BICYCLIC COMPOUNDS AS PEST CONTROL AGENTS

Abstract

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

Claims

1. The compound of the formula (I) ##STR00175## in which A represents an A radical from the group consisting of (A-a) to (A-f) ##STR00176## where the broken line represents the bond to the nitrogen atom of the bicyclic system 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.2 a) represents a radical from the group consisting of (B-1) to (B-36) ##STR00177## ##STR00178## ##STR00179## where the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 b) represents a D radical from the group consisting of (D-1) to (D-3) ##STR00180## where the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 c) represents a radical of the formula ##STR00181## where the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 d) represents a radical of the formula ##STR00182## where the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), or R.sup.2 e) represents an F radical from the group consisting of (F-1) to (F-11) ##STR00183## ##STR00184## where the broken line denotes the bond to the carbon atom of the bicyclic system of 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, alkoxycarbonylalkyl, saturated or unsaturated cycloalkyl which is optionally substituted and optionally interrupted by one or more heteroatoms, cycloalkylalkyl, alkoxy, haloalkoxy, alkoxyalkyl, halogenated alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, bis(alkoxy)alkyl, bis(haloalkoxy)alkyl, alkoxy(alkylsulfanyl)alkyl, alkoxy (alkyl sulfinyl)alkyl, alkoxy (alkyl sulfonyl)alkyl, bi s (alkyl sulfanyl)alkyl, bis(haloalkylsulfanyl)alkyl, bis(hydroxyalkylsulfanyl)alkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alpha-hydroxyiminoalkoxycarbonylalkyl, alpha-alkoxyiminoalkoxycarbonylalkyl, C(X.sup.2)NR.sup.3R.sup.4, NR.sup.6R.sup.7, alkylthio, alkylsulfinyl, alkylsulfonyl, the heterocyclyl radicals dioxanyl, dioxolanyl, dioxepanyl, dioxocanyl, oxathianyl, oxathiolanyl, oxathiepanyl, oxathiocanyl, dithianyl, dithiolanyl, dithiepanyl, dithiocanyl, oxathianyl oxide, oxathiolanyl oxide, oxathiepanyl oxide, oxathiocanyl oxide, oxathianyl dioxide, oxathiolanyl dioxide, oxathiepanyl dioxide, oxathiocanyl dioxide, morpholinyl, triazolinonyl, oxazolinyl, dihydrooxadiazinyl, dihydrodioxazinyl, dihydrooxazolyl, dihydrooxazinyl and pyrazolinonyl (which for their part may be substituted by alkyl, haloalkyl, alkoxy and alkoxyalkyl), phenyl (which for its part 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 part 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 part 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) ##STR00185## where the broken line denotes the bond to the radicals (B-1) to (B-36), X represents oxygen or sulfur, 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, sulfur, NR.sup.5 or NOH, L represents oxygen or sulfur, 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, alkylsulfinylalkyl, alkylsulfonylalkyl, 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 sulfur, 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, alkylsulfinylalkyl, alkylsulfonylalkyl, 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 sulfur, 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 alkylsulfonyl, 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 sulfur, 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), together with the N—S(O)n group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting of sulfur, 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 and R.sup.10 in the (C-2) and (F-2) radicals, together with the nitrogen atoms to which they are attached, may also represent 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 sulfur, 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), together with the N—S(O)n group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting of sulfur, 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), together with the phosphorus atom to which they are attached, may also form a saturated or unsaturated and optionally substituted 5- to 7-membered ring which may contain one or two heteroatoms from the group consisting of oxygen (where oxygen atoms must not be directly adjacent to one another) and sulfur, 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 sulfur, 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), together with the N—S(O)n group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting of sulfur, 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 sulfur, 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), together with the nitrogen atom to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting of sulfur, 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 sulfur, 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), together with the N—C(X) group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which may contain one or more further heteroatoms from the group consisting of sulfur, 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, alkylsulfinylalkyl, alkylsulfonylalkyl, 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 sulfur, 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, alkylsulfinylalkyl, alkylsulfonylalkyl 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, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylthioalkyloxy, alkylsulfinylalkyloxy, alkylsulfonylalkyloxy, haloalkylthioalkyl, halogenalkylsulfinylalkyl, haloalkylsulfonylalkyl, alkylthioalkenyl, alkylsulfinylalkenyl, alkylsulfonylalkenyl, alkenylthioalkyl, alkenylsulfinylalkyl, alkenylsulfonylalkyl, alkylcarbonylalkyl, haloalkylcarbonylalkyl, alkoxyalkyl, haloalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxycarbonylalkyl, alkylaminosulfonyl, di(alkylamino)sulfonyl, 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 ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## 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, alkylsulfonyloxy, alkylamino, alkenylamino, alkynylamino, cycloalkylamino, alkylthio, haloalkylthio, alkenylthio, alkynylthio, cycloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxyiminoalkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminosulfonyl, alkylsulfonylamino, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, cycloalkylcarbonylamino, alkoxycarbonylamino, alkylthiocarbonylamino, bicycloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy, where the substituents are independently of one another selected from halogen, cyano, nitro, hydroxy, amino, alkyl and haloalkyl, R.sup.21 represents a radical from the group consisting of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulfonyl and haloalkylsulfonyl, 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 a radical from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl and cyanoalkyl.

2. The compound of the formula (I) as claimed in claim 1, in which A represents a radical from the group consisting of (A-a), (A-b) and (A-f) ##STR00191## where the broken line represents the bond to the nitrogen atom of the bicyclic system 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, B.sup.2 represents hydrogen, T represents an electron pair, R.sup.2 c) represents the radical of the formula ##STR00192## where the broken line denotes the bond to the carbon atom of the bicyclic system of the formula (I), X represents oxygen, R.sup.3 represents C.sub.1-C.sub.4-alkyl, R.sup.22 represents a radical from the group consisting of C.sub.1-C.sub.6-alkyl, 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-alkylsulfonyl and di-(C.sub.1-C.sub.4-alkyl)-aminosulfonyl and R.sup.23 represents hydrogen or C.sub.1-C.sub.6-alkyl.

3. The compound of the formula (I) as claimed in claim 1 in which A represents the radical (A-b).

4. The compound of the formula (I) as claimed in claim 1 in which A represents the radical (A-f).

5. The compound of the formula (I) as claimed in claim 1 in which A represents the radical (A-a).

6. A composition comprising a content of at least one compound of the formula (I) as claimed in claim 1 and one or more customary extenders and/or surfactants.

7. A product comprising one or more compounds of the formula (I) as claimed in claim 1 or a composition thereof for controlling pests.

Description

EXAMPLES 1 or 38

[0617] ##STR00093##

[0618] Step 1:

[0619] Synthesis of Compounds of the Formula (A-3) (R.sup.2═CO—OCH.sub.3)

##STR00094##

[0620] 1 equivalent of a heterocyclic amino compound (A-2), 0.12 equivalent (3.4 mmol) of para-toluenesulfonic acid (PTSA) and 6 g of 4 A molecular sieve were added to a solution of 28.3 ml of 2-substituted 5-nitro-4-pyridinecarboxaldehyde of the formula (A-1) in 200 ml of toluene. The reaction mixture was then stirred at 110° C. for 16 hours. The reaction mixture was filtered and the filtrate gave, after concentration, the crude products (A-3), which were reacted further without further purification.

[0621] Step 2

Synthesis of 5-substituted 2-(hetaryl)-2H-pyrazolo[3,4-c]pyridines of the formula (I)

[0622] 1 equivalent of the compounds of the formula (A-3) was dissolved in 30 ml of triethyl phosphite, and the reaction mixture was then stirred at 140° C. for about 16 hours. After concentration of the reaction mixture under reduced pressure, the residue that remained was purified by column chromatography.

General synthesis of 5-substituted 2-(hetaryl)-2H-pyrazolo[3,4-c]pyridine-5-carboxylic acids of the formula (I, R.SUP.2.═COOH)

[0623] ##STR00095##

[0624] 1 equivalent of a compound of the formula (I; R.sup.2═COOCH.sub.3) was dissolved in a mixture of 100 ml of water and 100 ml of tetrahydrofuran, and 3 equivalents of lithium hydroxide monohydrate were added. The reaction mixture was then stirred at 25° C. for about 16 hours. Subsequently, the tetrahydrofuran was removed under reduced pressure and the aqueous phase was adjusted to pH=2 with 1M hydrochloric acid. After extraction with 100 ml of ethyl acetate, the organic phase was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product that remained was used in the next reaction step without further purification.

a) 2-(1H-7-Azabenzotriazol-1-yl)-1,1,3,3-tetramethyluroniummethanaminium hexafluorophosphate (HATU) coupling method

[0625] 1.0 equivalent of 5-substituted 2-(hetaryl)-2H-pyrazolo[3,4-c]pyridine-5-carboxylic acid was dissolved in 3 ml of N,N-dimethylformaldehyde, and 2.4 equivalents (1.2 mmol) of HATU and 6.0 equivalents of N,N-diisopropylethylamine were added. The reaction mixture was then stirred at room temperature for 10 minutes, and 1.2 equivalents of the sulfonamide component were then added. After about 16 hours of stirring at room temperature, the reaction mixture was concentrated under reduced pressure and the residue that remained was purified by preparative chromatography (HPLC).

b) 2-(1H-7-Azabenzotriazol-1-yl)-1,1,3,3-tetramethyluroniummethanaminium hexafluorophosphate (HATU) coupling method

[0626] 1.0 equivalent of 5-substituted 2-(hetaryl)-2H-pyrazolo[3,4-c]pyridine-5-carboxylic acid was dissolved in 3 ml of N,N-dimethylformaldehyde, and 2.4 equivalents (1.2 mmol) of HATU and 2.4 equivalents of N,N-diisopropylethylamine were added. The reaction mixture was then stirred at room temperature for 10 minutes, and 1.2 equivalents of the amine component were then added. After about 16 hours of stirring at room temperature, the reaction mixture was concentrated under reduced pressure and the residue that remained was purified by preparative chromatography (HPLC).

[0627] Synthesis of Intermediates

Methyl 4-[(1E)-2-(dimethylamino)ethenyl]-5-nitro-2-pyridinecarboxylate

[0628] ##STR00096##

[0629] 86.4 g (0.73 mmol) of N,N-dimethylformamide O,O-dimethyl acetal were added to a solution of 65 g (0.33 mol) of methyl 5-methyl-6-nitro-3-pyridinecarboxylate (Y. Morisawa et al., J. Med. Chem. 21, 194-199, 1978) in 415 ml of N,N-dimethylformamide. The reaction mixture was then stirred at 90° C. for 6 hours. The solvent was then removed under reduced pressure and the residue that remained was purified by column chromatography. This gave 56 g (yield 66.7% of theory) of methyl 4-[(1E)-2-(dimethylamino)ethenyl]-5mitro-2-pyridinecarboxylate.

Methyl 4-formyl-5-nitro-2-pyridinecarboxylate

[0630] ##STR00097##

[0631] 142 g (41.98 mmol) of sodium periodate were added to a solution of 56 g (0.22 mol) of methyl 4-[(1E)-2-(dimethylamino)ethenyl]-5-nitro-2-pyridinecarboxylate in 550 ml of water and 550 ml of tetrahydrofuran. The reaction mixture was then stirred at 25° C. for 16 hours. The reaction mixture was then diluted with 700 ml of ethyl acetate and then washed with saturated aqueous sodium bicarbonate solution and brine. The combined organic phases were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue that remained was purified by column chromatography. This gave 45 g (yield 97.3% of theory) of methyl 4-formyl-5-nitro-2-pyridinecarboxylate as a brown solid.

TABLE-US-00001 TABLE 1 Compounds of the formula [00098] Yield Purity Compound No. A R.sup.2 [in mg] [in %] 1*) [00099] [00100]  9.07  95.1 2 *) [00101] [00102]  5.10 100 3 *) [00103] [00104]  8.57  89.0 4 *) [00105] [00106]  13.24  99.3 5 *) [00107] [00108]  8.79  93.8 6 *) [00109] [00110]  12.50 100 7 *) [00111] [00112]  17.53  99.5 8 *) [00113] [00114]  20.95  96.5 9 *) [00115] [00116]  26.45  93.7 10 *) [00117] [00118]  24.42  95.4 11 [00119] [00120]  42.50  92.2 12 [00121] [00122]  29.41  99.4 13 [00123] [00124]  29.98 100 14 [00125] [00126]  33.50  94.9 15 *) [00127] [00128]  24.77  98.8 16 [00129] [00130]  24.33  98.1 17 [00131] [00132]  31.38  98.7 18 *) [00133] [00134]  24.47  87.3 19 [00135] [00136]  36.67 100 20 [00137] [00138]  37.27  99.5 21*) [00139] [00140]  22.16  98.5 22 [00141] [00142]  42.52  99.1 23 *) [00143] [00144]  85.10 100 24 *) [00145] [00146]  72.03 100 25 [00147] [00148]  93.41  90.8 26 [00149] [00150]  39.12  99.1 27 [00151] [00152]  46.42  97.1 28 *) [00153] [00154]  42.0  99.3 29 [00155] [00156]  53.29  97.7 30 *) [00157] [00158]  40.7  99.4 31 [00159] [00160]  43.30  99.1 32 *) [00161] [00162] 107.27  95.0 33 *) [00163] [00164]  55.0  95.7 34 *) [00165] [00166]  46.38 100 35 *) [00167] [00168]  26.48  99.6 36 [00169] [00170]  33.96  99.2 37 *) [00171] [00172]  21.32  98.2 38 [00173] [00174]  21.1  91.8 *) crystallizes with 1 x HCOOH

TABLE-US-00002 TABLE 2 Analytical data for the compounds 1-38 Reten- tion Ex. time No. [min] .sup.1H NMR [δ (ppm)] or LC-MS [m/z] 1 2.922 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.65 (t, 3H, CH.sub.3); 3.85 (m, 2H, CH.sub.2); 8.57; 8.78; 8.90; 8.96; 9.44; 9.58 (6H, ═CH, aryl/hetaryl). LC-MS = 319.1 (M + 1) [without HCOOH] 2 2.553 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.24 (d, 6H, 2xCH.sub.3); 4.17 (m, 1H, CH); 8.43; 8.51; 8.77; 8.88; 9.39; 9.56 (6H, ═CH, aryl/hetaryl). LC-MS = 283.2 (M + 1); [without HCOOH] 3 2.843 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.78; 6.20 (2m, 3H, CH.sub.2CHF.sub.2); 8.51; 8.61; 8.80; 9.31; 9.40; 9.57 (6H, ═CH, aryl/hetaryl); 9.05 (br., 1H, NH). LC-MS = 322.1 (M + 1); [without HCOOH] 4 2.141 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.15-1.26 (t + m, 5H, CH.sub.2CH.sub.3); 8.43; 9.37; 9.57; 9.60 (4H, ═CH, aryl/hetaryl); 8.80 (br., 1H, NH). LC-MS = 269.1 (M + 1) [without HCOOH] 5 2.474 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.76; 6.20 (2m, 3H, CH.sub.2CHF.sub.2); 8.48; 8.56; 8.77; 8.89; 9.42; 9.57 (6H, ═CH, aryl/hetaryl); 9.05 (br., 1H, NH). LC-MS = 305.1 (M + 1) [without HCOOH] 6 2.339 .sup.1H-NMR(400.0 MHz, CDCl.sub.3): δ = 1.66 (t, 3H, CH.sub.3); 3.84 (m, 2H, CH.sub.2); 8.55; 9.37; 9.43; 9.60 (4H, ═CH, aryl/hetaryl); 8.96 (br., 1H, NH). LC-MS = 319.0 (M + 1) [without HCOOH] 7 1.889 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.01; 3.04 (2s, 6H, 2xCH.sub.3); 7.72; 8.01; 8.57; 8.75; 9.34; 9.38; 9.41 (7H, ═CH, aryl/hetaryl). LC-MS = 268.0 (M + 1) [without HCOOH] 8 2.237 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.42 (s, 3H, CH.sub.3; 8.65; 8.82; 9.33; 9.43; 9.64 (5H, ═CH, aryl/hetaryl). LC-MS = 335.9 (M + 1) [without HCOOH] 9 3.125 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.16 (t, 3H, CH.sub.3); 3.37 (m, 2H, CH.sub.2); 3.95 (s, 3H, CH.sub.3); 3.57 (2s 6H, 2xCH.sub.3); 8.17; 8.41; 8.54; 9.11; 9.23 (5H, ═CH, aryl/ hetaryl). LC-MS = 271.1 (M + 1) [without HCOOH] 10 2.575 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.93 (s, 6H, 2xCH.sub.3); 8.62; 8.65; 8.82; 9.32; 9.42; 9.64 (6H, ═CH, aryl/hetaryl). LC-MS = 365.1 (M + 1) [without HCOOH] 11 2.138 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.32; 3.72 (2s 6H, 2xCH.sub.3); 7.73; 8.10; 8.57; 9.46 (4H, ═CH, aryl/hetaryl). LC-MS = 284.1 (M + 1); 283.28 (calculated) 12 2.409 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.16 (t 3H, CH.sub.3); 3.37 (m, 2H, CH.sub.2); 8.45; 8.61; 8.80; 9.31; 9.36; 9.55 (6H, ═CH, aryl/hetaryl). LC-MS = 286.0 (M + 1) 285.27 (calculated) 13 2.592 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 0.71 (m 4H, CH.sub.2CH.sub.2); 8.51; 8.77; 8.88; 9.37; 9.55; 9.58 (6H, ═CH, aryl/hetaryl). LC-MS = 281.0 (M + 1) 280.28 (calculated) 14 1.963 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.86 (d, 3H, CH.sub.3); 8.50; 8.77; 8.88; 9.39; 9.56 (5H, ═CH, aryl/ hetaryl). LC-MS = 255.0 (M + 1) 254.24 (calculated) 15 2.044 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.03 (d, 6H, 2xCH.sub.3); 8.02; 8.77; 8.88; 9.37; 9.48; 9.56 (6H, ═CH, aryl/hetaryl). LC-MS = 269.1 (M + 1) [without HCOOH] 16 1.960 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.18 (t, 3H, CH.sub.3); 3.37 (m, 2H, CH.sub.2); 8.50; 8.77; 8.88; 9.39; 9.56; (5H, ═CH, aryl/hetaryl). LC-MS = 269.0 (M + 1) 268.27 (calculated) 17 2.602 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.20 (d, 6H, 2xCH.sub.3); 4.16 (m, 1H, CH); 8.60; 8.63; 8.80; 9.31; 9.37; 9.56 (7H, ═CH, aryl/hetaryl). LC-MS = 300.0 (M + 1); 299.30 (calculated) 18 2.567 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.95; 2.92 (2s, 6H, 2xCH.sub.3); 8.20; 8.55; 8.58; 9.22; 9.28 (5H, ═CH, aryl/ hetaryl). LC-MS = 350.1 (M + 1) [without HCOOH] 19 2.521 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.87 (d, 3H, CH.sub.3); 8.45; 8.61; 8.80; 9.31; 9.36; 9.55 (6H, ═CH, aryl/ hetaryl). LC-MS = 271.9 (M.sup.+); 271.24 (calculated) 20 2.420 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.02 (d, 6H, 2xCH.sub.3); 8.01; 8.61; 8.79; 9.31; 9.34; 9.48 (6H, ═CH, aryl/hetaryl). LC-MS = 285.9 (M.sup.+); 285.2763 (calculated) 21 2.099 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.32; 3.72 (2s, 6H, 2xCH.sub.3); 8.10; 8.77; 8.88; 9.39; 9.50, 9.56 (6H, ═CH, aryl/hetaryl). LC-MS = 285.1 (M + 1) [without HCOOH] 22 1.834 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.31; 3.71 (2s, 6H, 2xCH.sub.3); 8.11; 9.36; 9.51; 9.60 (4H, ═CH, aryl/ hetaryl). LC-MS = 285.1 (M + 1); 284.27 (calculated) 23 2.104 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.99; 3.02 (2s, 6H, 2xCH.sub.3); 7.94; 8.16; 8.54; 9.02; 9.29 (5H, ═CH, aryl/ hetaryl). LC-MS = 285.1 (M + 1) [without HCOOH] 24 2.251 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.40; 3.95 (2s, 6H, 2xCH.sub.3); 8.20; 8.59; 9.22; 9.29 (4H, ═CH, aryl/ hetaryl). LC-MS = 321.1 (M + 1) [without HCOOH] 25 2.376 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.64 (t, 3H, CH.sub.3); 3.81 (m, 2H, CH.sub.2); 3.94 (s, 3H, CH.sub.3); 8.18; 8.46; 8.56; 9.14; 9.26 (5H, ═CH, aryl/hetaryl); 8.92 (br., 1H, NH). LC-MS = 321.0 (M + 1); 320.29 (calculated) 26 2.112 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.71; (s, 3H, CH.sub.3); 8.08; 8.61; 8.79; 9.31; 9.35; 9.49 (6H, ═CH, aryl/ hetaryl). LC-MS = 302.0 (M + 1); 301.27 (calculated) 27 2.647 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.65 (t, 3H, CH.sub.3); 3.83 (m, 2H, CH.sub.2); 8.51; 8.60; 8.80; 9.31; 9.40; 9.58 (6H, ═CH, aryl/hetaryl); 8.96 (br, 1H, NH). LC-MS = 336.0 (M + 1); 335.28 (calculated) 28 2.485 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.64 (s, 3H, CH.sub.3); 3.83 (m, 2H, CH.sub.2); 7.71; 8.51; 8.56;8.74; 9.38; 9.53 (6H, ═CH, aryl/hetaryl); 8.95 (br., 1H, NH). LC-MS = 318.1 (M + 1) [without HCOOH] 29 1.888 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 0.71 (m, 4H, CH.sub.2CH.sub.2); 2.94 (m, 1H, CH); 7.71; 8.44; 8.55; 8.68; 8.74; 9.32; 9.37; 9.50 (7H, ═CH, aryl/hetaryl + NH). LC-MS = 280.0 (M + 1); 279.29 (calculated) 30 2.040 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.86 (d, 3H, CH.sub.3); 7.71; 8.44; 8.54; 8.75; 9.35; 9.37; 9.50 (7H, ═CH, aryl/hetaryl). LC-MS = 254.0 (M + 1) [without HCOOH] 31 2.629 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.15 (t, 3H, CH.sub.3); 3.36 (m, 2H, CH2); 7.71; 8.45; 8.56; 8.76; 8.80; 9.37; 9.51 (7H, ═CH, aryl/hetaryl). LC-MS = 268.0 (M + 1); 267.28 (calculated) 32 2.133 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.30; 3.71; 3.94 (3s, 9H, 3xCH.sub.3); 8.03; 8.17; 8.55; 9.06; 9.22 (5H, ═CH, aryl/hetaryl). LC-MS = 287.1 (M + 1) [without HCOOH] 33 2.182 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.24 (d, 6H, 2xCH.sub.3); 4.16 (m, 1H, CH); 8.17; 8.40; 8.54; 9.12; 9.22 (5H, ═CH, aryl/hetaryl). 34 2.167 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.75 (br, 2H, CH.sub.2); 6.17 (dt, 1H, CH); 8.17; 8.45; 8.55; 9.14; 9.25 (5H, ═CH, aryl/hetaryl); 9.02 (br., 1H, NH). LC-MS = 307.1 (M + 1) [without HCOOH] 35 1.840 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 2.84 (d, 3H, CH.sub.3); 3.94 (s, 3H, CH3); 8.16; 8.40; 8.54; 9.11; 9.22 (5H, ═CH, aryl/hetaryl), 8.72 (1H, NH). LC-MS = 257.0 (M + 1) [without HCOOH] 36 3.085 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 3.76 (m, 2H, CH.sub.2); 6.18 (dt, 1H, CH); 7.71; 8.50; 8.56; 8.75; 9.05; 9.38; 9.53 (7H, ═CH, aryl/hetaryl). LC-MS = 304.1 (M + 1); 303.26 (calculated) 37 2.469 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 0.70 (m, 4H, CH.sub.2CH.sub.3); 2.92 (m, 1H, CH); 8.16; 8.40; 8.54; 9.11; 9.19 (5H, ═CH, aryl/hetaryl), 8.63 (1H, NH). LC-MS = 283.1 (M + 1) [without HCOOH] 38 2.792 .sup.1H-NMR(400.0 MHz, d.sub.6-DMSO): δ = 1.21; 1.23 (2s, 6H, 2xCH.sub.3); 4.15 (m, 1H, CH); 7.71; 8.44; 8.55; 8.74; 9.36; 9.38; 9.51 (7H, ═CH, aryl/hetaryl). LC-MS = 282.1 (M + 1); 281.31 (calculated)

BIOLOGICAL EXAMPLES

[0632] Myzus Persicae—Spray Test

[0633] Solvent: 78 parts by weight of acetone [0634] 1.5 parts by weight of dimethylformamide

[0635] Emulsifier: alkylaryl polyglycol ether

[0636] 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.

[0637] 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.

[0638] 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.

[0639] 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, 4, 6, 7, 8, 10.

[0640] 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: 3, 5, 11, 14, 15, 19, 20, 26, 28, 29, 30, 31, 36.

[0641] Tetranychus Urticae—Spray Test, OP-Resistant

[0642] Solvent: 78.0 parts by weight of acetone [0643] 1.5 parts by weight of dimethylformamide

[0644] Emulsifier: alkylaryl polyglycol ether

[0645] 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.

[0646] 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.

[0647] 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.

[0648] 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: 3.

[0649] Musca Domestica Test

[0650] Solvent: dimethyl sulfoxide

[0651] 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 water to the desired concentration.

[0652] Vessels containing a sponge treated with sugar solution and the active compound formulation of the desired concentration are populated with 10 adult houseflies (Musca domestica).

[0653] After 2 days, the kill in % is determined. 100% means that all of the flies have been killed; 0% means that none of the flies have been killed.

[0654] In this test, for example, the following compounds of the preparation examples showed an efficacy of 80% at an application rate of 100 ppm: 14, 15.