B  2 [00192] S H [00193] B  3 [00194] S H [00195] B  4 [00196] S H [00197] B  5 [00198] S H [00199] B  6 [00200] S H [00201] B  7 [00202] S H [00203] B  8 [00204] S H [00205] B  9 [00206] S H [00207] B 10 [00208] S H [00209] B 11 [00210] S H [00211] I 12 [00212] S H [00213] I 13 [00214] S H [00215] B 14 [00216] S H [00217] I 15 [00218] S H [00219] I 16 [00220] S H [00221] B 17 [00222] S H [00223] I 18 [00224] S H [00225] B 19 [00226] S H [00227] I 20 [00228] S H [00229] I 21 [00230] S H [00231] B 22 [00232] S H [00233] I 23 [00234] S H [00235] D 24 [00236] S H [00237] D 25 [00238] S H [00239] E 26 [00240] S H [00241] E 27 [00242] S H [00243] E 28 [00244] S H [00245] E 29 [00246] S H [00247] E 30 [00248] S H [00249] E 31 [00250] S H [00251] E 32 [00252] S H [00253] E 33 [00254] S H [00255] E 34 [00256] S H [00257] E 35 [00258] S H [00259] E 36 [00260] S H [00261] E 37 [00262] S H [00263] E 38 [00264] S H [00265] E 39 [00266] S H [00267] G 40 [00268] S H [00269] G 41 [00270] S H [00271] G 42 [00272] S H [00273] G 43 [00274] S H [00275] G 44 [00276] S H [00277] G 45 [00278] S H [00279] G 46 [00280] S H [00281] G 47 [00282] S H [00283] G 48 [00284] S H [00285] G 49 [00286] S H [00287] G 50 [00288] S H [00289] G 51 [00290] S H [00291] G 52 [00292] S H [00293] G 53 [00294] S H [00295] G 54 [00296] S H [00297] G 55 [00298] S H [00299] G 56 [00300] S H [00301] G 57 [00302] S H [00303] I 58 [00304] S H [00305] H2 59 [00306] S H [00307] A I-a-1 [00308] S H Br G I-j-1 [00309] S H [00310] G I-j-2 [00311] S H [00312] H2 I-s-1 [00313] S H [00314] H2 I-s-2 [00315] S H [00316]

TABLE-US-00002 TABLE 2 Analytical data for the compounds reported Ex. No. LogP[a] logP[b] 1H-NMR [σ (ppm)] or LC-MS [m/z] 1 2.47 2.56 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.366 (4.5); 9.361 (4.6); 9.084 (7.0); 9.079 (8.7); 9.029 (7.7); 9.023 (6.6); 8.830 (3.7); 8.826 (4.1); 8.818 (4.0); 8.814 (4.1); 8.574 (2.2); 8.570 (2.9); 8.564 (2.3); 8.554 (2.4); 8.549 (3.1); 8.544 (2.4); 8.316 (0.3); 7.875 (5.1); 7.871 (7.3); 7.853 (7.7); 7.692 (2.8); 7.690 (2.9); 7.678 (2.9); 7.672 (2.8); 7.670 (2.8); 7.660 (2.7); 7.658 (2.8); 7.585 (3.8); 7.567 (8.4); 7.547 (5.3); 7.495 (3.1); 7.492 (2.0); 7.481 (1.2); 7.476 (4.3); 7.471 (1.1); 7.458 (1.4); 3.762 (0.6); 3.569 (0.6); 3.351 (267.6); 3.349 (243.9); 3.340 (242.3); 3.335 (116.9); 2.682 (0.4); 2.677 (0.9); 2.673 (1.2); 2.668 (0.9); 2.526 (2.6); 2.521 (3.9); 2.513 (61.0); 2.508 (126.9); 2.504 (172.8); 2.499 (131.6); 2.495 (67.2); 2.335 (0.8); 2.331 (1.2); 2.326 (0.8); 2.075 (16.0); 0.146 (0.5); 0.008 (3.7); 0.000 (122.8); −0.008 (5.0); −0.150 (0.5) 2 2.76 2.8 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.366 (2.3); 9.361 (2.3); 8.833 (1.7); 8.829 (1.9); 8.821 (1.8); 8.817 (1.9); 8.753 (2.7); 8.748 (4.7); 8.735 (4.4); 8.730 (2.6); 8.573 (1.0); 8.569 (1.5); 8.564 (1.0); 8.553 (1.1); 8.549 (1.5); 8.544 (1.0); 7.693 (1.4); 7.681 (1.4); 7.673 (1.3); 7.661 (1.3); 7.404 (0.5); 7.393 (2.4); 7.390 (2.7); 7.383 (3.6); 7.376 (3.2); 7.369 (3.3); 7.362 (4.8); 7.355 (1.5); 7.349 (1.1); 7.340 (0.4); 3.329 (15.8); 2.526 (0.8); 2.508 (33.3); 2.504 (44.1); 2.500 (33.0); 2.383 (0.4); 2.331 (0.4); 2.315 (16.0); 0.008 (1.8); 0.000 (50.9); −0.009 (2.0) 3 2.91 2.95 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.362 (2.9); 9.357 (2.9); 9.066 (3.5); 9.060 (4.2); 9.008 (4.0); 9.003 (3.7); 8.824 (2.3); 8.815 (2.1); 8.812 (2.2); 8.563 (1.8); 8.559 (1.3); 8.548 (1.3); 8.543 (1.9); 8.539 (1.3); 7.688 (5.2); 7.676 (2.1); 7.668 (1.9); 7.656 (3.4); 7.636 (2.1); 7.463 (1.6); 7.444 (3.2); 7.425 (1.7); 7.297 (2.2); 7.279 (1.7); 3.346 (101.5); 3.339 (98.5); 2.673 (0.5); 2.508 (59.8); 2.504 (75.9); 2.500 (59.5); 2.424 (16.0); 2.330 (0.5); 2.076 (0.4); 0.000 (41.3) 4 2.91 2.96 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.358 (3.1); 9.353 (3.2); 9.060 (4.6); 9.054 (5.4); 8.992 (5.5); 8.987 (4.9); 8.824 (2.4); 8.820 (2.7); 8.812 (2.5); 8.808 (2.7); 8.564 (1.4); 8.559 (2.0); 8.554 (1.5); 8.544 (1.5); 8.539 (2.1); 8.534 (1.5); 7.914 (1.2); 7.766 (5.5); 7.746 (6.3); 7.685 (2.1); 7.672 (2.0); 7.665 (2.1); 7.652 (1.8); 7.378 (5.1); 7.358 (4.6); 3.328 (39.8); 2.677 (0.4); 2.672 (0.6); 2.668 (0.5); 2.544 (0.3); 2.525 (1.8); 2.512 (34.6); 2.508 (69.0); 2.503 (91.4); 2.499 (69.9); 2.388 (16.0); 2.330 (0.7); 2.326 (0.5); 2.298 (1.2); 0.146 (0.5); 0.008 (3.8); 0.000 (98.0); −0.008 (4.7); −0.150 (0.5) 5 2.51 2.54 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.373 (11.3); 9.369 (11.2); 9.367 (10.9); 8.952 (7.9); 8.947 (14.9); 8.943 (13.7); 8.933 (12.1); 8.928 (15.9); 8.923 (7.2); 8.837 (9.0); 8.833 (10.0); 8.825 (9.6); 8.821 (9.8); 8.582 (5.5); 8.578 (7.1); 8.577 (6.9); 8.573 (5.6); 8.562 (5.9); 8.558 (7.1); 8.557 (7.6); 8.553 (5.7); 8.318 (2.6); 8.189 (1.8); 8.091 (0.4); 8.071 (0.5); 7.998 (1.3); 7.758 (3.8); 7.754 (4.3); 7.738 (7.0); 7.734 (8.3); 7.718 (4.2); 7.714 (4.9); 7.697 (7.1); 7.695 (7.1); 7.684 (6.6); 7.683 (6.8); 7.677 (6.6); 7.675 (6.8); 7.664 (6.4); 7.663 (6.6); 7.570 (1.7); 7.566 (2.0); 7.557 (2.0); 7.552 (4.2); 7.548 (4.0); 7.540 (2.9); 7.535 (4.5); 7.532 (5.5); 7.527 (3.4); 7.518 (3.1); 7.514 (2.9); 7.454 (6.4); 7.436 (4.4); 7.433 (4.7); 7.426 (14.0); 7.407 (16.0); 7.389 (4.9); 7.386 (4.5); 7.321 (0.8); 7.318 (0.7); 7.308 (2.2); 7.249 (0.7); 7.229 (0.7); 7.152 (0.4); 7.075 (0.4); 6.600 (0.3); 5.162 (0.6); 4.497 (0.9); 4.482 (0.8); 4.038 (0.6); 4.020 (0.7); 3.397 (0.4); 3.328 (888.9); 3.295 (0.5); 3.005 (0.7); 2.987 (0.7); 2.676 (4.7); 2.671 (6.6); 2.667 (4.9); 2.663 (2.4); 2.525 (16.1); 2.520 (24.4); 2.511 (350.0); 2.507 (724.8); 2.502 (967.1); 2.498 (711.5); 2.493 (349.4); 2.403 (0.6); 2.374 (0.7); 2.338 (2.1); 2.334 (4.6); 2.329 (6.4); 2.325 (4.8); 2.320 (2.3); 1.989 (2.6); 1.355 (0.7); 1.260 (0.9); 1.249 (0.4); 1.242 (1.8); 1.234 (1.4); 1.224 (0.9); 1.212 (0.3); 1.193 (1.0); 1.175 (1.6); 1.157 (0.7); 0.000 (2.4) 6 2.77 2.78 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.373 (8.3); 9.368 (8.3); 8.854 (12.7); 8.848 (16.0); 8.839 (6.8); 8.835 (7.3); 8.827 (7.2); 8.823 (7.4); 8.806 (15.3); 8.800 (12.6); 8.582 (3.8); 8.577 (5.2); 8.572 (4.0); 8.562 (4.2); 8.556 (5.6); 8.552 (4.1); 8.318 (0.5); 7.696 (5.5); 7.687 (8.6); 7.681 (5.0); 7.676 (10.0); 7.672 (4.5); 7.664 (11.9); 7.655 (1.3); 7.651 (0.7); 7.634 (0.7); 7.626 (5.0); 7.618 (3.6); 7.614 (6.6); 7.608 (4.5); 7.602 (8.0); 7.594 (1.3); 7.589 (0.6); 7.567 (0.5); 7.555 (0.6); 7.548 (2.3); 7.543 (1.4); 7.535 (12.8); 7.530 (7.4); 7.524 (10.0); 7.518 (6.5); 7.512 (9.2); 7.500 (1.3); 7.493 (0.5); 6.535 (1.3); 5.758 (0.8); 3.569 (0.4); 3.328 (120.3); 2.681 (0.6); 2.677 (1.2); 2.672 (1.6); 2.668 (1.2); 2.526 (4.2); 2.521 (6.4); 2.512 (87.3); 2.508 (178.1); 2.503 (238.6); 2.499 (179.7); 2.495 (92.4); 2.335 (1.2); 2.330 (1.6); 2.326 (1.2); 2.076 (0.4); 0.146 (1.3); 0.008 (9.3); 0.000 (278.6); −0.008 (12.8); −0.020 (0.7); −0.0256 (0.3); −0.0263 (0.3); −0.150 (1.3) 7 2.98 3.01 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.374 (8.4); 9.368 (8.3); 9.117 (11.3); 9.111 (15.3); 9.084 (16.0); 9.078 (11.2); 8.834 (6.6); 8.830 (6.7); 8.822 (6.8); 8.818 (6.5); 8.582 (3.8); 8.577 (5.3); 8.572 (3.6); 8.562 (4.1); 8.557 (5.5); 8.552 (3.5); 8.317 (1.9); 7.969 (6.9); 7.964 (12.0); 7.960 (6.7); 7.857 (5.8); 7.838 (6.5); 7.811 (0.4); 7.693 (5.3); 7.681 (5.2); 7.673 (5.1); 7.661 (4.9); 7.611 (4.5); 7.591 (10.7); 7.572 (7.8); 7.547 (7.4); 7.530 (2.8); 7.527 (3.2); 7.289 (0.4); 6.937 (0.5); 6.925 (0.4); 6.914 (0.4); 5.757 (0.7); 3.744 (3.2); 3.327 (467.3); 2.676 (4.1); 2.671 (5.6); 2.667 (4.1); 2.602 (0.5); 2.524 (15.1); 2.507 (606.6); 2.502 (788.2); 2.498 (575.0); 2.333 (3.8); 2.329 (5.2); 2.325 (3.7); 2.170 (0.5); 1.355 (0.5); 1.277 (0.4); 1.259 (0.5); 1.232 (5.8); 1.154 (0.4); 1.136 (0.6); 1.118 (0.4); 0.853 (0.7); 0.836 (0.4); 0.146 (2.7); 0.082 (0.4); 0.073 (6.2); 0.008 (20.0); 0.000 (579.1); −0.009 (21.1); −0.150 (2.8) 8 2.98 3.03 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.366 (4.0); 9.362 (3.8); 9.087 (5.4); 9.082 (6.9); 9.044 (7.1); 9.039 (5.5); 8.830 (3.1); 8.826 (3.3); 8.818 (3.2); 8.814 (3.2); 8.574 (1.8); 8.569 (2.5); 8.564 (1.8); 8.554 (1.9); 8.549 (2.6); 8.544 (1.8); 8.321 (3.9); 7.920 (1.0); 7.915 (1.3); 7.909 (7.7); 7.904 (3.1); 7.892 (3.1); 7.887 (9.1); 7.688 (2.5); 7.676 (2.4); 7.668 (2.4); 7.656 (2.3); 7.635 (8.9); 7.613 (7.6); 7.194 (0.5); 7.175 (0.6); 5.758 (0.3); 3.339 (24.8); 2.677 (0.7); 2.673 (1.0); 2.668 (0.7); 2.543 (0.8); 2.508 (100.8); 2.503 (131.2); 2.499 (99.0); 2.335 (0.6); 2.330 (0.9); 2.326 (0.6); 2.183 (0.4); 1.571 (16.0); 1.355 (3.1); 1.231 (0.4); 0.146 (0.6); 0.008 (5.1); 0.000 (130.0); −0.008 (6.4); −0.150 (0.6) 9 2.96 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.364 (1.9); 9.360 (1.9); 9.094 (2.7); 9.089 (3.3); 9.046 (3.4); 9.040 (2.7); 8.827 (1.5); 8.823 (1.6); 8.815 (1.6); 8.811 (1.5); 8.570 (0.9); 8.565 (1.1); 8.560 (0.9); 8.550 (1.0); 8.545 (1.2); 8.544 (1.2); 8.540 (0.9); 7.696 (1.5); 7.692 (2.6); 7.687 (2.3); 7.674 (1.2); 7.673 (1.2); 7.666 (1.2); 7.665 (1.1); 7.654 (1.1); 7.653 (1.0); 7.626 (1.1); 7.609 (1.2); 7.606 (1.4); 7.505 (1.2); 7.485 (2.3); 7.466 (1.2); 7.364 (1.3); 7.362 (1.3); 7.344 (1.0); 7.342 (1.0); 3.331 (13.1); 2.586 (16.0); 2.573 (0.8); 2.514 (7.5); 2.510 (14.4); 2.506 (18.7); 2.501 (13.5); 2.497 (6.7) 10 3.36 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.369 (4.3); 9.364 (4.5); 9.150 (0.3); 9.087 (5.0); 9.082 (6.4); 9.050 (6.4); 9.044 (5.1); 9.029 (0.4); 8.830 (3.4); 8.826 (3.3); 8.818 (3.6); 8.815 (3.2); 8.575 (1.9); 8.571 (2.7); 8.566 (1.9); 8.555 (2.1); 8.551 (2.8); 8.546 (1.9); 7.871 (0.4); 7.852 (0.5); 7.747 (5.6); 7.690 (2.6); 7.678 (2.7); 7.670 (3.2); 7.668 (3.3); 7.659 (3.8); 7.644 (3.2); 7.566 (0.4); 7.515 (2.3); 7.496 (4.8); 7.476 (2.8); 7.409 (3.3); 7.389 (2.2); 3.331 (74.9); 3.140 (2.4); 3.121 (7.6); 3.103 (7.9); 3.085 (2.7); 2.673 (0.7); 2.508 (86.2); 2.504 (107.9); 2.500 (82.1); 2.335 (0.5); 2.331 (0.7); 2.087 (0.8); 1.312 (7.8); 1.294 (16.0); 1.275 (7.6); 1.259 (1.0); 1.230 (2.9); 1.088 (0.5); 0.867 (0.3); 0.852 (0.6); 0.834 (0.4); 0.147 (0.5); 0.008 (4.7); 0.000 (101.5); −0.149 (0.5) 11 3.34 3.37 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.362 (3.2); 9.357 (3.1); 9.090 (0.4); 9.080 (5.0); 9.075 (5.8); 9.048 (0.4); 9.017 (6.1); 9.011 (5.1); 8.826 (2.5); 8.822 (2.6); 8.814 (2.6); 8.810 (2.5); 8.569 (1.5); 8.565 (2.0); 8.559 (1.5); 8.549 (1.7); 8.544 (2.1); 8.539 (1.5); 8.317 (0.6); 7.911 (0.4); 7.889 (0.4); 7.829 (6.2); 7.812 (2.2); 7.808 (7.2); 7.688 (1.9); 7.686 (1.9); 7.674 (1.9); 7.666 (1.9); 7.656 (1.8); 7.654 (1.8); 7.637 (0.4); 7.616 (0.3); 7.484 (7.1); 7.463 (6.3); 3.327 (229.5); 3.099 (2.3); 3.081 (7.2); 3.063 (7.4); 3.044 (2.4); 2.676 (1.5); 2.671 (2.1); 2.667 (1.5); 2.663 (0.8); 2.525 (5.5); 2.520 (8.3); 2.511 (107.6); 2.507 (217.5); 2.502 (288.2); 2.498 (211.9); 2.493 (104.2); 2.334 (1.3); 2.329 (1.9); 2.325 (1.3); 1.308 (7.7); 1.290 (16.0); 1.272 (7.5); 1.234 (0.6); 0.146 (1.8); 0.008 (13.1); 0.000 (372.2); −0.009 (13.9); −0.150 (1.7) 12 1.58 1.86 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.375 (4.2); 9.370 (4.2); 9.145 (5.6); 9.140 (7.4); 9.107 (7.5); 9.102 (5.8); 8.835 (3.1); 8.831 (3.4); 8.823 (3.3); 8.819 (3.4); 8.583 (1.8); 8.577 (2.5); 8.573 (1.9); 8.563 (2.0); 8.557 (2.7); 8.553 (1.9); 8.084 (7.3); 8.063 (8.9); 7.824 (8.7); 7.803 (7.7); 7.693 (2.4); 7.681 (2.4); 7.673 (2.4); 7.661 (2.3); 5.759 (0.4); 4.039 (0.3); 4.021 (0.3); 3.331 (69.7); 3.154 (0.5); 3.135 (1.8); 3.117 (2.1); 3.101 (2.4); 3.083 (2.2); 3.065 (0.7); 2.887 (0.6); 2.868 (2.2); 2.850 (2.5); 2.834 (2.0); 2.816 (1.8); 2.798 (0.5); 2.677 (0.6); 2.673 (0.8); 2.668 (0.6); 2.545 (0.5); 2.540 (0.6); 2.526 (2.3); 2.508 (95.9); 2.503 (127.4); 2.499 (95.8); 2.335 (0.6); 2.330 (0.8); 2.326 (0.6); 1.230 (0.4); 1.182 (0.7); 1.166 (1.1); 1.151 (0.6); 1.096 (7.4); 1.078 (16.0); 1.059 (7.2); 0.000 (3.6) 13 1.85 1.85 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.385 (4.0); 9.379 (4.3); 9.174 (3.9); 9.168 (7.7); 9.158 (8.0); 9.152 (4.2); 9.142 (0.9); 9.111 (0.8); 9.105 (0.6); 8.853 (0.6); 8.841 (2.9); 8.837 (3.3); 8.829 (3.1); 8.825 (3.3); 8.594 (1.6); 8.589 (2.4); 8.584 (1.9); 8.574 (1.8); 8.568 (2.6); 8.564 (1.9); 8.317 (1.3); 8.167 (5.9); 8.146 (9.0); 8.085 (1.0); 8.060 (9.1); 8.039 (6.1); 7.824 (1.0); 7.804 (0.8); 7.698 (2.4); 7.686 (2.3); 7.678 (2.4); 7.666 (2.3); 5.757 (0.7); 4.037 (0.8); 4.021 (0.8); 3.413 (2.2); 3.395 (6.9); 3.377 (7.2); 3.358 (3.3); 3.329 (568.0); 3.293 (2.4); 2.675 (2.8); 2.671 (3.9); 2.667 (3.0); 2.545 (0.9); 2.540 (1.0); 2.524 (11.0); 2.506 (445.4); 2.502 (589.5); 2.498 (444.2); 2.467 (4.1); 2.430 (1.1); 2.422 (0.5); 2.371 (0.9); 2.333 (2.9); 2.329 (3.9); 2.324 (3.0); 1.232 (1.3); 1.173 (8.4); 1.154 (16.0); 1.136 (7.0); 1.095 (0.9); 1.077 (1.8); 1.059 (0.8); 0.007 (0.5); 0.000 (14.8) 14 3.12 3.13 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.364 (3.7); 9.359 (3.7); 8.834 (2.8); 8.831 (3.0); 8.823 (3.0); 8.819 (2.9); 8.742 (4.8); 8.736 (6.6); 8.713 (6.5); 8.707 (4.7); 8.572 (1.6); 8.568 (2.3); 8.563 (1.6); 8.553 (1.8); 8.548 (2.4); 8.543 (1.6); 8.317 (0.4); 8.070 (6.5); 7.695 (2.2); 7.683 (2.2); 7.675 (2.1); 7.663 (2.0); 7.540 (2.1); 7.522 (3.9); 7.520 (3.9); 7.493 (1.8); 7.488 (1.9); 7.475 (2.3); 7.471 (2.7); 7.455 (1.1); 7.451 (1.4); 7.414 (1.8); 7.410 (2.1); 7.395 (4.0); 7.391 (3.4); 7.365 (3.2); 7.362 (3.2); 7.345 (4.2); 7.328 (2.3); 7.325 (2.4); 7.315 (0.8); 7.311 (0.7); 7.297 (0.9); 7.294 (0.9); 7.278 (0.4); 7.274 (0.4); 7.177 (0.6); 7.174 (0.7); 7.159 (1.0); 7.156 (1.0); 7.141 (0.4); 7.138 (0.4); 4.038 (0.5); 4.020 (0.6); 3.568 (0.4); 3.328 (165.3); 2.936 (2.2); 2.918 (7.2); 2.904 (3.7); 2.900 (7.5); 2.886 (3.1); 2.882 (2.7); 2.868 (0.9); 2.676 (1.1); 2.671 (1.5); 2.667 (1.1); 2.524 (4.1); 2.507 (166.9); 2.502 (217.8); 2.498 (164.7); 2.334 (1.1); 2.329 (1.5); 2.325 (1.1); 1.989 (2.2); 1.242 (0.4); 1.234 (0.3); 1.212 (2.8); 1.194 (6.2); 1.186 (7.9); 1.175 (4.5); 1.167 (16.0); 1.157 (1.3); 1.149 (7.4); 0.000 (0.5) 15 1.58 1.59 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.374 (4.2); 9.370 (4.3); 8.866 (6.3); 8.860 (7.5); 8.843 (3.2); 8.839 (3.5); 8.831 (3.4); 8.827 (3.5); 8.805 (7.3); 8.800 (6.2); 8.585 (1.8); 8.580 (2.5); 8.575 (1.9); 8.565 (2.0); 8.559 (2.7); 8.555 (1.9); 8.318 (0.3); 8.006 (2.9); 8.003 (3.1); 7.987 (3.4); 7.984 (3.5); 7.799 (1.4); 7.795 (1.5); 7.780 (3.2); 7.777 (3.2); 7.761 (2.2); 7.757 (2.2); 7.740 (2.0); 7.736 (2.1); 7.721 (3.3); 7.718 (3.4); 7.701 (3.5); 7.699 (3.7); 7.688 (2.4); 7.681 (2.3); 7.669 (2.2); 7.667 (2.2); 7.571 (3.6); 7.569 (3.6); 7.553 (3.0); 7.550 (2.9); 5.758 (1.5); 3.332 (197.0); 2.783 (0.5); 2.764 (1.8); 2.746 (2.1); 2.731 (2.4); 2.712 (2.2); 2.694 (0.7); 2.677 (0.8); 2.672 (1.0); 2.668 (0.8); 2.542 (0.6); 2.525 (2.5); 2.508 (116.7); 2.503 (153.0); 2.499 (113.2); 2.444 (0.7); 2.426 (2.1); 2.408 (2.4); 2.392 (2.1); 2.374 (1.8); 2.355 (0.6); 2.334 (0.7); 2.330 (1.0); 2.325 (0.8); 0.905 (7.4); 0.887 (16.0); 0.869 (7.1); 0.000 (6.3) 16 1.86 1.87 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.371 (4.2); 9.365 (4.1); 8.840 (3.2); 8.836 (3.3); 8.828 (3.3); 8.824 (3.3); 8.764 (5.8); 8.759 (7.2); 8.719 (7.0); 8.713 (5.7); 8.580 (1.8); 8.575 (2.5); 8.571 (1.9); 8.561 (1.9); 8.555 (2.6); 8.551 (1.8); 8.318 (1.8); 8.132 (3.1); 8.115 (3.4); 8.112 (3.4); 7.889 (1.6); 7.873 (3.3); 7.870 (3.3); 7.854 (2.3); 7.851 (2.2); 7.815 (2.1); 7.812 (2.5); 7.795 (3.0); 7.792 (3.1); 7.776 (1.3); 7.773 (1.3); 7.699 (2.5); 7.686 (2.5); 7.679 (2.5); 7.666 (2.4); 7.627 (0.5); 7.601 (3.6); 7.598 (3.7); 7.583 (3.2); 7.580 (3.1); 5.757 (1.7); 4.040 (0.5); 4.022 (0.5); 3.376 (0.5); 3.327 (653.5); 3.012 (2.1); 2.993 (7.0); 2.975 (7.2); 2.957 (2.2); 2.675 (4.7); 2.671 (6.3); 2.667 (4.8); 2.623 (0.3); 2.524 (17.2); 2.510 (380.2); 2.506 (748.3); 2.502 (973.4); 2.497 (719.5); 2.372 (0.3); 2.333 (4.7); 2.328 (6.4); 2.324 (4.8); 2.299 (0.4); 2.206 (0.3); 1.355 (0.3); 1.234 (1.4); 1.165 (1.7); 1.026 (7.4); 1.008 (16.0); 0.989 (7.2); 0.146 (17.1); 0.096 (0.3); 0.086 (0.7); 0.070 (0.7); 0.058 (1.2); 0.047 (1.5); 0.007 (153.7); 0.000 (3211.2); −0.009 (157.6); −0.068 (0.9); −0.075 (0.9); −0.095 (0.6); −0.121 (0.4); −0.150 (16.9) 17 3.74 3.68 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.366 (3.2); 9.361 (3.2); 9.360 (3.1); 9.125 (4.6); 9.120 (5.3); 9.042 (5.4); 9.036 (4.8); 8.827 (2.5); 8.823 (2.8); 8.815 (2.7); 8.811 (2.8); 8.570 (1.4); 8.566 (1.9); 8.561 (1.5); 8.550 (1.6); 8.545 (2.1); 8.541 (1.5); 7.975 (3.8); 7.971 (4.0); 7.693 (2.0); 7.687 (3.0); 7.673 (4.1); 7.668 (3.2); 7.654 (1.8); 7.653 (1.8); 7.443 (3.2); 7.423 (2.8); 4.223 (1.3); 4.197 (4.1); 4.171 (4.3); 4.145 (1.5); 3.333 (12.5); 2.528 (0.7); 2.515 (13.7); 2.510 (27.0); 2.506 (35.7); 2.502 (27.0); 2.428 (16.0); 0.008 (1.8); 0.000 (45.7); −0.008 (2.1) 18 2.4 2.34 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.378 (2.7); 9.373 (2.8); 9.196 (0.3); 9.191 (0.4); 9.168 (3.5); 9.162 (4.8); 9.153 (0.5); 9.133 (4.7); 9.127 (3.6); 8.921 (0.3); 8.834 (2.1); 8.830 (2.3); 8.822 (2.2); 8.818 (2.3); 8.753 (0.3); 8.749 (0.4); 8.584 (1.2); 8.579 (1.7); 8.574 (1.3); 8.564 (1.3); 8.558 (1.8); 8.554 (1.4); 8.317 (0.6); 8.295 (3.7); 8.290 (3.9); 8.150 (1.8); 8.024 (1.8); 8.020 (1.8); 8.004 (2.0); 8.000 (2.0); 7.693 (1.7); 7.681 (1.7); 7.674 (1.8); 7.660 (1.7); 7.562 (2.8); 7.542 (2.5); 4.256 (1.0); 4.229 (3.2); 4.202 (3.3); 4.174 (1.1); 3.328 (135.7); 2.738 (0.4); 2.676 (1.4); 2.671 (2.0); 2.667 (1.5); 2.525 (5.7); 2.507 (215.8); 2.502 (284.3); 2.498 (216.6); 2.470 (16.0); 2.429 (0.3); 2.417 (0.9); 2.333 (1.4); 2.329 (1.9); 2.325 (1.5); 2.275 (0.8); 1.754 (2.0); 1.351 (0.7); 1.230 (1.0); 0.146 (1.1); 0.008 (9.5); 0.000 (247.0); −0.008 (11.8); −0.150 (1.2) 19 3.97 3.95 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.370 (2.7); 9.366 (2.7); 9.365 (2.7); 8.834 (2.3); 8.830 (2.5); 8.822 (2.4); 8.818 (2.5); 8.759 (2.5); 8.753 (8.0); 8.749 (7.8); 8.744 (2.3); 8.578 (1.3); 8.574 (1.7); 8.568 (1.3); 8.558 (1.4); 8.553 (1.8); 8.548 (1.3); 8.318 (0.3); 7.694 (1.6); 7.693 (1.6); 7.682 (1.6); 7.681 (1.6); 7.674 (1.6); 7.673 (1.6); 7.662 (1.5); 7.661 (1.5); 7.536 (5.9); 7.297 (4.6); 4.035 (1.2); 4.009 (3.8); 3.982 (4.0); 3.956 (1.4); 3.328 (100.9); 2.676 (0.7); 2.672 (0.9); 2.667 (0.7); 2.525 (2.7); 2.520 (3.9); 2.512 (49.4); 2.507 (100.6); 2.503 (133.6); 2.498 (97.4); 2.494 (47.0); 2.418 (14.4); 2.334 (0.6); 2.329 (0.9); 2.325 (0.6); 2.275 (16.0); 1.233 (0.4); 0.146 (0.8); 0.019 (0.4); 0.008 (6.1); 0.000 (176.8); −0.009 (6.0); −0.150 (0.8) 20 2.54 2.52 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.379 (3.2); 9.374 (3.0); 8.830 (7.8); 8.825 (9.1); 8.586 (1.4); 8.581 (1.9); 8.577 (1.3); 8.566 (1.5); 8.561 (2.0); 8.557 (1.3); 8.317 (0.5); 8.145 (0.6); 7.820 (6.5); 7.697 (1.8); 7.685 (1.8); 7.676 (1.8); 7.664 (1.7); 7.400 (4.8); 5.758 (2.3); 4.197 (1.1); 4.170 (3.3); 4.142 (3.5); 4.115 (1.2); 3.366 (0.8); 3.329 (136.7); 2.891 (0.7); 2.731 (0.6); 2.695 (0.4); 2.676 (1.3); 2.671 (1.7); 2.667 (1.3); 2.539 (1.9); 2.507 (193.1); 2.502 (244.6); 2.498 (184.8); 2.431 (15.1); 2.398 (0.8); 2.378 (16.0); 2.334 (1.3); 2.329 (1.7); 2.325 (1.3); 1.234 (1.0); 1.165 (1.0); 1.150 (0.6); 0.000 (6.2) 21 1.91 1.86 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 8.927 (4.0); 8.861 (2.0); 8.854 (9.9); 8.848 (2.3); 8.841 (0.8); 8.830 (0.4); 8.814 (0.3); 8.690 (0.3); 8.466 (2.0); 8.448 (2.1); 8.317 (1.3); 8.148 (0.5); 8.104 (2.1); 8.084 (2.3); 7.846 (0.5); 7.818 (7.0); 7.680 (2.2); 7.663 (2.3); 7.660 (2.3); 7.643 (1.9); 7.555 (0.4); 7.401 (4.8); 7.383 (0.3); 5.757 (2.2); 4.194 (1.1); 4.167 (3.4); 4.140 (3.6); 4.113 (1.2); 4.037 (0.4); 4.020 (0.4); 3.428 (0.3); 3.416 (0.4); 3.402 (0.5); 3.368 (1.5); 3.330 (615.1); 3.294 (2.0); 2.891 (1.5); 2.731 (1.3); 2.695 (1.2); 2.676 (2.8); 2.671 (3.9); 2.667 (3.0); 2.545 (2.0); 2.540 (2.2); 2.524 (10.1); 2.507 (425.8); 2.502 (566.6); 2.498 (425.9); 2.430 (14.9); 2.392 (2.1); 2.372 (16.0); 2.333 (2.6); 2.329 (3.6); 2.324 (2.8); 1.234 (2.2); 1.165 (1.4); 1.149 (0.8); 0.853 (0.4); 0.008 (0.5); 0.000 (15.0); −0.008 (0.7) 22 3.83 3.78 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.375 (3.0); 9.370 (3.0); 8.953 (9.2); 8.950 (9.1); 8.836 (2.4); 8.833 (2.6); 8.824 (2.6); 8.821 (2.7); 8.583 (1.3); 8.578 (1.8); 8.573 (1.4); 8.563 (1.5); 8.558 (2.0); 8.553 (1.4); 7.902 (3.1); 7.882 (3.1); 7.693 (1.8); 7.681 (1.8); 7.673 (1.8); 7.663 (1.7); 7.661 (1.8); 7.422 (2.7); 7.393 (2.7); 5.758 (0.6); 4.114 (1.3); 4.088 (4.0); 4.062 (4.2); 4.036 (1.5); 3.328 (42.3); 2.677 (0.5); 2.673 (0.6); 2.668 (0.5); 2.526 (1.6); 2.521 (2.5); 2.512 (35.8); 2.508 (72.9); 2.503 (97.3); 2.499 (72.8); 2.495 (36.8); 2.468 (16.0); 2.403 (0.5); 2.335 (0.5); 2.330 (0.7); 2.326 (0.5); 2.076 (1.5); 0.146 (0.5); 0.008 (3.9); 0.000 (116.1); −0.009 (4.6); −0.150 (0.5) 23 2.5 2.46 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.383 (12.6); 9.378 (12.3); 9.036 (15.7); 9.033 (14.8); 9.022 (12.3); 9.018 (16.0); 9.013 (7.6); 8.841 (9.7); 8.837 (10.6); 8.829 (10.1); 8.825 (10.6); 8.590 (5.6); 8.586 (7.4); 8.581 (5.7); 8.570 (6.1); 8.565 (8.1); 8.560 (5.8); 8.317 (1.4); 8.159 (13.2); 8.139 (13.3); 7.697 (7.3); 7.685 (7.1); 7.679 (6.9); 7.677 (7.0); 7.667 (6.7); 7.665 (6.9); 7.644 (0.6); 7.627 (0.8); 7.624 (0.8); 7.615 (0.7); 7.597 (0.8); 7.575 (0.6); 7.567 (0.7); 7.538 (10.5); 7.509 (10.2); 5.758 (3.5); 4.329 (0.4); 4.302 (1.4); 4.293 (2.2); 4.276 (2.8); 4.266 (7.1); 4.253 (6.9); 4.239 (7.4); 4.225 (7.4); 4.212 (2.8); 4.198 (2.7); 4.189 (1.6); 4.161 (0.5); 4.056 (1.0); 4.038 (2.9); 4.020 (3.0); 4.002 (1.0); 3.827 (0.4); 3.812 (0.5); 3.640 (0.6); 3.407 (0.3); 3.392 (0.7); 3.334 (1093.5); 3.268 (0.5); 3.175 (0.4); 3.162 (0.4); 2.677 (2.9); 2.672 (4.1); 2.668 (2.9); 2.645 (0.3); 2.525 (11.2); 2.512 (231.5); 2.508 (469.6); 2.503 (621.0); 2.499 (458.4); 2.494 (229.3); 2.485 (73.3); 2.434 (0.9); 2.410 (0.6); 2.388 (0.5); 2.372 (0.6); 2.334 (3.1); 2.330 (4.2); 2.325 (3.3); 1.990 (12.4); 1.909 (1.8); 1.298 (1.4); 1.259 (2.1); 1.233 (5.3); 1.193 (3.5); 1.175 (6.8); 1.157 (3.4); 0.853 (0.8); 0.836 (0.4); 0.146 (0.7); 0.008 (6.1); 0.000 (167.9); −0.008 (6.2); −0.150 (0.8) 24 2.25 2.27 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.251 (8.5); 9.247 (8.3); 9.245 (8.3); 8.790 (13.0); 8.758 (6.7); 8.754 (7.6); 8.746 (7.2); 8.742 (7.6); 8.465 (13.4); 8.458 (14.8); 8.445 (4.0); 8.441 (5.3); 8.439 (5.2); 8.435 (4.1); 8.425 (4.3); 8.419 (5.7); 8.415 (4.2); 8.326 (14.2); 8.319 (13.4); 7.637 (4.9); 7.635 (5.3); 7.623 (5.2); 7.617 (4.8); 7.615 (5.1); 7.605 (4.7); 7.603 (5.0); 7.350 (6.7); 7.329 (13.8); 7.310 (11.1); 7.231 (16.0); 7.212 (10.7); 6.980 (4.4); 6.962 (7.8); 6.943 (3.7); 3.326 (508.1); 2.731 (0.3); 2.676 (4.4); 2.671 (6.2); 2.667 (4.7); 2.524 (15.3); 2.520 (23.1); 2.511 (313.8); 2.507 (651.6); 2.502 (883.9); 2.498 (671.9); 2.494 (345.0); 2.447 (0.7); 2.431 (0.5); 2.338 (2.0); 2.333 (4.3); 2.329 (6.0); 2.324 (4.5); 1.055 (0.4); 0.146 (3.4); 0.032 (0.4); 0.008 (25.2); 0.000 (779.5); −0.009 (30.2); −0.150 (3.4) 25 2.66 2.69 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.269 (6.7); 9.264 (6.8); 8.962 (11.3); 8.772 (5.4); 8.768 (5.9); 8.760 (5.8); 8.756 (5.9); 8.483 (9.8); 8.476 (13.1); 8.465 (3.5); 8.461 (4.5); 8.456 (3.4); 8.445 (3.7); 8.440 (5.6); 8.436 (16.0); 8.429 (10.0); 8.317 (1.2); 7.647 (4.3); 7.646 (4.3); 7.635 (4.1); 7.627 (4.1); 7.626 (4.1); 7.615 (4.0); 7.614 (3.9); 7.356 (0.3); 7.339 (4.5); 7.319 (9.7); 7.299 (6.0); 7.189 (4.3); 7.184 (10.1); 7.179 (7.2); 7.170 (5.9); 7.150 (4.0); 7.146 (3.3); 6.967 (4.5); 6.964 (4.4); 6.947 (3.9); 6.944 (4.1); 5.757 (0.5); 3.326 (236.5); 2.891 (1.4); 2.732 (1.2); 2.680 (1.3); 2.676 (2.6); 2.671 (3.6); 2.667 (2.7); 2.662 (1.3); 2.525 (8.9); 2.520 (13.4); 2.511 (186.4); 2.507 (384.3); 2.502 (519.2); 2.498 (389.2); 2.493 (195.6); 2.338 (1.2); 2.333 (2.5); 2.329 (3.5); 2.325 (2.6); 2.086 (4.0); 2.075 (1.1); 0.146 (2.0); 0.008 (14.5); 0.000 (450.0); −0.009 (17.3); −0.150 (2.0) 26 1.62 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 11.160 (0.7); 10.721 (0.7); 9.345 (14.2); 9.294 (15.7); 9.162 (14.9); 8.822 (10.6); 8.814 (10.8); 8.761 (0.5); 8.697 (15.8); 8.551 (8.4); 8.531 (8.8); 8.475 (0.5); 8.429 (0.4); 7.894 (16.0); 7.799 (0.4); 7.684 (7.1); 7.667 (8.7); 7.654 (6.8); 7.235 (0.5); 7.220 (0.4); 7.216 (0.4); 6.673 (14.6); 5.935 (0.7); 4.134 (0.5); 3.391 (0.6); 3.326 (63.2); 2.671 (2.1); 2.503 (265.8); 2.329 (2.3); 2.283 (0.7); 2.265 (0.6); 2.244 (0.5); 2.234 (0.5); 2.209 (0.4); 2.205 (0.4); 2.178 (0.4); 2.160 (0.4); 2.155 (0.4); 2.141 (0.4); 2.087 (4.1); 2.058 (0.6); 2.044 (0.4); 1.983 (0.7); 1.926 (0.4); 1.907 (0.5); 1.886 (0.4); 1.870 (0.4); 1.852 (0.4); 1.821 (0.4); 1.743 (1.2); 1.678 (0.5); 1.671 (0.5); 1.625 (1.4); 1.532 (0.7); 1.511 (0.7); 1.463 (0.6); 1.453 (0.6); 1.433 (0.6); 1.416 (0.6); 1.367 (0.9); 1.349 (1.1); 1.297 (3.4); 1.257 (4.8); 1.230 (8.0); 1.171 (2.8); 1.146 (4.1); 1.136 (4.0); 1.088 (1.2); 1.065 (1.0); 1.042 (0.9); 1.036 (0.9); 0.981 (0.6); 0.943 (0.6); 0.928 (0.7); 0.863 (3.1); 0.755 (0.5); 0.724 (0.4); 0.701 (0.4); 0.145 (0.9); 0.123 (0.4); 0.105 (0.5); 0.095 (0.6); −0.001 (131.7); −0.150 (1.2); −0.190 (0.4); −0.201 (0.4) 27 2.57 .sup.1H-NMR (601.6 MHz, CD3CN): δ = 9.373 (4.7); 9.355 (0.8); 9.156 (8.3); 9.151 (8.5); 8.877 (8.9); 8.873 (8.7); 8.789 (3.3); 8.782 (3.4); 8.734 (0.6); 8.729 (0.6); 8.511 (2.6); 8.508 (3.8); 8.505 (2.6); 8.498 (3.3); 8.495 (3.9); 8.492 (3.0); 8.488 (1.3); 8.485 (1.1); 8.476 (0.6); 8.385 (5.8); 8.383 (5.8); 7.585 (3.2); 7.577 (3.3); 7.572 (3.3); 7.564 (3.3); 7.545 (0.5); 7.466 (0.6); 7.452 (1.5); 7.446 (0.9); 7.441 (0.7); 7.433 (0.7); 7.238 (0.5); 7.234 (0.4); 7.224 (0.4); 7.220 (0.4); 6.953 (6.6); 6.949 (6.5); 5.448 (0.7); 2.828 (1.2); 2.748 (0.6); 2.575 (2.2); 2.563 (2.3); 2.501 (0.5); 2.172 (9.1); 2.107 (5.6); 2.087 (3.1); 2.076 (2.7); 2.059 (3.2); 2.055 (4.1); 2.051 (5.1); 2.047 (3.9); 2.043 (2.7); 1.965 (67.2); 1.957 (37.4); 1.952 (51.3); 1.949 (253.4); 1.945 (433.6); 1.940 (624.6); 1.936 (441.3); 1.932 (228.3); 1.916 (4.5); 1.883 (1.7); 1.850 (1.1); 1.842 (1.1); 1.834 (2.0); 1.830 (3.1); 1.826 (4.2); 1.822 (3.0); 1.818 (1.8); 1.567 (0.5); 1.434 (0.5); 1.340 (13.1); 1.319 (2.0); 1.308 (2.5); 1.298 (2.3); 1.285 (16.0); 1.269 (9.4); 1.248 (1.2); 1.227 (1.0); 1.217 (1.0); 1.206 (1.0); 1.184 (1.3); 1.173 (1.2); 1.153 (0.8); 1.134 (0.8); 1.112 (0.7); 1.083 (0.8); 1.071 (0.7); 1.048 (0.6); 1.038 (0.6); 1.022 (4.4); 1.010 (8.3); 0.999 (4.3); 0.914 (0.7); 0.893 (1.2); 0.882 (2.1); 0.870 (1.5); 0.844 (1.3); 0.000 (2.8) 28 2.48 2.53 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.366 (16.0); 9.362 (16.0); 9.356 (13.8); 9.312 (12.2); 9.306 (15.8); 9.302 (7.3); 9.288 (2.1); 9.238 (13.8); 9.232 (14.5); 9.214 (1.9); 8.836 (6.5); 8.832 (8.2); 8.824 (8.0); 8.820 (8.7); 8.569 (4.3); 8.564 (6.1); 8.560 (6.2); 8.550 (5.7); 8.544 (7.2); 8.540 (6.6); 8.370 (14.4); 8.352 (2.5); 8.238 (1.2); 8.166 (1.1); 7.690 (4.8); 7.678 (5.4); 7.673 (6.7); 7.660 (5.3); 7.659 (5.1); 7.642 (1.0); 3.320 (121.7); 3.303 (20.7); 2.676 (1.3); 2.671 (1.7); 2.667 (1.6); 2.507 (200.6); 2.502 (274.7); 2.498 (253.0); 2.494 (174.9); 2.329 (1.6); 2.325 (1.5); 2.075 (1.5); 2.071 (0.7); −0.001 (54.0); −0.005 (24.7); −0.019 (6.3) 29 1.00 1.07 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.331 (1.1); 8.822 (1.1); 8.762 (4.6); 8.727 (6.8); 8.533 (1.6); 8.513 (1.6); 7.678 (1.1); 7.665 (1.2); 7.658 (1.2); 7.646 (1.1); 3.683 (16.0); 3.330 (24.3); 2.678 (0.4); 2.509 (58.9); 2.337 (0.4); 2.081 (0.8) 30 1.23 1.42 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.336 (0.6); 9.317 (2.7); 9.310 (3.0); 9.307 (3.9); 9.300 (3.8); 9.119 (3.3); 9.113 (3.3); 8.808 (2.1); 8.800 (2.2); 8.796 (2.0); 8.712 (0.4); 8.543 (0.4); 8.522 (1.4); 8.518 (1.8); 8.512 (1.4); 8.502 (1.4); 8.497 (1.6); 8.493 (1.2); 7.673 (1.3); 7.661 (1.6); 7.655 (1.5); 7.643 (1.3); 3.556 (0.4); 3.322 (46.2); 3.255 (17.4); 3.177 (1.4); 3.141 (0.4); 3.127 (0.6); 3.122 (0.5); 3.076 (0.3); 3.060 (2.0); 2.755 (0.3); 2.736 (0.4); 2.728 (0.5); 2.670 (2.4); 2.666 (2.1); 2.505 (269.8); 2.501 (349.1); 2.497 (274.9); 2.356 (0.9); 2.338 (16.0); 2.250 (1.0); 2.227 (0.7); 2.119 (1.8); 1.234 (0.5); 0.883 (0.4); 0.000 (50.2) 31 0.97 1.21 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.318 (0.6); 8.816 (0.4); 8.806 (0.4); 8.701 (0.7); 8.695 (1.0); 8.668 (0.9); 8.662 (0.8); 8.524 (0.4); 8.504 (0.4); 7.669 (0.4); 7.657 (0.4); 7.649 (0.4); 3.557 (4.4); 3.387 (0.7); 3.319 (4.7); 2.506 (37.0); 2.501 (51.1); 2.497 (42.5); 2.406 (4.4); 2.328 (0.3); 2.291 (0.5); 1.158 (2.3); 1.069 (16.0); 0.000 (7.1); −0.002 (4.9) 32 1.15 1.25 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.347 (1.8); 9.341 (1.9); 8.830 (1.2); .826 (1.4); 8.815 (4.1); 8.809 (3.9); 8.757 (3.5); 8.750 (2.9); 8.559 (0.8); 8.554 (1.1); 8.549 (0.9); 8.539 (0.9); 8.533 (1.2); 8.529 (0.9); 7.690 (1.0); 7.678 (1.0); 7.671 (1.0); 7.658 (1.0); 5.747 (0.8); 3.882 (0.5); 3.601 (0.5); 3.415 (879.7); 3.409 (917.4); 3.297 (0.8); 3.274 (0.7); 3.238 (0.4); 3.221 (0.3); 3.213 (0.4); 3.123 (16.0); 3.099 (0.4); 3.038 (15.3); 3.018 (0.3); 3.007 (0.4); 2.977 (0.3); 2.969 (0.5); 2.683 (0.8); 2.679 (1.0); 2.674 (0.7); 2.532 (2.0); 2.527 (3.1); 2.519 (55.9); 2.514 (120.3); 2.510 (163.2); 2.505 (117.1); 2.501 (55.4); 2.345 (0.4); 2.341 (0.7); 2.336 (1.0); 2.332 (0.7) 33 2.21 2.21 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.318 (2.6); 9.313 (2.6); 9.253 (3.4); 9.247 (3.7); 9.067 (3.8); 9.061 (3.5); 8.811 (1.7); 8.807 (1.9); 8.799 (1.8); 8.795 (1.9); 8.520 (1.0); 8.515 (1.4); 8.511 (1.0); 8.501 (1.0); 8.495 (1.5); 8.491 (1.0); 7.672 (1.4); 7.660 (1.3); 7.652 (1.3); 7.640 (1.3); 5.240 (1.2); 5.218 (3.7); 5.197 (3.9); 5.175 (1.3); 3.316 (54.1); 3.189 (16.0); 2.891 (0.8); 2.732 (0.7); 2.675 (0.4); 2.671 (0.6); 2.667 (0.5); 2.506 (74.0); 2.502 (103.4); 2.497 (79.9); 2.333 (0.5); 2.328 (0.6); 2.324 (0.5); 0.146 (0.3); 0.008 (3.0); 0.000 (70.0); −0.008 (3.0); −0.150 (0.3) 34 1.84 1.87 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.317 (1.4); 9.313 (1.4); 9.306 (3.1); 9.300 (3.1); 9.110 (3.2); 9.103 (3.0); 8.807 (1.0); 8.798 (1.0); 8.521 (0.8); 8.516 (1.0); 8.511 (0.8); 8.501 (0.8); 8.495 (1.1); 8.491 (0.8); 7.670 (0.9); 7.658 (1.0); 7.650 (0.9); 7.638 (0.9); 3.319 (6.7); 3.264 (0.5); 3.225 (13.6); 3.000 (0.4); 2.689 (16.0); 2.676 (0.4); 2.671 (0.5); 2.667 (0.3); 2.525 (1.0); 2.511 (22.4); 2.507 (47.2); 2.502 (66.0); 2.498 (49.3); 2.493 (23.7); 2.455 (0.5); 2.329 (0.4); 0.008 (1.0); 0.000 (31.8); −0.008 (1.1) 35 2.17 2.25 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.322 (2.0); 9.318 (1.9); 9.301 (3.2); 9.294 (3.3); 9.113 (3.3); 9.106 (3.1); 8.822 (0.4); 8.810 (1.4); 8.801 (1.4); 8.798 (1.3); 8.526 (0.9); 8.522 (1.3); 8.517 (0.9); 8.506 (1.0); 8.501 (1.3); 8.497 (0.9); 7.674 (1.2); 7.662 (1.2); 7.654 (1.2); 7.642 (1.1); 5.756 (3.9); 3.318 (65.6); 3.275 (1.4); 3.257 (4.1); 3.239 (4.4); 3.225 (16.0); 2.675 (0.5); 2.671 (0.6); 2.666 (0.5); 2.510 (41.1); 2.506 (81.7); 2.502 (107.0); 2.497 (77.1); 2.493 (37.4); 2.333 (0.5); 2.329 (0.6); 2.324 (0.5); 1.445 (4.6); 1.426 (9.6); 1.408 (4.5); 0.008 (2.9); 0.000 (67.0); −0.008 (2.7) 36 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.328 (4.1); 9.324 (3.8); 9.322 (4.0); 9.305 (6.7); 9.299 (7.1); 9.146 (7.1); 9.140 (6.6); 8.817 (3.0); 8.813 (3.3); 8.805 (3.2); 8.801 (3.3); 8.533 (1.7); 8.528 (2.2); 8.523 (1.7); 8.513 (1.9); 8.508 (2.4); 8.503 (1.7); 8.314 (0.3); 7.676 (2.2); 7.664 (2.1); 7.657 (1.9); 7.656 (2.1); 7.645 (1.9); 7.644 (2.1); 4.309 (1.5); 4.283 (4.7); 4.258 (4.9); 4.232 (1.7); 3.923 (2.2); 3.318 (93.5); 3.297 (28.7); 2.676 (0.6); 2.671 (0.8); 2.667 (0.6); 2.525 (2.0); 2.520 (3.0); 2.511 (45.6); 2.507 (96.4); 2.502 (135.1); 2.498 (100.4); 2.493 (47.8); 2.334 (0.6); 2.329 (0.8); 2.325 (0.6); 1.481 (0.4); 1.159 (0.4); 1.069 (16.0); 0.783 (0.4); 0.008 (0.8); 0.000 (27.0); −0.009 (0.8) 37 1.69 1.79 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.325 (0.9); 9.296 (3.0); 9.290 (3.1); 9.113 (3.7); 9.107 (3.5); 8.815 (0.8); 8.523 (1.3); 8.502 (1.3); 7.677 (0.9); 7.664 (1.0); 7.657 (1.0); 7.645 (0.9); 3.840 (8.3); 3.328 (15.5); 3.318 (69.4); 2.671 (0.6); 2.506 (74.1); 2.502 (100.0); 2.497 (77.7); 2.333 (0.5); 2.329 (0.6); 2.135 (16.0); 2.075 (0.7); 0.000 (29.6) 38 1.1 1.15 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.346 (2.1); 9.342 (2.2); 8.828 (1.5); 8.824 (1.8); 8.815 (2.0); 8.812 (4.5); 8.806 (4.1); 8.765 (4.1); 8.759 (3.2); 8.556 (0.9); 8.551 (1.1); 8.547 (1.0); 8.536 (1.1); 8.531 (1.3); 8.527 (1.0); 7.683 (1.1); 7.671 (1.2); 7.663 (1.1); 7.652 (1.1); 7.651 (1.1); 5.757 (1.5); 3.320 (12.5); 3.122 (16.0); 3.035 (15.1); 2.672 (0.3); 2.525 (1.0); 2.511 (18.4); 2.507 (38.7); 2.502 (54.2); 2.498 (40.4); 2.494 (19.4); 1.234 (0.6); 0.008 (0.9); 0.000 (24.3); −0.008 (0.9) 39 1.29 1.36 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.356 (8.6); 8.902 (8.8); 8.897 (11.6); 8.877 (11.6); 8.871 (8.2); 8.834 (6.1); 8.823 (6.3); 8.763 (1.1); 8.755 (1.0); 8.731 (0.9); 8.711 (0.9); 8.561 (5.1); 8.542 (5.7); 8.313 (0.5); 8.177 (0.4); 7.953 (1.0); 7.879 (16.0); 7.692 (4.3); 7.681 (5.2); 7.673 (4.7); 7.661 (4.5); 7.647 (0.9); 7.550 (0.8); 7.539 (0.7); 7.529 (0.7); 7.517 (0.6); 5.308 (0.4); 3.432 (0.6); 3.320 (260.1); 3.256 (48.0); 3.190 (0.5); 3.153 (0.4); 3.076 (0.3); 2.995 (3.2); 2.891 (4.8); 2.732 (4.6); 2.711 (1.2); 2.671 (2.4); 2.645 (0.4); 2.630 (0.5); 2.541 (215.4); 2.502 (389.5); 2.368 (2.0); 2.329 (3.0); 2.295 (0.8); 2.277 (0.7); 2.243 (0.6); 2.220 (0.7); 2.200 (0.6); 2.189 (1.2); 2.173 (0.6); 2.131 (0.6); 2.117 (0.9); 2.105 (0.7); 2.086 (0.6); 2.073 (0.6); 2.036 (0.6); 2.005 (0.5); 1.997 (0.5); 1.990 (0.5); 1.980 (0.5); 1.942 (0.5); 1.909 (5.1); 1.840 (0.9); 1.816 (0.4); 1.809 (0.4); 1.762 (0.4); 1.754 (0.4); 1.722 (0.3); 1.704 (0.4); 1.673 (0.3); 1.621 (0.3); 1.610 (0.4); 1.605 (0.4); 1.603 (0.4); 1.585 (0.4); 1.574 (0.4); 1.536 (0.5); 1.514 (0.6); 1.507 (0.6); 1.500 (0.6); 1.490 (0.6); 1.466 (0.7); 1.458 (0.6); 1.386 (1.4); 1.380 (1.4); 1.347 (1.8); 1.335 (1.8); 1.298 (1.7); 1.259 (1.7); 1.234 (2.6); 1.201 (1.3); 1.141 (1.4); 1.085 (0.5); 1.070 (0.6); 1.054 (0.5); 1.045 (0.5); 1.035 (0.5); 0.988 (0.5); 0.968 (0.4); 0.922 (0.3); 0.892 (0.4); 0.864 (0.6); 0.852 (0.9); 0.830 (1.3); 0.756 (0.5); 0.726 (0.3); 0.000 (43.1) 40 0.83 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.369 (2.9); 9.323 (0.4); 9.317 (0.4); 9.230 (0.4); 9.225 (0.4); 9.152 (5.1); 9.147 (6.5); 9.110 (5.6); 9.104 (4.8); 8.847 (3.7); 8.837 (3.5); 8.571 (1.7); 8.567 (2.4); 8.562 (1.8); 8.551 (1.8); 8.546 (2.4); 8.542 (1.6); 7.696 (2.1); 7.684 (2.1); 7.677 (2.0); 7.664 (1.9); 3.955 (1.5); 3.903 (16.0); 3.511 (0.4); 3.339 (354.7); 3.337 (355.7); 3.175 (1.4); 3.162 (1.4); 2.866 (13.6); 2.854 (13.6); 2.678 (1.1); 2.673 (1.5); 2.669 (1.1); 2.526 (3.9); 2.513 (87.9); 2.508 (186.6); 2.504 (262.5); 2.499 (195.4); 2.495 (93.0); 2.340 (0.5); 2.335 (1.1); 2.331 (1.4); 2.326 (1.1); 1.234 (0.4); 0.008 (0.4); 0.000 (11.9); −0.008 (0.4) 41 1.19 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.244 (6.1); 9.157 (6.1); 9.151 (8.2); 9.116 (7.1); 9.110 (6.5); 8.873 (5.3); 8.866 (5.6); 8.806 (2.3); 8.795 (2.3); 8.519 (1.8); 8.513 (2.7); 8.508 (2.0); 8.496 (1.8); 8.490 (2.7); 8.485 (1.9); 3.992 (0.4); 3.902 (10.4); 3.509 (0.5); 3.345 (426.7); 3.170 (1.1); 2.869 (15.8); 2.857 (16.0); 2.802 (0.3); 2.677 (1.0); 2.672 (1.4); 2.668 (1.1); 2.512 (81.1); 2.508 (169.0); 2.503 (238.2); 2.499 (183.7); 2.335 (0.9); 2.330 (1.3); 2.326 (1.0); 1.351 (0.4); 1.258 (0.4); 1.232 (1.4); 0.000 (7.1) 42 1.29 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.245 (7.9); 8.870 (6.8); 8.863 (7.3); 8.850 (9.3); 8.845 (12.2); 8.810 (12.7); 8.805 (10.3); 8.521 (2.6); 8.514 (3.5); 8.509 (2.7); 8.497 (2.7); 8.493 (3.3); 8.491 (3.5); 8.486 (2.7); 8.309 (0.3); 3.902 (16.0); 3.509 (0.8); 3.360 (944.6); 3.176 (0.7); 3.165 (0.6); 3.062 (12.0); 3.013 (12.6); 2.868 (0.9); 2.679 (1.2); 2.674 (1.7); 2.670 (1.3); 2.528 (4.3); 2.514 (95.1); 2.510 (201.4); 2.505 (282.5); 2.501 (211.4); 2.496 (101.5); 2.337 (1.1); 2.332 (1.6); 2.327 (1.1); 1.275 (0.4); 1.259 (0.8); 1.245 (0.7); 1.234 (0.4); 0.000 (7.8) 43 0.96 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.363 (3.6); 9.267 (0.7); 9.262 (0.9); 9.212 (0.8); 9.207 (0.8); 8.841 (2.6); 8.830 (2.6); 8.823 (7.2); 8.818 (9.1); 8.790 (9.2); 8.784 (7.3); 8.576 (1.9); 8.571 (3.1); 8.566 (2.4); 8.556 (2.2); 8.551 (3.2); 8.546 (2.2); 7.699 (2.4); 7.687 (2.6); 7.679 (2.5); 7.667 (2.3); 3.902 (16.0); 3.509 (0.7); 3.364 (596.5); 3.171 (1.6); 3.060 (9.1); 3.014 (9.4); 2.678 (1.0); 2.674 (1.3); 2.669 (1.0); 2.513 (72.9); 2.509 (152.8); 2.505 (214.9); 2.500 (163.4); 2.496 (80.5); 2.336 (0.8); 2.331 (1.2); 2.327 (0.9); 1.233 (0.8); 0.000 (5.6) 44 1.23 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.361 (5.8); 8.840 (4.3); 8.829 (4.9); 8.791 (2.9); 8.746 (2.1); 8.571 (3.4); 8.566 (4.8); 8.561 (3.4); 8.551 (3.7); 8.546 (5.0); 8.541 (3.5); 8.313 (0.4); 7.696 (4.0); 7.684 (4.1); 7.676 (4.0); 7.664 (3.7); 3.902 (16.0); 3.539 (1.9); 3.523 (2.0); 3.509 (1.8); 3.346 (693.4); 3.170 (1.1); 3.020 (6.3); 2.989 (6.0); 2.677 (1.8); 2.673 (2.4); 2.668 (1.8); 2.579 (0.4); 2.526 (6.4); 2.512 (144.2); 2.508 (304.1); 2.503 (426.5); 2.499 (317.6); 2.495 (151.3); 2.339 (0.9); 2.335 (1.7); 2.330 (2.4); 2.326 (1.7); 1.352 (0.4); 1.259 (0.5); 1.233 (1.7); 1.188 (3.4); 1.122 (3.5); 0.853 (0.4); 0.000 (7.2) 45 1.55 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.242 (6.8); 8.869 (6.0); 8.862 (6.5); 8.843 (1.6); 8.817 (1.8); 8.798 (1.6); 8.766 (1.5); 8.518 (2.1); 8.512 (3.0); 8.507 (2.2); 8.495 (2.2); 8.488 (3.0); 8.483 (2.2); 3.902 (16.0); 3.525 (1.8); 3.510 (1.6); 3.365 (833.6); 3.171 (2.1); 3.023 (4.5); 2.986 (4.4); 2.804 (0.4); 2.679 (1.2); 2.674 (1.6); 2.670 (1.2); 2.544 (1.0); 2.527 (4.2); 2.514 (90.1); 2.510 (189.9); 2.505 (266.6); 2.501 (199.8); 2.496 (95.7); 2.336 (1.1); 2.332 (1.5); 2.327 (1.1); 1.351 (0.3); 1.233 (1.3); 1.189 (2.4); 1.119 (2.5); 0.000 (6.6) 46 1.54 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.478 (2.0); 9.463 (4.1); 9.447 (2.0); 9.374 (4.9); 9.189 (6.7); 9.184 (12.4); 9.172 (11.8); 9.167 (6.7); 8.847 (3.4); 8.837 (3.3); 8.583 (2.7); 8.578 (3.7); 8.573 (2.7); 8.563 (3.0); 8.558 (4.0); 8.553 (2.7); 8.311 (0.3); 7.699 (3.2); 7.687 (3.2); 7.680 (3.1); 7.667 (2.9); 4.233 (1.3); 4.216 (1.5); 4.208 (4.0); 4.192 (4.1); 4.184 (4.3); 4.168 (4.1); 4.160 (1.7); 4.144 (1.5); 4.107 (0.3); 4.094 (0.4); 3.955 (1.3); 3.902 (16.0); 3.547 (0.5); 3.508 (0.7); 3.346 (618.3); 3.170 (5.7); 2.682 (0.7); 2.678 (1.3); 2.673 (1.8); 2.669 (1.3); 2.526 (4.9); 2.513 (102.4); 2.509 (214.9); 2.504 (300.2); 2.500 (221.5); 2.495 (103.8); 2.340 (0.5); 2.335 (1.1); 2.331 (1.6); 2.326 (1.1); 1.249 (0.4); 1.232 (0.8); 0.000 (8.1) 47 1.90 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.488 (1.0); 9.473 (1.9); 9.457 (0.9); 9.257 (3.9); 9.201 (16.0); 8.880 (3.5); 8.873 (3.6); 8.536 (1.2); 8.530 (1.6); 8.525 (1.1); 8.513 (1.2); 8.506 (1.5); 8.501 (1.1); 4.234 (0.6); 4.218 (0.7); 4.210 (1.8); 4.194 (1.9); 4.186 (2.0); 4.170 (1.8); 4.162 (0.7); 4.146 (0.6); 3.902 (7.6); 3.341 (184.8); 3.334 (195.9); 3.169 (0.5); 2.677 (0.6); 2.672 (0.9); 2.668 (0.6); 2.525 (2.7); 2.512 (52.7); 2.508 (107.6); 2.503 (148.5); 2.499 (111.1); 2.494 (54.0); 2.334 (0.6); 2.330 (0.8); 2.326 (0.6); 1.234 (0.4); 0.000 (5.8) 48 1.20 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.362 (1.8); 8.997 (3.0); 8.992 (3.7); 8.945 (3.8); 8.940 (3.2); 8.844 (1.2); 8.833 (1.2); 8.573 (0.9); 8.567 (1.3); 8.563 (1.0); 8.553 (1.0); 8.547 (1.4); 8.543 (1.0); 7.697 (1.1); 7.685 (1.2); 7.677 (1.1); 7.665 (1.1); 3.902 (4.2); 3.608 (16.0); 3.424 (0.6); 3.353 (185.0); 3.347 (193.9); 3.170 (0.8); 2.673 (0.6); 2.669 (0.4); 2.526 (1.4); 2.509 (66.8); 2.504 (94.1); 2.500 (71.7); 2.335 (0.4); 2.331 (0.5); 2.326 (0.4); 1.233 (0.4); 0.000 (2.7) 49 1.54 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.245 (3.0); 9.026 (3.2); 9.021 (3.9); 8.962 (3.9); 8.957 (3.5); 8.875 (2.6); 8.868 (2.8); 8.523 (0.9); 8.517 (1.2); 8.512 (1.0); 8.499 (1.0); 8.493 (1.2); 8.488 (0.9); 3.902 (5.6); 3.607 (16.0); 3.354 (200.7); 3.346 (249.7); 3.170 (0.4); 2.678 (0.5); 2.673 (0.7); 2.669 (0.5); 2.526 (2.1); 2.513 (38.5); 2.508 (80.5); 2.504 (112.9); 2.499 (86.6); 2.495 (43.4); 2.335 (0.5); 2.331 (0.6); 2.326 (0.5); 1.234 (0.8); 0.000 (3.4) 50 1. 45 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.382 (2.0); 9.209 (1.1); 9.193 (2.3); 9.185 (4.9); 9.180 (7.3); 9.159 (6.3); 9.154 (4.4); 8.854 (1.4); 8.845 (1.4); 8.582 (1.3); 8.577 (1.9); 8.573 (1.4); 8.562 (1.5); 8.557 (2.0); 8.553 (1.4); 7.701 (1.6); 7.689 (1.6); 7.682 (1.6); 7.669 (1.5); 3.902 (16.0); 3.853 (1.3); 3.837 (1.3); 3.818 (2.6); 3.802 (2.6); 3.783 (1.4); 3.767 (1.3); 3.509 (0.4); 3.349 (364.2); 3.344 (447.4); 3.341 (452.3); 3.176 (0.8); 3.163 (0.8); 2.677 (1.0); 2.673 (1.4); 2.668 (1.1); 2.664 (0.5); 2.526 (3.6); 2.521 (5.4); 2.513 (80.5); 2.508 (172.3); 2.504 (243.6); 2.499 (179.6); 2.495 (84.0); 2.340 (0.4); 2.335 (0.9); 2.330 (1.3); 2.326 (1.0); 1.727 (4.3); 1.679 (9.7); 1.632 (4.8); 0.000 (5.0) 51 1.80 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ =9.348 (0.4); 9.343 (0.4); 9.256 (8.0); 9.242 (0.9); 9.222 (2.2); 9.206 (4.4); 9.201 (6.9); 9.196 (12.5); 9.188 (11.9); 9.183 (5.9); 8.878 (7.2); 8.872 (7.3); 8.534 (2.4); 8.528 (3.3); 8.523 (2.4); 8.511 (2.5); 8.504 (3.2); 8.499 (2.3); 8.316 (0.3); 4.428 (0.5); 4.410 (0.5); 4.110 (0.4); 4.098 (0.4); 3.958 (0.4); 3.902 (14.3); 3.854 (2.2); 3.839 (2.2); 3.819 (4.5); 3.803 (4.4); 3.784 (2.4); 3.768 (2.3); 3.598 (0.4); 3.559 (0.4); 3.528 (0.5); 3.508 (0.7); 3.490 (0.6); 3.341 (647.7); 3.176 (2.2); 3.163 (2.1); 2.677 (1.6); 2.672 (2.3); 2.668 (1.6); 2.594 (0.4); 2.588 (0.4); 2.525 (6.1); 2.512 (127.9); 2.508 (267.9); 2.503 (375.8); 2.499 (283.5); 2.494 (138.3); 2.335 (1.5); 2.330 (2.0); 2.326 (1.5); 1.728 (7.3); 1.680 (16.0); 1.633 (8.0); 1.405 (0.4); 1.388 (0.9); 1.370 (0.4); 1.244 (0.3); 1.233 (0.5); 0.008 (0.4); 0.000 (11.4) 52 1.39 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.365 (1.2); 9.153 (2.3); 9.148 (2.8); 9.101 (2.7); 9.096 (2.4); 8.981 (0.5); 8.967 (1.0); 8.953 (0.5); 8.843 (0.9); 8.831 (0.8); 8.574 (0.7); 8.568 (1.0); 8.564 (0.7); 8.554 (0.7); 8.548 (1.0); 8.544 (0.8); 7.695 (0.8); 7.683 (0.8); 7.676 (0.8); 7.664 (0.8); 3.902 (4.0); 3.556 (0.8); 3.540 (1.6); 3.522 (1.6); 3.507 (0.9); 3.356 (130.8); 3.349 (200.4); 2.724 (1.7); 2.706 (2.5); 2.689 (1.6); 2.678 (0.4); 2.673 (0.5); 2.669 (0.3); 2.526 (1.2); 2.513 (24.8); 2.509 (53.4); 2.504 (76.2); 2.500 (58.4); 2.495 (28.7); 2.331 (0.4); 2.326 (0.3); 2.128 (16.0); 0.000 (2.5) 53 1.72 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.248 (2.1); 9.169 (2.2); 9.164 (2.8); 9.130 (2.5); 9.124 (2.1); 8.991 (0.5); 8.977 (1.0); 8.962 (0.5); 8.875 (1.9); 8.868 (2.0); 8.524 (0.6); 8.518 (0.9); 8.513 (0.7); 8.501 (0.7); 8.495 (0.9); 8.490 (0.6); 3.902 (4.2); 3.558 (0.8); 3.542 (1.6); 3.524 (1.6); 3.508 (0.9); 3.348 (170.0); 2.725 (1.8); 2.706 (2.6); 2.689 (1.7); 2.678 (0.4); 2.673 (0.5); 2.669 (0.4); 2.526 (1.2); 2.513 (27.8); 2.509 (58.7); 2.504 (82.4); 2.500 (61.3); 2.495 (29.3); 2.335 (0.3); 2.331 (0.5); 2.326 (0.3); 2.128 (16.0); 0.000 (1.9) 54 0.84 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.372 (1.9); 9.152 (3.4); 9.147 (4.5); 9.125 (1.7); 9.115 (4.8); 9.109 (4.2); 8.849 (1.3); 8.838 (1.3); 8.576 (1.0); 8.571 (1.4); 8.567 (1.1); 8.556 (1.1); 8.551 (1.5); 8.547 (1.1); 7.698 (1.2); 7.686 (1.2); 7.678 (1.2); 7.666 (1.1); 3.955 (0.6); 3.902 (8.0); 3.777 (0.9); 3.760 (2.4); 3.745 (2.5); 3.729 (1.2); 3.455 (2.2); 3.438 (4.0); 3.421 (1.9); 3.344 (186.2); 3.336 (242.0); 3.176 (0.6); 3.162 (0.6); 3.075 (16.0); 2.677 (0.6); 2.672 (0.8); 2.668 (0.6); 2.543 (0.6); 2.526 (2.1); 2.512 (47.9); 2.508 (101.9); 2.503 (144.1); 2.499 (111.8); 2.334 (0.6); 2.330 (0.8); 2.325 (0.6); 0.000 (3.8) 55 1.12 .sup.1H-NMR (601.6 MHz, d.sub.6-DMSO): δ = 9.254 (1.8); 9.252 (2.8); 9.194 (0.8); 9.185 (1.7); 9.177 (4.0); 9.173 (5.2); 9.161 (5.1); 9.158 (3.3); 8.876 (3.0); 8.872 (3.0); 8.527 (1.0); 8.524 (1.2); 8.523 (1.2); 8.520 (1.0); 8.512 (1.0); 8.508 (1.3); 8.507 (1.2); 8.504 (1.0); 7.953 (0.5); 3.769 (1.0); 3.758 (2.5); 3.748 (2.5); 3.737 (1.2); 3.454 (2.1); 3.442 (3.9); 3.431 (1.9); 3.324 (361.5); 3.281 (0.4); 3.076 (16.0); 2.986 (0.5); 2.891 (4.0); 2.7313 (3.2); 2.7307 (3.1); 2.689 (0.5); 2.617 (1.3); 2.614 (1.8); 2.611 (1.3); 2.523 (3.2); 2.520 (4.2); 2.517 (4.3); 2.508 (97.1); 2.505 (201.1); 2.502 (270.3); 2.499 (198.0); 2.496 (95.1); 2.389 (1.3); 2.386 (1.7); 2.383 (1.3); 0.937 (0.4); 0.000 (7.3) 56 3.14 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 10.867 (7.7); 9.395 (4.2); 9.284 (6.7); 9.278 (9.8); 9.257 (9.3); 9.252 (6.8); 8.855 (3.0); 8.846 (3.0); 8.602 (2.2); 8.597 (3.1); 8.593 (2.3); 8.582 (2.4); 8.577 (3.4); 8.573 (2.3); 8.313 (0.4); 8.277 (6.2); 8.032 (2.9); 8.030 (2.8); 8.009 (3.2); 7.708 (2.8); 7.696 (2.8); 7.688 (2.7); 7.676 (2.6); 7.603 (3.1); 7.583 (6.6); 7.563 (4.4); 7.507 (4.3); 7.487 (2.7); 4.108 (0.8); 4.095 (0.8); 4.083 (0.3); 3.902 (16.0); 3.508 (0.5); 3.495 (0.4); 3.346 (476.4); 3.340 (619.0); 3.176 (6.2); 3.163 (6.1); 2.677 (1.3); 2.672 (1.7); 2.668 (1.3); 2.664 (0.7); 2.526 (4.7); 2.512 (103.2); 2.508 (217.0); 2.503 (304.9); 2.499 (228.7); 2.494 (110.1); 2.335 (1.2); 2.330 (1.7); 2.326 (1.2); 1.249 (0.3); 0.008 (0.4); 0.000 (12.2); −0.009 (0.4) 57 3.53 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 10.872 (8.7); 9.298 (6.5); 9.293 (10.8); 9.277 (16.0); 8.887 (6.9); 8.880 (7.1); 8.555 (2.2); 8.549 (3.3); 8.544 (2.4); 8.532 (2.3); 8.525 (3.3); 8.521 (2.3); 8.308 (0.3); 8.273 (7.1); 8.025 (3.4); 8.004 (3.7); 7.605 (3.2); 7.585 (7.0); 7.565 (4.6); 7.509 (5.1); 7.490 (3.2); 3.902 (15.3); 3.705 (0.4); 3.657 (0.4); 3.603 (0.6); 3.508 (1.4); 3.361 (1440.1); 3.174 (0.6); 2.678 (1.6); 2.674 (2.2); 2.670 (1.6); 2.582 (0.4); 2.544 (1.6); 2.509 (266.9); 2.505 (367.0); 2.500 (281.7); 2.336 (1.5); 2.331 (2.0); 1.233 (0.6); 0.000 (7.6) 58 2.54 .sup.1H-NMR (601.6 MHz, d.sub.6-DMSO): δ = 11.037 (1.3); 9.317 (7.8); 9.313 (14.4); 9.306 (16.0); 9.302 (8.6); 9.278 (8.6); 8.887 (8.8); 8.883 (10.4); 8.833 (0.9); 8.829 (0.8); 8.825 (0.9); 8.554 (2.8); 8.551 (3.7); 8.547 (2.8); 8.539 (3.0); 8.536 (3.8); 8.532 (2.6); 8.452 (8.0); 8.270 (1.6); 8.189 (0.8); 8.176 (0.9); 8.160 (4.1); 8.147 (4.3); 8.145 (4.3); 8.022 (0.8); 8.007 (0.8); 7.760 (4.0); 7.746 (8.2); 7.733 (4.8); 7.646 (5.2); 7.634 (4.1); 7.596 (0.7); 7.583 (1.5); 7.569 (0.9); 7.505 (1.0); 7.493 (0.8); 3.322 (411.9); 2.614 (2.3); 2.611 (1.7); 2.541 (1.0); 2.523 (4.5); 2.520 (5.8); 2.517 (6.8); 2.505 (256.7); 2.502 (334.0); 2.499 (250.5); 2.386 (2.0); 1.231 (0.6); 0.000 (7.3) 59 1.65 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.231 (6.6); 8.861 (5.8); 8.854 (6.1); 8.761 (8.3); 8.508 (1.9); 8.503 (2.6); 8.485 (1.9); 8.480 (2.6); 8.475 (1.8); 3.902 (16.0); 3.508 (0.4); 3.342 (396.2); 3.338 (410.6); 3.176 (0.7); 3.164 (0.7); 2.677 (1.1); 2.672 (1.5); 2.668 (1.2); 2.548 (0.6); 2.525 (4.3); 2.512 (90.4); 2.508 (185.6); 2.503 (257.8); 2.499 (197.1); 2.335 (1.2); 2.330 (1.5); 2.325 (1.2); 2.199 (0.5); 2.143 (0.6); 2.130 (0.6); 2.112 (0.6); 2.074 (0.4); 1.249 (0.3); 1.235 (0.3); 0.969 (4.6); 0.008 (0.4); 0.000 (10.5) I-a-1 1.95 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 9.339 (8.2); 9.337 (8.7); 9.333 (8.6); 9.332 (8.2); 9.046 (15.3); 9.040 (16.0); 8.842 (15.8); 8.836 (15.1); 8.830 (7.6); 8.827 (7.8); 8.818 (7.7); 8.814 (7.5); 8.548 (4.4); 8.544 (5.4); 8.543 (5.3); 8.538 (4.3); 8.528 (4.7); 8.524 (5.4); 8.523 (5.8); 8.518 (4.4); 8.318 (0.4); 7.679 (5.3); 7.677 (5.4); 7.667 (5.2); 7.665 (5.3); 7.659 (5.2); 7.657 (5.1); 7.647 (5.0); 7.645 (5.0); 3.757 (1.1); 3.329 (112.8); 2.678 (0.5); 2.674 (0.7); 2.669 (0.5); 2.527 (1.9); 2.514 (39.9); 2.509 (80.5); 2.505 (105.7); 2.500 (75.9); 2.496 (35.9); 2.336 (0.5); 2.331 (0.7); 2.327 (0.5); 0.146 (0.7); 0.008 (5.9); 0.000 (157.7); −0.009 (5.5); −0.150 (0.7) I-j-1 LC-MS: m/z 272 [M + H.sup.+] I-j-2 LC-MS: m/z 290 [M + H.sup.+] I-s-1 LC-MS: m/z 229 [M + H.sup.+] I-s-2 LC-MS: m/z 247 [M + H.sup.+]

Biological Examples

[0897] Myzus persicae—Spray Test

[0898] Solvent: 78 parts by weight of acetone [0899] 1.5 parts by weight of dimethylformamide

[0900] Emulsifier: alkylaryl polyglycol ether

[0901] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0902] Discs of Chinese cabbage leaves (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active ingredient formulation of the desired concentration.

[0903] After 6 days, the efficacy in % is determined. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.

[0904] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 500 g/ha: 2, 4, 6, 7, 9, 19, 22, 30, 41, 42, 43, 44

[0905] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: 13, 16, 17, 18, 20, 23, 25, 26, 31, 32, 39, 45, 48, 49

Tetranychus urticae—Spray Test, OP-Resistant

[0906] Solvent: 78.0 parts by weight of acetone [0907] 1.5 parts by weight of dimethylformamide

[0908] Emulsifier: alkylaryl polyglycol ether

[0909] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0910] Discs of bean leaves (Phaseolus vulgaris) infested with all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active ingredient formulation of the desired concentration.

[0911] After 6 days, the efficacy in % is determined. 100% means that all the spider mites have been killed; 0% means that no spider mites have been killed.

[0912] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: 22

Phaedon cochleariae—Spray Test

[0913] Solvent: 78.0 parts by weight of acetone [0914] 1.5 parts by weight of dimethylformamide

[0915] Emulsifier: alkylaryl polyglycol ether

[0916] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

[0917] Discs of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active ingredient preparation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

[0918] After 7 days, the efficacy in % is determined. 100% means that all the beetle larvae have been killed; 0% means that no beetle larvae have been killed.

[0919] In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 500 g/ha: 39

Myzus persicae—Spray Test

[0920] Solvent: 7 parts by weight of dimethylformamide

[0921] Emulsifier: alkylaryl polyglycol ether

[0922] To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up with water containing an emulsifier concentration of 1000 ppm until the desired concentration is attained. To produce further test concentrations, the formulation is diluted with emulsifier-containing water. If the addition of ammonium salts or/and penetrants is required, these are each added in a concentration of 1000 ppm to the formulation solution.

[0923] Bell pepper plants (Capsicum annuum) severely infested with the green peach aphid (Myzus persicae) are treated by spraying with the active ingredient formulation in the desired concentration.

[0924] After 6 days, the kill in % is determined. 100% means that all of the aphids have been killed; 0% means that none of the aphids have been killed.

[0925] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 4 ppm: 21