BICYCLIC COMPOUNDS AS PEST CONTROL AGENTS

Abstract

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

Claims

1. A compound of formula (I) ##STR00441## A represents a radical from the group consisting of (A-b) to (A-f) ##STR00442## where the broken line represents the bond to the nitrogen atom of the bicycle of the formula (I) and B.sup.2 represents a radical from the group consisting of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and in each case optionally substituted cycloalkyl and cycloalkenyl, R.sup.1 represents a radical from the group consisting of hydrogen, alkyl, alkoxy and cyano, R.sup.2 a) represents a B radical from the group consisting of ##STR00443## ##STR00444## ##STR00445## ##STR00446## where the broken line represents the bond to the carbon atom of the bicycle of the formula (I) or R.sup.2 b) represents a radical from the group consisting of (D-1) to (D-3) ##STR00447## where the broken line represents the bond to the carbon atom of the bicycle of the formula (I) or R.sup.2 c) represents a radical of the formula ##STR00448## or R.sup.2 d) represents a radical of the formula ##STR00449## or R.sup.2 e) represents a radical from the group consisting of (F-1) to (F-11) ##STR00450## ##STR00451## where the broken line represents the bond to the carbon atom in the formula (I) or R.sup.2 f) represents a radical from the group consisting of haloalkyl, carboxyl and amino, in which G.sup.2 represents hydrogen or a radical from the group consisting 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 turn may be substituted by alkyl, haloalkyl, alkoxy and alkoxyalkyl), phenyl (which for its turn may 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 turn may 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 turn may be substituted by halogen and alkyl), or G.sup.2 represents a C radical from the group consisting of (C-1) to (C-9) ##STR00452## where the broken line represents the bond to the B radicals, X represents oxygen or sulphur, X.sup.1 represents a radical from the group consisting of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy and haloalkoxy, X.sup.2 represents oxygen, sulphur, NR.sup.5 or NOH, L represents oxygen or sulphur, V—Z represents R.sup.24CH—CHR.sup.25 or R.sup.24C═CR.sup.25, n represents 1 or 2, m represents 1, 2, 3 or 4, R represents NR.sup.18R.sup.19, or represents an in each case optionally substituted radical from the group consisting 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 represents hydrogen or alkyl, R.sup.4 represents a radical from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, aryl, arylalkyl and hetarylalkyl, R.sup.5 represents a radical from the group consisting 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 attached form a ring which may contain one or more further heteroatoms from the group consisting of nitrogen, oxygen and sulphur, or R.sup.3 and R.sup.5 together with the nitrogen atoms to which they are attached form a ring, R.sup.6 represents hydrogen or alkyl, R.sup.7 represents a radical from the group consisting 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 attached form a ring which may contain one or more further heteroatoms from the group consisting of nitrogen, oxygen and sulphur, R.sup.8 represents a radical from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulphonyl, optionally halogen-substituted alkoxycarbonyl, optionally halogen-, alkyl-, alkoxy-, haloalkyl- and cyano-substituted cycloalkylcarbonyl, or a cation, or an optionally alkyl- or arylalkyl-substituted ammonium ion, R.sup.9 represents a radical from the group consisting 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 consisting 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 radicals (C-1) and (F-1) may also form, together with the N—S(O)n group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents hydrogen or alkyl, R.sup.8 und R.sup.10 in the radicals (C-2) and (F-2) may also represent, together with the nitrogen atoms to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain at least one further heteroatom from the group consisting 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 radicals (C-2) and (F-2) may also form, together with the N—S(O)n group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents an in each case optionally substituted radical from the group consisting 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 represents an in each case optionally substituted radical from the group consisting 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 radicals (C-3) and (F-3) may also form, together with the phosphorus atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered ring which may contain one or two heteroatoms from the group consisting of oxygen (where oxygen atoms must not be directly adjacent to one another) and sulphur, R.sup.13 represents an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.14 represents an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.15 represents a radical from the group consisting 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 consisting 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 radicals (C-6) and (F-6) may also form, together with the N—S(O)n group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents a radical from the group consisting 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 consisting 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 radicals (C-7) and (F-7) may also form, together with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents a radical from the group consisting 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 consisting 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 radicals (C-8) and (F-8) may also form, together with the N—C(X) group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents a radical from the group consisting 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 consisting 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 represents a radical from the group consisting of hydrogen, represents an alkali metal or alkaline earth metal ion or represents an ammonium ion which is optionally mono- to tetrasubstituted by C.sub.1-C.sub.4-alkyl or represents an in each case optionally halogen- or cyano-substituted alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl radical, Y.sup.1 and Y.sup.2 independently of one another represent C═O or S(O).sub.2, Y.sup.3 represents a radical from the group consisting of hydrogen, halogen, cyano, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy and NR.sup.20R.sup.21, W represents a radical from the group consisting of O, S, SO and SO.sub.2, R.sup.22 represents a radical from the group consisting of alkyl, optionally halogen-, carbamoyl-, thiocarbamoyl- or cyano-substituted cycloalkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkylthio, haloalkylsulphinyl, haloalkylsulphonyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, alkylthioalkyloxy, alkylsulphinylalkyloxy, alkylsulphonylalkyloxy, haloalkylthioalkyl, halogenalkylsulphinylalkyl, haloalkylsulphonylalkyl, alkylthioalkenyl, alkylsulphinylalkenyl, alkylsulphonylalkenyl, alkenylthioalkyl, alkenylsulphinylalkyl, alkenylsulphonylalkyl, alkylcarbonylalkyl, haloalkylcarbonylalkyl, alkoxyalkyl, haloalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxycarbonylalkyl, alkylaminosulphonyl, di(alkylamino)sulphonyl, or, in the case R.sup.2=d), R.sup.22 also represents optionally substituted aryl or represents a radical from the group consisting of E-1 to E-51 ##STR00453## ##STR00454## ##STR00455## ##STR00456## ##STR00457## ##STR00458## R.sup.20 represents a radical from the group consisting 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 independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, alkyl and haloalkyl, R.sup.21 represents a radical from the group consisting of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulphonyl and haloalkylsulphonyl, R.sup.23 represents a radical from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl, alkoxyalkyl and R.sup.24 represents hydrogen or an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl and R.sup.25 represents hydrogen or an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.27 represents hydrogen or alkyl and R.sup.26 represents hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl or cyanoalkyl and compounds of the formula (I) in which A represents the A radical (A-a) ##STR00459## where the broken line represents the bond to the nitrogen atom of the bicycle of the formula (I) and G.sup.1 represents N or C—B.sup.1, B.sup.1 represents a radical from the group consisting of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and in each case optionally substituted cycloalkyl and cycloalkenyl, B.sup.2 represents a radical from the group consisting of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy and in each case optionally substituted cycloalkyl and cycloalkenyl, T represents oxygen or an electron pair, R.sup.1 represents a radical from the group consisting of hydrogen, alkyl, alkoxy and cyano, R.sup.2 a) represents a B radical from the group consisting of ##STR00460## ##STR00461## ##STR00462## where the broken line represents the bond to the carbon atom of the bicycle of the formula (I), where G.sup.2 represents hydrogen or a radical from the group consisting of halogen, nitro, amino, cyano, alkylamino, haloalkylamino, dialkylamino, alkyl, haloalkyl, alkoxycarbonylalkyl, 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 turn may be substituted by alkyl, haloalkyl, alkoxy and alkoxyalkyl), phenyl (which for its turn may 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 turn may 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 turn may be substituted by halogen and alkyl), or R.sup.2 aa) represents one of the B radicals below ##STR00463## ##STR00464## where the broken line represents the bond to the carbon atom of the bicycle of the formula (I), where G.sup.2 represents a radical from the group consisting of halogen, nitro, amino, cyano, alkylamino, haloalkylamino, dialkylamino, saturated or unsaturated cycloalkyl which is optionally substituted and optionally interrupted by one or more heteroatoms, cycloalkylalkyl, haloalkoxy, alkoxyalkyl, halogenated alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, haloalkylthioalkyl, haloalkylsulphinylalkyl, haloalkylsulphonylalkyl, 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 turn may be substituted by alkyl, haloalkyl, alkoxy and alkoxyalkyl), phenyl (which for its turn may be substituted by halogen, cyano, nitro, alkyl and haloalkyl), the heteroaryl radicals imidazolyl, pyrazolyl, oxazolyl, furanyl, thienyl, triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, triazinyl, tetrazinyl and isoquinolinyl (which for their turn may 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 turn may be substituted by halogen and alkyl), or G.sup.2, if R.sup.2 represents one of the radicals listed under a) or aa), also represents a C radical from the group consisting of ##STR00465## where the broken line represents the bond to the B radicals, or R.sup.2 c) represents a radical of the formula ##STR00466## or R.sup.2 d) represents a radical of the formula ##STR00467## or R.sup.2 e) represents an F radical from the group consisting of ##STR00468## where the broken line represents the bond to the carbon atom in the formula (I) or R.sup.2 f) represents a radical from the group consisting of haloalkyl, carboxyl and amino, X represents oxygen or sulphur, X.sup.2 represents oxygen, sulphur, NR.sup.5 or NOH, L represents oxygen or sulphur, V—Z represents R.sup.24CH—CHR.sup.25 or R.sup.24C═CR.sup.25, n represents 1 or 2, m represents 1, 2, 3 or 4, R.sup.3 represents hydrogen or alkyl, R.sup.4 represents a radical from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, aryl, arylalkyl and hetarylalkyl, R.sup.5 represents a radical from the group consisting 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 attached form a ring which may contain one or more further heteroatoms from the group consisting of nitrogen, oxygen and sulphur, or R.sup.3 and R.sup.5 together with the nitrogen atoms to which they are attached form a ring, R.sup.6 represents hydrogen or alkyl, R.sup.7 represents a radical from the group consisting 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 attached form a ring which may contain one or more further heteroatoms from the group consisting of nitrogen, oxygen and sulphur, R.sup.8 represents a radical from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulphonyl, optionally halogen-substituted alkoxycarbonyl, optionally halogen-, alkyl-, alkoxy-, haloalkyl- and cyano-substituted cycloalkylcarbonyl, or a cation, or an optionally alkyl- or arylalkyl-substituted ammonium ion, R.sup.9 represents a radical from the group consisting 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 consisting 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.10 represents hydrogen or alkyl, R.sup.8 and R.sup.10 in the radicals (C-2) and (F-2) may also represent, together with the nitrogen atoms to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain at least one further heteroatom from the group consisting 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 radicals (C-2) and (F-2) may also form, together with the N—S(O)n group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents an in each case optionally substituted radical from the group consisting 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 represents an in each case optionally substituted radical from the group consisting 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 radicals (C-3) and (F-3) may also form, together with the phosphorus atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered ring which may contain one or two heteroatoms from the group consisting of oxygen (where oxygen atoms must not be directly adjacent to one another) and sulphur, R.sup.13 represents an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.14 represents an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.15 represents a radical from the group consisting 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 consisting 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 radicals (C-6) and (F-6) may also form, together with the N—S(O)n group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents a radical from the group consisting 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 consisting 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 radicals (C-7) and (F-7) may also form, together with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting 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 represents a radical from the group consisting 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 consisting 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 radicals (C-8) and (F-8) may also form, together with the N—C(X) group to which they are attached, a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting of sulphur, oxygen (where oxygen atoms must not be directly adjacent to one another) and nitrogen and/or at least one carbonyl group, Y.sup.1 and Y.sup.2 independently of one another represent C═O or S(O).sub.2, R.sup.22 represents a radical from the group consisting of (D-1) to (D-3) ##STR00469## where the broken line represents the bond to the nitrogen atom in the radical c) or to the carbon atom in the radical d), X.sup.1 represents a radical from the group consisting of hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cycloalkyl, alkoxy and haloalkoxy, Y.sup.3 represents a radical from the group consisting of hydrogen, halogen, cyano, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy and NR.sup.20R.sup.21, W represents a radical from the group consisting of S, SO and SO.sub.2 and R represents NR.sup.18R.sup.19, or represents an in each case optionally substituted radical from the group consisting 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.18 represents a radical from the group consisting 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 consisting 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 represents a radical from the group consisting of hydrogen, represents an alkali metal or alkaline earth metal ion or represents an ammonium ion which is optionally mono- to tetrasubstituted by C.sub.1-C.sub.4-alkyl or represents an in each case optionally halogen- or cyano-substituted alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl radical, R.sup.20 represents a radical from the group consisting 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 independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, alkyl and haloalkyl, R.sup.21 represents a radical from the group consisting of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulphonyl and haloalkylsulphonyl, or R.sup.22 represents a radical from the group consisting of E-1 to E-51 ##STR00470## ##STR00471## ##STR00472## ##STR00473## ##STR00474## ##STR00475## R.sup.23 represents a radical from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl, alkoxyalkyl, R.sup.24 represents hydrogen or an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl and R.sup.25 represents hydrogen or an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R.sup.27 represents hydrogen or alkyl and R.sup.26 represents hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl or cyanoalkyl.

2. A compound of formula (I) according to claim 1, wherein A represents an A radical from the group consisting of (A-b) and (A-f) ##STR00476## where the broken line represents the bond to the nitrogen atom of the bicycle of the formula (I), B.sup.2 represents hydrogen, R.sup.1 represents hydrogen, R.sup.2 c) represents a radical of the formula ##STR00477## or R.sup.2 d) represents a radical of the formula ##STR00478## X represents oxygen, R.sup.3 represents C.sub.1-C.sub.4-alkyl, R.sup.22, if R.sup.2 represents the radical c), represents a radical from the group consisting of C.sub.1-C.sub.6-alkyl, optionally cyano-substituted C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-alkylsulphonyl, C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.4-alkyl, di-(C.sub.1-C.sub.4-alkyl)aminosulphonyl, R.sup.23, if R.sup.2 represents the radical c), represents a radical from the group consisting of hydrogen and C.sub.1-C.sub.6-alkyl, R.sup.22, if R.sup.2 represents the radical d), represents a radical from the group consisting of C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkylsulphinyl-C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkylsulphonyl-C.sub.1-C.sub.4-alkyl, R.sup.23, if R.sup.2 represents the radical d), represents a radical from the group consisting of hydrogen and C.sub.1-C.sub.6-alkyl, and in the case R.sup.2=d), R.sup.22 also represents optionally halogen-, C.sub.1-C.sub.6-alkyl- and C.sub.1-C.sub.6-haloalkylsulphinyl-substituted phenyl and compounds of the formula (I) in which A represents the A radical ##STR00479## where the broken line represents the bond to the nitrogen atom of the bicycle of the formula (I), G.sup.1 represents N or C—B.sup.1, B.sup.1 represents a radical from the group consisting of hydrogen and fluorine, T represents an electron pair, R.sup.1 represents hydrogen, R.sup.2 aa) represents a radical from the group consisting of ##STR00480## in which G.sup.2 represents a radical from the group consisting of halogen, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-alkylsulphinyl, C.sub.1-C.sub.4-alkylsulphonyl, C.sub.1-C.sub.4-haloalkylthio, C.sub.1-C.sub.4-haloalkylsulphinyl, C.sub.1-C.sub.4-haloalkylsulphonyl, C.sub.1-C.sub.4-alkylthio-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkylsulphinyl-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkylsulphonyl-C.sub.1-C.sub.4-alkyl, or R.sup.2 c) represents a radical of the formula ##STR00481## or R.sup.2 d) represents a radical of the formula ##STR00482## or R.sup.2 f) represents haloalkyl, X represents oxygen, R.sup.22 represents a radical from the group consisting of (D-1) to (D-3) ##STR00483## where the broken line represents the bond to the nitrogen atom in the radical c) or to the carbon atom in the radical d), R represents C.sub.1-C.sub.4-alkyl, in each case optionally mono-, di-, tri-, tetra- or pentasubstituted by fluorine, chlorine, X.sup.1 represents a radical from the group consisting of hydrogen, fluorine, chlorine, bromine, methyl and ethyl, W represents a radical from the group consisting of S, SO and SO.sub.2, Y.sup.3 represents a radical from the group consisting of hydrogen, fluorine, chlorine, bromine, methyl and ethyl,

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

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

5. Compound of formula ##STR00484##

Description

DESCRIPTION OF THE PROCESSES AND INTERMEDIATES

[0862] 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).

[0863] 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:

[0864] [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.

[0865] [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.

[0866] 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).

[0867] 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.

[0868] The .sup.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 δ value−signal intensity number pairs for different signal peaks are listed with separation from one another by semicolons.

[0869] The peak list for one example therefore has the form: [0870] δ.sub.1 (intensity 1); δ.sub.2 (intensity 2); . . . ; δ.sub.i (intensity i); . . . ; δ.sub.n (intensity n)

[0871] 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.

[0872] Calibration of the chemical shift of .sup.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.

[0873] The lists of the .sup.1H NMR peaks are similar to the conventional .sup.1H NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.

[0874] In addition, like conventional .sup.1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds which are likewise provided by the invention, and/or peaks of impurities.

[0875] In the reporting of compound signals within the delta range of solvents and/or water, our lists of .sup.1H NMR peaks show the standard solvent peaks, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water, which usually have a high intensity on average.

[0876] 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%).

[0877] 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”.

[0878] 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 peak picking in question in conventional .sup.1H NMR interpretation.

[0879] Further details of .sup.1H NMR peak lists can be found in the Research Disclosure Database Number 564025.

General Synthesis of 4,5-Disubstituted 2-(Hetaryl)Indazoles of the Formula (I); Examples 1 to 52

[0880] ##STR00154##

Step 1: Synthesis of Compounds of the Formula (A-3)

[0881] ##STR00155##

[0882] 19.6 mmol of a heterocyclic amino compound (A-2), 1.0 mmol of para-toluenesulphonic acid (PTSA), 5.9 mmol of 4A molecular sieve and magnesium sulphate were added to a solution of 119.6 mmol of ortho-nitrobenzaldehyde of the formula (A-1) in 75 mmol of toluene. The reaction mixture was then stirred at reflux temperature for 18 hours. Thin-layer chromatogram (mobile phase: ethyl acetate) showed that the reaction had ended. The reaction mixture was filtered and the filtrate gave, after concentration, the crude products (A-3), which were reacted further without further purification.

Step 2: Synthesis of 4,5-disubstituted 2-(hetaryl)indazoles of the Formula (I)

[0883] At room temperature, 58.8 mmol of triethyl phosphite were added to 19.6 mmol of the compounds of the formula (A-3). The reaction mixture was then stirred at 140° C. for about 18 hours. Thin-layer chromatogram (mobile phase: petroleum ether:ethyl acetate=1:1) showed that the reaction had ended. After concentration of the reaction mixture under reduced pressure, the residue that remained was purified by CombiFlash chromatography (mobile phase gradient: 100% petroleum ether to 70% ethyl acetate/petroleum ether).

General Synthesis of 4-substituted 2-(hetaryl)indazole-5-carboxylic Acids of the Formula (I, R.SUP.2.═COOH)

Method A:

[0884] ##STR00156##

[0885] At room temperature, 21.1 mmol of aqueous sodium hydroxide solution were added to 7.03 mmol of the compounds of the formula (I; R.sup.2═COOCH.sub.3) in a mixture of 10 ml of tetrahydrofuran and 10 ml of water. The reaction mixture was then stirred at 70° C. for about 18 hours. Thin-layer chromatogram (mobile phase: petroleum ether:ethyl acetate=1:1) showed that the reaction had ended. After concentration of the reaction mixture under reduced pressure, the residue that remained was adjusted with 12N hydrochloric acid to pH=3. Thereafter, the precipitated solid was filtered off, washed with water and dried.

Method B:

[0886] 1 equiv. of the compounds of the formula (I; R.sup.2═COOCH.sub.3) were dissolved in methanol (3 ml/mmol), and 1.5 equiv. of 1M lithium hydroxide solution were added at room temperature. The reaction mixture was then stirred at 50° C. for 2 hours. Subsequently, the reaction mixture was adjusted to pH=3 by addition of 1M hydrochloric acid. If a solid had formed, this was filtered off and dried. Otherwise, the reaction solution was extracted with dichloromethane (3×3 ml/mmol). The combined organic phases were dried over magnesium sulphate and concentrated under reduced pressure.

2-(1-Methyl-1H-pyrazol-4-yl)-2H-indazole-5-carboxylic acid (I, A=1-methyl-1H-pyrazol-4-yl; R.SUP.1.═H, R.SUP.2.═COOH)

[0887] ##STR00157##

[0888] This compound was prepared from 3.46 g (13.5 mmol) of methyl 2-(1-methyl-1H-pyrazol-4-yl)-2H-indazole-5-carboxylate in accordance with the general synthesis mentioned. This gave 2.87 g (88% yield) of the title compound.

[0889] APCI MS, m/z=243 [M+H].sup.+

General Synthesis of 4-substituted 2-(hetaryl)indazole-5-carboxamides of the Formula (I, R.SUP.2.═CONHR)

[0890] ##STR00158##

a) Carbonyldiimidazole (CDI) Method

[0891] In a first reaction step, at room temperature, 134 mg (0.84 mmol) of carbonyldiimidazole (CDI) were added to a solution of 0.84 mmol of 2-(hetaryl)indazole-5-carboxylic acid in 8 ml of N,N-dimethylformamide, and the reaction mixture was then stirred for 2 hours. In a second reaction step, 1.04 mmol of 60% pure sodium hydride were added at room temperature to 1.04 mmol of the reactive component prepared in this manner in 8 ml of N,N-dimethylformamide. After one hour, 0.84 mmol of the respective amine were added and the mixture was stirred at room temperature for a further 18 hours. For work-up, water was added, the reaction was concentrated under reduced pressure and the residue that remained was purified by column chromatography on silica gel (mobile phase gradient: dichloromethane:methanol=50:1 to 5:1).

b) Phosgene Method

[0892] In a first reaction step, at 0° C., 5 drops of N,N-dimethylformamide and 3 mmol of phosgene were added to a solution of 1.0 mmol of 2-(hetaryl)indazole-5-carboxylic acid in 12 ml of dichloromethane. The reaction mixture was then stirred at room temperature for 3 hours. Concentration of the reaction mixture under reduced pressure gave 2-(hetaryl)indazole-5-carbonyl chloride.

[0893] In a second reaction step, 1.0 mmol of the 2-(hetaryl)indazole-5-carbonyl chloride in 15 ml of dichloromethane was stirred at room temperature, and 3.0 mmol of the respective amine and 4 mmol of N,N-diisopropylethylamine (DIPEA) were added. The reaction mixture was then stirred at room temperature for 18 hours. For work-up, the reaction mixture was concentrated under reduced pressure and the residue that remained was purified by CombiFlash (mobile phase gradient: dichloromethane to 4% methanol in dichloromethane).

General Synthesis of 4-substituted 2-(hetaryl)-5-trifluoromethylindazoles of the Formula (I, R.SUP.2.═CF.SUB.3.)

[0894] ##STR00159##

Step 1: Synthesis of 2-nitro-5-(trifluoromethyl)benzaldehyde (A-1)

[0895] At room temperature, 63.7 mmol of N,N-dimethylformamide O,O-dimethyl acetal were added dropwise to a solution of 4.9 mmol of 2-methyl-1-nitro-4-(trifluoromethyl)benzene in 15 ml of N,N-dimethylformamide. The reaction mixture was then stirred at 140° C. for 18 hours. The reaction mixture was then concentrated under reduced pressure and 15 ml of tetrahydrofuran and 15 ml of water were added to the residue that remained. 147 mmol of sodium periodate (NaIO.sub.4) were then added, and the reaction mixture was stirred at room temperature for a further 18 hours. The reaction mixture was then extracted with dichloromethane and the organic phase was concentrated under reduced pressure. The residue that remained was chromatographed by ISCO (mobile phase gradient: 100% petroleum ether to 10% ethyl acetate in petroleum ether).

Step 2: Synthesis of Compounds of the Formula (A-3; R.SUP.1.═H; R.SUP.2.═CF.SUB.3.)

[0896] ##STR00160##

[0897] 1.095 mmol of a heterocyclic amino compound (A-2), 0.046 mmol PTSA, 0.27 mmol 4A molecular sieve and magnesium sulphate were added to a solution of 0.913 mmol of 2-nitro-5-trifluoromethylbenzaldehyde (A-1, R.sup.1═H) in 75 ml of toluene. The reaction mixture was then stirred at reflux temperature for 18 hours. The reaction mixture was filtered and the filtrate gave, after concentration, the crude products (A-3), which were reacted further without further purification.

Step 3: Synthesis of 4-substituted 2-(hetaryl)-5-trifluoromethylindazoles of the Formula (I; R.SUP.1.═H; R.SUP.2.═CF.SUB.3.)

[0898] ##STR00161##

[0899] At room temperature, 2.739 mmol of triethyl phosphite were added to 0.913 mmol of the compounds of the formula (A-3). The reaction mixture was then stirred at 140° C. for about 18 hours. Thin-layer chromatogram (mobile phase: petroleum ether:ethyl acetate=1:1) showed that the reaction had ended. After concentration of the reaction mixture under reduced pressure, the residue that remained was chromatographed by ISCO (mobile phase gradient: 100% petroleum ether to 20% ethyl acetate/petroleum ether).

Example 49: 5-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylsuphanyl)phenyl]-2-(3-pyridyl)indazole

Step 1

Synthesis of (E/Z)—N-[(5-bromo-2-nitrophenyl)methylidene]pyridine-3-amine

[0900] ##STR00162##

[0901] 35.75 g (155.42 mmol) of 5-bromo-2-nitrobenzaldehyde, 15.04 g (159.81 mmol) of pyridine-3-amine and 200 ml of ethanol were added to a 500 ml round-bottom flask. The reaction mixture was then stirred on an oil bath at 80° C. for about 18 hours. The course of the reaction was monitored by LCMS. Thereafter, the reaction mixture was concentrated under reduced pressure. This gave 45 g of crude (Z/E)-N-[(5-bromo-2-nitrophenyl)methylidene]pyridine-3-amine as a brown solid.

[0902] LC-MS (ES, m/z): 305.9 [M+H]

Step 2

Synthesis of 5-bromo-2-(3-pyridyl)-2H-indazole

[0903] ##STR00163##

[0904] 45 g (147.00 mmol) of (Z/E)-N-[(5-bromo-2-nitrophenyl)methylidene]pyridine-3-amine and 75 g (451.38 mmol) of triethyl phosphite were stirred in a 500 ml round-bottom flask. The solution was then stirred in an oil bath at 90° C. for about 18 hours. The course of the reaction was monitored by LCMS. The reaction mixture was then washed with sodium hydroxide. The solution formed was extracted three times with 50 ml of ethyl acetate and the organic phases were combined. The organic phase was then washed three times with 50 ml of water and, after drying, concentrated under reduced pressure. The residue that remained was purified by column chromatography using the gradient ethyl acetate:petroleum ether=(25:75). This gave 12.3 g (yield: 30% of theory) of 5-bromo-2-(3-pyridyl)-2H-indazole as a yellow solid.

[0905] LC-MS (ES, m/z): 274.0 [M+H] and 276.0[M+H]

[0906] .sup.1H-NMR (400.0 MHz, CDCl.sub.3): δ=9.21 (s, 1H), 8.71 (d, J=4.0 Hz, 1H), 8.44 (s, 1H), 8.32 (d, J=7.2 Hz, 1H), 7.92 (s, 1H), 7.70 (d, J=9.2 Hz, 1H), 7.54-7.57 (m, 1H), 7.43 (d, J=9.2 Hz, 1H) ppm.

Step 3

5-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole

[0907] ##STR00164##

[0908] Similar to the reaction procedure from US 2013/0267493, a solution of 77 mg (0.73 mmol) of sodium carbonate in 375 μl of water and 1.5 ml of 1,4-dioxane were added to a mixture of 100 mg (365 μmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2) and 105 mg (392 μmol) of [2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]boronic acid. The reaction mixture was repeatedly flushed with a stream of argon, 15 mg (19 μmol) of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) were added and the vessel was closed. The mixture was heated in a CEM Discover microwave reactor at 90° C. for 40 min and, after cooling to room temperature, filtered through a depth filter which was rinsed with ethyl acetate. The reaction was carried out three times in total and the batches were combined prior to purification. After the solvent has been removed under reduced pressure, the residue is separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.50:50). This gave 392 mg (93% pure, 86% yield) of 5-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole.

[0909] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.374 (3.5); 9.367 (3.5); 9.306 (5.9); 9.305 (5.9); 8.686 (2.4); 8.682 (2.6); 8.674 (2.5); 8.671 (2.6); 8.541 (1.3); 8.537 (1.5); 8.534 (1.5); 8.531 (1.3); 8.520 (1.5); 8.516 (1.5); 8.513 (1.7); 8.510 (1.4); 8.228 (0.3); 7.975 (3.7); 7.860 (2.7); 7.837 (3.1); 7.774 (3.1); 7.754 (3.2); 7.687 (1.9); 7.675 (1.9); 7.666 (1.9); 7.655 (1.9); 7.558 (1.3); 7.553 (2.2); 7.549 (1.3); 7.535 (1.1); 7.531 (2.0); 7.527 (1.1); 7.338 (2.8); 7.309 (2.7); 4.066 (1.3); 4.040 (4.2); 4.014 (4.4); 3.988 (1.5); 3.335 (28.4); 2.893 (0.4); 2.528 (0.5); 2.514 (12.2); 2.510 (24.6); 2.505 (32.5); 2.501 (24.0); 2.496 (11.9); 2.453 (16.0); 2.406 (0.4); 1.397 (1.7).

Example 50: 5-[4-Methyl-3-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole

[0910] ##STR00165##

[0911] The preparation of 5-[4-methyl-3-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole was carried out analogously to the synthesis of 5-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphanyl) phenyl]-2-(3-pyridyl)indazole. Here, 100 mg (365 μmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2) and 98 mg (0.39 mmol) of [4-methyl-3-(2,2,2-trifluoroethylsulphanyl)phenyl]boronic acid were employed. The reaction was carried out twice and the batches were combined prior to purification. This gave 149 mg of 5-[4-methyl-3-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole (97% pure, 50% yield).

[0912] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.377 (3.4); 9.371 (3.5); 9.274 (5.9); 9.272 (6.2); 8.678 (2.3); 8.675 (2.6); 8.666 (2.5); 8.663 (2.7); 8.542 (1.4); 8.539 (1.6); 8.536 (1.6); 8.532 (1.4); 8.522 (1.5); 8.518 (1.6); 8.515 (1.7); 8.511 (1.5); 8.072 (4.1); 7.858 (2.7); 7.855 (2.3); 7.851 (3.7); 7.847 (3.9); 7.835 (3.6); 7.731 (2.9); 7.727 (2.9); 7.708 (2.1); 7.704 (2.1); 7.681 (1.9); 7.669 (1.9); 7.660 (1.9); 7.648 (1.9); 7.587 (1.9); 7.583 (1.9); 7.568 (2.3); 7.563 (2.3); 7.380 (3.2); 7.360 (2.6); 4.171 (1.3); 4.145 (4.3); 4.119 (4.4); 4.093 (1.5); 3.349 (0.4); 3.334 (63.3); 2.673 (0.3); 2.526 (0.8); 2.513 (18.3); 2.509 (37.9); 2.504 (50.6); 2.499 (37.8); 2.495 (19.1); 2.416 (16.0); 2.331 (0.3); 1.397 (0.4).

Example 51: 5-[2,4-Dimethyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole

[0913] ##STR00166##

[0914] Similar to the reaction procedure from T. Furuya et al., J. Am. Chem. Soc., 2010, 132, 3793-3807, under argon, 60 mg (0.43 mmol) of potassium carbonate, 100 mg (289 μmol) of 2-[2,4-dimethyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 17 mg (15 μmol) of tetrakis(triphenylphosphine)palladium were added to a solution of 79 mg (0.28 mmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2) in 1.0 ml of 1,2-dimethoxyethane and 1.0 ml of water. The reaction mixture was stirred at 100° C. for 3 hours and, after cooling to room temperature, water was added. The phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with saturated sodium chloride solution and dried with sodium sulphate, and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.60:40) and then once more by HPLC (gradient: H.sub.2O/acetonitrile 90:10.fwdarw.0:100). This gave 37 mg (98% pure, 30% yield) of 5-[2,4-dimethyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole.

[0915] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.366 (3.2); 9.359 (3.2); 9.247 (5.6); 9.245 (5.6); 8.679 (2.2); 8.676 (2.4); 8.667 (2.3); 8.664 (2.4); 8.533 (1.3); 8.529 (1.5); 8.526 (1.5); 8.523 (1.3); 8.512 (1.4); 8.508 (1.5); 8.505 (1.6); 8.502 (1.4); 7.810 (2.7); 7.788 (3.0); 7.706 (4.1); 7.681 (1.8); 7.670 (1.7); 7.661 (1.7); 7.649 (1.7); 7.441 (5.8); 7.352 (2.5); 7.348 (2.5); 7.329 (2.3); 7.325 (2.4); 7.236 (4.8); 3.979 (1.3); 3.953 (4.0); 3.927 (4.2); 3.901 (1.4); 3.335 (13.6); 2.528 (0.4); 2.524 (0.6); 2.515 (8.4); 2.510 (17.5); 2.506 (23.5); 2.501 (17.5); 2.497 (8.7); 2.409 (14.6); 2.242 (16.0); 0.000 (1.1).

Example 52: 5-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole

[0916] ##STR00167##

[0917] At 0° C., 56 mg (0.23 mmol) of meta-chloroperbenzoic acid (70% pure) were added to a solution of 56 mg (0.23 mmol) of 5-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole (Example 49) in 5 ml of methylene chloride. The reaction mixture was stirred at room temperature for 2 hours, and saturated sodium carbonate solution was then added. After 15 minutes, the phases were separated, the aqueous phase was extracted with methylene chloride and the combined organic phases were dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.50:50). This gave 60 mg (100% pure, 62% yield) of 5-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole.

[0918] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.377 (3.5); 9.371 (3.5); 9.323 (6.1); 9.321 (5.9); 8.692 (2.5); 8.688 (2.7); 8.680 (2.6); 8.677 (2.7); 8.545 (1.4); 8.541 (1.6); 8.538 (1.5); 8.535 (1.4); 8.524 (1.6); 8.521 (1.6); 8.518 (1.7); 8.514 (1.4); 8.059 (7.0); 8.039 (3.4); 7.900 (2.8); 7.878 (3.3); 7.693 (1.9); 7.692 (1.9); 7.681 (1.8); 7.673 (1.8); 7.661 (1.8); 7.660 (1.8); 7.613 (1.3); 7.609 (2.3); 7.605 (1.3); 7.591 (1.2); 7.587 (2.0); 7.582 (1.1); 7.447 (2.6); 7.418 (2.5); 4.298 (0.5); 4.288 (0.5); 4.271 (0.7); 4.261 (1.7); 4.243 (0.4); 4.233 (2.1); 4.203 (1.8); 4.193 (0.6); 4.175 (0.6); 4.166 (0.6); 3.329 (42.3); 2.677 (0.4); 2.672 (0.5); 2.668 (0.4); 2.525 (1.4); 2.512 (28.8); 2.508 (57.1); 2.503 (74.6); 2.499 (54.0); 2.494 (25.9); 2.451 (16.0); 2.334 (0.4); 2.330 (0.5); 2.325 (0.4); 1.990 (0.7); 1.176 (0.4); 0.008 (1.4); 0.000 (41.3); −0.009 (1.3).

[0919] In an analogous manner, the compound 74 listed in Tables 1 and 3 was obtained from compound 63 by oxidation of the sulphur.

Example 53: 5-[4-Methyl-3-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole

[0920] ##STR00168##

[0921] The preparation of 5-[4-methyl-3-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole was carried out analogously to the synthesis of Example 52. Here, 104 mg (217 μmol) of 5-[4-methyl-3-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole and 54 mg (0.22 mmol) of meta-chloroperbenzoic acid (70% pure) were employed. This gave 64 mg (100% pure, 71% yield) of 5-[4-methyl-3-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole.

[0922] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.379 (3.6); 9.373 (3.7); 9.294 (6.2); 9.293 (6.0); 8.686 (2.5); 8.683 (2.7); 8.674 (2.7); 8.671 (2.7); 8.546 (1.4); 8.542 (1.7); 8.539 (1.6); 8.536 (1.4); 8.525 (1.6); 8.521 (1.7); 8.518 (1.8); 8.515 (1.5); 8.196 (4.0); 8.191 (4.2); 8.144 (4.2); 7.910 (2.1); 7.900 (2.9); 7.890 (2.4); 7.885 (2.4); 7.877 (3.7); 7.778 (2.9); 7.774 (2.8); 7.755 (2.0); 7.751 (2.0); 7.689 (1.9); 7.677 (1.9); 7.669 (1.9); 7.657 (1.8); 7.485 (3.0); 7.465 (2.7); 4.257 (0.4); 4.247 (0.6); 4.230 (0.8); 4.220 (1.9); 4.206 (1.8); 4.193 (2.0); 4.178 (2.0); 4.166 (0.8); 4.151 (0.7); 4.142 (0.4); 3.331 (136.6); 2.676 (0.5); 2.672 (0.7); 2.667 (0.5); 2.525 (1.9); 2.512 (38.7); 2.507 (77.7); 2.503 (102.1); 2.498 (75.9); 2.494 (38.6); 2.437 (16.0); 2.334 (0.5); 2.330 (0.7); 2.325 (0.5); 1.989 (0.6); 0.008 (0.5); 0.000 (14.6); −0.008 (0.7).

Example 54: 5-[2,4-Dimethyl-5-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole

[0923] ##STR00169##

[0924] The preparation of 5-[2,4-dimethyl-5-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole was carried out analogously to the synthesis of Example 52. Here, 117 mg of 5-[2,4-dimethyl-5-(2,2,2-trifluoroethylsulphanyl)phenyl]-2-(3-pyridyl)indazole (purity <70%) and 71 mg (0.28 mmol) of meta-chloroperbenzoic acid (70% pure) were employed. This gave 54 mg (100% pure) of 5-[2,4-dimethyl-5-(2,2,2-trifluoroethylsulphinyl)phenyl]-2-(3-pyridyl)indazole.

[0925] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.371 (3.3); 9.365 (3.5); 9.263 (5.7); 8.681 (2.5); 8.672 (2.5); 8.669 (2.6); 8.536 (1.6); 8.534 (1.6); 8.515 (1.7); 8.513 (1.7); 8.510 (1.4); 7.847 (2.6); 7.825 (2.9); 7.788 (4.4); 7.753 (6.3); 7.687 (1.8); 7.675 (1.8); 7.666 (1.8); 7.654 (1.7); 7.404 (2.3); 7.400 (2.4); 7.381 (2.2); 7.378 (2.2); 7.331 (4.8); 4.173 (1.1); 4.146 (3.4); 4.118 (3.5); 4.091 (1.2); 3.329 (83.0); 2.672 (0.9); 2.562 (0.3); 2.507 (107.3); 2.503 (138.4); 2.498 (111.3); 2.403 (14.9); 2.341 (16.0); 1.989 (0.6); 0.146 (0.9); 0.000 (175.9); −0.150 (0.9).

Example 55: 2-(3-Pyridyl)-5-[4-(trifluoromethyl)pyrazol-1-yl]indazole

[0926] ##STR00170##

[0927] Similar to the reaction procedure from J. C. Antilla et al., J. Org. Chem., 2004, 69, 5578-5587, under argon, 100 mg (365 μmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2) and 20 μl (0.12 mmol) of trans-N,N′-dimethylcyclohexane-1,2-diamine in 1.0 ml of degassed toluene were added to a mixture of 12 mg (63 μmol) copper(I) iodide, 41 mg (0.30 mmol) of 4-(trifluoromethyl)-1H-pyrazole and 88 mg (0.64 mmol) of potassium carbonate. The vessel was closed and the reaction mixture was heated in a CEM Discover microwave reactor to 120° C. for 18 hours. After cooling to room temperature, the mixture was filtered though a depth filter which was subsequently rinsed with ethyl acetate. After the solvent has been removed under reduced pressure, the residue is separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.50:50). This gave 17 mg (94% pure, 16% yield) of 2-(3-pyridyl)-5-[4-(trifluoromethyl)pyrazol-1-yl]indazole.

[0928] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.379 (2.7); 9.361 (13.4); 9.259 (7.9); 9.210 (0.4); 8.695 (2.3); 8.686 (2.4); 8.550 (2.2); 8.547 (2.6); 8.544 (2.5); 8.541 (2.1); 8.529 (2.4); 8.526 (2.6); 8.523 (2.7); 8.520 (2.2); 8.285 (8.4); 8.237 (9.1); 7.947 (16.0); 7.943 (15.7); 7.693 (2.6); 7.681 (2.6); 7.672 (2.6); 7.660 (2.5); 5.759 (0.7); 3.333 (56.9); 2.678 (0.5); 2.673 (0.7); 2.527 (2.0); 2.513 (40.5); 2.509 (79.4); 2.505 (102.3); 2.500 (75.1); 2.336 (0.5); 2.331 (0.6); 1.245 (0.5); 1.230 (0.5); 0.146 (0.9); 0.022 (0.5); 0.008 (8.3); 0.000 (189.5); −0.009 (7.9); −0.150 (1.0).

Example 56: 2-(3-Pyridyl)-5-[3-(trifluoromethyl)pyrazol-1-yl]indazole

[0929] ##STR00171##

[0930] The preparation of 2-(3-pyridyl)-5-[3-(trifluoromethyl)pyrazol-1-yl]indazole was carried out analogously to the synthesis of Example 55. Here, 100 mg (735 μmol) of 3-(trifluoromethyl)-1H-pyrazole, 242 mg (882 μmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2), 7.1 mg (37 μmol) of copper(I) iodide, 213 mg (1.54 mmol) of potassium carbonate and 24 μl (0.15 mmol) of trans-N,N′-dimethylcyclohexane-1,2-diamine were employed. The reaction was carried out in degassed toluene (1 ml) and the reaction time was 6 hours. This gave 167 mg (100% pure, 69% yield) of 2-(3-pyridyl)-5-[3-(trifluoromethyl)pyrazol-1-yl]indazole.

[0931] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.375 (8.8); 9.368 (8.8); 9.346 (16.0); 8.809 (7.3); 8.806 (7.4); 8.699 (5.9); 8.696 (6.4); 8.688 (6.1); 8.684 (6.3); 8.547 (3.4); 8.543 (3.9); 8.540 (3.8); 8.537 (3.4); 8.526 (3.7); 8.522 (3.9); 8.519 (4.1); 8.516 (3.4); 8.318 (0.5); 8.277 (9.1); 8.274 (8.8); 7.968 (3.2); 7.944 (11.9); 7.930 (9.9); 7.925 (9.3); 7.907 (2.6); 7.902 (2.8); 7.695 (4.7); 7.683 (4.6); 7.674 (4.6); 7.662 (4.4); 7.076 (8.5); 7.070 (8.5); 3.332 (215.6); 2.677 (0.9); 2.673 (1.2); 2.669 (0.9); 2.526 (3.4); 2.513 (66.6); 2.508 (131.4); 2.504 (171.9); 2.499 (127.4); 2.335 (0.8); 2.331 (1.2); 2.326 (0.8); 1.990 (0.6); 0.000 (0.7).

Example 57: 2,5-Bis(3-pyridyl)indazole

[0932] ##STR00172##

[0933] Similar to the reaction procedure from H. Dong et al., Org. Lett., 2011, 13, 2726-2729, under argon [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), 4.0 ml of 1,4-dioxane, 1.0 ml of water and 100 mg (365 μmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2) were added to a mixture of 58 mg (0.47 mmol) of 3-pyridylboronic acid, 155 mg (1.46 mmol) of sodium carbonate and 13.0 mg (18 μmol). The reaction mixture was heated at 80° C. for 2.5 hours and, after cooling to room temperature, filtered through cotton and then made basic with 1 M aqueous sodium hydroxide solution. The phases were separated and the aqueous phase was extracted repeatedly with methylene chloride. The combined organic phases were dried with sodium sulphate and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.100:0). This gave 80 mg (100% pure, 81% yield) of 2,5-bis(3-pyridyl)indazole.

[0934] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.384 (9.1); 9.377 (9.3); 9.309 (16.0); 8.988 (8.7); 8.983 (8.9); 8.685 (5.7); 8.682 (6.6); 8.673 (6.1); 8.670 (6.6); 8.591 (5.6); 8.587 (6.3); 8.579 (6.0); 8.575 (6.2); 8.554 (3.3); 8.550 (3.9); 8.547 (4.0); 8.544 (3.5); 8.533 (3.6); 8.529 (4.0); 8.527 (4.3); 8.523 (3.6); 8.318 (0.3); 8.179 (3.3); 8.173 (4.8); 8.169 (3.6); 8.154 (15.7); 7.898 (6.3); 7.876 (8.7); 7.754 (7.1); 7.750 (7.3); 7.732 (5.3); 7.727 (5.5); 7.686 (5.1); 7.674 (5.0); 7.665 (5.0); 7.653 (4.8); 7.528 (4.8); 7.516 (4.7); 7.508 (4.6); 7.496 (4.4); 3.332 (103.5); 2.677 (0.7); 2.673 (0.9); 2.669 (0.7); 2.526 (2.4); 2.508 (102.3); 2.504 (136.8); 2.499 (104.3); 2.335 (0.6); 2.331 (0.9); 2.326 (0.7); 1.990 (0.4); 1.259 (0.4); 1.250 (0.3); 1.230 (0.5); 0.000 (5.7).

Example 58: 5-(1-Methylpyrazol-4-yl)-2-(3-pyridyl)indazole

[0935] ##STR00173##

[0936] Similar to the reaction procedure from Ch. O. Ndubaku et al., J. Med. Chem., 2013, 56, 4597-4610, 1.2 ml of water and 0.6 ml of acetonitrile were added to a mixture of 100 mg (365 μmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2) and 107 mg (1.09 mmol) of potassium acetate. The reaction mixture was repeatedly flushed with a stream of argon, and 114 mg (547 μmol) of 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole as a solution in 0.6 ml of acetonitrile followed by 42 mg (36 μmol) of tetrakis(triphenylphosphine)palladium were then added. The vessel was closed and the reaction mixture was heated in a CEM Discover microwave reactor to 120° C. for 60 min. The reaction mixture was filtered through a depth filter which was rinsed with ethyl acetate. The filtrate was washed with water, the phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were dried with sodium sulphate and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.100:0). This gave 26 mg (100% pure, 26% yield) of 5-(1-methylpyrazol-4-yl)-2-(3-pyridyl)indazole.

[0937] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.349 (2.4); 9.343 (2.4); 9.149 (4.2); 9.147 (4.1); 8.656 (1.7); 8.653 (1.8); 8.645 (1.8); 8.641 (1.8); 8.511 (1.0); 8.507 (1.2); 8.504 (1.1); 8.501 (1.0); 8.490 (1.1); 8.486 (1.2); 8.483 (1.2); 8.480 (1.0); 8.199 (4.4); 7.943 (4.6); 7.942 (4.5); 7.913 (3.2); 7.757 (1.8); 7.735 (2.5); 7.664 (1.3); 7.663 (1.3); 7.652 (1.3); 7.643 (1.3); 7.631 (1.3); 7.630 (1.3); 7.618 (2.1); 7.614 (2.1); 7.596 (1.6); 7.592 (1.6); 3.885 (16.0); 3.334 (44.0); 2.526 (0.9); 2.512 (17.3); 2.508 (34.2); 2.504 (44.4); 2.499 (32.6); 2.495 (16.2); 1.232 (0.8); 0.000 (7.6).

Example 59: 5-(2-Pyridyl)-2-(3-pyridyl)indazole

Step 1: 2-(3-Pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indazole (59a)

[0938] ##STR00174##

[0939] Similar to the reaction procedure from T. Ishiyama et al., J. Org. Chem., 1995, 60, 7508-7510, under argon, degassed 1,4-dioxane (6.0 ml) was added to a mixture of 500 mg (1.82 mmol) of 5-bromo-2-(3-pyridyl)indazole (cf. Example 49, step 2), 486 mg (1.92 mmol) of bis(pinacolato)diboron, 537 mg (5.47 mmol) of potassium acetate, 45 mg (55 μmol) of [1,1′-bis(diphenylphosphino)ferrocene]dichlorpalladium(II) (1:1 adduct with methylene chloride) and 30 mg (55 μmol) of 1,1′-bis(diphenylphosphino)ferrocene. The reaction mixture was heated under reflux for 6 hours and, after cooling to room temperature, filtered through a depth filter which was rinsed with ethyl acetate. Water and methylene chloride were added to the filtrate, the phases were separated and the aqueous phase was extracted with methylene chloride. The combined organic phases were dried with sodium sulphate and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.50:50). This gave 343 mg (70% pure, 42% yield) of 2-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indazole as a mixture with 2-(3-pyridyl)indazole. Without further purification, this mixture was used for subsequent reactions.

[0940] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.349 (1.4); 9.342 (1.4); 9.287 (1.4); 9.285 (1.4); 9.216 (1.2); 9.214 (1.2); 8.678 (0.6); 8.674 (0.6); 8.666 (1.1); 8.663 (1.1); 8.655 (0.5); 8.651 (0.5); 8.523 (0.3); 8.520 (0.4); 8.517 (0.4); 8.513 (0.6); 8.510 (0.4); 8.506 (0.4); 8.503 (0.6); 8.499 (0.5); 8.496 (0.5); 8.492 (0.7); 8.489 (0.4); 8.486 (0.4); 8.217 (1.3); 7.810 (0.6); 7.789 (0.6); 7.754 (0.5); 7.752 (0.5); 7.732 (0.6); 7.730 (0.6); 7.716 (0.6); 7.694 (0.8); 7.673 (0.5); 7.669 (0.5); 7.668 (0.5); 7.661 (0.5); 7.655 (0.6); 7.654 (0.6); 7.648 (0.5); 7.640 (0.5); 7.636 (0.4); 7.559 (0.8); 7.557 (0.8); 7.537 (0.6); 7.535 (0.6); 7.354 (0.4); 7.352 (0.4); 7.349 (0.3); 7.332 (0.3); 7.330 (0.3); 7.157 (0.4); 7.155 (0.4); 7.140 (0.4); 7.139 (0.4); 7.136 (0.4); 7.134 (0.4); 3.939 (0.4); 3.336 (6.5); 2.510 (8.3); 2.505 (10.7); 2.501 (7.9); 1.397 (1.3); 1.328 (16.0); 1.072 (2.3).

Step 2: 5-(2-Pyridyl)-2-(3-pyridyl)indazole

[0941] ##STR00175##

[0942] Similar to the reaction procedure from T. Furuya et al., J. Am. Chem. Soc., 2010, 132, 3793-3807, under argon, 39 mg (0.28 mmol) of potassium carbonate, 100 mg (218 μmol) of 2-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indazole (70% pure) and 11 mg (9.6 μmol) of tetrakis(triphenylphosphine)palladium were added to a solution of 18 μl (0.19 mmol) of 2-bromopyridine in 1.0 ml of 1,2-dimethoxyethane. The reaction mixture was heated at 100° C. for 3 hours and, after cooling to room temperature, water was added. The phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were dried with sodium sulphate and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.100:0). This gave 25 mg (100% pure, 41% yield) of 5-(2-pyridyl)-2-(3-pyridyl)indazole.

[0943] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.378 (9.5); 9.371 (9.4); 9.330 (15.8); 9.329 (16.0); 8.697 (5.2); 8.695 (5.4); 8.684 (11.3); 8.681 (10.9); 8.672 (6.8); 8.669 (6.8); 8.548 (3.8); 8.544 (4.4); 8.541 (4.4); 8.537 (4.3); 8.527 (14.6); 8.520 (5.2); 8.517 (3.9); 8.318 (0.6); 8.167 (6.3); 8.163 (6.1); 8.144 (7.2); 8.140 (7.2); 8.078 (6.7); 8.058 (8.6); 7.926 (3.6); 7.921 (3.6); 7.906 (5.6); 7.902 (5.5); 7.887 (3.1); 7.883 (3.1); 7.856 (8.5); 7.833 (7.4); 7.686 (5.2); 7.675 (5.0); 7.666 (5.0); 7.654 (4.8); 7.373 (4.1); 7.371 (4.3); 7.359 (4.5); 7.355 (4.3); 7.353 (4.0); 7.342 (3.8); 7.340 (3.8); 3.336 (231.2); 2.677 (1.2); 2.672 (1.6); 2.668 (1.2); 2.526 (4.3); 2.512 (90.3); 2.508 (177.5); 2.503 (229.6); 2.499 (167.1); 2.495 (82.5); 2.335 (1.1); 2.330 (1.5); 2.326 (1.1); 2.237 (0.6); 0.008 (2.4); 0.000 (66.9); −0.008 (2.5).

[0944] The compounds 61 to 73, 101 and 104 listed in Tables 1 and 3 were prepared in an analogous manner.

Example 60: 2-(3-Pyridyl)-5-pyrimidin-2-yl-indazole

[0945] ##STR00176##

[0946] Similar to the reaction procedure from WO 2010/151601, under argon, degassed acetonitrile (1.0 ml) and a solution of 86 mg (0.81 mmol) of sodium carbonate in degassed water (1.0 ml) were added to a mixture of 32 mg (0.20 mmol) of 2-bromopyrimidine, 109 mg (238 μmol) of 2-(3-pyridyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indazole (70% pure) and 7 mg (6 μmol) of tetrakis(triphenylphosphine)palladium. The reaction mixture was heated at 73° C. for 24 hours and, after cooling to room temperature, water and ethyl acetate were added. The phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were dried with magnesium sulphate and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 50:50.fwdarw.75:2). This gave 60 mg (96% pure, yield 88%) of 2-(3-pyridyl)-5-pyrimidin-2-ylindazole.

[0947] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.408 (7.7); 9.406 (7.6); 9.373 (4.0); 9.367 (4.0); 8.934 (14.4); 8.922 (16.0); 8.918 (6.0); 8.915 (4.4); 8.695 (2.8); 8.691 (3.0); 8.683 (2.9); 8.679 (3.0); 8.544 (1.8); 8.541 (2.1); 8.538 (2.0); 8.534 (1.8); 8.524 (2.0); 8.520 (2.1); 8.517 (2.2); 8.513 (1.9); 8.418 (3.6); 8.414 (3.5); 8.395 (3.9); 8.391 (3.9); 7.871 (4.3); 7.848 (4.0); 7.694 (2.3); 7.693 (2.3); 7.682 (2.3); 7.681 (2.3); 7.673 (2.3); 7.672 (2.3); 7.661 (2.2); 7.660 (2.2); 7.456 (3.9); 7.443 (7.3); 7.431 (3.8); 5.761 (0.7); 3.340 (50.8); 2.529 (0.6); 2.524 (0.9); 2.516 (14.0); 2.511 (28.9); 2.507 (38.4); 2.502 (27.9); 2.498 (13.6); 0.000 (5.9).

Example 75: N-Cyclopropyl-N-methyl-2-(pyridin-3-yl)-2H-indazole-5-carboxamide

[0948] ##STR00177##

[0949] A solution of 57 mg (0.24 mmol) of 2-(pyridin-3-yl)-2H-indazole-5-carboxylic acid, 17 mg (0.24 mmol) of N-methylcyclopropanamine, 55 mg (0.29 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and 3.2 mg (24 μmol) of 1-hydroxy-1H-benzotriazole in 3 ml of pyridine was stirred at room temperature for 4 hours. The reaction mixture was diluted with water and ethyl acetate. The phases were separated and the aqueous phase was then extracted three times with ethyl acetate. The combined organic phases were dried with sodium sulphate and filtered and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.100:0). This gave 30 mg (100% pure, 43% yield) of N-cyclopropyl-N-methyl-2-(pyridin-3-yl)-2H-indazole-5-carboxamide.

[0950] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.350 (3.2); 9.343 (3.3); 9.287 (5.6); 9.285 (5.5); 8.681 (2.1); 8.677 (2.3); 8.669 (2.3); 8.666 (2.3); 8.522 (1.2); 8.518 (1.4); 8.515 (1.4); 8.512 (1.3); 8.501 (1.3); 8.497 (1.4); 8.495 (1.5); 8.491 (1.3); 7.978 (3.7); 7.761 (2.5); 7.738 (2.9); 7.677 (1.8); 7.665 (1.7); 7.656 (1.7); 7.644 (1.7); 7.468 (2.0); 7.465 (2.0); 7.446 (1.7); 7.442 (1.8); 5.755 (3.4); 3.319 (22.1); 3.008 (16.0); 2.987 (1.3); 2.978 (0.9); 2.970 (0.7); 2.960 (0.4); 2.672 (0.4); 2.525 (0.7); 2.511 (19.0); 2.507 (38.5); 2.503 (51.1); 2.498 (37.7); 2.494 (18.9); 0.561 (1.8); 0.547 (1.8); 0.458 (2.1); 0.008 (0.8); 0.000 (23.7); −0.008 (1.0) ppm.

Example 76: 5-[4-(Ethylsulphanyl)pyridin-2-yl]-2-(pyridin-3-yl)-2H-indazole

[0951] ##STR00178##

[0952] 93 mg (0.89 mmol) of sodium ethanethiolate were added to a solution of 27 mg (89 μmol) of 5-(4-chloropyridin-2-yl)-2-(pyridin-3-yl)-2H-indazole in 4 ml of absolute dimethylformamide. The reaction mixture was stirred at room temperature overnight, and then the solvent was removed under reduced pressure. The residue was taken up in ethyl acetate and water, the phases were separated and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried with sodium sulphate and filtered and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.50:0). This gave 11 mg (100% pure, 38% yield) of 5-[4-(ethylsulphanyl)pyridin-2-yl]-2-(pyridin-3-yl)-2H-indazole.

[0953] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.375 (4.2); 9.369 (4.3); 9.309 (7.2); 8.683 (2.9); 8.680 (3.1); 8.672 (3.1); 8.669 (3.1); 8.545 (6.4); 8.534 (1.8); 8.523 (1.9); 8.519 (2.0); 8.516 (2.1); 8.513 (1.7); 8.486 (4.3); 8.473 (4.4); 8.150 (2.8); 8.146 (2.7); 8.127 (3.2); 8.123 (3.1); 7.852 (5.0); 7.850 (5.1); 7.837 (4.0); 7.814 (3.4); 7.685 (2.3); 7.673 (2.2); 7.664 (2.2); 7.652 (2.1); 7.236 (3.1); 7.232 (3.1); 7.223 (3.1); 7.219 (3.0); 3.318 (62.4); 3.232 (2.2); 3.214 (6.9); 3.195 (7.1); 3.177 (2.3); 2.676 (0.6); 2.671 (0.8); 2.667 (0.6); 2.507 (87.7); 2.502 (113.3); 2.498 (84.3); 2.333 (0.6); 2.329 (0.7); 2.325 (0.5); 1.363 (7.6); 1.345 (16.0); 1.327 (7.4); 1.259 (0.4); 1.250 (0.7); 1.230 (0.6); 0.000 (2.0) ppm.

[0954] The compounds 77 to 80 listed in Tables 1 and 3 were prepared in an analogous manner.

Example 81: N-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-(pyridin-3-yl)-2H-indazole-5-carboxamide

[0955] ##STR00179##

[0956] Under an atmosphere of argon, 0.53 ml (1.07 mmol) of a 2M solution of trimethylaluminium in toluene was slowly added dropwise to a solution of 251 mg (1.07 mmol) of 2,4-dimethyl-5-[(2,2,2-trifluoroethyl)sulphanyl]aniline in 5 ml of 1,2-dichloroethane. The solution was stirred at room temperature for 30 minutes, 200 mg (0.71 mmol) of methyl 2-(pyridin-3-yl)-2H-indazole-5-carboxylate were added and the mixture was then stirred at 100° C. overnight. After cooling to room temperature, a saturated potassium sodium tartrate solution was added to the reaction mixture carefully, and the mixture was then extracted repeatedly with dichloromethane. The combined organic phases were dried with sodium sulphate and filtered and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 0:100.fwdarw.100:0). This gave 102 mg (90% pure, 28% yield) of N-{2,4-dimethyl-5-[(2,2,2-trifluoroethyl) sulphanyl]phenyl}-2-(pyridin-3-yl)-2H-indazole-5-carboxamide.

[0957] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.967 (3.6); 9.462 (5.6); 9.448 (0.4); 9.390 (3.2); 9.384 (3.3); 8.702 (2.3); 8.699 (2.5); 8.690 (2.4); 8.687 (2.5); 8.557 (5.0); 8.539 (1.5); 8.536 (1.8); 8.533 (1.9); 8.529 (1.5); 7.921 (1.4); 7.918 (1.3); 7.899 (2.6); 7.895 (2.6); 7.851 (3.5); 7.828 (1.8); 7.698 (1.8); 7.686 (1.8); 7.678 (1.8); 7.666 (1.7); 7.571 (5.2); 7.208 (4.7); 4.038 (0.4); 4.021 (0.4); 3.892 (1.1); 3.866 (3.5); 3.840 (3.6); 3.814 (1.2); 3.317 (32.3); 2.675 (0.4); 2.671 (0.5); 2.666 (0.4); 2.524 (1.5); 2.510 (31.3); 2.506 (61.7); 2.502 (81.3); 2.497 (60.7); 2.493 (30.4); 2.385 (14.2); 2.333 (0.5); 2.329 (0.6); 2.324 (0.5); 2.226 (16.0); 2.204 (1.4); 2.185 (0.9); 1.988 (1.9); 1.193 (0.5); 1.175 (1.0); 1.158 (0.5); 0.008 (1.4); 0.000 (38.9); −0.008 (1.4) ppm.

[0958] The compounds 82 to 93 listed in Tables 1 and 3 were prepared in an analogous manner.

Example 94: N-{4-Methyl-3-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-2-(pyridin-3-yl)-2H-indazole-5-carboxamide

[0959] ##STR00180##

[0960] A catalytic amount of sodium tungstate was added to a solution of 50 mg (0.11 mmol) of N-{4-methyl-3-[(2,2,2-trifluoroethyl)sulphanyl]phenyl}-2-(pyridin-3-yl)-2H-indazole-5-carboxamide in 2.5 ml of acetic acid, and 98 μl (0.11 mmol) of 3.5% strength hydrogen peroxide solution were added at 0° C. The reaction mixture was stirred at 0° C. for one hour and overnight at room temperature. 4 μl (44 μmol) of 35% strength hydrogen peroxide solution were then added, and the mixture was stirred at room temperature for a further night. The reaction mixture was diluted with water and dichloromethane. The organic phase was separated off and washed successively with water and concentrated sodium bisulphite solution. The organic phase was then dried with sodium sulphate and filtered and the solvent was removed under reduced pressure. The residue was separated chromatographically by MPLC on silica gel (gradient: ethyl acetate/cyclohexane 20:80.fwdarw.100:0). This gave 19.8 mg (95% pure, 37% yield) of N-{4-methyl-3-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-2-(pyridin-3-yl)-2H-indazole-5-carboxamide.

[0961] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=10.618 (4.2); 9.478 (6.2); 9.394 (3.7); 9.387 (3.8); 8.706 (2.5); 8.703 (2.8); 8.695 (2.7); 8.691 (2.9); 8.600 (4.5); 8.563 (1.4); 8.560 (1.7); 8.557 (1.6); 8.553 (1.5); 8.543 (1.6); 8.539 (1.7); 8.536 (1.8); 8.532 (1.5); 8.373 (3.9); 8.368 (4.2); 8.314 (0.3); 8.000 (1.9); 7.995 (1.9); 7.980 (2.1); 7.974 (2.1); 7.940 (1.7); 7.936 (1.8); 7.917 (3.3); 7.913 (3.5); 7.869 (4.0); 7.847 (2.1); 7.703 (2.0); 7.691 (1.9); 7.682 (1.9); 7.670 (1.9); 7.367 (3.0); 7.346 (2.8); 4.181 (1.0); 4.171 (0.5); 4.153 (1.1); 4.143 (1.3); 4.126 (0.5); 4.116 (1.3); 4.089 (0.4); 3.949 (0.3); 3.922 (1.2); 3.913 (0.4); 3.895 (1.4); 3.885 (1.1); 3.868 (0.5); 3.858 (1.0); 3.832 (0.3); 3.318 (50.7); 2.791 (0.6); 2.676 (0.6); 2.671 (0.8); 2.667 (0.6); 2.635 (0.5); 2.524 (2.4); 2.511 (44.9); 2.507 (91.6); 2.502 (122.3); 2.497 (92.4); 2.493 (47.8); 2.351 (16.0); 2.333 (0.9); 2.329 (1.0); 2.324 (0.8); 1.336 (0.7); 1.299 (0.5); 1.259 (0.8); 1.250 (1.0); 1.234 (0.5); 0.146 (0.6); 0.008 (5.1); 0.000 (138.3); −0.008 (6.3); −0.150 (0.6) ppm.

[0962] The compounds 95 to 97 listed in Tables 1 and 3 were prepared in an analogous manner.

Example 98: 5-(1H-Pyrazol-4-yl)-2-(pyridin-3-yl)-2H-indazole

[0963] ##STR00181##

[0964] 1.06 g (5.47 mmol) of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole in 15 ml of N,N-dimethylformamide and 8.25 ml of water were initially charged in a 50 ml round-bottom flask. The flask was flushed with argon and kept under a stream of argon while 1.74 g (16.42 mmol) of sodium carbonate, 1.50 g (5.47 mmol) of 5-bromo-2-(3-pyridyl)indazole and 0.31 g (0.27 mmol) of tetrakis(triphenylphosphine)palladium were added. The reaction mixture was then stirred on an oil bath at 120° C. for about 18 hours. After cooling, the reaction mixture was filtered and the filter was rinsed with ethyl acetate. The filtrate was washed repeatedly with water. The organic phase was separated off and washed with water. The combined organic phases were dried over dried sodium sulphate, filtered and freed of the solvent under reduced pressure. For further purification, the residue was subjected to incipient dissolution in dichloromethane and separated from insoluble constituents by filtration. The filtrate was stirred with water and the insoluble fraction was filtered off and dried under reduced pressure. This gave 505 mg (100% pure by LC/MS, 35% yield) of the title compound.

[0965] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=12.941 (2.9); 9.350 (9.6); 9.344 (9.6); 9.136 (16.0); 8.655 (6.5); 8.652 (7.1); 8.643 (6.8); 8.640 (7.0); 8.510 (3.7); 8.507 (4.5); 8.505 (4.5); 8.501 (3.8); 8.490 (4.0); 8.486 (4.6); 8.484 (4.8); 8.480 (3.8); 8.314 (0.7); 8.257 (4.7); 8.007 (4.6); 7.951 (12.7); 7.755 (5.7); 7.732 (9.9); 7.676 (8.2); 7.673 (8.3); 7.662 (5.6); 7.650 (9.7); 7.641 (5.2); 7.629 (4.7); 3.321 (105.7); 2.891 (0.4); 2.732 (0.4); 2.672 (1.3); 2.507 (159.7); 2.503 (205.5); 2.498 (160.5); 2.329 (1.3); 0.000 (5.4) ppm.

Example 99: 2-(Pyridin-3-yl)-5-[1-(2,2,2-trifluoroethyl)-1H-pyrazol-4-yl]-2H-indazole

[0966] ##STR00182##

[0967] 100 mg (0.38 mmol) of 5-(1H-pyrazol-4-yl)-2-(pyridin-3-yl)-2H-indazole were initially charged in 2 ml of dried N,N-dimethylformamide. 79 mg (0.57 mmol) of potassium carbonate were added, the flask was kept under a stream of argon and 83 μl (133 mg, 0.57 mmol) of 2,2,2-trifluoroethyl trifluoromethanesulphonate were added. The reaction mixture was then stirred at room temperature overnight. The progress of the reaction was monitored by thin-layer chromatography and LC/MS. After addition of 28 μl (0.11 mmol) of trifluoroethyl trifluoromethanesulphonate, the reaction mixture was stirred at room temperature over the weekend. The filtrate was washed repeatedly with water and the combined organic phases were dried over dried sodium sulphate, filtered and freed of the solvent under reduced pressure. For further purification, the residue was subjected to incipient dissolution in dichloromethane and separated from insoluble constituents by filtration. The filtrate was stirred with water and the resulting solid was isolated by filtration. This gave 505 mg (100% pure by LC/MS, 35% yield) of the title compound.

[0968] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=9.356 (8.4); 9.350 (8.8); 9.175 (14.9); 8.661 (6.6); 8.649 (6.7); 8.513 (4.1); 8.492 (4.4); 8.349 (15.0); 8.139 (16.0); 7.998 (11.7); 7.786 (6.0); 7.763 (8.2); 7.667 (4.5); 7.655 (4.9); 7.646 (11.1); 7.635 (4.8); 7.623 (5.3); 5.206 (2.9); 5.183 (9.2); 5.160 (9.6); 5.137 (3.3); 3.323 (45.8); 2.673 (0.7); 2.504 (114.3); 2.330 (0.7); 1.990 (0.9); 1.176 (0.5); 0.146 (0.6); 0.000 (109.6); −0.150 (0.6) ppm.

General Synthesis of 2-(hetaryl)-2H-indazole-5-amines of the Formula (I, R.SUP.2.═NH.SUB.2.)

[0969] ##STR00183##

[0970] Under an atmosphere of protective gas (argon), the 4-substituted 2-(hetaryl)indazole-5-carboxylic acids of the formula (I; R.sup.2═COOH) were dissolved in dried 1,4-dioxane (4 ml/mmol), and 1.5 equiv. of diphenylphosporyl azide (DPPA) and 1.5 equiv. of triethylamine were then added. The reaction mixture was then stirred at room temperature for 3 hours. After addition of 1M hydrochloric acid (4 ml/mmol), the reaction mixture was stirred at 100° C. for 30 minutes. After cooling to room temperature, the pH was adjusted to 7 by addition of a sodium carbonate solution and the reaction mixture was extracted with dichloromethane (3×4 ml/mmol). The organic phase was dried over magnesium sulphate and concentrated under reduced pressure. The crude product that remained was purified on a silica gel column; the mobile phase used was a gradient from 0% to 5% methanol in dichloromethane.

2-(1-Methyl-1H-pyrazol-4-yl)-2H-indazole-5-amines of the Formula (I, A=1-methyl-1H-pyrazol-4-yl; R.SUP.1.═H, R.SUP.2.═NH.SUB.2.)

[0971] ##STR00184##

[0972] This compound was prepared, for example, from 2.87 g (11.8 mmol) of 2-(1-methyl-1H-pyrazol-4-yl)-2H-indazole-5-carboxylic acid in accordance with the general synthesis mentioned. This gave 2.06 g (81% yield of theory; purity according to HPLC-MS 98%) of the title compound.

[0973] APCI MS, m/z=214 [M+H].sup.+

General Synthesis of N-methyl-2-(hetaryl)-2H-indazole-5-amines of the Formula (I, R.SUP.2.═NHCH.SUB.3.)

Method A:

[0974] ##STR00185##

[0975] A sodium methoxide solution which had been prepared from 5 equiv. of sodium and methanol (5 ml/mmol) was added to a suspension consisting of the corresponding 2-(hetaryl)-2H-indazole-5-amines of the formula (I, R.sup.2═NH.sub.2) and 5 equiv. of paraformaldehyde in methanol (50 ml/mmol). The reaction mixture was then stirred at reflux temperature for one hour, and 5 equiv. of sodium borohydride were added. The reaction mixture was then stirred for a further 30 minutes and cooled to room temperature. 1M sodium hydroxide solution (50 ml/mmol) was added and the reaction mixture was extracted with dichloromethane (3×50 ml/mmol). The combined organic phase was dried over magnesium sulphate, filtered and concentrated under reduced pressure.

N-Methyl-2-(1-methyl-1H-pyrazol-4-yl)-2H-indazole-5-amines of the formula (I, A=1-methyl-1H-pyrazol-4-yl; R.SUP.1.═H, R.SUP.2.═NH.SUB.2.)

[0976] ##STR00186##

[0977] This compound was prepared, for example, from 9.90 g (4.6 mmol) of 2-(1-methyl-1H-pyrazol-4-yl)-2H-indazole-5-amine in accordance with the general synthesis mentioned. This gave 1.20 g (100% yield of theory; purity according to HPLC-MS 99%) of the title compound.

[0978] APCI MS, m/z=228 [M+H].sup.+

Method B:

Step 1

[0979] Under an atmosphere of protective gas (argon), the 5-bromo-2-(hetaryl)-2H-indazoles (cf. compound 49, step 2) were dissolved in dried 1,4-dioxane (3 ml/mmol), and 1.2 equiv. of tert-butyl carbamate, 2 equiv. of caesium carbonate, 0.05 equiv. of tris(dibenzylideneacetone)dipalladium and 0.1 equiv. of Xantphos were then added. The reaction mixture was stirred at reflux temperature for 6 hours and then cooled to room temperature. Water (3 ml/mmol) was then added, and the reaction mixture was extracted with ethyl acetate (3×3 ml/mmol). The organic phase was dried over magnesium sulphate, filtered and concentrated under reduced pressure. The crude product that remained was purified on a silica gel column; the mobile phase used was a gradient from 0% to 7% methanol in dichloromethane.

tert-Butyl (2-(2-pyridin-3-yl)-2H-indazol-5-yl)carbamates of the formula (I-f, A=pyridin-3-yl-; R.SUP.1.═H, R.SUP.2.═NH—CO—C(CH.SUB.3.).SUB.3

[0980] ##STR00187##

[0981] This compound was prepared, for example, from 2.47 g (9 mmol) of 5-bromo-2-(pyridin-3-yl)-2H-indazole in accordance with the general synthesis mentioned. This gave 1.67 g (60% yield of theory; purity according to HPLC-MS 98%) of the title compound.

[0982] APCI MS, m/z=311 [M+H].sup.+

Step 2

[0983] Under an atmosphere of protective gas (argon), the tert-butyl (2-hetaryl)-2H-indazol-5-yl)carbamates were dissolved in dried tetrahydrofuran (20 ml/mmol), and 2,5 equiv. of lithium aluminium hydride were then added a little at a time. The reaction mixture was then stirred at reflux temperature for 10 hours, another 1 equiv. of lithium aluminium hydride was added and the mixture was stirred at reflux temperature for a further 20 hours. 1M aqueous sodium hydroxide solution (1 ml/mmol) was then added, and the mixture was filtered. The filtrate was concentrated under reduced pressure and the residue that remained was taken up in dichloromethane (10 ml/mmol). The resulting solution was washed with aqueous sodium carbonate solution (10 ml/mmol), dried over magnesium sulphate, filtered and concentrated under reduced pressure. The crude product that remained was purified on a silica gel column; the mobile phase used was a gradient from 0% to 5% methanol in dichloromethane.

N-Methyl-(2-pyridin-3-yl)-2H-indazole-5-amines of the Formula (I, A=pyridin-3-yl-; R.SUP.1.═H, R.SUP.2.═NH.SUB.2.)

[0984] ##STR00188##

[0985] This compound was prepared, for example, from 1.67 g (5.4 mmol) of tert-butyl (2-(2-pyridin-3-yl)-2H-indazol-5-yl)carbamate in accordance with the general synthesis mentioned. This gave 686 mg (57% yield of theory; purity according to HPLC-MS 93%) of the title compound.

[0986] APCI MS, m/z=225 [M+H].sup.+

General Synthesis of Compounds of the Formula (I-g)

Method A:

[0987] ##STR00189##

[0988] The respective N-methyl-2-(hetaryl)-2H-indazole-5-amines of the formula (I, A=hetaryl; R.sup.1═H, R.sup.2═NH—CH.sub.3) were dissolved in dried dichloromethane (5 ml/mmol) and, at 0° C. and with stirring, 1.2 equiv. of the appropriate acids, 2.4 equiv. of diisopropylethylamine (Hünig base) and 1.5 equiv. of a 50% strength solution of propylphosphonic anhydride (T3P) in tetrahydrofuran were added. The reaction mixture was then stirred at 0° C. for a further 30 minutes and subsequently at room temperature for 20 hours. After the reaction had ended, the reaction mixture was dissolved in dichloromethane (5 ml/mmol) and washed first with aqueous potassium carbonate solution (5 ml/mmol) and then with water (5 ml/mmol). The organic phase was dried over magnesium sulphate, filtered and concentrated under reduced pressure. The crude product that remained was purified on a silica gel column; the mobile phase used was a gradient from 0% to 5% methanol in dichloromethane.

Example 105: N,2-Dimethyl-N-(2-(1-methyl-1H-pyrazol-4-yl)-2H-indazol-5-yl)-3-(methylthio) propanamide

[0989] ##STR00190##

[0990] This compound was prepared, for example, from 300 mg (1.3 mmol) of 2-(1-methyl-1H-pyrazol-4-yl)-2H-indazole-5-amine in accordance with the general synthesis mentioned. This gave 389 mg (86% yield of theory; purity according to HPLC-MS 98%) of the title compound.

[0991] APCI MS, m/z=344 [M+H].sup.+

[0992] .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ=0.99 (3H, d, J=6.4 Hz), 1.79 (3H, s), 2.30 (1H, dd, J1=11.8 Hz, J2=4.9 Hz), 2.57-2.77 (2H, m), 3.21 (3H, s), 3.93 (3H, s), 7.22 (1H, dd, J1=9.0 Hz, J2=1.7 Hz), 7.71-7.81 (2H, m), 8.08 (1H, s), 8.43 (1H, s), 8.86 (1H, s) ppm.

Method B:

[0993] At 0° C., 1.2 equiv. of pyridine were added to the respective N-methyl-2-(hetaryl)-2H-indazole-5-amines of the formula (I, A=hetaryl; R.sup.1═H, R.sup.2═NH—CH.sub.3) in dried dichloromethane (10 ml/mmol). 1.1 equiv. of the appropriate acid chloride were then added dropwise and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then washed with water (2×5 ml/mmol). The organic phase was dried, filtered through magnesium sulphate and concentrated under reduced pressure. The crude product that remained was purified by HPLC.

Example 106: N-Methyl-N-(2-(1-methyl-1H-pyrazol-4-yl)-2H-indazol-5-yl)-3-(methylthio) propanamide

[0994] ##STR00191##

[0995] This compound was prepared, for example, from 300 mg (1.3 mmol) of 2-(1-methyl-1H-pyrazol-4-yl)-2H-indazole-5-amine in accordance with the general synthesis mentioned. This gave 452 mg (100% yield of theory; purity according to HPLC-MS 97%) of the title compound.

[0996] APCI MS, m/z=330 [M+H]

[0997] .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ=1.88 (3H, s), 2.34 (2H, t, J=7.1 Hz), 2.62 (2H, t, J=7.1 Hz), 3.20 (3H, s), 3.93 (3H, s), 7.21 (1H, dd, J1=8.9 Hz, J2=1.5 Hz), 7.70-7.79 (2H, m), 8.08 (1H, s), 8.44 (1H, s), 8.85 (1H, s).

[0998] The compounds 107 to 113 listed in Tables 1 and 2 were prepared in an analogous manner.

Method C:

[0999] The respective N-methyl-2-(hetaryl)-2H-indazole-5-amines of the formula (I, A=hetaryl; R.sup.1═H, R.sup.2═NH—CH.sub.3) were stirred in N,N-dimethylformamide (3 ml/mmol), 1.0 equiv. of the appropriate carboxylic acid, 1.1 equiv. of 1-hydroxybenzotriazole (HOBt), 1.1 equiv. of diisopropylethylamine (Hünig base) and 1.1 equiv. of 1-ethyl-3-(3-dimethylaminopropyl)carbodimide (EDCI) were added and the mixture was stirred at 60° C. for 8 hours. The reaction mixture is then dissolved in dichloromethane (5 ml/mmol) and washed with water (3×5 ml/mmol). The organic phase was dried, filtered through magnesium sulphate and concentrated under reduced pressure. The crude product that remained was purified by HPLC.

[1000] The compounds 114 to 118 listed in Tables 1 and 2 were prepared in an analogous manner.

General Sulphonyl Oxidation Method

[1001] 0.9 equiv. of sodium perborate hydrate (NaBO.sub.3 4H.sub.2O) were added to a solution of the respective amide in glacial acetic acid (5 ml/mmol), and the reaction mixture was stirred at 60° C. for 1 hour. Saturated sodium bicarbonate solution was then added until the evolution of gas had ceased. The reaction mixture was then extracted with ethyl acetate (3×5 ml/mmol). The organic phase was dried, filtered through magnesium sulphate and concentrated under reduced pressure. The crude product that remained was purified on a silica gel column; the mobile phase used was a gradient from 0% to 5% methanol in dichloromethane.

Example 119: N-Methyl-N-(2-(1-methyl-1H-pyrazol-4-yl)-2H-indazol-5-yl)-3-(methylsulphinyl) propanamide

[1002] ##STR00192##

[1003] This compound was prepared, for example, from 80 mg (0.24 mmol) of N-methyl-N-(2-(1-methyl-1H-pyrazol-4-yl)-2H-indazol-5-yl)-3-(methylthio)propanamide in accordance with the general synthesis mentioned. This gave 71 mg (85% yield of theory; purity according to HPLC-MS 86%) of the title compound.

[1004] APCI MS, m/z=346 [M+H].sup.+

[1005] .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ=2.55 (3H, s), 2.59-2.72 (2H, m), 2.79-2.90 (1H, m), 3.05-318 (1H, m), 3.33 (3H, s), 4.00 (3H, s), 7.10 (1H, dd, J1=9.0 Hz, J2=1.9 Hz), 7.54 (1H, d, J=1.3 Hz), 7.80 (1H, d, J=9.0 Hz), 7.89 (1H, s), 7.94 (1H, s), 8.22 (1H, s) ppm.

[1006] The compounds 120 to 124 listed in Tables 1 and 2 were prepared in an analogous manner.

General Sulphonyl Oxidation Method

[1007] 2.2 equiv. of sodium perborate hydrate (NaBO.sub.3 4H.sub.2O) were added to a solution of the respective amide in glacial acetic acid (5 ml/mmol), and the reaction mixture was stirred at 60° C. for 1 hour. Saturated sodium bicarbonate solution was then added until the evolution of gas had ceased. The reaction mixture was then extracted with ethyl acetate (3×5 ml/mmol). The organic phase was dried, filtered through magnesium sulphate and concentrated under reduced pressure. The crude product that remained was purified on a silica gel column; the mobile phase used was a gradient from 0% to 5% methanol in dichloromethane.

Example 125: N-Methyl-N-(2-(1-methyl-1H-pyrazol-4-yl)-2H-indazol-5-yl)-3-(methylsulphonyl) propanamide

[1008] ##STR00193##

[1009] This compound was prepared, for example, from 80 mg (0.24 mmol) of N-methyl-N-(2-(1-methyl-1H-pyrazol-4-yl)-2H-indazol-5-yl)-3-(methylthio)propanamide in accordance with the general synthesis mentioned. This gave 60 mg (68% yield of theory; purity according to HPLC-MS 97%) of the target compound.

[1010] APCI MS, m/z=362 [M+H].sup.+

[1011] .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ=2.70 (2H, t, J=7.2 Hz), 2.94 (3H, s), 3.35 (3H, s), 3.40 (2H, t, J=7.2 Hz), 4.03 (3H, s), 7.12 (1H, dd, J1=9.0 Hz, J2=1.6 Hz), 7.57 (1H, s), 7.83 (1H, d, J=8.8 Hz), 7.92 (1H, s), 7.97 (1H, s), 8.25 (1H, s) ppm.

[1012] The compounds 126 to 130 listed in Tables 1 and 2 were prepared in an analogous manner.

Synthesis of the Intermediates

4-Bromo-1-[(methylsulphanyl)methyl]-1H-pyrazole

[1013] ##STR00194##

[1014] At 0° C., 41 mg (1.02 mmol) of sodium hydride were added a little at a time to a solution of 100 mg (0.68 mmol) of 4-bromo-1H-pyrazole in absolute dimethylformamide. The reaction mixture was stirred at room temperature for 15 min, 0.11 ml (1.4 mmol) of chlorodimethyl sulphide were added and the mixture was stirred at room temperature overnight. Water was then added, and the mixture was extracted repeatedly with ethyl acetate. The combined organic phases were dried with sodium sulphate and filtered and the solvent was removed under reduced pressure. This gave 100 mg (93% pure, 66% yield) of 4-bromo-1-[(methylsulphanyl)methyl]-1H-pyrazole.

[1015] .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ=8.069 (4.4); 7.591 (3.9); 5.242 (10.2); 3.319 (8.9); 2.502 (15.8); 2.157 (0.5); 2.121 (16.0); 2.029 (0.4); 2.024 (0.5); 1.236 (0.4); 0.002 (7.1); 0.000 (10.0)

Methyl 4-methyl-3-((2,2,2-trifluoroethyl)sulphinyl)benzoate

[1016] ##STR00195##

Step 1: Synthesis of methyl 4-methyl-3-((2,2,2-trifluoroethyl)thio)benzoate

[1017] 1.07 g (7.8 mmol) of potassium carbonate and 5.61 μl (1.1 mmol) of 2,2,2-trifluoroethyl iodide were added to a solution of 943 mg (5.17 mmol) of methyl 3-mercapto-4-methylbenzoate (see preparation in WO 2010/094695 A1) in 15 ml of DMF. The reaction mixture was then stirred at room temperature for 20 hours. The reaction mixture was then diluted with 50 ml of water and extracted twice with 50 ml of dichloromethane. The combined organic phases were dried with magnesium sulphate and filtered and the solvent was removed under reduced pressure. The crude product that remained was purified by flash chromatography; the mobile phase used was a gradient from 0% to 10% ethyl acetate in n-heptane. This gave 990 mg (purity: 93%; 72% yield) of methyl 4-methyl-3-((2,2,2-trifluoroethyl)thio)benzoate.

[1018] APCI MS, m/z=265 [M+H].sup.+

Step 2

[1019] 559 mg (3.6 mmol; 1.0 equiv.) of sodium perborate hydrate (NaBO.sub.3 4H.sub.2O) were added to a solution of 960 mg (3.6 mmol) of methyl 4-methyl-3-((2,2,2-trifluoroethyl)thio)benzoate in 27 ml of, and the reaction mixture was stirred at 60° C. for 1 hour. Saturated sodium bicarbonate solution was then added until the evolution of gas had ceased. The reaction mixture was then extracted with ethyl acetate (3×30 ml/mmol). The organic phase was dried, filtered through magnesium sulphate and concentrated under reduced pressure. This gave 1.08 g (purity: 96%; 100% yield) of methyl 4-methyl-3-((2,2,2-trifluoroethyl)thio)benzoate.

[1020] APCI MS, m/z=281 [M+H].sup.+

[1021] Compounds of the formula (I) and also those not embraced by formula (I) are listed in the table below. The compounds not embraced by formula (I) also form part of the subject-matter of the invention.

TABLE-US-00001 TABLE 1 compounds of the formula [00196] Yield Purity: Compound No. A R.sup.1 R.sup.2 [in mg] [in %]  1 [00197] H [00198] 105.6 94.4  2 [00199] H [00200] 89.4 94.7  3 [00201] H [00202] 144.4 97.7  4 *) [00203] H [00204] 11.5 98.9  5 *) [00205] H [00206] 17.2 86.4  6 *) [00207] H [00208] 30.0 99.1  7 *) [00209] H [00210] 51.3 98.4  8 *) [00211] H [00212] 32.6 99.4  9 *) [00213] H [00214] 43.6 97.2  10 *) [00215] H [00216] 33.7 99.3  11 *) [00217] H [00218] 54.4 99.9  12 *) [00219] H [00220] 56.7 99.2  13 *) [00221] H [00222] 41.2 99.1  14 *) [00223] H [00224] 41.5 99.8  15 *) [00225] H [00226] 41.6 99.0  16 [00227] H [00228] 45.9 96.9  17 [00229] H [00230] 97.5 97.1  18 [00231] H [00232] 138.4 96.3  19 [00233] H [00234] 96.3 98.5  20 *) [00235] H [00236] 32.1 95.8  21 *) [00237] H [00238] 23.8 95.9  22 *) [00239] H [00240] 55.2 98.7  23 *) [00241] H [00242] 40.2 98.2  24 *) [00243] H [00244] 33.1 96.6  25 *) [00245] H [00246] 67.3 100  26 [00247] H [00248] 64.3 91.8  27 [00249] H [00250] 45.6 96.5  28 [00251] H [00252] 67.2 96.8  29 [00253] H [00254] 35.6 85.8  30 [00255] H [00256] 10.9 87.1  31 [00257] H [00258] 14.3 85.8  32 [00259] H [00260] 11.7 86.5  33 [00261] H [00262] 12.6 94.0  34 [00263] H [00264] 76.2 94.4  35 [00265] H [00266] 106.5 98.4  36 [00267] H [00268] 259.8 91.9  37 [00269] H [00270] 78.7 96.7  38 [00271] H [00272] 80.5 99.7  39 [00273] H [00274] 51.8 92.8  40 [00275] H [00276] 53.7 99.2  41 [00277] H [00278] 60.4 99.6  42 [00279] H [00280] 37.7 100  43 [00281] H [00282] 67.4 99.4  44 [00283] H [00284] 78.3 98.5  45 [00285] H [00286] 64.7 98.6  46 [00287] H [00288] 78.5 98.7  47 [00289] H [00290] 62.7 99.4  48 [00291] H [00292] 65.3 98.4  49 [00293] H [00294] 392 93  50 [00295] H [00296] 149 97  51 [00297] H [00298] 37 98  52 [00299] H [00300] 60 100  53 [00301] H [00302] 64 100  54 [00303] H [00304] 54 100  55 [00305] H [00306] 17 94  56 [00307] H [00308] 167 100  57 [00309] H [00310] 80 100  58 [00311] H [00312] 26 100  59 [00313] H [00314] 25 100  60 [00315] H [00316] 60 96  61 [00317] H [00318] 56 100  62 [00319] H [00320] 10 97  63 [00321] H [00322] 62 100  64 [00323] H [00324] 34 96  65 [00325] H [00326] 40 98  66 [00327] H [00328] 49 100  67 [00329] H [00330] 73 97  68 [00331] H [00332] 55 97  69 [00333] H [00334] 46 100  71 [00335] H [00336] 39 98  73 [00337] H [00338] 21 100  74 [00339] H [00340] 55 91  75 [00341] H [00342] 43 100  76 [00343] H [00344] 38 100  77 [00345] H [00346] 37 100  79 [00347] H [00348] 100 96  80 [00349] H [00350] 32 97  81 [00351] H [00352] 28 90  82 [00353] H [00354] 32 99  85 [00355] H [00356] 48 100  86 [00357] H [00358] 55 100  87 [00359] H [00360] 81 100  88 [00361] H [00362] 11 100  89 [00363] H [00364] 12 100  90 [00365] H [00366] 65 100  91 [00367] H [00368] 93 99  92 [00369] H [00370] 79 100  93 [00371] H [00372] 49 100  94 [00373] H [00374] 37 95  95 [00375] H [00376] 59 100  96 [00377] H [00378] 51 95  97 [00379] H [00380] 15 97  98 [00381] H [00382] 35 100  99 [00383] H [00384] 35 100 101 [00385] H [00386] 104 [00387] H [00388] 105 [00389] H [00390] 40.8 98 106 [00391] H [00392] 54.5 97 107 [00393] H [00394] 59.7 98 108 [00395] H [00396] 58.4 98 109 [00397] H [00398] 41.3 100 110 [00399] H [00400] 50.9 97 111 [00401] H [00402] 42.1 98 112 [00403] H [00404] 44.4 99 113 [00405] H [00406] 334.2 89 114 [00407] H [00408] 42.4 89 115 [00409] H [00410] 44 99 116 [00411] H [00412] 42.4 89 117 [00413] H [00414] 45.5 96 118 [00415] H [00416] 42.9 94 119 [00417] H [00418] 43.7 86 120 [00419] H [00420] 60.1 95 121 [00421] H [00422] 45.6 85 122 [00423] H [00424] 42.6 99 123 [00425] H [00426] 42.9 98 124 *) [00427] H [00428] 55.7 100 125 [00429] H [00430] 59.9 97 126 **) [00431] H [00432] 73.3 97 127 **) [00433] H [00434] 54 98 128 [00435] H [00436] 44.2 95 129 [00437] H [00438] 41.3 100 130 [00439] H [00440] 42.7 100 *) crystallizes with 1 x HCOOH; **) crystallizes with 1 x CH.sub.3COOH

TABLE-US-00002 TABLE 2 Analytical data for the compounds 1-48 and 105-128 reported Ex. No. Retention time [min] .sup.1H NMR [δ (ppm)] or LC-MS [m/z] 1 1.725 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.01 (s, 6H, 2 × CH.sub.3); 7.36; 7.67; 7.79; 7.88; 8.50; 8.67; 9.29; 9.34 (8H, ═CH, aryl/hetaryl). LC-MS = 267.1 (M + 1); 266.29 (calculated) 2 1.203 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.23 (s, 3H, CH.sub.3); 7.66; 7.76; 7.86; 7.52; 8.68; 9.36; 9.44 (8H, ═CH, aryl/hetaryl); 12.4 (br. 1H, NH). LC-MS = 317.1 (M + 1); 316.33 (calculated) 3 1.203 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 4.13 (m, 2H, CH.sub.2); 7.67; 7.83; 8.51; 8.54; 8.69; 9.17; 9.36; 9.45 (8H, ═CH, aryl/hetaryl). LC-MS = 320.9 (M.sup.+); 320.26 (calculated) 4 2.391 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.15; 3.4 (t + m, 5H, CH.sub.2CH.sub.3); 7.66; 7.78; 8.36; 8.53; 8.67; 9.35; 9.39 (8H, ═CH, aryl/hetaryl). LC-MS = 267.3 (M + 1) [without HCOOH] 5 2.875 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.34 (s, 3H, CH.sub.3); 7.67; 7.81; 8.53; 8.58; 8.68; 9.36; 9.48 (8H, ═CH, aryl/hetaryl); 11.9 (br. 1H, NH). LC-MS = 346.1 (M + 1) [without HCOOH] 6 2.881 .sup.1H-NMR (400.0 MHz, CDCl.sub.3): δ = 7.53; 7.90; 8.11; 8.31; 8.61; 8.73; 9.21 (8H, ═CH, aryl/hetaryl). LC-MS = 364.0 (M + 1); 263.21 (calculated) 7 2.319 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.64; 3.76 (t + m, 5H, CH.sub.2CF.sub.2CH.sub.3); 7.66; 7.81; 8.45; 8.52; 8.68; 8.92; 9.36; 9.42 (8H, ═CH, aryl/hetaryl). LC-MS = 317.1 (M + 1) [without HCOOH] 8 2.536 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.19; 4.12 (d + m, 7H, CH(CH.sub.3)); 7.67; 7.79; 8.31; 8.37; 8.51; 8.68; 8.67; 9.37 (8H, ═CH, aryl/hetaryl). LC-MS = 281.3 (M + 1) [without HCOOH] 9 2.448 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.34; 3.57 (2s 6H, 2 × CH.sub.3); 7.53; 7.66; 7.76; 8.13; 8.50; 8.67; 9.33 (8H, ═CH, aryl/hetaryl). LC-MS = 283.2 (M + 1) [without HCOOH] 10 2.422 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 0.60; 0.69, 2.86 (3m 5H, Cyclopropyl); 7.65; 7.76; 8.33; 8.51; 8.66; 9.35; 9.38 (8H, ═CH, aryl/hetaryl). LC-MS = 279.3 (M + 1) [without HCOOH] 11 2.261 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.81 (s 3H, CH.sub.3); 7.66; 7.78; 8.35; 8.51; 8.67; 9.35; 9.40 (8H, ═CH, aryl/ hetaryl). LC-MS = 253.2 (M + 1) [without HCOOH] 12 2.017 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.81 (s 3H, CH.sub.3); 7.67; 7.79; 8.40; 8.52; 8.68; 9.36; 9.40; 9.44 (8H, ═CH, aryl/hetaryl). LC-MS = 304.2 (M + 1) [without HCOOH] 13 2.497 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.72; 6.16 (2m 3H, CH.sub.2CHF.sub.2); 7.67; 7.82; 8.44; 8.53; 8.68; 8.95; 9.36; 9.43 (8H, ═CH, aryl/hetaryl). LC-MS = 303.2 (M + 1) [without HCOOH] 14 2.342 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.64; 3.76 (t + m 5H, CH.sub.2CF.sub.2CH.sub.3); 7.79; 7.83; 8.44; 8.54; 8.71; 8.91; 9.29; 9.46 (8H, ═CH, aryl/hetaryl). LC-MS = 335.1 (M + 1) [without HCOOH] 15 3.106 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 0.60; 0.70; 2.86 (3m 5H, Cyclopropyl); 7.74; 7.78; 8.33; 8.55; 8.71; 9.28; 9.42 (7H, ═CH, aryl/hetaryl). LC-MS = 297.0 (M + 1) [without HCOOH] 16 2.902 .sup.1H-NMR (400.0 MHz, CDCl.sub.3): δ = 7.53; 7.88; 8.10; 8.14; 8.58; 8.63; 9.04 (7H, ═CH, aryl/hetaryl). LC-MS = 282.0 (M + 1); 281.20 (calculated) 17 3.142 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.1 (s, 3H, CH.sub.3); 7.72; 7.91; 8.49; 8.55; 8.71; 9.29; 9.45 (7H, ═CH, aryl/ hetaryl), 12.3 (br, 1H, NH). LC-MS = 335.0 (M + 1); 334.32 (calculated) 18 1.983 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.01 (s, 6H, 2 × CH.sub.3); 7.37; 7.79; 7.89; 8.54; 8.72; 9.28; 9.35 (7H, ═CH, aryl/hetaryl). LC-MS = 385.1 (M + 1); 284.28 (calculated) 19 2.745 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 4.13 (m, 2H, CH.sub.2); 7.83; 8.47; 8.56; 8.72; 9.18; 9.30; 9.48 (7H, ═CH, aryl/hetaryl). LC-MS = 339.1 (M + 1); 338.25 (calculated) 20 2.962 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.15; 3.31 (t + q, 5H, CH.sub.2CH.sub.3); 7.76; 7.80; 8.36; 8.53; 8.71; 9.29; 9.43 (7H, ═CH, aryl/hetaryl). LC-MS = 285.0 (M + 1) [without HCOOH] 21 2.248 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.32; 1.58 (2m, 4H, CH.sub.2CH.sub.2); 8.54; 8.55; 8.57; 8.73; 9.29; 9.41; 9.48 (7H, ═CH, aryl/hetaryl). LC-MS = 322.2 (M + 1) [without HCOOH] 22 2.820 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.19; 4.12 (d + m, 7H, CH(CH.sub.3)); 7.76; 7.81; 8.37; 8.56; 8.71; 9.29; 9.42 (7H, ═CH, aryl/hetaryl). LC-MS = 299.2 (M + 1) [without HCOOH] 23 2.732 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.30; 3.57 (d + m, 7H, CH(CH.sub.3)); 7.53; 7.76; 8.13; 8.54; 8.72; 9.27; 9.39 (7H, ═CH, aryl/hetaryl). LC-MS = 301.2 (M + 1) [without HCOOH] 24 2.781 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.70; 6.16 (2m 3H, CH.sub.2CHF.sub.2); 7.82; 8.44; 8.56; 8.72; 8.96; 9.29; 9.47 (7H, ═CH, aryl/hetaryl). LC-MS = 321.2 (M + 1) [without HCOOH] 25 2.344 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.81 (s, 3H, CH.sub.3); 7.78; 7.82; 8.35; 8.55; 8.71; 9.28; 9.44 (7H, ═CH, aryl/ hetaryl). LC-MS = 271.0 (M + 1) [without HCOOH] 26 2.132 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 4.14 (m, 2H, CH.sub.2); 7.83; 8.49; 9.18; 9.30; 9.37; 9.51; 9.58 (7H, ═CH, aryl/hetaryl). LC-MS = 322.0 (M + 1); 321.25 (calculated) 27 1.768 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.99 (s, 6H, 2 × CH.sub.3); 7.35; 7.37; 7.78; 7.89; 9.27; 9.34; 9.54 (7H, ═CH, aryl/hetaryl). LC-MS = 268.1 (M + 1); 267.28 (calculated) 28 2.349 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.87 (s, 3H, CH.sub.3); 7.63; 7.98; 8.40; 9.26; 9.37; 9.55 (7H, ═CH, aryl/ hetaryl). LC-MS = 318.2 (M + 1); 317.32 (calculated) 29 1.872 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.87 (s, 3H, CH.sub.3); 7.80; 8.38; 8.56; 9.29; 9.46; 9.57 (7H, ═CH, aryl/ hetaryl). LC-MS = 268.2 (M + 1); 267.28 (calculated) 30 1.969 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.87 (s, 3H, CH.sub.3); 7.83; 8.45; 8.95; 9.29; 9.49; 9.57 (7H, ═CH, aryl/ hetaryl). LC-MS = 304.2 (M + 1); 303.26 (calculated) 31 1.967 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.81 (s, 3H, CH.sub.3); 7.80; 8.37; 8.52; 9.28; 9.46; 9.56 (7H, ═CH, aryl/ hetaryl). LC-MS = 254.1 (M + 1); 253.25 (calculated) 32 1.895 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.30; 3.57 (2s, 6H, 2 × CH.sub.3); 7.55; 8.79; 8.15; 9.29; 9.40; 9.55 (7H, ═CH, aryl/hetaryl). LC-MS = 284.2 (M + 1); 283.28 (calculated) 33 2.031 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.64; 3.77 (t + m, 5H, CH.sub.2CF.sub.2CH.sub.3); 7.82; 8.46; 8.92; 9.29; 9.48; 9.57 (7H, ═CH, aryl/hetaryl). LC-MS = 318.1 (M + 1); 317.29 (calculated) 34 2.034 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.00 (s, 6H, 2 × CH.sub.3); 7.38; 7.80; 7.91; 8.71; 8.79; 9.34; 9.50 (7H, ═CH, aryl/hetaryl). LC-MS = 268.0 (M + 1); 267.28 (calculated) 35 2.322 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 4.12 (m, 2H, CH.sub.2); 7.83; 7.48; 7.72; 8.80; 9.20; 9.50 (7H, ═CH, aryl/ hetaryl). LC-MS = 322.1 (M + 1); 321.25 (calculated) 36 2.042 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.86 (s, 3H, CH.sub.3); 7.63; 7.97; 8.46; 8.68; 8.76; 9.35; 9.48 (7H, ═CH, aryl/ hetaryl). LC-MS = 318.0 (M + 1); 317.32 (calculated) 37 2.447 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.92 (s, 3H, CH.sub.3); 4.11 (m, 2H, CH.sub.2); 7.71; 7.77; 8.10; 8.44; 9.02; 9.09 (6H, ═CH, aryl/hetaryl). LC-MS = 324.0 (M + 1); 323.27 (calculated) 38 1.690 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.99 (s, 6H, 2 × CH.sub.3); 3.92 (s, 3H, CH.sub.3); 7.29; 7.68; 7.82; 8.08; 8.43; 8.87 (6H, ═CH, aryl/hetaryl). LC-MS = 270.1 (M + 1); 269.30 (calculated) 39 1.037 .sup.1H-NMR (300.0 MHz, d.sub.6-DMSO): δ = 3.39; 3.93 (2s, 6H, 2 × CH.sub.3); 7.74; 8.12; 8.48; 8.53; 9.09 (6H, ═CH, aryl/hetaryl). LC-MS = 320.0 (M + 1); 319.33 (calculated) 40 1.997 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 0.59; 0.69; 2.85 (3m, 5H, Cyclopropyl); 3.92 (s, 3H, CH.sub.3); 7.66; 7.73; 8.09; 8.27; 8.45; 8.96 (6H, ═CH, aryl/hetaryl). LC-MS = 282.1 (M + 1); 281.31 (calculated) 41 1.843 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.80; 3.92; (2s, 6H, 2 × CH.sub.3); 7.67; 7.73; 8.09; 8.29; 8.45; 8.98 (6H, ═CH, aryl/hetaryl). LC-MS = 282.1 (M + 1); 255.27 (calculated) 42 1.695 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 2.89; 3.92; (2s, 6H, 2 × CH.sub.3); 7.71; 7.75; 7.76; 8.12; 8.48; 9.06 (6H, ═CH, aryl/hetaryl), 11.79 (br, 1H, NH). LC-MS = 349.1 (M + 1); 348.38 (calculated) 43 2.350 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.63; 3.76 (t + m, 5H, CH.sub.2CF.sub.2CH.sub.3); 3.92 (s, 1H, CH.sub.3); 7.74; 8.10; 8.38; 8.46; 8.84; 9.00 (6H, ═CH, aryl/hetaryl). LC-MS = 320.1 (M + 1); 319.3093 44 2.454 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.68; 6.14 (2m, 3H, CH.sub.2CHF.sub.2); 3.92 (s, 1H, CH.sub.3); 7.75; 8.10; 8.37; 8.45; 8.88; 9.01 (6H, ═CH, aryl/hetaryl). LC-MS = 306.1 (M + 1); 305.28 (calculated) 45 2.033 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 3.28; 3.33; 3.92 (2s, 9H, 3 × CH.sub.3); 3.92 (s, 1H, CH.sub.3); 7.49; 7.68; 8.09; 8.44; 8.93 (6H, ═CH, aryl/hetaryl). LC-MS = 286.1 (M + 1); 285.30 (calculated) 46 2.053 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.29; 1.56; (2m, 4H, 2 × CH.sub.2); 3.92 (s, 1H, CH.sub.3); 7.71; 8.10; 8.34; 8.46; 9.02; 9.34 (6H, ═CH, aryl/hetaryl). LC-MS = 307.1 (M + 1); 306.32 (calculated) 47 1.968 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.14; 3.29; (t + q, 5H, CH.sub.2CH.sub.3); 3.92 (s, 1H, CH.sub.3); 7.67; 7.75; 8.09; 8.30; 8.49; 8.97 (6H, ═CH, aryl/hetaryl). LC-MS = 270.1 (M + 1); 269.30 (calculated) 48 2.127 .sup.1H-NMR (400.0 MHz, d.sub.6-DMSO): δ = 1.18; 4.13 (d + m, 5H, CH(CH.sub.3).sub.2); 3.92 (s, 3H, CH.sub.3); 7.70; 8.09; 8.24; 8.31; 8.45; 8.95 (6H, ═CH, aryl/hetaryl). LC-MS = 284.2 (M + 3); 283.32 (calculated) 105 .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ = 0.99 (3H, d, J = 6.4 Hz), 1.79 (3H, s), 2.30 (1H, dd, J1 = 11.8 Hz, J2 = 4.9 Hz), 2.57-2.77 (2H, m), 3.21 (3H, s), 3.93 (3H, s), 7.22 (1H, dd, J1 = 9.0 Hz, J2 = 1.7 Hz), 7.71-7.81 (2H, m), 8.08 (1H, s), 8.43 (1H, s), 8.86 (1H, s). 106 1.10 .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ = 1.88 (3H, s), 2.34 (2H, t, J = 7.1 Hz), 2.62 (2H, t, J = 7.1 Hz), 3.20 (3H, s), 3.93 (3H, s), 7.21 (1H, dd, J1 = 8.9 Hz, J2 = 1.5 Hz), 7.70-7.79 (2H, m), 8.08 (1H, s), 8.44 (1H, s), 8.85 (1H, s). LC-MS = 330.2 (M + 1); 329.42 (calculated) 108 1.20 .sup.1H-NMR (300.0 MHz, d.sub.6-DMSO): δ = 1.22; 1.89; 2.34; 2.62; 3.21 (alkyl); 7.30; 7.83; 5.52; 8.70; 9.26; 9.30 (7H, ═CH, aryl/hetaryl). LC-MS = 345.2 (M + 1); 344.41 (calculated) 109 1.26 .sup.1H-NMR (300.0 MHz, d.sub.6-DMSO): δ = 0.99; 1.02; 1.81; 2.69-2.73; 3.21 (alkyl); 7.29; 7.32; 7.82; 7.84; 7.87; 8.51; 8.54; 8.71; 8.72; 9.27; 9.32 (7H, ═CH, aryl/ hetaryl). LC-MS = 359.2 (M + 1); 358.44 (calculated) 119 1.16 .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ = 2.55 (3H, s), 2.59-2.72 (2H, m), 2.79-2.90 (1H, m), 3.05-318 (1H, m), 3.33 (3H, s), 4.00 (3H, s), 7.10 (1H, dd, J1 = 9.0 Hz, J2 = 1.9 Hz), 7.54 (1H, d, J = 1.3 Hz), 7.80 (1H, d, J = 9.0 Hz), 7.89 (1H, s), 7.94 (1H, s), 8.22 (1H, s). LC-MS = 346.2 (M + 1); 345.42 (calculated) 120 0.86 .sup.1H-NMR (300.0 MHz, d.sub.6-CDCl.sub.3): δ = 1.13; 1.21; 2.50; 3.14; 3.25; 3.33; 3.99 (alkyl); 7.12-7.18; 7.55-7.8; 8.23 (6H, = CH, aryl/hetaryl). LC-MS = 360.2 (M + 1); 359.45 (calculated) 121 0.94 .sup.1H-NMR (300.0 MHz, d.sub.6-CDCl.sub.3): δ = 1.25; 1.62; (alkyl); 7.14; 7.60; 7.84; 8.09; 8.12; 8.51; 8.56; 9.02 (7H, ═CH, aryl/hetaryl). LC-MS = 361.2 (M + 1); 360.41 (calculated) 125 0.90 .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ = 2.70 (2H, t, J = 7.2 Hz), 2.94 (3H, s), 3.35 (3H, s), 3.40 (2H, t, J = 7.2 Hz), 4.03 (3H, s), 7.12 (1H, dd, J1 = 9.0 Hz, J2 = 1.6 Hz), 7.57 (1H, s), 7.83 (1H, d, J = 8.8 Hz), 7.92 (1H, s), 7.97 (1H, s), 8.25 (1H, s) LC-MS = 362.2 (M + 1); 361.42 (calculated) 126 1.05 .sup.1H-NMR (300.0 MHz, d.sub.6-DMSO): δ = 1.05; 1.07; 1.76; 2.86; 3.21 (alkyl); 7.32; 7.35; 7.85; 7.88; 8.51; 8.55; 8.71; 9.27; 9.34 (7H, ═CH, aryl/hetaryl). LC-MS = 490.1 (M + 1); [without CH.sub.3COOH] 127 0.92 .sup.1H-NMR (300.0 MHz, d.sub.6-DMSO): δ = 1.04; 1.78; 2.96; 3.92 (alkyl); 7.24; 7.75; 7.78; 8.08; 8.43; 8.88 (6H, ═CH, aryl/hetaryl). LC-MS = 376.1 (M + 1); [without CH.sub.3COOH] 128 2.12 .sup.1H-NMR (300.0 MHz, d.sub.6-CDCl.sub.3): δ = 2.69; 2.94; 3.38; 3.42 (alkyl); 7.15; 7.60; 7.86; 7.89; 8.12; 8.55; 9.01 (7H, ═CH, aryl/hetaryl). LC-MS = 377.1 (M + 1); 376.41 (calculated)

TABLE-US-00003 TABLE 3 Analytical data for the compounds 49-104 reported Ex. No. logP[a] logP[b] .sup.1H NMR [δ (ppm)] or LC-MS [m/z] 49 4.23 4.11 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.374 (3.5); 9.367 (3.5); 9.306 (5.9); 9.305 (5.9); 8.686 (2.4); 8.682 (2.6); 8.674 (2.5); 8.671 (2.6); 8.541 (1.3); 8.537 (1.5); 8.534 (1.5); 8.531 (1.3); 8.520 (1.5); 8.516 (1.5); 8.513 (1.7); 8.510 (1.4); 8.228 (0.3); 7.975 (3.7); 7.860 (2.7); 7.837 (3.1); 7.774 (3.1); 7.754 (3.2); 7.687 (1.9); 7.675 (1.9); 7.666 (1.9); 7.655 (1.9); 7.558 (1.3); 7.553 (2.2); 7.549 (1.3); 7.535 (1.1); 7.531 (2.0); 7.527 (1.1); 7.338 (2.8); 7.309 (2.7); 4.066 (1.3); 4.040 (4.2); 4.014 (4.4); 3.988 (1.5); 3.335 (28.4); 2.893 (0.4); 2.528 (0.5); 2.514 (12.2); 2.510 (24.6); 2.505 (32.5); 2.501 (24.0); 2.496 (11.9); 2.453 (16.0); 2.406 (0.4); 1.397 (1.7). 50 4.12 4.07 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.377 (3.4); 9.371 (3.5); 9.274 (5.9); 9.272 (6.2); 8.678 (2.3); 8.675 (2.6); 8.666 (2.5); 8.663 (2.7); 8.542 (1.4); 8.539 (1.6); 8.536 (1.6); 8.532 (1.4); 8.522 (1.5); 8.518 (1.6); 8.515 (1.7); 8.511 (1.5); 8.072 (4.1); 7.858 (2.7); 7.855 (2.3); 7.851 (3.7); 7.847 (3.9); 7.835 (3.6); 7.731 (2.9); 7.727 (2.9); 7.708 (2.1); 7.704 (2.1); 7.681 (1.9); 7.669 (1.9); 7.660 (1.9); 7.648 (1.9); 7.587 (1.9); 7.583 (1.9); 7.568 (2.3); 7.563 (2.3); 7.380 (3.2); 7.360 (2.6); 4.171 (1.3); 4.145 (4.3); 4.119 (4.4); 4.093 (1.5); 3.349 (0.4); 3.334 (63.3); 2.673 (0.3); 2.526 (0.8); 2.513 (18.3); 2.509 (37.9); 2.504 (50.6); 2.499 (37.8); 2.495 (19.1); 2.416 (16.0); 2.331 (0.3); 1.397 (0.4). 51 4.42 4.40 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.366 (3.2); 9.359 (3.2); 9.247 (5.6); 9.245 (5.6); 8.679 (2.2); 8.676 (2.4); 8.667 (2.3); 8.664 (2.4); 8.533 (1.3); 8.529 (1.5); 8.526 (1.5); 8.523 (1.3); 8.512 (1.4); 8.508 (1.5); 8.505 (1.6); 8.502 (1.4); 7.810 (2.7); 7.788 (3.0); 7.706 (4.1); 7.681 (1.8); 7.670 (1.7); 7.661 (1.7); 7.649 (1.7); 7.441 (5.8); 7.352 (2.5); 7.348 (2.5); 7.329 (2.3); 7.325 (2.4); 7.236 (4.8); 3.979 (1.3); 3.953 (4.0); 3.927 (4.2); 3.901 (1.4); 3.335 (13.6); 2.528 (0.4); 2.524 (0.6); 2.515 (8.4); 2.510 (17.5); 2.506 (23.5); 2.501 (17.5); 2.497 (8.7); 2.409 (14.6); 2.242 (16.0); 0.000 (1.1). 52 2.80 2.74 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.377 (3.5); 9.371 (3.5); 9.323 (6.1); 9.321 (5.9); 8.692 (2.5); 8.688 (2.7); 8.680 (2.6); 8.677 (2.7); 8.545 (1.4); 8.541 (1.6); 8.538 (1.5); 8.535 (1.4); 8.524 (1.6); 8.521 (1.6); 8.518 (1.7); 8.514 (1.4); 8.059 (7.0); 8.039 (3.4); 7.900 (2.8); 7.878 (3.3); 7.693 (1.9); 7.692 (1.9); 7.681 (1.8); 7.673 (1.8); 7.661 (1.8); 7.660 (1.8); 7.613 (1.3); 7.609 (2.3); 7.605 (1.3); 7.591 (1.2); 7.587 (2.0); 7.582 (1.1); 7.447 (2.6); 7.418 (2.5); 4.298 (0.5); 4.288 (0.5); 4.271 (0.7); 4.261 (1.7); 4.243 (0.4); 4.233 (2.1); 4.203 (1.8); 4.193 (0.6); 4.175 (0.6); 4.166 (0.6); 3.329 (42.3); 2.677 (0.4); 2.672 (0.5); 2.668 (0.4); 2.525 (1.4); 2.512 (28.8); 2.508 (57.1); 2.503 (74.6); 2.499 (54.0); 2.494 (25.9); 2.451 (16.0); 2.334 (0.4); 2.330 (0.5); 2.325 (0.4); 1.990 (0.7); 1.176 (0.4); 0.008 (1.4); 0.000 (41.3); −0.009 (1.3). 53 2.72 2.68 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.379 (3.6); 9.373 (3.7); 9.294 (6.2); 9.293 (6.0); 8.686 (2.5); 8.683 (2.7); 8.674 (2.7); 8.671 (2.7); 8.546 (1.4); 8.542 (1.7); 8.539 (1.6); 8.536 (1.4); 8.525 (1.6); 8.521 (1.7); 8.518 (1.8); 8.515 (1.5); 8.196 (4.0); 8.191 (4.2); 8.144 (4.2); 7.910 (2.1); 7.900 (2.9); 7.890 (2.4); 7.885 (2.4); 7.877 (3.7); 7.778 (2.9); 7.774 (2.8); 7.755 (2.0); 7.751 (2.0); 7.689 (1.9); 7.677 (1.9); 7.669 (1.9); 7.657 (1.8); 7.485 (3.0); 7.465 (2.7); 4.257 (0.4); 4.247 (0.6); 4.230 (0.8); 4.220 (1.9); 4.206 (1.8); 4.193 (2.0); 4.178 (2.0); 4.166 (0.8); 4.151 (0.7); 4.142 (0.4); 3.331 (136.6); 2.676 (0.5); 2.672 (0.7); 2.667 (0.5); 2.525 (1.9); 2.512 (38.7); 2.507 (77.7); 2.503 (102.1); 2.498 (75.9); 2.494 (38.6); 2.437 (16.0); 2.334 (0.5); 2.330 (0.7); 2.325 (0.5); 1.989 (0.6); 0.008 (0.5); 0.000 (14.6); −0.008 (0.7). 54 2.99 2.92 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.371 (3.3); 9.365 (3.5); 9.263 (5.7); 8.681 (2.5); 8.672 (2.5); 8.669 (2.6); 8.536 (1.6); 8.534 (1.6); 8.515 (1.7); 8.513 (1.7); 8.510 (1.4); 7.847 (2.6); 7.825 (2.9); 7.788 (4.4); 7.753 (6.3); 7.687 (1.8); 7.675 (1.8); 7.666 (1.8); 7.654 (1.7); 7.404 (2.3); 7.400 (2.4); 7.381 (2.2); 7.378 (2.2); 7.331 (4.8); 4.173 (1.1); 4.146 (3.4); 4.118 (3.5); 4.091 (1.2); 3.329 (83.0); 2.672 (0.9); 2.562 (0.3); 2.507 (107.3); 2.503 (138.4); 2.498 (111.3); 2.403 (14.9); 2.341 (16.0); 1.989 (0.6); 0.146 (0.9); 0.000 (175.9); −0.150 (0.9). 0.000 (16.1); −0.008 (0.6) 55 2.77 2.74 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.379 (2.7); 9.361 (13.4); 9.259 (7.9); 9.210 (0.4); 8.695 (2.3); 8.686 (2.4); 8.550 (2.2); 8.547 (2.6); 8.544 (2.5); 8.541 (2.1); 8.529 (2.4); 8.526 (2.6); 8.523 (2.7); 8.520 (2.2); 8.285 (8.4); 8.237 (9.1); 7.947 (16.0); 7.943 (15.7); 7.693 (2.6); 7.681 (2.6); 7.672 (2.6); 7.660 (2.5); 5.759 (0.7); 3.333 (56.9); 2.678 (0.5); 2.673 (0.7); 2.527 (2.0); 2.513 (40.5); 2.509 (79.4); 2.505 (102.3); 2.500 (75.1); 2.336 (0.5); 2.331 (0.6); 1.245 (0.5); 1.230 (0.5); 0.146 (0.9); 0.022 (0.5); 0.008 (8.3); 0.000 (189.5); −0.009 (7.9); −0.150 (1.0). 56 2.83 2.79 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.375 (8.8); 9.368 (8.8); 9.346 (16.0); 8.809 (7.3); 8.806 (7.4); 8.699 (5.9); 8.696 (6.4); 8.688 (6.1); 8.684 (6.3); 8.547 (3.4); 8.543 (3.9); 8.540 (3.8); 8.537 (3.4); 8.526 (3.7); 8.522 (3.9); 8.519 (4.1); 8.516 (3.4); 8.318 (0.5); 8.277 (9.1); 8.274 (8.8); 7.968 (3.2); 7.944 (11.9); 7.930 (9.9); 7.925 (9.3); 7.907 (2.6); 7.902 (2.8); 7.695 (4.7); 7.683 (4.6); 7.674 (4.6); 7.662 (4.4); 7.076 (8.5); 7.070 (8.5); 3.332 (215.6); 2.677 (0.9); 2.673 (1.2); 2.669 (0.9); 2.526 (3.4); 2.513 (66.6); 2.508 (131.4); 2.504 (171.9); 2.499 (127.4); 2.335 (0.8); 2.331 (1.2); 2.326 (0.8); 1.990 (0.6); 0.000 (0.7). 57 0.88 1.71 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.384 (9.1); 9.377 (9.3); 9.309 (16.0); 8.988 (8.7); 8.983 (8.9); 8.685 (5.7); 8.682 (6.6); 8.673 (6.1); 8.670 (6.6); 8.591 (5.6); 8.587 (6.3); 8.579 (6.0); 8.575 (6.2); 8.554 (3.3); 8.550 (3.9); 8.547 (4.0); 8.544 (3.5); 8.533 (3.6); 8.529 (4.0); 8.527 (4.3); 8.523 (3.6); 8.318 (0.3); 8.179 (3.3); 8.173 (4.8); 8.169 (3.6); 8.154 (15.7); 7.898 (6.3); 7.876 (8.7); 7.754 (7.1); 7.750 (7.3); 7.732 (5.3); 7.727 (5.5); 7.686 (5.1); 7.674 (5.0); 7.665 (5.0); 7.653 (4.8); 7.528 (4.8); 7.516 (4.7); 7.508 (4.6); 7.496 (4.4); 3.332 (103.5); 2.677 (0.7); 2.673 (0.9); 2.669 (0.7); 2.526 (2.4); 2.508 (102.3); 2.504 (136.8); 2.499 (104.3); 2.335 (0.6); 2.331 (0.9); 2.326 (0.7); 1.990 (0.4); 1.259 (0.4); 1.250 (0.3); 1.230 (0.5); 0.000 (5.7). 58 1.51 1.57 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.349 (2.4); 9.343 (2.4); 9.149 (4.2); 9.147 (4.1); 8.656 (1.7); 8.653 (1.8); 8.645 (1.8); 8.641 (1.8); 8.511 (1.0); 8.507 (1.2); 8.504 (1.1); 8.501 (1.0); 8.490 (1.1); 8.486 (1.2); 8.483 (1.2); 8.480 (1.0); 8.199 (4.4); 7.943 (4.6); 7.942 (4.5); 7.913 (3.2); 7.757 (1.8); 7.735 (2.5); 7.664 (1.3); 7.663 (1.3); 7.652 (1.3); 7.643 (1.3); 7.631 (1.3); 7.630 (1.3); 7.618 (2.1); 7.614 (2.1); 7.596 (1.6); 7.592 (1.6); 3.885 (16.0); 3.334 (44.0); 2.526 (0.9); 2.512 (17.3); 2.508 (34.2); 2.504 (44.4); 2.499 (32.6); 2.495 (16.2); 1.232 (0.8); 0.000 (7.6). 59 1.13 1.93 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.378 (9.5); 9.371 (9.4); 9.330 (15.8); 9.329 (16.0); 8.697 (5.2); 8.695 (5.4); 8.684 (11.3); 8.681 (10.9); 8.672 (6.8); 8.669 (6.8); 8.548 (3.8); 8.544 (4.4); 8.541 (4.4); 8.537 (4.3); 8.527 (14.6); 8.520 (5.2); 8.517 (3.9); 8.318 (0.6); 8.167 (6.3); 8.163 (6.1); 8.144 (7.2); 8.140 (7.2); 8.078 (6.7); 8.058 (8.6); 7.926 (3.6); 7.921 (3.6); 7.906 (5.6); 7.902 (5.5); 7.887 (3.1); 7.883 (3.1); 7.856 (8.5); 7.833 (7.4); 7.686 (5.2); 7.675 (5.0); 7.666 (5.0); 7.654 (4.8); 7.373 (4.1); 7.371 (4.3); 7.359 (4.5); 7.355 (4.3); 7.353 (4.0); 7.342 (3.8); 7.340 (3.8); 3.336 (231.2); 2.677 (1.2); 2.672 (1.6); 2.668 (1.2); 2.526 (4.3); 2.512 (90.3); 2.508 (177.5); 2.503 (229.6); 2.499 (167.1); 2.495 (82.5); 2.335 (1.1); 2.330 (1.5); 2.326 (1.1); 2.237 (0.6); 0.008 (2.4); 0.000 (66.9); −0.008 (2.5). 60 1.72 1.73 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.408 (7.7); 9.406 (7.6); 9.373 (4.0); 9.367 (4.0); 8.934 (14.4); 8.922 (16.0); 8.918 (6.0); 8.915 (4.4); 8.695 (2.8); 8.691 (3.0); 8.683 (2.9); 8.679 (3.0); 8.544 (1.8); 8.541 (2.1); 8.538 (2.0); 8.534 (1.8); 8.524 (2.0); 8.520 (2.1); 8.517 (2.2); 8.513 (1.9); 8.418 (3.6); 8.414 (3.5); 8.395 (3.9); 8.391 (3.9); 7.871 (4.3); 7.848 (4.0); 7.694 (2.3); 7.693 (2.3); 7.682 (2.3); 7.681 (2.3); 7.673 (2.3); 7.672 (2.3); 7.661 (2.2); 7.660 (2.2); 7.456 (3.9); 7.443 (7.3); 7.431 (3.8); 5.761 (0.7); 3.340 (50.8); 2.529 (0.6); 2.524 (0.9); 2.516 (14.0); 2.511 (28.9); 2.507 (38.4); 2.502 (27.9); 2.498 (13.6); 0.000 (5.9). 61 2.79 2.80 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.372(9.4); 9.366 (9.6); 9.351(16.0); 9.350(15.8); 8.692(6.4); 8.688(7.0); 8.680(6.8); 8.677(7.0); 8.555(11.1); 8.542(4.0); 8.538(4.4); 8.535(4.2); 8.532(3.8); 8.521(4.1); 8.517(4.4); 8.514(4.6); 8.511(3.9); 8.315 (0.5); 8.104(8.0); 8.098(6.9); 8.094(6.6); 8.085(10.7); 8.075(7.8); 8.071(7.8); 7.985(7.3); 7.965(12.8); 7.946(6.1); 7.875(9.0); 7.852(7.4); 7.691(5.0); 7.690(5.0); 7.679(4.9); 7.670(4.9); 7.658 (4.7); 7.477(10.2); 7.458(9.4); 3.320(58.1); 2.677(0.8); 2.672 (1.1); 2.668(0.8); 2.525(2.9); 2.512(61.4); 2.508(125.1); 2.503 (166.2); 2.499(123.8); 2.494(62.2); 2.334(0.8); 2.330(1.1); 2.325 (0.8); 1.398(4.1); 0.146(0.4); 0.008(3.0); 0.000(90.2); −0.008 (3.8); −0.150(0.4) 62 1.97 2.11 .sup.1H-NMR(601.6 MHz, CDCl.sub.3): δ = 9.216(1.9); 9.212(1.9); 9.199(0.3); 8.704(1.3); 8.702(1.4); 8.697 (1.4); 8.694(1.3); 8.554(3.4); 8.553(3.3); 8.440(0.5); 8.323(0.8); 8.320(0.9); 8.318(0.9); 8.316(0.8); 8.309(0.9); 8.306(1.1); 8.304 (1.0); 8.302(0.9); 7.900(3.0); 7.882(1.7); 7.867(1.8); 7.854 (0.5); 7.814(0.6); 7.596(2.8); 7.593(2.8); 7.537(1.1); 7.529(1.2); 7.523(1.0); 7.515(1.2); 7.464(1.7); 7.462(1.6); 7.449(1.5); 7.447 (1.5); 7.261(23.5); 6.412(2.9); 6.409(2.8); 5.220(8.1); 5.210(0.6); 5.196(1.3); 5.082(0.5); 2.289(16.0); 2.248(0.8); 2.228(0.9); 2.200(2.2); 1.574(8.2); 0.005(0.8); 0.000(21.7); −0.006(0.9) 63 2.02 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.353(2.1); 9.347(2.1); 9.158(3.6); 8.659(1.4); 8.656(1.6); 8.648 (1.5); 8.644(1.5); 8.515(0.8); 8.511(0.9); 8.509(0.9); 8.505(0.8); 8.494(0.9); 8.491(0.9); 8.488(1.0); 8.484(0.8); 8.337(3.9); 8.031 (4.0); 7.965(2.6); 7.771(1.4); 7.748(2.0); 7.664(1.2); 7.652 (1.2); 7.645(2.3); 7.643(2.6); 7.631(1.2); 7.623(1.3); 7.619(1.3); 5.290(8.0); 3.322(10.6); 2.525(0.5); 2.512(9.7); 2.508(19.6); 2.503 (26.1); 2.499(19.5); 2.494(10.0); 2.190(16.0); 0.008(0.6); 0.000 (15.6); −0.008(0.7) 64 1.06 2.41 .sup.1H-NMR(600.1 MHz, CDCl.sub.3): δ = 9.217(2.7); 9.213(2.7); 8.675(1.8); 8.674(1.8); 8.668(1.9); 8.666 (1.8); 8.532(4.8); 8.371(3.5); 8.323(1.0); 8.321(1.2); 8.320(1.2); 8.317(1.0); 8.309(1.1); 8.307(1.3); 8.306(1.3); 8.303(1.0); 8.045 (1.7); 8.042(1.7); 8.030(2.0); 8.027(2.0); 7.873(2.4); 7.858 (2.0); 7.676(1.3); 7.663(2.9); 7.650(1.8); 7.590(2.6); 7.577(1.9); 7.514(1.4); 7.506(1.4); 7.500(1.4); 7.493(1.3); 7.262(6.2); 7.118 (2.3); 7.106(2.2); 2.657(16.0); 1.652(2.9); 0.000(5.3) 65 1.23 2.25 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): □ = 9.371(3.6); 9.364(3.6); 9.299(6.0); 8.678(2.4); 8.675(2.6); 8.666 (2.5); 8.663(2.5); 8.539(1.5); 8.535(1.8); 8.528(3.7); 8.521(3.4); 8.515(1.9); 8.512(1.8); 8.508(1.4); 8.476(4.4); 8.141(2.3); 8.138 (2.2); 8.118(2.7); 8.115(2.6); 7.969(2.8); 7.949(3.3); 7.833(3.1); 7.810(2.8); 7.728(1.8); 7.723(1.9); 7.707(1.6); 7.702(1.6); 7.680(2.0); 7.669(1.9); 7.660(1.9); 7.648(1.9); 3.318(61.0); 2.675 (0.6); 2.671(0.8); 2.667(0.6); 2.506(97.9); 2.502(126.3); 2.498 (93.1); 2.353(16.0); 2.333(0.8); 2.329(0.9); 2.324(0.7); 0.146 (0.6); 0.008(5.6); 0.000(126.5); −0.008(5.1); −0.150(0.6) 66 0.97 2.2 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.377(3.1); 9.372(3.2); 9.309(5.4); 9.307(5.3); 8.682(2.2); 8.679 (2.4); 8.670(2.4); 8.667(2.4); 8.544(1.8); 8.540(4.4); 8.534(1.7); 8.527(3.3); 8.523(2.1); 8.520(1.8); 8.516(2.1); 8.513(4.1); 8.510 (4.1); 8.157(2.3); 8.153(2.2); 8.134(2.6); 8.130(2.6); 7.907 (3.7); 7.840(3.0); 7.817(2.6); 7.683(1.7); 7.681(1.7); 7.671(1.6); 7.670(1.6); 7.662(1.7); 7.661(1.6); 7.650(1.6); 7.649(1.6); 7.190 (2.0); 7.189(2.0); 7.178(2.0); 7.176(2.0); 3.326(10.1); 2.527(0.4); 2.514(9.5); 2.509(19.3); 2.505(25.5); 2.500(19.0); 2.496(9.5); 2.418(16.0); 0.008(1.1); 0.000(32.7); −0.008(1.5) 67 2.8 2.78 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.374(8.4); 9.369(8.5); 9.338(14.7); 9.336(14.2); 8.724(7.9); 8.723 (8.3); 8.718(8.4); 8.717(8.0); 8.686(6.0); 8.682(6.6); 8.674 (6.4); 8.670(6.5); 8.544(12.8); 8.542(12.8); 8.534(4.1); 8.524(3.9); 8.520(4.0); 8.517(4.3); 8.514(3.6); 8.314(0.6); 8.136(12.2); 8.132(7.9); 8.113(16.0); 8.109(8.4); 8.036(8.1); 8.029(7.8); 8.014 (5.4); 8.008(5.5); 7.862(8.2); 7.839(7.1); 7.686(4.7); 7.684(4.6); 7.674(4.5); 7.672(4.4); 7.665(4.5); 7.663(4.4); 7.653(4.5); 7.651 (4.3); 7.627(0.5); 7.615(0.3); 7.598(0.4); 3.321(179.5); 2.676 (1.0); 2.672(1.3); 2.667(1.0); 2.663(0.5); 2.525(3.2); 2.520(5.0); 2.512(71.7); 2.507(149.0); 2.503(198.9); 2.498(144.8); 2.494 (69.7); 2.338(0.4); 2.334(0.9); 2.329(1.3); 2.325(1.0); 1.989 (0.8); 1.176(0.4); 0.146(0.4); 0.008(2.9); 0.000(98.3); −0.009 (3.3); −0.150(0.4) 68 2.17 2.21 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.371(8.7); 9.365(8.7); 9.336(15.4); 9.334(16.0); 8.689(6.1); 8.686 (6.8); 8.678(6.6); 8.674(7.4); 8.671(8.5); 8.667(8.2); 8.659 (7.9); 8.656(8.0); 8.540(3.7); 8.537(4.3); 8.534(4.2); 8.530(3.8); 8.520(4.1); 8.516(4.3); 8.513(4.6); 8.509(3.9); 8.160(7.5); 8.158 (10.3); 8.157(10.4); 8.154(8.5); 8.090(7.4); 8.086(7.8); 8.069 (8.2); 8.066(8.0); 7.851(7.4); 7.831(5.4); 7.829(9.3); 7.827(5.9); 7.689(4.8); 7.687(5.0); 7.677(4.8); 7.675(4.9); 7.665(10.3); 7.661 (8.7); 7.656(5.3); 7.655(5.1); 7.642(6.7); 7.638(6.9); 7.629(0.8); 7.617(0.4); 7.601(0.5); 7.567(0.4); 7.552(0.3); 7.549(0.3); 7.473 (8.2); 7.462(7.9); 7.453(7.6); 7.441(7.7); 5.756(7.7); 3.324 (44.9); 2.674(0.4); 2.528(1.0); 2.523(1.6); 2.514(19.5); 2.510(40.5); 2.505(55.7); 2.501(42.3); 2.496(20.8); 2.332(0.4); 1.250 (0.3); 0.008(0.5); 0.000(15.6); −0.009(0.5) 69 2.62 2.66 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.382(9.0); 9.376(9.2); 9.341(16.0); 8.687(6.1); 8.684(6.6); 8.676 (6.6); 8.673(6.7); 8.663(10.4); 8.650(10.4); 8.619(11.1); 8.553 (3.6); 8.549(4.2); 8.546(4.1); 8.543(3.6); 8.532(3.9); 8.528(4.3); 8.526(4.4); 8.522(3.6); 8.313(0.6); 8.231(10.8); 8.227(11.2); 8.181(6.0); 8.177(6.0); 8.158(6.9); 8.154(7.0); 7.857(8.3); 7.834 (7.3); 7.686(4.9); 7.674(4.8); 7.665(4.8); 7.653(4.6); 7.501(6.7); 7.496(6.8); 7.488(6.5); 7.483(6.5); 3.316(106.8); 2.676(0.9); 2.671(1.2); 2.667(0.9); 2.525(3.7); 2.507(133.7); 2.502(180.6); 2.498(138.2); 2.334(0.9); 2.329(1.3); 2.325(1.0); 0.008(1.2); 0.000(32.1); −0.008(1.3) 71 1.58 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.347(2.4); 9.340(2.5); 9.190(4.2); 8.662(1.6); 8.659(1.8); 8.650 (1.7); 8.647(1.7); 8.511(0.9); 8.508(1.1); 8.505(1.1); 8.502(0.9); 8.491(1.0); 8.487(1.1); 8.484(1.1); 8.481(0.9); 8.128(3.2); 7.885 (1.4); 7.882(1.4); 7.862(2.0); 7.859(2.1); 7.763(2.5); 7.750 (3.0); 7.744(3.5); 7.666(1.3); 7.654(1.9); 7.646(1.4); 7.634(1.2); 6.770(3.2); 6.765(3.3); 6.440(0.7); 6.435(0.7); 3.904(16.0); 3.839 (3.7); 3.309(16.0); 2.670(0.4); 2.523(1.2); 2.506(48.7); 2.501 (64.0); 2.497(47.7); 2.328(0.4); 0.008(0.3); 0.000(9.5) 73 1.81 1.82 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.348(4.9); 9.342(4.9); 9.141(8.6); 8.652(3.6); 8.643(3.5); 8.641 (3.5); 8.506(2.3); 8.503(2.3); 8.485(2.4); 8.482(2.5); 8.252(8.9); 7.945(9.1); 7.920(6.6); 7.755(3.3); 7.732(4.7); 7.661(2.6); 7.650 (2.7); 7.640(2.7); 7.629(6.1); 7.608(2.8); 7.605(2.8); 4.196 (2.3); 4.178(7.1); 4.159(7.2); 4.141(2.4); 3.319(26.8); 2.671(0.8); 2.502(113.9); 2.329(0.7); 1.447(7.7); 1.428(16.0); 1.410(7.6); 1.336(0.4); 1.250(0.5); 0.146(0.5); 0.000(95.4); −0.150(0.5) 74 1.17 1.19 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.354(2.8); 9.349(3.1); 9.172(4.7); 8.658(2.2); 8.647(2.3); 8.512 (1.5); 8.491(1.6); 8.360(0.4); 8.274(4.9); 8.213(0.4); 8.175(5.0); 8.014(0.3); 7.997(3.8); 7.784(1.9); 7.761(2.7); 7.665(1.7); 7.655 (3.8); 7.645(1.8); 7.633(3.2); 5.769(0.5); 5.755(0.7); 5.545 (2.1); 5.512(2.8); 5.325(2.9); 5.293(2.2); 3.321(17.1); 3.075(1.0); 2.671(0.4); 2.596(16.0); 2.503(58.2); 2.330(0.4); 2.075(0.5); 0.000(19.0) 75 1.47 1.5 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.350(3.2); 9.343(3.3); 9.287(5.6); 9.285(5.5); 8.681(2.1); 8.677 (2.3); 8.669(2.3); 8.666(2.3); 8.522(1.2); 8.518(1.4); 8.515(1.4); 8.512(1.3); 8.501(1.3); 8.497(1.4); 8.495(1.5); 8.491(1.3); 7.978 (3.7); 7.761(2.5); 7.738(2.9); 7.677(1.8); 7.665(1.7); 7.656 (1.7); 7.644(1.7); 7.468(2.0); 7.465(2.0); 7.446(1.7); 7.442(1.8); 5.755(3.4); 3.319(22.1); 3.008(16.0); 2.987(1.3); 2.978(0.9); 2.970 (0.7); 2.960(0.4); 2.672(0.4); 2.525(0.7); 2.511(19.0); 2.507 (38.5); 2.503(51.1); 2.498(37.7); 2.494(18.9); 0.561(1.8); 0.547 (1.8); 0.458(2.1); 0.008(0.8); 0.000(23.7); −0.008(1.0) 76 1.62 2.84 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.375(4.2); 9.369(4.3); 9.309(7.2); 8.683(2.9); 8.680(3.1); 8.672 (3.1); 8.669(3.1); 8.545(6.4); 8.534(1.8); 8.523(1.9); 8.519(2.0); 8.516(2.1); 8.513(1.7); 8.486(4.3); 8.473(4.4); 8.150(2.8); 8.146 (2.7); 8.127(3.2); 8.123(3.1); 7.852(5.0); 7.850(5.1); 7.837 (4.0); 7.814(3.4); 7.685(2.3); 7.673(2.2); 7.664(2.2); 7.652(2.1); 7.236(3.1); 7.232(3.1); 7.223(3.1); 7.219(3.0); 3.318(62.4); 3.232 (2.2); 3.214(6.9); 3.195(7.1); 3.177(2.3); 2.676(0.6); 2.671(0.8); 2.667(0.6); 2.507(87.7); 2.502(113.3); 2.498(84.3); 2.333 (0.6); 2.329(0.7); 2.325(0.5); 1.363(7.6); 1.345(16.0); 1.327(7.4); 1.259(0.4); 1.250(0.7); 1.230(0.6); 0.000(2.0) 77 2.53 1.93 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.364(3.9); 9.358(4.0); 9.306(6.8); 9.304(6.7); 8.682(2.8); 8.678 (3.1); 8.670(3.0); 8.667(3.1); 8.534(1.6); 8.531(1.9); 8.528(1.8); 8.524(1.7); 8.514(1.8); 8.510(1.9); 8.507(2.0); 8.503(1.7); 8.461 (3.0); 8.458(3.3); 8.450(3.3); 8.446(3.3); 7.989(4.8); 7.987 (3.8); 7.883(2.7); 7.879(2.8); 7.862(3.0); 7.859(3.0); 7.819(3.3); 7.796(3.9); 7.685(2.2); 7.683(2.2); 7.673(2.1); 7.672(2.1); 7.664 (2.1); 7.663(2.1); 7.652(2.1); 7.651(2.0); 7.564(3.4); 7.560(3.4); 7.541(2.9); 7.537(3.0); 7.396(3.2); 7.384(3.0); 7.376(2.9); 7.364 (2.9); 5.754(2.5); 3.318(64.0); 2.983(2.1); 2.965(6.8); 2.947 (6.9); 2.928(2.2); 2.676(0.5); 2.671(0.6); 2.667(0.5); 2.525(1.7); 2.520(2.7); 2.511(34.0); 2.507(69.0); 2.502(92.0); 2.498(68.4); 2.493(34.2); 2.334(0.4); 2.329(0.6); 2.324(0.4); 1.352(1.8); 1.336(1.3); 1.299(0.4); 1.259(0.7); 1.250(1.9); 1.232(1.8); 1.228 (1.8); 1.208(7.6); 1.189(16.0); 1.171(7.3); 0.000(1.9) 79 3.57 3.57 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.375(3.2); 9.369(3.2); 9.347(6.5); 9.346(6.7); 8.683(2.3); 8.680 (2.4); 8.671(2.4); 8.669(2.4); 8.549(5.0); 8.543(2.5); 8.539(2.1); 8.536(1.9); 8.533(1.7); 8.522(1.8); 8.518(1.9); 8.515(2.0); 8.512 (1.6); 8.314(0.4); 8.157(2.7); 8.153(2.7); 8.134(3.1); 8.130 (3.2); 7.866(3.7); 7.844(3.2); 7.788(1.7); 7.786(2.0); 7.769(4.7); 7.767(4.5); 7.751(3.8); 7.732(4.8); 7.713(1.9); 7.685(2.0); 7.673 (2.0); 7.665(2.0); 7.652(1.9); 7.240(3.4); 7.238(3.7); 7.221(3.2); 7.219(3.4); 3.319(52.8); 3.305(2.4); 3.287(6.8); 3.268(6.9); 3.250(2.2); 2.891(0.5); 2.732(0.4); 2.676(0.6); 2.671(0.8); 2.667 (0.6); 2.525(2.2); 2.511(45.8); 2.507(91.2); 2.502(119.4); 2.498 (88.9); 2.494(44.6); 2.334(0.6); 2.329(0.8); 2.325(0.6); 1.419 (7.4); 1.401(16.0); 1.383(7.2); 1.232(0.3); 0.922(0.4); 0.146(0.5); 0.008(4.1); 0.000(106.0); −0.008(4.7); −0.150(0.5) 80 2.87 3.03 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.371(3.9); 9.365(3.9); 9.314(6.6); 8.681(2.7); 8.678(2.9); 8.669 (2.8); 8.666(2.8); 8.618(3.8); 8.613(3.8); 8.540(1.6); 8.537(1.8); 8.534(1.7); 8.530(1.5); 8.513(6.5); 8.146(2.6); 8.142(2.4); 8.123 (2.9); 8.119(2.9); 8.039(3.0); 8.018(3.9); 7.882(3.0); 7.876 (2.9); 7.861(2.4); 7.855(2.4); 7.845(3.5); 7.822(3.0); 7.682(2.1); 7.671(2.0); 7.662(2.0); 7.650(2.0); 3.318(79.7); 3.113(2.3); 3.095 (7.4); 3.076(7.5); 3.058(2.5); 2.676(0.6); 2.671(0.8); 2.667(0.6); 2.524(2.4); 2.511(45.8); 2.507(90.2); 2.502(117.9); 2.498 (87.2); 2.493(44.0); 2.334(0.6); 2.329(0.8); 2.325(0.6); 1.352(0.9); 1.336(0.4); 1.295(7.8); 1.276(16.0); 1.258(7.8); 1.250(0.9); 1.232(1.0); 0.000(1.9) 81 3.15 3.12 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.967(3.6); 9.462(5.6); 9.448(0.4); 9.390(3.2); 9.384(3.3); 8.702 (2.3); 8.699(2.5); 8.690(2.4); 8.687(2.5); 8.557(5.0); 8.539(1.5); 8.536(1.8); 8.533(1.9); 8.529(1.5); 7.921(1.4); 7.918(1.3); 7.899 (2.6); 7.895(2.6); 7.851(3.5); 7.828(1.8); 7.698(1.8); 7.686 (1.8); 7.678(1.8); 7.666(1.7); 7.571(5.2); 7.208(4.7); 4.038(0.4); 4.021(0.4); 3.892(1.1); 3.866(3.5); 3.840(3.6); 3.814(1.2); 3.317 (32.3); 2.675(0.4); 2.671(0.5); 2.666(0.4); 2.524(1.5); 2.510(31.3); 2.506(61.7); 2.502(81.3); 2.497(60.7); 2.493(30.4); 2.385 (14.2); 2.333(0.5); 2.329(0.6); 2.324(0.5); 2.226(16.0); 2.204(1.4); 2.185(0.9); 1.988(1.9); 1.193(0.5); 1.175(1.0); 1.158(0.5); 0.008 (1.4); 0.000(38.9); −0.008(1.4) 82 3.22 3.15 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.340(4.2); 9.465(6.6); 9.464(6.2); 9.390(3.5); 9.384(3.6); 8.705 (2.5); 8.701(2.7); 8.693(2.6); 8.689(2.7); 8.559(1.5); 8.555(1.8); 8.552(1.7); 8.549(1.6); 8.538(6.1); 8.535(4.9); 8.528(1.7); 8.313 (0.4); 8.005(3.7); 8.000(3.8); 7.907(1.4); 7.903(1.3); 7.884 (3.8); 7.880(4.0); 7.861(4.6); 7.838(1.6); 7.718(2.0); 7.713(2.0); 7.699(3.3); 7.692(2.6); 7.689(2.5); 7.680(1.9); 7.668(1.9); 7.667 (1.8); 7.278(3.1); 7.257(2.8); 3.916(1.4); 3.891(4.5); 3.865(4.7); 3.839(1.6); 3.316(37.0); 2.676(0.5); 2.671(0.7); 2.667(0.5); 2.524(2.1); 2.511(39.5); 2.506(79.7); 2.502(106.8); 2.497(80.0); 2.493(39.9); 2.370(16.0); 2.333(0.6); 2.329(0.8); 2.324(0.6); 1.988(0.8); 1.176(0.4); 0.008(1.6); 0.000(47.8); −0.009(1.7) 85 1.45 1.5 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.411(3.6); 9.366(1.8); 9.360(1.8); 8.700(0.5); 8.690(1.8); 8.687 (2.2); 8.678(1.6); 8.675(1.7); 8.536(0.7); 8.532(0.8); 8.529(0.8); 8.526(0.7); 8.515(0.8); 8.511(0.9); 8.508(0.9); 8.505(0.7); 8.377 (2.5); 7.799(2.5); 7.795(3.6); 7.792(3.1); 7.686(1.0); 7.674 (1.0); 7.665(0.9); 7.653(0.9); 3.514(0.7); 3.498(1.5); 3.480(1.5); 3.464(0.8); 3.319(45.1); 2.704(1.8); 2.685(2.5); 2.676(0.4); 2.668 (1.8); 2.525(0.8); 2.511(17.8); 2.507(36.3); 2.502(48.0); 2.498 (35.2); 2.493(17.3); 2.122(16.0); 0.008(0.6); 0.000(20.4); −0.008 (0.8) 86 1.55 1.55 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.350(2.9); 9.344(3.1); 9.311(5.6); 8.687(2.3); 8.678(2.1); 8.675 (2.3); 8.524(1.2); 8.520(1.5); 8.517(1.5); 8.514(1.4); 8.503(1.3); 8.499(1.5); 8.496(1.6); 8.493(1.4); 7.912(1.3); 7.826(2.6); 7.804 (2.9); 7.683(1.7); 7.671(1.7); 7.662(1.7); 7.650(1.6); 7.366 (1.0); 7.345(0.9); 6.295(0.6); 5.755(1.1); 3.893(0.7); 3.323(9.7); 3.088(16.0); 2.508(22.2); 2.504(30.2); 2.500(24.3); 0.000(5.7) 87 1.14 1.16 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.346(8.9); 9.340(9.0); 9.303(15.2); 9.302(16.0); 8.686(5.7); 8.683 (6.4); 8.674(6.0); 8.671(6.4); 8.520(3.4); 8.517(3.9); 8.514 (3.9); 8.510(3.5); 8.500(3.7); 8.496(3.9); 8.493(4.2); 8.489(3.6); 8.313(0.7); 7.896(11.8); 7.813(7.2); 7.790(8.0); 7.680(5.1); 7.668 (4.9); 7.659(4.8); 7.647(4.6); 7.377(6.8); 7.373(7.0); 7.354(6.2); 7.351(6.5); 4.056(0.4); 4.038(1.2); 4.020(1.2); 4.003(0.4); 3.628 (10.1); 3.548(4.7); 3.415(0.3); 3.355(0.4); 3.339(0.6); 3.315 (198.6); 2.716(0.5); 2.675(1.4); 2.671(1.9); 2.666(1.4); 2.662 (0.7); 2.565(0.4); 2.524(4.8); 2.510(94.3); 2.506(194.6); 2.501 (267.1); 2.497(203.5); 2.493(103.2); 2.333(1.3); 2.328(1.8); 2.324 (1.3); 1.988(5.2); 1.336(0.9); 1.299(0.3); 1.259(0.5); 1.250(1.2); 1.235(0.5); 1.193(1.4); 1.175(2.7); 1.157(1.3); 0.008(1.5); 0.000 (50.0); −0.008(1.9) 88 1.43 1.48 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.412(0.3); 9.348(8.9); 9.342(9.0); 9.293(16.0); 9.291(15.5); 8.683 (6.2); 8.679(6.7); 8.671(6.4); 8.668(6.6); 8.523(3.8); 8.519 (4.4); 8.516(4.2); 8.512(3.7); 8.502(4.1); 8.498(4.4); 8.495(4.6); 8.492(3.8); 8.313(1.6); 8.005(12.2); 7.781(7.8); 7.758(9.0); 7.729 (0.3); 7.678(5.1); 7.677(5.1); 7.667(5.0); 7.657(4.8); 7.646(4.7); 7.644(4.5); 7.481(7.9); 7.477(7.8); 7.459(6.7); 7.455(6.9); 7.183 (0.4); 5.920(0.5); 5.753(1.0); 3.902(1.1); 3.503(10.8); 3.492 (10.9); 3.371(0.3); 3.315(234.6); 2.675(2.4); 2.671(3.3); 2.666 (2.5); 2.595(0.5); 2.524(9.5); 2.511(169.3); 2.506(342.2); 2.502 (458.1); 2.497(343.6); 2.493(171.5); 2.333(2.1); 2.328(2.9); 2.324(2.1); 2.043(0.5); 2.009(0.5); 1.898(4.5); 1.883(4.8); 1.865 (3.8); 1.848(4.9); 1.833(4.5); 1.352(0.6); 1.336(4.4); 1.298(2.0); 1.259(3.1); 1.250(6.1); 1.235(2.8); 1.188(0.4); 0.854(0.5); 0.146 (1.1); 0.016(0.8); 0.008(9.3); 0.000(270.2); −0.009(9.9); −0.150 (1.1) 89 1.63 1.65 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.342(8.9); 9.336(8.9); 9.271(15.2); 9.270(16.0); 8.682(5.9); 8.678 (6.6); 8.670(6.2); 8.667(6.5); 8.517(3.5); 8.513(4.1); 8.511 (4.0); 8.507(3.6); 8.496(3.8); 8.493(4.1); 8.490(4.4); 8.486(3.6); 8.314(0.5); 7.834(0.5); 7.804(15.5); 7.803(15.6); 7.779(8.1); 7.676 (5.1); 7.665(4.9); 7.656(4.8); 7.644(4.7); 7.307(6.9); 7.303 (6.7); 7.285(6.1); 7.281(6.5); 4.303(0.5); 3.671(0.9); 3.375(2.5); 3.356(2.5); 3.345(2.4); 3.335(2.4); 3.317(58.3); 2.676(0.7); 2.671 (0.9); 2.667(0.7); 2.524(2.8); 2.507(106.2); 2.502(142.9); 2.498 (108.9); 2.494(56.1); 2.466(0.5); 2.463(0.5); 2.334(0.7); 2.329 (1.0); 2.325(0.7); 1.336(1.0); 1.299(0.5); 1.259(0.7); 1.250 (1.4); 1.233(0.7); 1.214(0.5); 1.197(0.9); 1.134(11.3); 0.146(0.8); 0.008(6.0); 0.000(158.8); −0.008(7.1); −0.150(0.8) 90 1.84 1.87 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.348(3.5); 9.342(3.5); 9.313(5.9); 8.693(2.4); 8.690(2.6); 8.681 (2.5); 8.678(2.5); 8.524(1.4); 8.521(1.7); 8.518(1.6); 8.514(1.4); 8.503(1.5); 8.500(1.7); 8.497(1.7); 8.493(1.4); 7.940(2.4); 7.840 (2.9); 7.817(3.1); 7.685(1.9); 7.674(1.9); 7.665(1.9); 7.653 (1.8); 7.368(1.6); 7.345(1.5); 4.425(0.4); 4.378(1.0); 4.361(1.0); 3.318(44.4); 3.143(0.4); 3.121(16.0); 2.672(0.5); 2.667(0.4); 2.507 (59.1); 2.502(76.5); 2.498(57.7); 2.333(0.4); 2.329(0.5); 2.325 (0.4); 0.000(2.5) 91 3.22 3.12 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.202(4.5); 9.474(6.5); 9.389(3.7); 9.383(3.8); 8.704(2.5); 8.701 (2.8); 8.693(2.7); 8.689(2.8); 8.576(4.5); 8.560(1.6); 8.556(1.8); 8.554(1.8); 8.550(1.6); 8.539(1.6); 8.536(1.8); 8.533(1.9); 8.529 (1.6); 8.313(0.3); 7.913(1.5); 7.909(1.5); 7.890(3.4); 7.886 (3.6); 7.857(4.3); 7.844(3.4); 7.834(2.3); 7.824(3.3); 7.699(2.0); 7.687(2.0); 7.678(2.0); 7.667(1.9); 7.313(2.8); 7.284(2.8); 3.918 (1.4); 3.892(4.3); 3.866(4.5); 3.840(1.6); 3.317(33.8); 2.676 (0.3); 2.671(0.5); 2.667(0.4); 2.511(26.0); 2.507(51.7); 2.502(70.1); 2.498(55.4); 2.465(0.6); 2.429(16.0); 2.333(0.4); 2.329(0.5); 2.324(0.4); 0.008(0.5); 0.000(11.8) 92 1.5 1.58 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.346(9.8); 9.340(10.0); 9.293(16.0); 8.682(7.3); 8.670(7.1); 8.514 (4.9); 8.493(5.0); 8.311(0.6); 7.883(13.3); 7.810(7.4); 7.788 (8.0); 7.678(5.0); 7.666(5.2); 7.657(5.0); 7.645(4.5); 7.352(7.3); 7.329(6.6); 4.056(0.6); 4.039(1.6); 4.021(1.7); 4.003(0.7); 3.768 (4.7); 3.626(0.5); 3.308(53.9); 2.671(15.8); 2.501(307.4); 2.328 (2.0); 1.988(6.2); 1.193(1.7); 1.176(3.3); 1.158(1.7); 0.000 (15.5) 93 0.87 1.03 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.353(9.2); 9.346(9.3); 9.323(16.0); 8.690(5.9); 8.687(6.8); 8.678 (6.2); 8.675(6.7); 8.526(3.2); 8.523(3.9); 8.520(4.0); 8.516(3.5); 8.505(3.5); 8.502(3.9); 8.499(4.3); 8.495(3.6); 8.310(0.7); 8.014 (12.3); 7.829(7.1); 7.807(8.0); 7.683(5.1); 7.671(4.9); 7.662 (4.8); 7.650(4.7); 7.457(0.4); 7.442(6.5); 7.439(6.9); 7.420(5.8); 7.417(6.3); 4.056(1.0); 4.050(0.8); 4.039(2.5); 4.021(2.6); 4.003 (1.4); 3.920(4.2); 3.793(0.4); 3.322(349.3); 3.294(11.0); 3.282 (12.9); 2.722(0.4); 2.675(1.1); 2.671(1.6); 2.666(1.3); 2.524 (3.9); 2.506(186.6); 2.502(251.0); 2.497(188.8); 2.333(1.1); 2.328 (1.6); 2.324(1.2); 1.988(9.0); 1.193(2.4); 1.176(4.6); 1.158 (2.3); 0.008(0.4); 0.000(13.4) 94 2.23 2.23 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.618(4.2); 9.478(6.2); 9.394(3.7); 9.387(3.8); 8.706(2.5); 8.703 (2.8); 8.695(2.7); 8.691(2.9); 8.600(4.5); 8.563(1.4); 8.560(1.7); 8.557(1.6); 8.553(1.5); 8.543(1.6); 8.539(1.7); 8.536(1.8); 8.532 (1.5); 8.373(3.9); 8.368(4.2); 8.314(0.3); 8.000(1.9); 7.995 (1.9); 7.980(2.1); 7.974(2.1); 7.940(1.7); 7.936(1.8); 7.917(3.3); 7.913(3.5); 7.869(4.0); 7.847(2.1); 7.703(2.0); 7.691(1.9); 7.682 (1.9); 7.670(1.9); 7.367(3.0); 7.346(2.8); 4.181(1.0); 4.171(0.5); 4.153(1.1); 4.143(1.3); 4.126(0.5); 4.116(1.3); 4.089(0.4); 3.949 (0.3); 3.922(1.2); 3.913(0.4); 3.895(1.4); 3.885(1.1); 3.868 (0.5); 3.858(1.0); 3.832(0.3); 3.318(50.7); 2.791(0.6); 2.676(0.6); 2.671(0.8); 2.667(0.6); 2.635(0.5); 2.524(2.4); 2.511(44.9); 2.507(91.6); 2.502(122.3); 2.497(92.4); 2.493(47.8); 2.351(16.0); 2.333(0.9); 2.329(1.0); 2.324(0.8); 1.336(0.7); 1.299(0.5); 1.259 (0.8); 1.250(1.0); 1.234(0.5); 0.146(0.6); 0.008(5.1); 0.000 (138.3); −0.008(6.3); −0.150(0.6) 95 0.9 0.95 96 2.19 2.14 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 10.415(4.3); 9.488(6.7); 9.391(3.8); 9.385(3.8); 8.707(2.8); 8.704 (2.7); 8.695(2.8); 8.692(2.7); 8.598(4.7); 8.562(1.5); 8.558(1.8); 8.556(1.7); 8.552(1.4); 8.541(1.6); 8.538(1.8); 8.535(1.8); 8.531 (1.4); 8.314(0.4); 8.167(3.2); 8.148(3.2); 7.923(1.5); 7.920 (1.4); 7.900(3.6); 7.897(3.5); 7.870(4.4); 7.847(1.8); 7.703(2.1); 7.691(2.0); 7.682(2.0); 7.670(1.9); 7.413(2.7); 7.385(2.7); 5.754 (0.5); 4.238(0.9); 4.229(0.5); 4.211(1.1); 4.201(1.3); 4.183(0.5); 4.174(1.3); 4.147(0.4); 4.055(0.4); 4.029(1.2); 4.020(0.4); 4.002 (1.4); 3.992(1.0); 3.974(0.5); 3.965(1.0); 3.317(62.0); 2.671 (1.7); 2.557(0.4); 2.524(3.1); 2.506(119.8); 2.502(153.5); 2.497 (112.4); 2.399(16.0); 2.333(0.7); 2.328(1.0); 2.324(0.7); 1.909 (3.4); 1.235(0.9); 0.146(1.0); 0.008(8.2); 0.000(206.2); −0.008 (8.5); −0.025(0.4); −0.150(1.0) 97 2.2 2.22 .sup.1H-NMR(601.6 MHz, DMF): δ = 10.128(0.3); 9.505(1.0); 9.504(0.9); 9.455(0.5); 9.451(0.5); 8.740 (0.4); 8.738(0.4); 8.732(0.4); 8.730(0.4); 8.705(0.7); 8.091(1.0); 8.052(0.4); 8.049(0.4); 8.037(0.7); 8.034(0.7); 8.024(5.2); 7.906 (0.6); 7.891(0.5); 7.326(0.8); 3.465(16.0); 2.921(2.9); 2.918 (5.7); 2.915(8.1); 2.912(5.6); 2.909(2.7); 2.751(3.1); 2.747(6.3); 2.744(9.0); 2.741(6.3); 2.738(3.1); 2.438(3.0); 2.433(2.9); 0.005 (0.5); 0.000(12.7); −0.006(0.4) 98 1.27 1.30 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 12.941(2.9); 9.350(9.6); 9.344(9.6); 9.136(16.0); 8.655(6.5); 8.652 (7.1); 8.643(6.8); 8.640(7.0); 8.510(3.7); 8.507(4.5); 8.505 (4.5); 8.501(3.8); 8.490(4.0); 8.486(4.6); 8.484(4.8); 8.480(3.8); 8.314(0.7); 8.257(4.7); 8.007(4.6); 7.951(12.7); 7.755(5.7); 7.732 (9.9); 7.676(8.2); 7.673(8.3); 7.662(5.6); 7.650(9.7); 7.641(5.2); 7.629(4.7); 3.321(105.7); 2.891(0.4); 2.732(0.4); 2.672(1.3); 2.507(159.7); 2.503(205.5); 2.498(160.5); 2.329(1.3); 0.000 (5.4) 99 2.12 2.12 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.356(8.4); 9.350(8.8); 9.175(14.9); 8.661(6.6); 8.649(6.7); 8.513 (4.1); 8.492(4.4); 8.349(15.0); 8.139(16.0); 7.998(11.7); 7.786 (6.0); 7.763(8.2); 7.667(4.5); 7.655(4.9); 7.646(11.1); 7.635 (4.8); 7.623(5.3); 5.206(2.9); 5.183(9.2); 5.160(9.6); 5.137(3.3); 3.323(45.8); 2.673(0.7); 2.504(114.3); 2.330(0.7); 1.990(0.9); 1.176(0.5); 0.146(0.6); 0.000(109.6); −0.150(0.6) 101 2.04 2.21 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 9.382(9.7); 9.375(9.6); 9.348(16.0); 8.730(5.1); 8.716(5.4); 8.707 (5.3); 8.693(5.9); 8.688(7.0); 8.685(7.1); 8.676(6.8); 8.673(6.8); 8.608(11.3); 8.551(3.6); 8.548(4.2); 8.545(4.1); 8.541(3.6); 8.531(3.9); 8.527(4.2); 8.524(4.4); 8.521(3.6); 8.315(0.4); 8.186 (6.1); 8.182(5.9); 8.163(7.0); 8.159(6.9); 8.045(5.1); 8.040(5.2); 8.017(5.3); 8.011(5.0); 7.859(8.5); 7.836(7.4); 7.686(5.0); 7.674 (4.9); 7.665(4.8); 7.653(4.7); 7.310(3.2); 7.304(3.0); 7.296 (3.3); 7.289(4.8); 7.283(3.0); 7.275(3.2); 7.269(2.8); 3.324(78.0); 3.322(83.3); 2.677(0.6); 2.673(0.8); 2.668(0.6); 2.508(103.2); 2.504(133.3); 2.499(96.6); 2.335(0.6); 2.331(0.8); 2.326(0.6); 0.008(2.0); 0.000(50.1); −0.008(2.0) 104 2.4 2.44

Biological Examples

[1022] Myzus persicae—Spray Test

[1023] Solvent: 78 parts by weight of acetone [1024] 1.5 parts by weight of dimethylformamide

[1025] Emulsifier: alkylaryl polyglycol ether

[1026] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved using 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.

[1027] Discs of Chinese cabbage leaves (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound formulation of the desired concentration.

[1028] 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.

[1029] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 500 g/ha: 1, 3, 5, 7, 16, 24, 30, 32, 33, 50, 52, 61, 67, 68, 69, 74, 79, 80, 86, 87, 88, 89, 92, 96, 97, 108, 109, 112, 115, 121, 122, 128

[1030] In this test, for example, the following compounds from the preparation examples showed an efficacy of 90% at an application rate of 500 g/ha: 4, 6, 8, 9, 10, 11, 13, 14, 15, 18, 19, 20, 22, 25, 27, 31, 37, 49, 51, 53, 54, 55, 56, 57, 58, 60, 62, 63, 64, 65, 66, 71, 73, 75, 76, 77, 81, 82, 85, 90, 94, 95, 99, 101, 104, 105, 110, 111, 113, 114, 116, 118, 123, 124, 126, 129, 130

[1031] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha: 23

[1032] In this test, for example, the following compounds from the preparation examples showed an efficacy of 90% at an application rate of 100 g/ha: 26, 29, 59, 91

Myzus persicae—Spray Test

[1033] Solvent: 7 parts by weight of dimethylformamide

[1034] Emulsifier: alkylaryl polyglycol ether

[1035] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved using 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.

[1036] Bell pepper plants (Capsicum annuum) severely infested with the green peach aphid (Myzus persicae) are treated by spraying with the active compound formulation in the desired concentration.

[1037] 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.

[1038] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 4 ppm: 51

Phaedon cochleariae—Spray Test

[1039] Solvent: 78.0 parts by weight of acetone [1040] 1.5 parts by weight of dimethylformamide

[1041] Emulsifier: alkylaryl polyglycol ether

[1042] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved using 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.

[1043] Discs of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

[1044] 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.

[1045] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 500 g/ha: 16, 38

Spodoptera frugiperda—Spray Test

[1046] Solvent: 78.0 parts by weight of acetone [1047] 1.5 parts by weight of dimethylformamide

[1048] Emulsifier: alkylaryl polyglycol ether

[1049] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved using 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.

[1050] Leaf discs of maize (Zea mays) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).

[1051] After 7 days, the efficacy in % is determined. 100% means that all the caterpillars have been killed; 0% means that no caterpillar has been killed.

[1052] In this test, for example, the following compounds from the preparation examples showed an efficacy of 100% at an application rate of 500 g/ha: 38

Tetranychus urticae—Spray Test, OP-Resistant

[1053] Solvent: 78.0 parts by weight of acetone [1054] 1.5 parts by weight of dimethylformamide

[1055] Emulsifier: alkylaryl polyglycol ether

[1056] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved using 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.

[1057] Discs of bean leaves (Phaseolus vulgaris) infested with all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active compound formulation of the desired concentration.

[1058] 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.

[1059] In this test, for example, the following compounds from the preparation examples showed an efficacy of 90% at an application rate of 500 g/ha: 117

Aphis gossypii—Spray Test

[1060] Solvent: 7 parts by weight of dimethylformamide

[1061] Emulsifier: alkylaryl polyglycol ether

[1062] To produce a suitable preparation of active compound, 1 part by weight of active compound is dissolved using 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.

[1063] Cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are sprayed with an active compound formulation of the desired concentration.

[1064] After 6 days, the kill in % is determined. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.

[1065] In this test, for example, the following compound from the preparation examples showed an efficacy of 80% at an application rate of 4 ppm: 12

Boophilus microplus—Injection Test

[1066] Solvent: dimethyl sulphoxide

[1067] To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration.

[1068] 1 μl of the active compound solution is injected into the abdomen of 5 engorged adult female cattle ticks (Boophilus microplus). The animals are transferred into dishes and kept in a climate-controlled room.

[1069] Efficacy is assessed after 7 days by laying of fertile eggs. Eggs which are not externally visibly fertile are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all the eggs are fertile.

[1070] In this test, for example, the following compound from the preparation examples showed an efficacy of 100% at an application rate of 20 μg/animal: 52

Cooperia curticei—Test

[1071] Solvent: dimethyl sulphoxide

[1072] To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with “Ringer's solution” to the desired concentration.

[1073] Vessels containing the active compound preparation of the desired concentration are populated with about 40 nematode larvae (Cooperia curticei).

[1074] After 5 days, the kill in % is determined. 100% means that all the larvae have been killed; 0% means that none of the larvae have been killed.

[1075] In this test, for example, the following compounds of the preparation examples show an efficacy of 90% at an application rate of 20 ppm: 56, 65

[1076] In this test, for example, the following compounds of the preparation examples showed an efficacy of 80% at an application rate of 20 ppm: 57, 67, 76

Haemonchus contortus—Test

[1077] Solvent: dimethyl sulphoxide

[1078] To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulfoxide and the concentrate is diluted with “Ringer's solution” to the desired concentration.

[1079] Vessels containing the active compound preparation of the desired concentration are populated with about 40 larvae of the red stomach worm (Haemonchus contortus).

[1080] After 5 days, the kill in % is determined. 100% means that all the larvae have been killed; 0% means that none of the larvae have been killed.

[1081] In this test, for example, the following compounds from the preparation examples showed an efficacy of 80% at an application rate of 20 ppm: 65, 67

Meloidogyne incognita—Test

[1082] Solvent: 125.0 parts by weight of acetone

[1083] To produce a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration.

[1084] Vessels are filled with sand, active compound solution, an egg/larvae suspension of the southern root-knot nematode (Meloidogyne incognita) and lettuce seeds. The lettuce seeds germinate and the plants develop. The galls develop on the roots.

[1085] After 14 days, the nematicidal efficacy in % is determined by the formation of galls. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to the untreated control.

[1086] In this test, for example, the following compounds from the preparation examples showed an efficacy of 90% at an application rate of 20 ppm: 99, 104