# Patent

## Title
Anthranilic diamide derivatives

## Abstract

The present invention relates to novel anthranilic acid derivatives of the general formula (I)




in which R1, R2, R3, R4, R5, R6, A, Q and n have the meanings given in the description, to their use as insecticides and acaricides for controlling animal pests, also in combination with other agents for activity boosting, and a plurality of processes for their preparation.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority to EP 10166064.5 filed Jun. 15, 2010 and U.S. Provisional Application No. 61/354,905 filed Jun. 15, 2010, the contents of which are incorporated herein by reference in their entireties.
BACKGROUND
1. Field of the Invention
The present invention relates to novel anthranilic acid derivatives, to their use as insecticides and acaricides for controlling animal pests, also in combination with other agents for activity boosting, and to a plurality of processes for their preparation.
2. Description of Related Art
Anthranilic acid derivatives having insecticidal properties have already been described in the literature, as for example in WO 01/70671, WO 03/015519, WO 03/016284, WO 03/015518, WO 03/024222, WO 03/016282, WO 03/016283, WO 03/062226, WO 03/027099, WO 04/027042, WO 04/033468, WO 2004/046129, WO 2004/067528, WO 2005/118552, WO 2005/077934, WO 2005/085234, WO 2006/023783, WO 2006/000336, WO 2006/040113, WO 2006/111341, WO 2007/006670, WO 2007/024833, WO2007/020877, WO 2007/144100, WO2007/043677, WO2008/126889, WO2008/126890, WO2008/126933.
In their application, however, the active compounds already known in accordance with the specifications identified above have disadvantages in some respects, whether it be that they exhibit a narrow spectrum of application or whether it be that they do not have satisfactory insecticidal or acaricidal activity.
SUMMARY
Novel anthranilic acid derivatives have now been found which have advantages over the compounds already known, examples being better biological or environmental properties, broader application methods, an improved insecticidal or acaricidal activity, and also high compatibility with useful plants. The anthranilic acid derivatives can be used in combination with other agents for improving the efficacy in particular against insects which are difficult to control.
The present invention accordingly provides novel anthranilic acid derivatives of the formula (I)




in which

R1 represents hydrogen, amino, hydroxyl or represents C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents, where the substituents independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, (C1-C4-alkoxy)carbonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino and (C1-C4-alkyl)-C3-C6-cycloalkylamino,
R2 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino, C1-C6-alkoxycarbonyl or C1-C6-alkylcarbonyl,
R3 represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, where the substituents are identical or different and independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C1-C6-alkoxycarbonyl, C1-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R3 furthermore represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, where the substituents are identical or different and independently of one another may be selected from the group consisting of amino, C3-C6-cycloalkylamino and a 5- or 6-membered heteroaromatic ring,
R3 likewise furthermore represents C3-C12-cycloalkyl, C3-C12-cycloalkyl-C1-C6-alkyl and C4-C12-bicycloalkyl, where the substituents independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, amino, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C1-C6-alkoxycarbonyl, C1-C6-alkylcarbonyl, C3-C6-trialkylsilyl and a 5- or 6-membered heteroaromatic ring,
R2 and R3 may be joined to one another via two to six carbon atoms and form a ring which optionally additionally contains a further nitrogen, sulphur or oxygen atom and may optionally be mono- to tetrasubstituted by C1-C2-alkyl, halogen, cyano, amino or C1-C2-alkoxy,
R2, R3 furthermore together represent ═S(C1-C4-alkyl)2, ═S(O)(C1-C4-alkyl)2,
R4 represents hydrogen, halogen, cyano, nitro, hydroxyl, amino, (C═O)OH, OCN, SCN, C1-C4-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy, SF5, C1-C4-alkylthio, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylcarbonylamino, N-methoxy-N-methylamino, C1-C4-alkoxycarbonyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, aminothiocarbonyl, C1-C4-alkylaminothiocarbonyl, C1-C4-dialkylaminothiocarbonyl, C3-C6-cycloalkylamino, (C1-C4-alkoxy)imino, (C1-C4-alkyl)(C1-C4-alkoxy)imino, (C1-C4-haloalkyl)(C1-C4-alkoxy)imino, C1-C4-alkylsulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl, C1-C4-dialkylaminosulphonyl, C1-C4-alkylsulphoximino, C3-C6-trialkylsilyl or represents a 3- to 6-membered saturated, partially saturated or aromatic ring which may optionally contain one to three heteroatoms from the group consisting of O, S and N and which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxyl, amino, carboxyl, C1-C4-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylcarbonylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, aminothiocarbonyl, C1-C4-alkylaminothiocarbonyl, C1-C4-dialkylaminothiocarbonyl, C3-C6-cycloalkylamino, C1-C4-alkylsulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl and C1-C4-dialkylaminosulphonyl,
two radicals R4 form, via adjacent carbon atoms, a ring which represents —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH═CH—)2—, —OCH2O—, —O(CH2)2O—, —OCF2O—, —(CF2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—, or
two radicals R4 furthermore form, via adjacent carbon atoms, the fused rings below which are optionally mono- or polysubstituted by identical or different substituents, where the substituents independently of one another may be selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C3-C6-halocycloalkyl, halogen, C1-C6-alkoxy, C1-C4-alkylthio(C1-C6-alkyl), C1-C4-alkylsulphinyl(C1-C6-alkyl), C1-C4-alkylsulphonyl(C1-C6-alkyl), C1-C4-alkylamino, di-(C1-C4-alkyl)amino and C3-C6-cycloalkylamino,




n represents 0 to 3,
R5 represents C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, halogen, cyano, nitro or C3-C6-trialkylsilyl,
A represents optionally mono- or polysubstituted —(C2-C6-alkenylene)-, —(C2-C6-alkynylene)-, C2-C6-alkylene-(C1-C6-alkyl), straight-chain —(C3-C6-alkylene)-, —R8—(C3-C6-cycloalkyl)-R8—, —R9—O—R9—, —R9—S—R9—, —R8—S(═O)—R8—, —R8—S(═O)2—R8—, —R9—N(C1-C6-alkyl)-R9—, —R8—CH2C═NO(C1-C6-alkyl)-R8, —R8—C(═O)—R8—, —R8—C(═O)NH—R8, R8—C(═O)N(C1-C6-alkyl)-R8, —R8—C(═O)NHNH—R8—, R8—C(═O)NH—R8—, —R8—C(═O)N(C1-C6-alkyl)-NH—R8—, —R8—C(═O)NHN(C1-C6-alkyl)-R8, —R8—O(C═O)—R8, —R8—O(C═O)NH—R8, —R8—O(C═O)N(C1-C6-alkyl)-R8, —R8—S(═O)2NH—R8, —R8—S(═O)2N(C1-C6-alkyl)-R8, —R8—S(C═O)—R8, —R8—S(C═O)NH—R8, —R8—S(C═O)N(C1-C6-alkyl)-R8, —R8—NHNH—R8, —R8—NHN(C1-C6-alkyl)-R8, —R8—N(C1-C6-alkyl)-NH—R8, —R8—N(C1-C6-alkyl)-N(C1-C6-alkyl)-R8, —R8—N═CH—O—R8, —R8—NH(C═O)O—R8, —R8—N(C1-C6-alkyl)-(C═O)O—R8, —R8—NH(C═O)NH—R8, —R8—NH(C═S)NH—R8, —R8—NHS(═O)2—R8, R8—NH—R8, R8—C(═O)—C(═O)—R8, R8—C(OH)—R8, R8—NH(C═O)—R8, R8-Qz-R8, R8—C(═N—NR′2)—R8, R8—C(═C—R′2)—R8, —R8—C(═S)—R8, R8—NH—(C1-C6-alkyl)-R8— or —R8—N(C1-C6-alkyl)S(═O)2—R8,
where the substituents independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C1-C6-alkyoxy, halo-C1-C6-alkyl, amino, (C1-C6-alkyl)amino, di(C1-C6-alkyl)amino, C3-C6-cycloalkyl
where —(C3-C6-cycloalkyl)- in the ring may optionally contain 1 or 2 heteroatoms selected from the group consisting of N, S, O,
A furthermore represents —(C1-C6)alkylene- which is mono- or polysubstituted independently by halogen, hydroxyl, nitro, amino, (C═O)OH, OCN, SCN, C1-C4-alkyoxy, halo-C1-C4-alkyl, halo-C1-C6-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylcarbonylamino, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, (C1-C6-alkyl)amino, Di(C1-C6-alkyl)amino, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, C3-C6-cycloalkylamino, C1-C4-alkylsulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl, C1-C4-dialkylaminosulphonyl or C3-C6-cycloalkyl,
R8 represents straight-chain or branched —(C1-C6-alkylene)- or represents a direct bond,
where a plurality of R8 radicals independently of one another represent straight-chain or branched —(C1-C6-alkylene)- or represent a direct bond,
for example, R8—O—R8— represents —(C1-C6-alkylene)-O—(C1-C6-alkylene)-, —(C1-C6-alkylene)-O—, —O—(C1-C6-alkylene)-, or —O—,
R9 represents straight-chain or branched —(C2-C6-alkylene)- or represents a direct bond,
where a plurality of R9 radicals independently of one another represent straight-chain or branched —(C2-C6-alkylene)- or represent a direct bond,
for example, R9—O—R9— represents —(C2-C6-alkylene)-O—(C2-C6-alkylene)-, —(C2-C6-alkylene)-O—, —O—(C2-C6-alkylene)-, or —O—,
where R′ represents alkyl, alkylcarbonyl, alkenyl, alkynyl which may optionally be mono- or polysubstituted by halogen,
Qz represents a 3- or 4-membered partially saturated or saturated or a 5- or 6-membered partially saturated, saturated or aromatic ring or represents a 6- to 10-membered bicyclic ring system,
where the ring or the bicyclic ring system may optionally contain 1-3 heteroatoms from the group consisting of N, S, O,
where the ring or the bicyclic ring system is optionally mono- or polysubstituted by identical or different substituents, and where the substituents independently of one another may be selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, CO2NH2, NO2, OH, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)aminocarbonyl, di-(C1-C4-alkyl)aminocarbonyl, (═O) or (═O)2,
Q represents phenyl which is mono- or polysubstituted by R10, or represents a 5- or 6-membered partially saturated or saturated heterocyclic or heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, where the ring or the ring system is optionally mono- or polysubstituted by identical or different R10,
R10 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, CO2H, CO2NH2, NO2, OH, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)aminocarbonyl, di-(C1-C4-alkyl)aminocarbonyl, tri-(C1-C2)alkylsilyl, (C1-C4-alkyl)(C1-C4-alkoxy)imino or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the ring may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, NO2, OH, C1-C4-alkoxy, C1-C4-haloalkoxy,
where R10 does not represent hydrogen if A represents R9—O—R9— or —R8—C(═O)—R8 and Q represents phenyl,
R6 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C6-cycloalkoxy or




R7 independently represents hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, halogen, cyano, nitro, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio,
p represents 0 to 4,
Z represents N, CH, CF, CCl, CBr or CI,
the compounds of the general formula (I) furthermore comprise N-oxides and salts.
If appropriate, the compounds of the formula (I) may be present in various polymorphic forms or as mixtures of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are provided by the invention and can be used according to the invention.
The compounds of the formula (I) optionally include diastereomers or enantiomers.


DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
The formula (I) provides a general definition of the compounds according to the invention. Preferred, particularly preferred and very particularly preferred are compounds of the formula (I) in which
R1 preferably represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, cyano(C1-C6-alkyl), C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylsulphinyl-C1-C4-alkyl or C1-C4-alkylsulphonyl-C1-C4-alkyl,
R1 particularly preferably represents hydrogen, methyl, cyclopropyl, cyanomethyl, methoxymethyl, methylthiomethyl, methylsulphinylmethyl or methylsulphonylmethyl,
R1 very particularly preferably represents hydrogen,
R2 preferably represents hydrogen or C1-C6-alkyl.
R2 particularly preferably represents hydrogen or methyl.
R2 very particularly preferably represents hydrogen.
R3 preferably represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, where the substituents are identical or different and independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R3 furthermore preferably represents C3-C12-cycloalkyl or C4-C10-bicycloalkyl, where the substituents independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R3 particularly preferably represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C1-C6-alkoxy, where the substituents are identical or different and independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R3 furthermore particularly preferably represents optionally mono- or polysubstituted C3-C6-cycloalkyl, where the substituents are identical or different and independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R3 very particularly preferably represents C1-C4-alkyl(methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl) or cyano-C1-C3-alkyl (cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyano-n-propyl, 2-cyano-n-propyl, 3-cyano-n-propyl, 1-cyanoisopropyl, 2-cyanoisopropyl).
R3 especially preferably represents methyl, isopropyl, tert-butyl or cyanomethyl.
R4 preferably represents hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, halogen, cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, nitro, hydroxyl, amino, (C═O)OH, C1-C4-alkylsulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylcarbonylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, aminothiocarbonyl, C1-C4-alkylaminothiocarbonyl, C1-C4-dialkylaminothiocarbonyl, C1-C4-alkylsulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl or C1-C4-dialkylaminosulphonyl,
two adjacent radicals R4 likewise preferably represent —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH═CH—)2—, —OCH2O—, —O(CH2)2O—, —OCF2O—, —(CF2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,
R4 particularly preferably represents hydrogen, C1-C4-alkyl, C1-C2-haloalkyl, halogen, cyano or C1-C2-haloalkoxy,
two adjacent radicals R4 particularly preferably represent —(CH2)4—, —(CH═CH—)2—, —O(CH2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,
R4 very particularly preferably represents hydrogen, methyl, trifluoromethyl, cyano, fluorine, chlorine, bromine, iodine or trifluoromethoxy. Moreover, two adjacent radicals R4 very particularly preferably represent —(CH2)4— or —(CH═CH—)2—.
R4 especially preferably represents chlorine or bromine,
R4 furthermore especially preferably represents iodine or cyano.
two adjacent radicals R4 especially preferably represent —(CH═CH—)2 
R5 preferably represents C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, halogen, cyano, nitro or C3-C6-trialkylsilyl,
R5 particularly preferably represents C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro or C3-C6-trialkylsilyl,
R5 very particularly preferably represents methyl, fluorine, chlorine, bromine or iodine,
R5 especially preferably represents methyl or chlorine,
A preferably represents optionally mono- or polysubstituted, —(C2-C4-alkenylene)-, —(C2-C4-alkynylene)-, C2-C6-alkylene-(C1-C6-alkyl), straight-chain —(C3-C4-alkylene)-, —R8—(C3-C6-cycloalkyl)-R8—, —R9—O—R9—, —R9— S—R9—, —R8—S(═O)—R8—, —R8—S(═O)2—R8—, —R9—N(C1-C4-alkyl)-R9, —R8—CH2C═NO(C1-C4-alkyl), —R8—C(═O)—R8, —R8—C(═S)—R8, —R8—C(═O)NH—R8, R8—C(═O)N(C1-C4-alkyl)-R8, —R8—S(═O)2NH—R8, —R8—S(═O)2N(C1-C4-alkyl)-R8, —R8—NH(C═O)O—R8, —R8—N(C1-C4-alkyl)-(C═O)O—R8, —R8—NH(C═O)NH—R8, —R8—NHS(═O)2—R8, —R8—N(C1-C4-alkyl)S(═O)2—R8, R8—NH—R8, R8—C(═O)—C(═O)—R8, R8—C(OH)—R8, R8-Qz-R8,
where the substituents independently of one another may be selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C1-C6-alkyoxy and halo-C1-C6-alkyl,
A furthermore preferably represents —(C1-C6)alkylene- which is mono- or polysubstituted independently by halogen, C1-C4-alkyoxy, halo-C1-C4-alkyl, halo-C1-C6-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl or C1-C4-haloalkylsulphonyl,
A particularly preferably represents —CH(Hal)-, —C(Hal)2-, —C(═O)—, —CH2(CO)—, —(CO)CH2—, —C(═O)—C(═O)—, CH2(CS)—, CH2CH(OH)—, —CH2NHSO2—, —CH2NMeSO2—, —CH2NHSO2CH2—, —CH2NMeSO2CH2—, —CH2N(SO2Me)CH2—, -cyclopropyl-, cyclobutyl, CH2(CO)CH2—, —CH═CH—, —C≡C—, phenyl, furan, thiophene, imidazole, thiazole, oxazole, pyridine, pyrimidine, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline, imidazolidine, imidazoline, isoxazoline, piperidine, piperazine, pyrrolidone, pyrrolidinone, imidazolidone, imidazolidinone, triazolinone, triazolidinone, tetrazolinone, tetrazolidinone, thiazolone, thiazolidinone, oxazolone, oxazolidinone,
A very particularly preferably represents —C(═O)—, —CH2(CO)—, CH2CH(OH)—, —C(═O)—C(═O)—, —CH═CH—, —C≡C—, isoxazoline, imidazolidone, —CH2NHSO2CH2—, —CH2NMeSO2CH2—, CH2N(SO2Me)CH2—, —(CO)CH2—, —CHCl—, —CCl2—, —CHF—, —CF2—,
Qz preferably represents a 3- or 4-membered partially saturated or saturated ring or represents a 5- or 6-membered partially saturated, saturated or aromatic ring, where the ring may optionally contain 1-3 heteroatoms from the group consisting of N, S, O,
where the ring is optionally mono- or polysubstituted by identical or different substituents and where the substituents independently of one another may be selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, OH, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl,
Qz particularly preferably represents a 3- to 4-membered, partially saturated or saturated ring or represents a 5- or 6-membered partially saturated, saturated or aromatic ring, where the ring may optionally contain 1-2 heteroatoms from the group consisting of N, S, O,
where the ring is optionally mono- or polysubstituted by identical or different substituents and where the substituents independently of one another may be selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, OH, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl,
Qz very particularly preferably represents phenyl, furan, thiophene, imidazole, thiazole, oxazole, pyridine, pyrimidine, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline, imidazolidine, imidazoline, isoxazoline, piperidine, piperazine, pyrrolidone, pyrrolidinone, imidazolidone, imidazolidinone, triazolinone, triazolidinone, tetrazolinone, tetrazolidinone, thiazolone, thiazolidinone, oxazolone, oxazolidinone,
R6 preferably represents C1-C6-alkyl or represents the radical




R6 furthermore preferably represents C3-C6-cycloalkoxy,
R6 particularly preferably represents methyl or represents the radical




R7 independently preferably represents hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylsulphonyl or (C1-C4-alkyl)-C1-C4-alkoxyimino,
R7 independently particularly preferably represents hydrogen, halogen or C1-C4-haloalkyl,
R7 very particularly preferably represents fluorine, chlorine or bromine,
R7 especially preferably represents chlorine or bromine,
p preferably represents 1, 2 or 3,
p particularly preferably represents 1 or 2,
p very particularly preferably represents 1,
Z preferably represents N, CH, CF, CCl, CBr or CI,
Z particularly preferably represents N, CH, CF, CCl or CBr,
Z very particularly preferably represents N, CCl or CH,
R8 preferably represents straight-chain or branched —(C1-C4-alkylene)- or represents a direct bond
R8 particularly preferably represents methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or isobutyl or a direct bond
R8 very particularly preferably represents methyl or ethyl or a direct bond
R9 preferably represents straight-chain or branched —(C2-C4-alkylene)- or represents a direct bond
R9 particularly preferably represents ethyl, propyl, isopropyl, n-butyl, sec-butyl or isobutyl or a direct bond
R9 very particularly preferably represents ethyl or a direct bond
R10 preferably represents hydrogen, C1-C3-alkyl, C1-C3-haloalkyl, C1-C2-alkoxy, halogen, cyano, hydroxyl, nitro, C1-C2-haloalkoxy or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the ring may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, NO2, OH, C1-C4-alkoxy and C1-C4-haloalkoxy,
where R10 does not represent hydrogen if A represents R9—O—R9— or —R8—C(═O)—R8 and Q represents phenyl,
R10 particularly preferably represents hydrogen, C1-C3-alkyl, C1-C3-haloalkyl, C1-C2-alkoxy, halogen, cyano, hydroxyl, C1-C2-haloalkoxy or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the ring may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of C1-C3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C3-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-halocycloalkyl, halogen, cyano, C1-C4-alkoxy, C1-C4-haloalkoxy,
where R10 does not represent hydrogen if A represents R9—O—R9— or —R8—C(═O)—R8 and Q represents phenyl,
R10 very particularly preferably represents methyl, ethyl, cyclopropyl, tert-butyl, chlorine, fluorine, iodine, bromine, cyano, difluoromethyl, trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, isoheptafluoropropyl or represents phenyl or a 5- or 6-membered heteroaromatic ring, where the substituents independently of one another may be selected from the group consisting of methyl, ethyl, cyclopropyl, tert-butyl, chlorine, fluorine, iodine, bromine, cyano, difluoromethyl, trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl and isoheptafluoropropyl,
Q preferably represents phenyl which is mono- or polysubstituted by R10 or represents a 5- or 6-membered partially saturated or saturated heterocyclic or heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, where the heteroatoms may be selected from the group consisting of N, S, O, where the ring or the ring system is optionally mono- or polysubstituted by identical or different R10,
Q particularly preferably represents phenyl which is mono- or polysubstituted by R10 or represents a 5- or 6-membered heteroaromatic ring from the group consisting of Q-1 to Q-53 and Q-58 to Q-59, Q62 to Q63 which is optionally mono- or polysubstituted by R10, an aromatic 9-membered fused heterobicyclic ring system Q-54 to Q-56 or represents a 5-membered heterocyclic ring Q-60 to Q-61,
Q very particularly preferably represents phenyl which is mono- or polysubstituted by R10 or represents a heteroaromatic ring from the group consisting of Q-6, Q 41, Q42, Q58, Q59, Q62 and Q63 which is mono- or polysubstituted by R10
















The rings or ring systems listed above may optionally independently of one another additionally be substituted by oxo, thioxo, (═O)═NH, (═O)═N—CN, (═O)2. Examples which may be mentioned are tetrahydrothiophene dioxide, imidazolidone.
In this case, the oxo group as substituent at a ring carbon atom means, for example, a carbonyl group in the heterocyclic ring. This also preferably comprises lactones and lactams. The oxo group may also be present at the hetero ring atoms, which may exist in various oxidation levels, for example in the case of nitrogen and sulphur, in which case they form, for example, the divalent groups —N(O)—, —S(O)— (also abbreviated as SO) and —S(O)2— (also abbreviated as SO2) in the heterocyclic ring. In the case of —N(O)— and —S(O)— groups, in each case both enantiomers are included.
In a heterocyclic ring, substituents other than the oxo group can also be attached to a heteroatom, for example a nitrogen atom, if a hydrogen atom at the nitrogen atom of the skeleton is replaced in the process. In the case of the nitrogen atom and also other heteroatoms such as, for example, the sulphur atom, there may also be further substitution with formation of quaternary ammonium compounds or sulphonium compounds.
The above-recited general radical definitions and elucidations or those recited in preference ranges may be combined arbitrarily with one another, in other words including combinations between the respective ranges and preference ranges. They apply both to the end products and, correspondingly, to precursors and intermediates.
Preference in accordance with the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred (preferably).
Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.
Very particular preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.
The compounds of the formulae (I) may be present more particularly in the form of different regioisomers: for example in the form of mixtures of compounds having the definition Q62 or Q63 or in the form of mixtures of Q58 and 59. The invention therefore also comprises mixtures of compounds of the formulae (I) where Q has the meanings Q62 and Q63 and also Q58 and Q59 and the compounds may be present in various mixing ratios. Preference in this context is given to mixing ratios of the compounds of the formula (I) in which the radical Q is Q62 or Q58 to compounds of the formula (I) in which the radical Q is Q63 or Q59, of 60:40 to 99:1, particularly preferably of 70:30 to 97:3, very particularly preferably of 80:20 to 95:5. Especially preferred are the following mixing ratios for a compound of the formula (I) where Q has the definition Q62 or Q58 to the compound of the formula (I) where Q has the definition Q63 or Q59: 80:20; 81:19; 82:18; 83:17; 84:16; 85:15, 86:14; 87:13; 88:12; 89:11; 90:10, 91:9; 92:8; 93:7; 96:6; 95:5.
Preparation Processes
Anthranilamides of the formula (I)




in which A, R1, R2, R3, R4, R5, R6, Q and n have the meanings given above are obtained when (A) anilines of the formula (II)





in which R1, R2, R3, R4, R5 and n have the meanings given above

are reacted, for example, with a carboxylic acid of the formula (III)





where

Q, A and R6 have the meanings given above,

in the presence of a condensing agent; or

(B) anilines of the formula (II)





in which R1, R2, R3, R4, R5 and n have the meanings given above

are reacted, for example, with carbonyl chlorides of the formula (IIIA)





where

Q, A and R6 have the meanings given above,

in the presence of an acid-binding agent; or

(C) for the synthesis of anthranilimides of the formula (I) in which R1 represents hydrogen,

for example benzoxazinones of the formula (IIIB)





in which R4, R5, R6, A, Q and n have the meanings given above

are reacted with an amine of the formula (IIIC)





in which R3 has the meanings given above

in the presence of a diluent to give compounds of the formula (I) according to the invention.

Description of the Preparation Processes and Intermediates

Carboxylic Acids of the Formula (III-1)
Carboxylic acids of the formula (III-1) are novel. They can be prepared by the reaction scheme below in which X represents a mesityl group or halogen, R represents hydrogen or alkyl and B represents a methylene group or a direct bond. The sulphonamides used for this purpose were prepared by known methods (for example WO2006/097292). The conversion of the compounds of the formula V into compounds of the formula III-1 can be carried out by known methods (for example WO2007/144100).




Carboxylic Acids of the Formulae (III-2) and (III-3)
Carboxylic acids of the formulae III-2 and III-3 are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from compounds of the formula VI. Compounds of the formula VI are known (for example WO 2003016283). The conversion of VI into VII can be carried out by known methods using, for example, a suitable substituted alkyne in the presence of copper(I) iodide and tetrakis(triphenylphosphine)palladium (for example Heterocycles, 78 (1), 71-91; 2009). The further conversion of the alkyne derivative VII into the diketone VIII is carried out using a suitable oxidizing agent such as, for example, potassium permanganate (cf. J. Med. Chem. 48 (7), 2270-2273; 2005). The hydrolysis to III-2 and III-3 is carried out using known methods (for example WO2006004903).




Carboxylic Acids of the Formula III-4
Carboxylic acids of the formula III-4 are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from compounds of the formula VI. Compounds of the formula VI are known (for example WO 2003016283). The conversion of VI into VII-a can be carried out by known methods using, for example, (1-ethoxyvinyl)tributylstannane with palladium catalysis (for example J. Med. Chem. 41, 1998, 3736). The further conversion into VIII-a is carried out using a suitable halogenating agent (for example Bioorganic & Medicinal Chemistry Letters, 19 (4), 1199-1205; 2009). Coupling with Q to give IX and hydrolysis to III-4 are carried out by known methods (for example Bioorganic & Medicinal Chemistry, 17 (6), 2410-2422; 2009 and WO2006004903).




Carboxylic Acids of the Formula III-5
Carboxylic acids of the formula III-5 are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from compounds of the formula VI. Compounds of the formula VI are known (for example WO 2003016283). The conversion of VI into VII-b can be carried out by known methods using, for example, a suitable diamine ligand with copper catalysis (for example J. Org. Chem. 69, 2004, 5578-5587). Hydrolysis to III-5 is carried out by known methods (for example WO2006004903).




Carboxylic Acids of the Formula III-6
Carboxylic acids of the formula III-6 are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from compounds of the formula VI-c. Compounds of the formula VI-c are known (for example WO 2004078732). The conversion of VI-c into VII-c can be carried out by known methods using, for example, a suitable tin reagent in the presence of a phosphine ligand and a palladium catalyst (for example Tetrahedron Lett. 45, 2004, 3797-3801). The oxidation to VIII-c is carried out using a suitable oxidizing agent such as, for example, manganese dioxide (for example WO 9800385). Hydrolysis to III-6 is carried out using known methods (for example WO2006004903).




Carboxylic Acids of the Formula III-7
Carboxylic acids of the formula III-7 are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from compounds of the formula VI-d. Compounds of the formula VI-d are known (for example WO 2003016283). The conversion of VI-d into VII-d and the cyclization to VIII-d can be carried out by known methods (for example WO 2004078732 and WO 2010020522). Hydrolysis to III-7 is carried out by known methods (WO2006004903).




Carboxylic Acids of the Formula (III-8)
Carboxylic acids of the formula (III-8) are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl and R* represents C1-C6 alkyl, from compounds of the formula VI-e.




Carboxylic Acids of the Formula III-9
Carboxylic acids of the formula (III-9) are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from compounds of the formula (X). Compounds of the formula (X) are known (for example WO 2006/000336).




Carboxylic Acids of the Formula III-10
Carboxylic acids of the formula (III-10) are novel. They can be prepared by the reaction scheme below, where R6 and Q have the meanings given above and R represents C1-C6-alkyl, from commercially available 3-nitropyrazole of the formula (XV).




Carboxylic Acids of the Formula (III-11)
Carboxylic acids of the formula (III-11) are novel. They can be prepared from compounds of the formula (I), according to the reaction scheme below. Here, R represents C1-C6-alkyl. Compounds of the formula (XXI) are known (for example WO2003/016283, WO2006/102025). The reaction of (XXI) with (XXII) to give (XXIII) can be carried out by known methods (for example WO2006/117370). Compounds of the formula (XXII) are commercially available or can be prepared by known methods (for example WO 2005/068460). The further reaction via compounds of the formula (XXIII) to compounds of the formula (III-11) can be carried out by known methods (e.g. WO2005/009344).




The active compounds according to the invention, in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They can preferably be used as crop protection compositions. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
From the class of the Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici. 
From the class of the Bivalva, for example, Dreissena spp.
From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.
From the order of the Coleoptera, for example, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
From the order of the Collembola, for example, Onychiurus armatus. 
From the order of the Dermaptera, for example, Forficula auricularia. 
From the order of the Diplopoda, for example, Blaniulus guttulatus. 
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp. Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.
From the class of the Gastropoda, for example, Anion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
From the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti. 
It is furthermore possible to control protozoa, such as Eimeria.
From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
From the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma pini, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii. 
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus and Porcellio scaber. 
From the order of the Isoptera, for example, Reticulitermes spp. and Odontotermes spp.
From the order of the Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Chematobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.
From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria. 
From the order of the Siphonaptera, for example, Ceratophyllus spp. and Xenopsylla cheopis. 
From the order of the Symphyla, for example, Scutigerella immaculata. 
From the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni and Thrips spp.
From the order of the Thysanura, for example, Lepisma saccharina. 
The phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans and Xiphinema spp.
The effectiveness of the compounds of the formula (I) can be increased by adding ammonium salts and phosphonium salts. The ammonium salts and phosphonium salts are defined by formula (XXIV)




in which

D represents nitrogen or phosphorus,

D preferably represents nitrogen,

R11, R12, R13 and R14 independently of one another represent hydrogen or in each case optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally substituted C1-C8-alkylene where the substituents may be selected from the group consisting of halogen, nitro and cyano,
R11, R12, R13 and R14 preferably independently of one another represent hydrogen or in each case optionally substituted C1-C4-alkyl, where the substituents may be selected from the group consisting of halogen, nitro and cyano,
R11, R12, R13 and R14 particularly preferably independently of one another represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl,
R11, R12, R13 and R14 very particularly preferably represent hydrogen,
m represents 1, 2, 3 or 4,
m preferably represents 1 or 2,
R15 represents an inorganic or organic anion,
R15 preferably represents bicarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate, sulphate, nitrate, thiosulphate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate, citrate or oxalate,
R15 particularly preferably represents lactate, sulphate, monohydrogenphosphate, dihydrogenphosphate, nitrate, thiosulphate, thiocyanate, citrate, oxalate or formate,
R15 very particularly preferably represents sulphate.
The ammonium salts and phosphonium salts of the formula (XXIV) can be used in a wide concentration range for increasing the effect of crop protection compositions comprising compounds of the formula (I). In general, the ammonium salts or phosphonium salts are used in the ready-to-use crop protection composition in a concentration of from 0.5 to 80 mmol/l, preferably 0.75 to 37.5 mmol/l, particularly preferably 1.5 to 25 mmol/l. In the case of a formulated product, the concentration of ammonium salt and/or phosphonium salt in the formulation is selected such that it is within these stated general, preferred or particularly preferred ranges following dilution of the formulation to the desired active compound concentration. The concentration of the salt in the formulation here is usually 1-50% by weight.
In one preferred embodiment of the invention, it is not only an ammonium salt and/or phosphonium salt, but a penetrant, that is added to the crop protection compositions to increase the activity. An activity increase can be observed even in these cases. The present invention thus also provides the use of a penetrant, and also the use of a combination of penetrant and ammonium salts and/or phosphonium salts for increasing the activity of crop protection compositions which comprise acaricidally/insecticidally active compounds of the formula (I) as active compound. Finally, the invention also provides the use of these compositions for controlling harmful insects.
Suitable penetrants in the present context are all those substances which are usually used for improving the penetration of agrochemical active compounds into plants. Penetrants are defined in this context by their ability to penetrate from the aqueous spray liquor and/or from the spray coating into the cuticle of the plant and thereby increase the mobility of active compounds in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used for determining this property.
Suitable penetrants are, for example, alkanol alkoxylates. Penetrants according to the invention are alkanol alkoxylates of the formula

R—O-(-AO)v—R′  (XXV)

in which

R represents straight-chain or branched alkyl having 4 to 20 carbon atoms
R′ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl,
AO represents an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or represents mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and
v represents a number from 2 to 30.
A preferred group of penetrants are alkanol alkoxylates of the formula

R—O-(-EO—)n—R′  (XXV-a)

in which

R has the meaning given above,
R′ has the meaning given above,
EO represents —CH2-CH2-O— and
n represents a number from 2 to 20.
A further preferred group of penetrants are alkanol alkoxylates of the formula

R—O-(-EO—)p—(—PO—)q—R′  (XXV-b)

in which

R has the meaning given above,
R′ has the meaning given above,
EO represents —CH2—CH2—O—,
PO represents




p represents a number from 1 to 10 and
q represents a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula

R—O—(—PO—)r-(EO—)s—R′  (XXV-c)

in which

R has the meaning given above,
R′ has the meaning given above,
EO represents —CH2—CH2—O—,
PO represents




r represents a number from 1 to 10 and
s represents a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula

R—O-(-EO—)p—(—BO—)q—R′  (XXV-d)

in which

R and R′ have the meanings given above,
EO represents —CH2—CH2—O—,
BO represents




p represents a number from 1 to 10 and
q represents a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula

R—O—(—BO-)r-(-EO—)s—R′  (XXV-e)

in which

R and R′ have the meanings given above,
BO represents




EO represents —CH2-CH2-O—,
r represents a number from 1 to 10 and
s represents a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula

CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—R′  (XXV-f)

in which

R′ has the meaning given above,
t represents a number from 8 to 13,
y represents a number from 6 to 17.
In the formulae given above,
R preferably represents butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, n-dodecyl, isododecyl, lauryl, myristyl, isotridecyl, trimethylnonyl, palmityl, stearyl or eicosyl.
As an example of an alkanol alkoxylate of the formula (XXV-c), mention may be made of 2-ethylhexyl alkoxylate of the formula




in which

EO represents —CH2-CH2-O—,
PO represents




and

the numbers 8 and 6 represent average values.

As an example of an alkanol alkoxylate of the formula (XII-d), mention may be made of the formula

CH3—(CH2)10—O-(-EO—)6—(—BO—)2—CH3  (XXV-d-1)

in which

EO represents —CH2—CH2—O—,
BO represents




and

the numbers 10, 6 and 2 represent average values.
Particularly preferred alkanol alkoxylates of the formula (XXV-f) are compounds of this formula in which
t represents a number from 9 to 12 and
u represents a number from 7 to 9.
With very particular preference, mention may be made of alkanol alkoxylate of the formula (XXV-f-1)

CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—R′  (XXV-f-1)

in which

t represents the average value 10.5 and
u represents the average value 8.4.
The above formulae provide general definitions of the alkanol alkoxylates. These substances are mixtures of substances of the stated type with different chain lengths. The indices are therefore average values which may also deviate from whole numbers.
The alkanol alkoxylates of the stated formulae are known, and some of them are commercially available or can be prepared by known methods (cf. WO 98/35 553, WO 00/35 278 and EP-A 0 681 865)
Suitable penetrants also include, for example, substances which promote the solubility of the compounds of the formula (I) in the spray coating. These include, for example, mineral and vegetable oils. Suitable oils are all mineral or vegetable oils—modified or otherwise—which can usually be used in agrochemical compositions. By way of example, mention may be made of sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maize seed oil, cottonseed oil and soybean oil or the esters of said oils. Preference is given to rapeseed oil, sunflower oil and their methyl or ethyl esters.
The concentration of penetrant can be varied within a wide range. In the case of a formulated crop protection composition, it is generally 1 to 95% by weight, preferably 1 to 55% by weight, particularly preferably 15-40% by weight. In the ready-to-use compositions (spray liquors), the concentrations are generally between 0.1 and 10 g/l, preferably between 0.5 and 5 g/l.
Inventively emphasized combinations of active compound, salt and penetrant are listed in the table below. Here, “according to test” means that any compound which acts as penetrant in the cuticle penetration test (Baur et al., 1997, Pesticide Science 51, 131-152) is suitable.














Active




#
compound
Salt
Penetrant


















1
I
ammonium sulphate
according to test


2
I
ammonium lactate
according to test


3
I
ammonium nitrate
according to test


4
I
ammonium thiosulphate
according to test


5
I
ammonium thiocyanate
according to test


6
I
ammonium citrate
according to test


7
I
ammonium oxalate
according to test


8
I
ammonium formate
according to test


9
I
ammonium hydrogenphosphate
according to test


10
I
ammonium dihydrogenphosphate
according to test


11
I
ammonium carbonate
according to test


12
I
ammonium benzoate
according to test


13
I
ammonium sulphite
according to test


14
I
ammonium benzoate
according to test


15
I
ammonium hydrogenoxalate
according to test


16
I
ammonium hydrogencitrate
according to test


17
I
ammonium acetate
according to test


18
I
tetramethylammonium sulphate
according to test


19
I
tetramethylammonium lactate
according to test


20
I
tetramethylammonium nitrate
according to test


21
I
tetramethylammonium
according to test




thiosulphate


22
I
tetramethylammonium
according to test




thiocyanate


23
I
tetramethylammonium citrate
according to test


24
I
tetramethylammonium oxalate
according to test


25
I
tetramethylammonium formate
according to test


26
I
tetramethylammonium
according to test




hydrogenphosphate


27
I
tetramethylammonium
according to test




dihydrogenphosphate


28
I
tetraethylammonium sulphate
according to test


29
I
tetraethylammonium lactate
according to test


30
I
tetraethylammonium nitrate
according to test


31
I
tetraethylammonium
according to test




thiosulphate


32
I
tetraethylammonium
according to test




thiocyanate


33
I
tetraethylammonium citrate
according to test


34
I
tetraethylammonium oxalate
according to test


35
I
tetraethylammonium formate
according to test


36
I
tetraethylammonium
according to test




hydrogenphosphate


37
I
tetraethylammonium
according to test




dihydrogenphosphate









If appropriate, the compounds according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural compounds impregnated with active compound, synthetic substances impregnated with active compound, fertilizers and also microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, i.e. liquid solvents, and/or solid carriers, optionally with the use of surfactants, i.e. emulsifiers and/or dispersants, and/or foam formers. The formulations are produced either in suitable plants or else before or during application.
Suitable for use as auxiliaries are substances which are suitable for imparting to the composition itself and/or to preparations derived therefrom (for example spray liquors, seed dressings) particular properties such as certain technical properties and/or also particular biological properties. Typical auxiliaries include: extenders, solvents and carriers.
Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, if appropriate, may also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).
If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulphoxide, and also water.
Suitable solid carriers are:
for example ammonium salts and natural rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as finely divided silica, alumina and silicates; useful solid carriers for granules include: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks; useful emulsifiers and/or foam-formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are nonionic and/or ionic substances, for example from the classes of the alcohol-POE and/or -POP ethers, acid and/or POP POE esters, alkylaryl and/or POP POE ethers, fat and/or POP POE adducts, POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugar adducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl or aryl phosphates or the corresponding PO-ether adducts. Furthermore, suitable oligomers or polymers, for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to use lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and also their adducts with formaldehyde.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Other possible additives are perfumes, mineral or vegetable oils which are optionally modified, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve chemical and/or physical stability, may also be present.
The formulations generally comprise between 0.01 and 98% by weight of active compound, preferably between 0.5 and 90%.
The active compound according to the invention can be present in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents for improving the plant properties, is also possible.
When used as insecticides, the inventive active compounds may also be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergists. Synergists are compounds which enhance the action of the active compounds, without any need for the synergist added to be active itself.
When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with inhibitors which reduce degradation of the active compound after use in the environment of the plant, on the surface of parts of plants or in plant tissues.
The active compound content of the use forms prepared from the commercially available formulations may vary within wide limits. The active compound concentration of the application forms may be from 0.00000001 to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
All plants and plant parts can be treated in accordance with the invention. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by varietal property rights. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.
As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms “parts” or “parts of plants” or “plant parts” have been explained above.
More preferably, plants of the plant cultivars which are each commercially available or in use are treated in accordance with the invention. Plant cultivars are to be understood as meaning plants having new properties (“traits”) and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may be cultivars, biotypes and genotypes.
Depending on the plant species or plant cultivars, and the location and growth conditions (soils, climate, vegetation period, diet) thereof, the inventive treatment may also result in superadditive (“synergistic”) effects. For example, possibilities include reduced application rates and/or broadening of the activity spectrum and/or an increase in the activity of the compounds and compositions usable in accordance with the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or higher nutritional value of the harvested products, increased storage life and/or processibility of the harvested products, which exceed the effects normally to be expected.
The transgenic plants or plant cultivars (those obtained by genetic engineering) which are to be treated with preference in accordance with the invention include all plants which, through the genetic modification, received genetic material which imparts particular advantageous useful properties (“traits”) to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or a higher nutritional value of the harvested products, better storage life and/or processibility of the harvested products. Further and particularly emphasized examples of such properties are an improved defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other types of vegetable, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis being given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized in particular are increased defense of the plants against insects, arachnids, nematodes and slugs and snails by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as “Bt plants”). Traits that are also particularly emphasized are the improved defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and also resistance genes and correspondingly expressed proteins and toxins. Traits that are additionally particularly emphasized are the increased tolerance of the plants to certain active herbicidal compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example the “PAT” gene). The genes which impart the desired traits in question may also be present in combinations with one another in the transgenic plants. Examples of “Bt plants” include maize varieties, cotton varieties, soya varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance against glyphosate, for example maize, cotton, soya beans), Liberty Link® (tolerance against phosphinothricin, for example oilseed rape), IMF® (tolerance against imidazolinones) and STS® (tolerance against sulphonylurea, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars which have these genetic traits or genetic traits which are still to be developed and will be developed and/or marketed in the future.
The plants stated can be treated particularly advantageously in accordance with the invention with the compounds of the general formula I or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
The active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ecto- and endoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.
From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.
from the order of the Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattella germanica and Supella spp.
From the subclass of the Acari (Acarina) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
The inventive active compounds of the formula (I) are also suitable for controlling arthropods which attack agricultural livestock, for example cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey-bees, other domestic animals such as, for example, dogs, cats, caged birds, aquarium fish, and experimental animals, for example hamsters, guinea pigs, rats and mice. The control of these arthropods is intended to reduce cases of death and reduced productivity (of meat, milk, wool, hides, eggs, honey etc.), and so more economic and easier animal husbandry is possible by use of the inventive active compounds.
The active compounds according to the invention are used in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.
When used for livestock, poultry, domestic animals and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) comprising the active compounds in an amount of 1 to 80% by weight, either directly or after 100 to 10 000-fold dilution, or they may be used as a chemical bath.
It has also been found that the inventive compounds have strong insecticidal action against insects which destroy industrial materials.
Preferred but nonlimiting examples include the following insects:
beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus; 
dermapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur; 
termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; 
bristletails, such as Lepisma saccarina. 
Industrial materials in the present connection are understood to mean inanimate materials, such as preferably plastics, adhesives, sizes, papers and cards, leather, wood, processed wood products and coating compositions.
The ready-to-use compositions may optionally also comprise other insecticides, and optionally one or more fungicides.
With respect to possible additional partners for mixing, reference is made to the insecticides and fungicides mentioned above.
Moreover, the compounds according to the invention can be employed for protecting objects which come into contact with saltwater or brackish water, in particular hulls, screens, nets, buildings, moorings and signalling systems, against fouling.
Furthermore, the compounds according to the invention can be used alone or in combinations with other active compounds as antifouling compositions.
The active compounds are also suitable for controlling animal pests in the domestic sector, in the hygiene sector and in the protection of stored products, especially insects, arachnids and mites, which are found in enclosed spaces, for example homes, factory halls, offices, vehicle cabins and the like. They can be used to control these pests alone or in combination with other active compounds and auxiliaries in domestic insecticide products. They are effective against sensitive and resistant species, and against all developmental stages. These pests include:
From the order of the Scorpionidea, for example, Buthus occitanus. 
From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae. 
From the order of the Araneae, for example, Aviculariidae, Araneidae. 
From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. 
From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber. 
From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.
From the order of the Chilopoda, for example, Geophilus spp.
From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus. 
From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa. 
From the order of the Saltatoria, for example, Acheta domesticus. 
From the order of the Dermaptera, for example, Forficula auricularia. 
From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp.
From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis spp.
From the order of the Coleoptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum. 
From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa. 
From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella. 
From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis. 
From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum. 
From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis. 
From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans. 
In the field of household insecticides, they are used alone or in combination with other suitable active compounds, such as phosphoric acid esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active compounds from other known classes of insecticides.
They are used in aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or plastic, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.
PREPARATION EXAMPLES
Synthesis of Carboxylic Acids of the Formula III-1
Example No. V
Synthesis of methyl 3-{[{[3,5-bis(trifluoromethyl)benzyl]sulphonyl}(methyl)amino]methyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate
5.00 g (14.4 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-[(methylsulphonyl)methyl]-1H-pyrazole-5-carboxylate were dissolved in 50 ml of acetonitrile, and 4.64 g (14.4 mmol) of 1-[3,5-bis(trifluoromethyl)phenyl]-N-methylmethanesulphonamide were added a little at a time at room temperature. Then 2.40 g (17.35 mmol) of potassium carbonate were added to the reaction solution, and the mixture was stirred at 50° C. for 12 hours. After cooling to room temperature, the reaction solution was freed from the solvent under reduced pressure. 250 ml of water were added to the residue, and the mixture was extracted with ethyl acetate (3×100 ml). The combined organic phases were dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by chromatography. (logP: 3.83; MH+: 571; 1H-NMR (400 MHz, DMSO, δ, ppm): 2.79 (s, 3H), 3.74 (s, 3H), 4.43 (s, 2H), 4.80 (s, 2H), 7.06 (s, 1H), 7.70 (dd, 1H), 8.12 (s, 2H), 8.15 (s, 1H), 8.26 (d, 1H), 8.57 (d, 1H).
Example No. III-1
Synthesis of 3-{[{[3,5-bis(trifluoromethyl)benzyl]sulphonyl}(methyl)amino]methyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid
3.30 g (5.78 mmol) of methyl 3-{[{[3,5-bis(trifluoromethyl)benzyl]sulphonyl}(methyl)amino]methyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate were dissolved in 50 ml of methanol, and aqueous sodium hydroxide solution (0.28 g of sodium hydroxide dissolved in 25 ml of water; 6.94 mmol) was added dropwise at 0° C. The reaction mixture was stirred at room temperature for 12 hours. The methanol was then removed under reduced pressure and the aqueous residue was extracted three times with methylene chloride. The organic phase was discarded. The aqueous phase was then adjusted to a pH of 3 using 5% strength hydrochloric acid and extracted with dichloromethane (2×100 ml). The combined organic phases were dried over sodium sulphate. (logP: 3.07; MH+: 557; 1H-NMR (400 MHz, DMSO, δ, ppm): 2.78 (s, 3H), 4.40 (s, 2H), 4.78 (s, 2H), 6.97 (s, 1H), 7.62 (dd, 1H), 8.05 (, 1H), 8.09 (s, 2H), 8.15 (d, 1H), 8.51 (d, 1H).
Synthesis of Carboxylic Acids of the Formulae III-2 and III-3
Example No. VII
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-{[4-(trifluoromethoxy)phenyl]ethinyl}-1H-pyrazole-5-carboxylate
1.0 g (3.00 mmol) of methyl 4-bromo-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate, 1.12 g of 4-trifluoromethoxyethynylbenzene, 0.15 g (0.78 mmol) of copper(I) iodide, 3.34 g (33.0 mmol) of triethylamine and 0.31 g (0.27 mmol) of tetrakis(triphenylphosphine)palladium were initially charged in DMF and stirred under argon at 80° C. for 30 min. The reaction mixture was filtered off with suction, the residue was washed with DMF and the combined mother liquors were concentrated. The desired product was obtained by chromatographic purification.
(logP: 4.46; MH+: 422; 1H-NMR (400 MHz, DMSO, δ, ppm): 3.74 (s, 3H), 7.27-7.43 (m, 3H), 7.66-7.74 (m, 3H), 8.21-8.26 (m, 1H), 8.54-8.58 (m, 1H).
Example No. VIII
Synthesis of ethyl 1-(3-chloropyridin-2-yl)-3-[(2,4-dichlorophenyl)(oxo)acetyl]-1H-pyrazole-5-carboxylate
600 mg (1.47 mmol) of ethyl 1-(3-chloropyridin-2-yl)-3-[(2,4-dichlorophenyl)ethynyl]-1H-pyrazole-5-carboxylate were initially charged in a mixture of 1.35 g (8.55 mmol) of potassium permanganate, 144 mg of Aliquat 336 (0.35 mmol), 18 ml of water, 24 ml of dichloromethane and 1 ml of glacial acetic acid and stirred under reflux for 1 h. 30 ml of 20% strength sodium bisulphite solution were added to the reaction, and the separated organic phase was dried over sodium sulphate and concentrated. The desired product was isolated by chromatographic purification.
(logP: 4.29; MH+: 453; 1H-NMR (400 MHz, DMSO, δ, ppm): 1.12 (t, 3H), 4.20 (q, 2H), 7.64-7.80 (m, 4H), 7.94 (d, 1H), 8.24 (d, 1H), 8.57 (dd, 1H).
Example No. III-2
Synthesis of 1-(3-chloropyridin-2-yl)-3-[(2,4-dichlorophenyl)(oxo)acetyl]-1H-pyrazole-5-carboxylic acid
420 mg (0.74 mmol) of ethyl 1-(3-chloropyridin-2-yl)-3-[(2,4-dichlorophenyl)(oxo)acetyl-1H-pyrazole-5-carboxylate were dissolved in 8 ml of ethanol, 445 mg (3.26 mmol) of 10% strength aqueous sodium hydroxide solution were added and the mixture was stirred at RT for 24 h. The solvent was distilled off under reduced pressure, the residue was taken up in water and the mixture was extracted once with methyl tert-butyl ether. The aqueous phase was then acidified with 2N hydrochloric acid and extracted three times with methyl tert-butyl ether. The combined organic phases were dried over sodium sulphate and concentrated.
(logP: 2.78; MH+: 424; 1H-NMR (400 MHz, DMSO, δ, ppm): 7.61-7.69 (m, 3H), 7.79 (s, 1H), 7.93 (d, 1H), 8.21 (d, 1H), 8.54 (dd, 1H).
Example No. III-3
Synthesis of 1-(3-chloropyridin-2-yl)-3-{[4-(trifluoromethoxy)phenyl]ethynyl}-1H-pyrazole-5-carboxylic acid
1.02 g (2.17 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{[4-(trifluoromethoxy)phenyl]ethynyl}-1H-pyrazole-5-carboxylate were dissolved in 20 ml of ethanol, 1.31 g (3.26 mmol) of 10% strength aqueous sodium hydroxide solution were added and the mixture was stirred at RT for 2 h. The solvent was distilled off under reduced pressure, the residue was taken up in water and the mixture was extracted once with methyl tert-butyl ether. The aqueous phase was then acidified with 2N hydrochloric acid and extracted three times with methyl tert-butyl ether. The combined organic phases were dried over sodium sulphate and concentrated.
(logP: 3.36; MH+: 408; 1H-NMR (400 MHz, DMSO, δ, ppm): 7.28 (s, 1H), 7.40-7.43 (m, 2H), 7.63-7.74 (m, 3H), 8.18-8.22 (m, 1H), 8.52-8.56 (m, 1H).
Synthesis of Carboxylic Acids of the Formula III-4
Example No. VII-a
Synthesis of ethyl 3-acetyl-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate
Under argon, 1.4 g (15.6 mmol) of methyl 4-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-2-carboxylate were dissolved in 40 ml of THF, and 1.63 g (4.37 mmol) of (1-ethoxyvinyl)tributylstannane, 0.54 g of lithium chloride and 0.24 g (0.2 mmol) of tetrakis(triphenylphosphine)palladium were added at room temperature and the mixture was stirred under reflux for 48 h. The solvent was then distilled off, the residue was taken up in methyl tert-butyl ether and the solution was washed in each case once with water, 5% strength ammonia solution and saturated sodium chloride solution, dried over sodium sulphate and concentrated using a rotary evaporator. The residue was dissolved in 40 ml of THF and stirred in the presence of 3 ml of 2N hydrochloric acid at RT for 24 h. Once more, the solvent was distilled off, and the residue was dissolved in 60 ml of methyl tert-butyl ether and, at RT, stirred vigorously with 60 ml of saturated potassium fluoride solution for 1 h. The organic phase was separated off and concentrated. The desired product was isolated by chromatographic purification.
(logP: 2.31; MH+: 294; 1H-NMR (400 MHz, DMSO, δ, ppm): 1.10 (t, 3H), 2.55 (s, 3H), 4.17 (q, 2H), 7.44 (s, 1H), 7.71-7.72 (m, 1H), 8.26 (dd, 1H), 8.59 (dd, 1H).
Example No. VIII-a
Synthesis of ethyl 3-(bromoacetyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate
1.20 g (4.40 mmol) of ethyl 3-acetyl-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate were initially charged in in each case 30 ml of dioxane and methyl tert-butyl ether and 776 mg (4.85 mmol) of bromine were added dropwise at RT. The mixture was then stirred under reflux for 6 h. The reaction mixture was added to water, and the organic phase was separated off, dried over sodium sulphate and concentrated. The residue was recrystallized from methyl tert-butyl ether.
(logP: 2.87; MH+: 373)
Example No. IX
Synthesis of ethyl 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]acetyl}-1H-pyrazole-5-carboxylate
1.24 g (2.04 mmol) of 5-(trifluoromethyl)-2H-tetrazole and 348 mg (2.52 mmol) of potassium carbonate were initially charged in 15 ml of acetonitrile and stirred at RT for 15 min. 693 mg (1.57 mmol) of ethyl 3-(bromoacetyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate, dissolved in 5 ml of acetonitrile, were added, and the reaction mixture was stirred at 70° C. for 5 min. Half of the solvent was distilled off, the residue was diluted with 80 ml of water and the mixture was extracted twice with dichloromethane. The combined organic phases are washed with sodium chloride solution, dried over sodium sulphate and concentrated. The desired product was isolated by chromatographic purification.
(logP: 3.50; MH+: 430; 1H-NMR (400 MHz, DMSO, δ, ppm): 1.12 (t, 3H), 4.21 (q, 2H), 6.72 (s, 2H), 7.72 (s, 1H), 7.80-7.82 (m, 1H), 8.39 (d, 1H), 8.65 (dd, 1H).
Example No. III-4
Synthesis of 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]acetyl}-1H-pyrazole-5-carboxylic acid
300 mg (0.58 mmol) of ethyl 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]acetyl}-1H-pyrazole-5-carboxylate were dissolved in 4 ml of ethanol, 282 mg (3.15 mmol) of 2N aqueous sodium hydroxide solution were added and the mixture was stirred at RT for 5 d. The solvent was distilled off under reduced pressure, the residue was taken up in water and the mixture was extracted once with methyl tert-butyl ether. The aqueous phase was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulphate and concentrated.
(logP: 2.25; MH+: 402; 1H-NMR (400 MHz, DMSO, δ, ppm): 6.69 (s, 2H), 7.60 (s, 1H), 7.75-7.78 (m, 1H), 8.32 (d, 1H), 8.61-8.63 (m, 1H).
Synthesis of Carboxylic Acids of the Formula III-5
Example No. VII-b
Synthesis of ethyl 3-{3-[3,5-bis(trifluoromethyl)phenyl]-2-oxoimidazolidin-1-yl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate
600 mg (1.76 mmol) of ethyl 4-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-2-carboxylate and 527 mg (1.76 mmol) of 1-[3,5-bis(trifluoromethyl)phenyl]imidazolidin-2-one were initially charged in 30 ml of toluene, and 40.4 mg (0.21 mmol) of copper(I) iodide, 31.2 mg (0.35 mmol) of N,N′-dimethylethylenediamine and 489 mg (3.53 mmol) of potassium carbonate were added successively at room temperature. The reaction mixture was stirred under reflux for 10 h. The solvent was then distilled off, the residue was taken up in ethyl acetate and the solution was washed in each case once with water and saturated sodium chloride solution, dried over sodium sulphate and concentrated using a rotary evaporator. The desired product was isolated by chromatographic purification.
(logP: 4.82; MH+: 548; 1H-NMR (400 MHz, DMSO, δ, ppm): 1.12-1.19 (m, 3H), 3.99-4.05 (m, 2H), 4.15-4.20 (m, 4H), 7.40 (s, 1H), 7.76-7.71 (m, 1H), 7.77 (s, 1H), 8.24 (d, 1H), 8.30 (s, 2H), 8.57 (dd, 1H).
Example No. III-5
Synthesis id of 3-{3-[3,5-bis(trifluoromethyl)phenyl]-2-oxoimidazolidin-1-yl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid
660 mg (1.20 mmol) of ethyl 3-{3-[3,5-bis(trifluoromethyl)phenyl]-2-oxoimidazolidin-1-yl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate were dissolved in 10 ml of ethanol, 72 mg (1.80 mmol) of 2N aqueous sodium hydroxide solution were added and the mixture was stirred at RT for 1 h. The solvent was distilled off under reduced pressure, the residue was taken up in water and the mixture was extracted once with methyl tert-butyl ether. The aqueous phase was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulphate and concentrated.
(logP: 3.47; MH+: 420; 1H-NMR (400 MHz, DMSO, δ, ppm): 3.98-4.04 (m, 2H), 4.14-4.18 (m, 1H), 7.32 (s, 1H), 7.64-7.67 (m, 1H), 7.77 (s, 1H), 8.21 (d, 1H), 8.30 (s, 2H), 8.56 (dd, 1H).
Synthesis of Carboxylic Acids of the Formula III-6
Example No. VII-c
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-{[6-(trifluoromethyl)pyridin-3-yl]methyl}-1H-pyrazole-5-carboxylate
Under argon, 0.8 g (2.36 mmol) of methyl 3-(bromomethyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate, 1.18 g (2.60 mmol) of 5-(tributylstannyl)-2-(trifluoromethyl)pyridine, 0.11 g (0.47 mmol) of tri-2-furylphosphine and 0.07 g (0.07 mmol) of tri(dibenzylideneacetone)dipalladium were stirred in NMP at 100° C. for 2 h. The solvent was distilled off under reduced pressure, and the residue was taken up in 80 ml of ethyl acetate and stirred vigorously with 70 ml of saturated potassium fluoride solution for 60 min. The organic phase was separated off, washed once with saturated sodium chloride solution, dried over sodium sulphate and concentrated using a rotary evaporator. The desired product was obtained by chromatographic purification.
(logP: 2.86; MH+: 397; 1H-NMR (400 MHz, DMSO, δ, ppm): 3.70 (s, 3H), 4.22 (s, 2H), 7.06 (s, 1H), 7.67 (dd, 1H), 7.86 (d, 1H), 7.99 (d, 1H), 8.22 (d, 1H), 8.54 (dd, 1H), 8.74 (s, 1H).
Example No. VIII-c
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-{[6-(trifluoromethyl)pyridin-3-yl]carbonyl}-1H-pyrazole-5-carboxylate
1.29 g (3.20 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{[6-(trifluoromethyl)pyridin-3-yl]methyl}-1H-pyrazole-5-carboxylate were dissolved in 80 ml of dioxane, 16.72 g (192 mmol) of manganese(IV) oxide were added and the mixture was stirred at reflux for 12 h. The mixture was filtered off with suction and the filtrate was freed from the solvent. The desired product was obtained by chromatographic purification.
(logP: 3.33; MH+: 411; 1H-NMR (400 MHz, DMSO, δ, ppm): 3.79 (s, 3H), 7.75-7.78 (m, 2H), 8.12 (d, 1H), 8.32 (d, 1H), 8.62 (dd, 1H), 8.71 (dd, 1H), 9.36 (s, 1H).
Example No. III-6
Synthesis of 1-(3-chloropyridin-2-yl)-3-{[6-(trifluoromethyl)pyridin-3-yl]carbonyl}-1H-pyrazole-5-carboxylic acid
29 mg (0.07 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{[6-(trifluoromethyl)pyridin-3-yl]carbonyl}-1H-pyrazole-5-carboxylate were dissolved in 2 ml of ethanol, 4 mg (0.1 mmol) of 2N aqueous sodium hydroxide solution were added and the mixture was stirred at RT for 30 min. The solvent was distilled off under reduced pressure, the residue was taken up in water and the mixture was extracted once with methyl tert-butyl ether. The aqueous phase was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulphate and concentrated.
(logP: 2.33; MH+: 397; 1H-NMR (400 MHz, DMSO, δ, ppm): 7.20 (s, 1H), 7.59 (dd, 1H), 8.09-8.15 (m 2H), 8.49 (dd, 1H), 8.69 (dd, 1H), 9.33 (s, 1H).
Synthesis of Carboxylic Acids of the Formula III-7
Example No. VII-d
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-[(hydroxyimino)methyl]-1H-pyrazole-5-carboxylate
Methyl 1-(3-chloropyridin-2-yl)-3-formyl-1H-pyrazole-5-carboxylate (0.99 g), hydroxylamine hydrochloride (0.39 g) and sodium acetate (0.61 g) were stirred at RT in a mixture of 5 ml of ethanol and 3 ml of water for 30 min. The mixture was diluted with methyl tert-butyl ether, washed with saturated sodium chloride solution and dried over sodium sulphate. Distillative removal of the solvent gave the desired target product.
1H-NMR (CD3CN) δ: (E/Z mixture) 3.73-3.74 (d, 3H), 7.23 (s), 7.53-7.67 (m, 2H), 7.67 (s), 8.02-8.05 (m, 1H), 8.14 (s), 8.49-8.51 (m, 1H), 9.07 (brs).
Example No. VIII-d
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-1H-pyrazole-5-carboxylate
N-Chlorosuccinimide (0.52 g) was added to a solution of 1-(3-chloropyridin-2-yl) 3-[(hydroxyimino)methyl]-1H-pyrazole-5-carboxylate (0.99 g) in 10 ml of DMF, and the mixture was stirred at 40° C. for 30 min. After cooling to RT, 1,3-dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene (0.56 g) and triethylamine (0.3 g) were added, and the reaction mixture was stirred at RT for 8 h. The mixture was diluted with methyl tert-butyl ether, washed with saturated sodium chloride solution and dried over sodium sulphate. After distillative removal of the solvent, the desired product is obtained by chromatographic purification.
1H-NMR (CD3CN) δ: 3.75 (s, 3H), 3.91-3.96 (m, 1H), 4.20 (d, 1H), 7.39 (s, 1H), 7.54-7.59 (m, 4H), 8.04-8.07 (m, 1H), 8.51-8.52 (m, 1H).
Example No. III-7
Synthesis of 1-(3-chloropyridin-2-yl)-3-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-1H-pyrazole-5-carboxylic acid
0.9 g of methyl 1-(3-chloropyridin-2-yl)-3-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazol-3-yl]-1H-pyrazole-5-carboxylate were dissolved in a mixture of 10 ml of water and 20 ml of ethanol, 0.2 g of sodium hydroxide were added and the mixture was stirred at RT for 3 h. The reaction was acidified with 2N hydrochloric acid, extracted three times with methyl tert-butyl ether and dried over magnesium sulphate. The product was obtained after distillative removal of the solvent.
1H-NMR (CD3CN) δ: 3.97 (d, 1H), 4.20 (d, 1H), 7.39 (s, 1H), 7.54-7.59 (m, 4H), 8.03-8.05 (m, 1H), 8.50-8.51 (m, 1H).
Synthesis of Carboxylic Acids of the Formula III-8
Example No. VII-e
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-formyl-1H-pyrazole-5-carboxylate
A little at a time, 3.90 g (44.9 mmol) of manganese(IV) oxide were added to a solution of 3.00 g (11.2 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-(hydroxymethyl)-1H-pyrazole-5-carboxylate in 162 mg of dichloromethane, and the mixture was stirred at 40° C. for 4 hours. After cooling to 20° C., a further 3.90 g (44.9 mmol) of manganese(IV) oxide were added, and the mixture was heated at 40° C. overnight. After cooling to 20° C., the mixture was filtered through Celite and the filtrate was freed from the solvent under reduced pressure.
(logP: 1.82)
Example No. VIII-e
Synthesis of 1-(3-chloropyridin-2-yl)-5-(methoxycarbonyl)-1H-pyrazole-3-carboxylic acid
2.00 g (7.53 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-formyl-1H-pyrazole-5-carboxylate were dissolved in 18 ml of tert-butanol, and 5 ml of water were then added. After cooling to 0° C., 2.35 g (15.1 mmol) sodium dihydrogenphosphate dihydrate, 2.73 g (30.1 mmol) of sodium chlorite and 3.17 g (45.2 mmol) of 2-methyl-2-butene were added in succession. After 1 hour at 20° C., water was added and the mixture was extracted twice with ethyl acetate. The combined organic phases were dried over sodium sulphate and the solvent was removed under reduced pressure (logP: 1.38)
Example No. IX-e
Synthesis of methyl 1-(3-chloropyridin-2-yl)-3-{[4-(trifluoromethyl)phenyl]carbamoyl}-1H-pyrazole-5-carboxylate
A solution of 1.00 g (3.55 mmol) of 1-(3-chloropyridin-2-yl)-5-(methoxycarbonyl)-1H-pyrazole-3-carboxylic acid in 13 ml of dichloromethane and 1.3 ml of N,N-dimethylformamide was cooled to 0° C., a solution of 0.86 g (5.33 mmol) of 4-(trifluoromethyl)aniline in 3 ml of dichloromethane was added dropwise and 0.68 g (3.55 mmol) of N-ethyl-N′-3-(dimethylaminopropyl)carbodiimide×HCl and 87 mg (710 μmol) of 4-dimethylaminopyridine were added a little at a time. The mixture was stirred at 0° C. for 2 hours and at 20° C. for 16 hours. The mixture was then diluted with dichloromethane and washed successively with 1 N aqueous hydrochloric acid and water. The organic phase was dried over sodium sulphate, the solvent was removed under reduced pressure and the residue was purified on silica gel using cyclohexane/ethyl acetate=3:1→2:1. (logP: 3.54).
Example No. III-8
Synthesis of 1-(3-chloropyridin-2-yl)-3-{[4-(trifluoromethyl)phenyl]carbamoyl-1H-pyrazole-5-carboxylic acid
0.98 g (2.45 mmol) of 10% strength aqueous sodium hydroxide solution was added dropwise to a mixture of 1.00 g (1.88 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{[4-(trifluoromethyl)phenyl]carbamoyl}-1H-pyrazole-5-carboxylate in 20 ml of ethanol, and the mixture was stirred at 20° C. for 2.5 hours. The solvent was then removed under reduced pressure, and 30 ml of water and 30 ml of ethyl acetate were added to the residue. The aqueous phase was adjusted to pH 1 using hydrochloric acid and extracted with ethyl acetate. The combined organic phases were dried over sodium sulphate and the solvent was removed under reduced pressure (logP: 2.67)
Synthesis of Carboxylic Acids of the Formula (III-9)
Example No. XI
Methyl 1-(3-chloropyridin-2-yl)-3-(oxiran-2-yl)-1H-pyrazole-5-carboxylate
5.00 g (18.8 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-formyl-1H-pyrazole-5-carboxylate (known from WO 2006/000336) and 5.76 g (28.2 mmol) of trimethylsulphonium iodide were initially charged in 12.5 ml of dimethyl sulphoxide, and 2.64 g (23.5 mmol) of t-BuOK in 12.5 ml of dimethyl sulphoxide were added dropwise at room temperature. After 1.5 hours of stirring at room temperature, 60 ml of water were carefully added dropwise with ice cooling, whereupon the reaction mixture was extracted repeatedly with ethyl acetate. The combined organic phases were washed three times with water and then dried over magnesium sulphate. The solvent was distilled off under reduced pressure and the residue was chromatographed on silica gel, which gave 1.10 g (21% of theory) of methyl 1-(3-chloropyridin-2-yl)-3-(oxiran-2-yl)-1H-pyrazole-5-carboxylate. (logP: 1.67; MH+: 280.0; 1H-NMR (400 MHz, CD3CN, δ, ppm): 3.10 (m, 2H), 3.71 (s, 3H), 3.98 (s, 1H), 6.92 (s, 1H), 7.56 (m, 1H), 8.07 (m, 1H), 8.51 (m, 1H).)
Example No. XII
Methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]ethyl}-1H-pyrazole-5-carboxylate/methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]ethyl}-1H-pyrazole-5-carboxylate
51.5 mg (2.14 mmol) of sodium hydride were initially charged in 15 ml of tetrahydrofuran, and a solution of 1380 mg (2.32 mmol) of a 25% strength solution of 5-(trifluoromethyl)-2H-tetrazole in tetrahydrofuran was added at 0° C. After 20 minutes of stirring at 0° C., 500 mg (1.78 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-(oxiran-2-yl)-1H-pyrazole-5-carboxylate were added, and the mixture was stirred at reflux temperature for 20 hours. The reaction mixture was poured into water, acidified with glacial acetic acid and then extracted repeatedly with ethyl acetate. The combined organic phases were washed with water and then dried over magnesium sulphate. The solvent was distilled off under reduced pressure and the residue was chromatographed on silica gel, which gave 286 mg (80% of theory) of methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]ethyl}-1H-pyrazole-5-carboxylate and methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]ethyl}-1H-pyrazole-5-carboxylate in a ratio of 66:34. (logP: 2.64/2.68; MH+: 418.0; 1H-NMR (400 MHz, CD3CN, δ, ppm): 3.73 (s, 3H), 4.31 (m, 2H), 4.48 (m, 1H), 7.10 (m, 1H), 7.54 (m, 1H), 8.05 (m, 1H), 8.50 (m, 1H).)
Example No. XIII
Methyl 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]vinyl}-1H-pyrazole-5-carboxylate/methyl 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]vinyl}-1H-pyrazole-5-carboxylate (No. XIII)
225 mg (0.54 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]ethyl}-1H-pyrazole-5-carboxylate and methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]ethyl}-1H-pyrazole-5-carboxylate in a ratio of 66:34 were initially charged in 7.0 ml of toluene, 75.3 mg (0.65 mmol) of methanesulphonyl chloride and 166 mg (1.64 mmol) of triethylamine were added at 0° C. and the mixture was stirred at reflux temperature for 10 hours. The reaction mixture was diluted with toluene and washed with sodium bicarbonate solution. The organic phases were dried over magnesium sulphate and the solvent was distilled off under reduced pressure. The residue was chromatographed on silica gel, which gave 132 mg (45% of theory) of methyl 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]vinyl}-1H-pyrazole-5-carboxylate and methyl 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]vinyl}-1H-pyrazole-5-carboxylate in a ratio of 69:31. (logP: 3.37/3.49; MH+: 400.1; 1H-NMR (400 MHz, CD3CN, δ, ppm): 3.78 (s, 3H), 7.35 (m, 1H), 7.60 (m, 1H), 7.75 (m, 1H), 8.08 (m, 1H), 8.32 (m, 1H), 8.55 (m, 1H).)
Example No. XIV
1-(3-Chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]vinyl}-1H-pyrazole-5-carboxylic acid/1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]vinyl}-1H-pyrazole-5-carboxylic acid
88.7 mg (0.23 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]vinyl}-1H-pyrazole-5-carboxylate and methyl 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]vinyl}-1H-pyrazole-5-carboxylate in a ratio of 66:34 were dissolved in 5.0 ml of ethanol, and 26.6 mg (0.29 mmol) of 45% strength aqueous sodium hydroxide solution were added. After 1 hour of stirring at room temperature, the mixture was diluted with water and acidified with dilute hydrochloric acid. The aqueous phase was extracted repeatedly with ethyl acetate and dried over magnesium sulphate. The solvent was distilled off under reduced pressure, which gave 43 mg (48% of theory) of 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]vinyl}-1H-pyrazole-5-carboxylic acid and 1-(3-chloropyridin-2-yl)-3-{(E)-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]vinyl}-1H-pyrazole-5-carboxylic acid in a ratio of 70:30. (logP: 2.79/2.86; MH+: 386.0/386.0; 1H-NMR (400 MHz, CD3CN, δ, ppm): 7.40 (m, 1H), 7.59 (m, 1H), 7.75 (m, 1H), 8.05 (m, 1H), 8.31 (m, 1H), 8.53 (m, 1H).)
Example No. III-9
1-(3-Chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]ethyl}-1H-pyrazole-5-carboxylic acid/1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]ethyl}-1H-pyrazole-5-carboxylic acid
72.5 mg (0.18 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]ethyl}-1H-pyrazole-5-carboxylate and methyl 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]ethyl}-1H-pyrazole-5-carboxylate in a ratio of 66:34 were dissolved in 5.0 ml of ethanol, and 21.0 mg (0.23 mmol) of 45% strength aqueous sodium hydroxide solution were added. After 1 hour of stirring at room temperature, the mixture was diluted with water and acidified with dilute hydrochloric acid. The aqueous phase was extracted repeatedly with ethyl acetate and dried over magnesium sulphate. The solvent was distilled off under reduced pressure, which gave 43 mg (48% of theory) of 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]ethyl}-1H-pyrazole-5-carboxylic acid and 1-(3-chloropyridin-2-yl)-3-{1-hydroxy-2-[5-(trifluoromethyl)-1H-tetrazol-1-yl]ethyl}-1H-pyrazole-5-carboxylic acid in a ratio of 73:27. (logP: 1.68/1.37; MH+: 404.0/404.0
Synthesis of Carboxylic Acids of the Formula III-10
Example No. III-10
1-(3-Chloropyridin-2-yl)-3-{[5-(trifluoromethyl)pyridin-2-yl]amino}-1H-pyrazole-5-carboxylic acid
Example No. XVI
3-Chloro-2-(3-nitro-1H-pyrazol-1-yl)pyridine
10.0 g (88.4 mmol) of 3-nitropyrazole and 14.4 g (97.2 mmol) of 2,3-dichloropyridine were initially charged in 50 ml of dimethylformamide, 23.9 g (173 mmol) of potassium carbonate were added and the reaction mixture was stirred at 125° C. for 18 hours. After cooling, the mixture was poured into water and the precipitated solid was filtered off. Recrystallization from isopropanol/water gave 18.1 g (90% of theory) of 3-chloro-2-(3-nitro-1H-pyrazol-1-yl)pyridine (log P: 1.83; MH+: 225.1; 1H-NMR (400 MHz, CD3CN, δ, ppm): 7.15 (s, 1H), 7.56 (d, 1H), 8.15 (d, 1H), 8.23 (d, 1H), 8.53 (m, 1H).
Example No. XVII
1-(3-Chloropyridin-2-yl)-3-nitro-1H-pyrazole-5-carboxylic acid
8.65 g (38.5 mmol) of 3-chloro-2-(3-nitro-1H-pyrazol-1-yl)pyridine were dissolved in 196 ml of tetrahydrofuran and, under argon, cooled to −78° C. 21.4 mL (42.7 mmol) of a 2 molar solution of lithium diisopropylamide in THF were then added dropwise. The mixture was allowed to stir for 1 hour at −78° C., and a total of 1500 g of powdered dry ice were then added a little at a time. The mixture was stirred at −78° C. until the evolution of carbon dioxide had ceased and then allowed to warm to room temperature. Initially, 679 ml of water were then added, and the pH was subsequently adjusted to 11 using 1N sodium hydroxide solution. The aqueous phase was extracted repeatedly with ethyl acetate. The combined organic phases were dried over magnesium sulphate and the solvent was distilled off under reduced pressure, which gave 5.0 g (47% of theory) of 1-(3-chloropyridin-2-yl)-3-nitro-1H-pyrazole-5-carboxylic acid. log P: 0.90; MH+: 269.0; 1H-NMR (400 MHz, CD3CN, δ, ppm): 7.77 (m, 2H), 8.33 (m, 1H), 8.62 (m, 1H).
Example No. XVIII
Methyl 1-(3-chloropyridin-2-yl)-3-nitro-1H-pyrazole-5-carboxylate
5.00 g (18.6 mmol) of 1-(3-chloropyridin-2-yl)-3-nitro-1H-pyrazole-5-carboxylic acid were initially charged in 66 ml of methylene chloride, 6.64 g (55.8 mmol) of thionyl chloride were added at room temperature and the reaction mixture was heated under reflux for 24 hours. The solvent was distilled off under reduced pressure, and the residue was directly reacted further.
With ice cooling, the acid chloride was dissolved in 32 ml of methanol, and 1.98 g (19.6 mmol) of triethylamine were added. After 18 hours of stirring at room temperature, the solvent was removed completely under reduced pressure and the residue was taken up in methylene chloride and washed with 0.5 N HCl. The organic phase was dried over magnesium sulphate, the solvent was distilled off under reduced pressure and the residue was chromatographed on silica gel, which gave 3.20 g (68% of theory) of methyl 1-(3-chloropyridin-2-yl)-3-nitro-1H-pyrazole-5-carboxylate. (log P: 2.18; MH+: 283.1); 1H-NMR (400 MHz, CD3CN, δ, ppm): 3.79 (s, 3H), 7.80 (m, 1H), 7.89 (s, 1H), 8.36 (m, 1H), 8.63 (d, 1H).)
Example No. XIX
Methyl 3-amino-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate
10.41 g (54.9 mmol) of tin(II) chloride were initially charged in 80 ml of ethanol, 3.20 g (11.3 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-nitro-1H-pyrazole-5-carboxylate were added and the mixture was stirred at reflux temperature for 3 hours. After cooling, the reaction mixture was poured onto ice and adjusted to pH 12 with sodium bicarbonate. The aqueous phase was extracted repeatedly with ethyl acetate and dried over magnesium sulphate. The solvent was distilled off under reduced pressure and the residue was chromatographed on silica gel, which gave 2.20 g (71% of theory) of methyl 3-amino-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate (log P: 1.09; MH+: 253.1); 1H-NMR (400 MHz, CD3CN, δ, ppm): 3.66 (s, 3H), 5.20 (s, 2H), 6.25 (s, 1H), 7.56 (m, 1H), 8.15 (d, 1H), 8.47 (m, 1H).)
Example No. XX
Methyl 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)pyridin-2-yl]amino}-1H-pyrazole-5-carboxylate
1.90 g (7.52 mmol) of methyl 3-amino-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate 1.50 g (8.27 mmol) of 2-chloro-5-trifluoromethylpyridine, 0.275 g (0.3 mmol) of tris(dibenzylacetone)dipalladium, 0.286 g (0.60 mmol) of 2-dicyclohexylphosphino-2,4,6-triisopropyl-1,1-biphenyl and 3.12 g (22.5 mmol) of potassium carbonate were initially charged in 190 ml of tert-butanol, and the reaction mixture was stirred at 100° C. for 24 hours. After cooling, the mixture was poured into water and extracted repeatedly with ethyl acetate, and the extracts were dried over magnesium sulphate. The solvent was distilled off under reduced pressure and the residue was chromatographed on silica gel, which gave 950 mg (29% of theory) of methyl 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)pyridin-2-yl]amino}-1H-pyrazole-5-carboxylate. (logP: 3.14; MH+: 398.0); 1H-NMR (400 MHz, CD3CN, δ, ppm): 3.74 (s, 3H), 7.26 (m, 1H), 7.37 (s, 1H), 7.66 (m, 1H), 7.95 (m, 1H), 8.25 (d, 1H), 8.56 (m, 2H).)
Example No. III-10
1-(3-Chloropyridin-2-yl)-3-{[5-(trifluoromethyl)pyridin-2-yl]amino}-1H-pyrazole-5-carboxylic acid
855 mg (2.15 mmol) of methyl 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)pyridin-2-yl]amino}-1H-pyrazole-5-carboxylate were dissolved in 10.0 ml of ethanol, and 248 mg (2.79 mmol) of 45% strength aqueous sodium hydroxide solution were added. After 24 hours of stirring at room temperature, the mixture was diluted with water and acidified with dilute hydrochloric acid. The aqueous phase was extracted repeatedly with ethyl acetate and dried over magnesium sulphate. The solvent was distilled off under reduced pressure, which gave 758 mg (92% of theory) of 1-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)pyridin-2-yl]amino}-1H-pyrazole-5-carboxylic acid. (logP: 2.79; MH+: 384.0; 1H-NMR (400 MHz, CD3CN, δ, ppm): 7.28 (m, 1H), 7.38 (m, 1H), 7.55 (m, 1H), 7.89 (m, 1H), 8.05 (m, 1H), 8.51 (m, 2H).
PREPARATION EXAMPLES
The preparation processes described above can be used to obtain the compounds of the formula (I), some of which may be present as regioisomers. With respect to the NMR data, the table below states the chemical shifts and the corresponding signal intensities; for example, for compound 1:
Signal 1:
10.20; 2.040; for 10.20 ppm (chemical shift), 2.040 (signal intensity);
Signal 2:
8.50; 2.770; for 8.50 ppm (chemical shift), 2.770 (signal intensity);














No.
Structure
log P
MH+
NMR



















1






(10.20; 2.040), (8.50; 2.770), (8.50; 2.750), (8.49; 2.870), (8.49; 2.900), (8.15; 2.480), (8.14; 2.460), (8.13; 2.840), (8.12; 2.490), (8.02; 1.140), (7.73; 2.360), (7.72; 4.230), (7.72; 3.050), (7.67; 7.660), (7.67; 7.450), (7.62; 2.640), (7.61; 2.720), (7.60; 2.650), (7.59; 2.500), (7.42; 2.710), (7.42; 3.000), (7.34; 3.250), (7.34; 2.890), (4.29; 1.680), (4.25; 4.120), (4.20; 2.890), (4.15; 1.280), (3.65; 0.880), (3.27; 0.810), (3.26; 0.860), (3.20; 1.000), (3.19; 1.330), (3.16; 2.450), (3.15; 2.980), (3.14; 3.840), (3.11; 1059.520), (3.08; 8.370), (3.07; 2.170), (2.68; 9.930), (2.67; 10.190), (2.66; 3.210), (2.66; 2.730), (2.65; 2.200), (2.55; 1.330), (2.53; 10.290), (2.50; 158.700), (2.49; 306.850), (2.49; 417.820), (2.48; 294.340), (2.48; 143.670), (2.45; 1.480), (2.32; 1.250), (2.32; 2.000), (2.31; 2.490), (2.31; 1.920), (2.16; 16.000), (2.04; 0.890), (1.90; 0.910), (1.25; 1.060), (1.11; 14.530), (0.89; 1.530), (0.01; 6.080), (−0.00; 123.470), (−0.01; 5.520)


 


2




3.53

(10.56; 0.920), (10.53; 0.420), (8.54; 2.480), (8.53; 2.860), (8.52; 2.930), (8.52; 3.040), (8.17; 2.370), (8.16; 2.610), (8.15; 2.820), (8.14; 2.810), (8.07; 4.020), (8.05; 4.560), (7.77; 2.040), (7.69; 4.330), (7.67; 4.070), (7.66; 0.540), (7.64; 2.730), (7.63; 2.680), (7.62; 2.550), (7.61; 2.540), (7.56; 2.550), (7.55; 2.930), (7.48; 3.100), (7.48; 2.890), (7.46; 0.460), (3.17; 0.720), (3.16; 0.860), (3.16; 0.880), (3.11; 611.470), (3.07; 2.120), (3.06; 1.130), (3.05; 1.310), (3.05; 0.920), (3.02; 0.440), (2.69; 9.550), (2.68; 9.500), (2.66; 0.710), (2.66; 0.840), (2.53; 5.360), (2.50; 42.200), (2.49; 82.380), (2.49; 112.620), (2.48; 79.570), (2.48; 38.940), (2.45; 0.560), (2.32; 0.510), (2.32; 0.710), (2.17; 16.000), (2.08; 1.750), (2.04; 1.260), (1.97; 1.420), (1.30; 0.550), (1.28; 0.420), (1.25; 1.270), (1.20; 0.540), (1.18; 0.900), (1.16; 0.520), (0.88; 0.800), (0.86; 0.700), (0.86; 0.530), (0.85; 0.420), (0.01; 1.000), (0.00; 18.920), (−0.01; 0.580)


 


3




4.02

(10.58; 0.280), (10.56; 0.400), (8.52; 2.120), (8.52; 2.190), (8.51; 2.240), (8.51; 2.070), (8.16; 2.110), (8.15; 2.000), (8.14; 2.220), (8.13; 2.050), (8.07; 2.880), (8.05; 3.170), (7.92; 0.360), (7.90; 0.340), (7.89; 0.290), (7.78; 1.810), (7.69; 3.360), (7.67; 2.920), (7.64; 0.320), (7.64; 2.060), (7.62; 2.080), (7.62; 1.930), (7.60; 1.840), (7.55; 2.020), (7.54; 2.180), (7.45; 2.260), (7.45; 1.990), (3.98; 0.250), (3.96; 0.640), (3.94; 0.950), (3.93; 0.910), (3.91; 0.620), (3.89; 0.260), (3.17; 0.390), (3.17; 0.290), (3.11; 205.150), (3.07; 0.370), (3.06; 0.390), (3.05; 0.380), (2.66; 0.220), (2.66; 0.350), (2.65; 0.260), (2.63; 0.260), (2.53; 2.430), (2.50; 19.490), (2.49; 38.450), (2.49; 53.040), (2.48; 37.680), (2.48; 18.670), (2.32; 0.280), (2.31; 0.290), (2.31; 0.240), (2.21; 0.380), (2.18; 11.770), (2.08; 1.420), (2.04; 0.500), (1.40; 0.320), (1.25; 0.250), (1.13; 0.330), (1.12; 0.350), (1.07; 15.970), (1.05; 16.000), (0.00; 9.610), (−0.01; 0.430)


 


4




3.96

(10.57; 2.380), (10.19; 1.420), (8.53; 2.150), (8.52; 2.140), (8.51; 2.270), (8.51; 2.100), (8.16; 2.100), (8.16; 2.100), (8.14; 2.320), (8.14; 2.160), (8.07; 2.800), (8.05; 3.070), (7.97; 0.500), (7.83; 1.030), (7.81; 2.630), (7.69; 3.220), (7.67; 2.840), (7.64; 2.180), (7.63; 2.060), (7.62; 2.000), (7.61; 1.920), (7.43; 2.210), (7.42; 2.350), (7.32; 2.450), (7.31; 2.120), (3.96; 0.670), (3.95; 1.000), (3.93; 0.950), (3.91; 0.670), (3.24; 0.660), (3.22; 0.670), (3.21; 0.720), (3.20; 0.930), (3.20; 0.980), (3.19; 1.070), (3.18; 1.230), (3.18; 1.330), (3.16; 2.100), (3.12; 1048.820), (3.07; 2.020), (3.06; 1.020), (3.05; 0.640), (2.67; 0.500), (2.66; 0.770), (2.66; 1.010), (2.65; 0.710), (2.53; 8.730), (2.50; 63.010), (2.49; 123.740), (2.49; 169.950), (2.48; 120.360), (2.48; 59.100), (2.32; 0.660), (2.32; 1.000), (2.31; 0.730), (2.19; 11.940), (2.04; 2.030), (1.97; 0.720), (1.25; 0.660), (1.07; 16.000), (1.05; 15.770), (0.01; 0.870), (−0.00; 20.350), (−0.01; 0.920)


 


5




3.46

(10.57; 2.810), (10.23; 0.770), (8.54; 2.720), (8.53; 2.890), (8.53; 2.900), (8.52; 2.810), (8.24; 5.280), (8.17; 2.650), (8.17; 2.700), (8.15; 2.980), (8.15; 2.870), (8.08; 3.600), (8.05; 4.370), (8.03; 0.930), (7.97; 0.410), (7.79; 2.370), (7.69; 4.150), (7.67; 3.750), (7.64; 2.820), (7.63; 2.810), (7.62; 2.620), (7.61; 2.580), (7.43; 2.600), (7.43; 2.960), (7.35; 3.150), (7.34; 2.820), (3.62; 0.410), (3.60; 1.010), (3.60; 0.440), (3.20; 0.390), (3.18; 0.560), (3.17; 0.680), (3.17; 1.040), (3.16; 1.070), (3.12; 525.300), (3.08; 1.140), (3.07; 0.760), (3.06; 0.530), (3.05; 0.490), (2.70; 9.970), (2.68; 9.810), (2.67; 0.390), (2.66; 0.510), (2.66; 0.670), (2.65; 0.450), (2.53; 4.470), (2.50; 32.490), (2.49; 63.900), (2.49; 87.960), (2.48; 62.340), (2.48; 30.770), (2.32; 0.420), (2.32; 0.530), (2.31; 0.400), (2.18; 16.000), (2.08; 2.570), (2.04; 0.510), (1.78; 0.450), (1.77; 0.490), (1.76; 1.210), (1.75; 0.460), (1.75; 0.400), (0.01; 0.420), (0.00; 8.750)


 


6




4.16

(10.93; 1.410), (10.26; 0.600), (8.61; 6.940), (8.55; 2.750), (8.54; 2.860), (8.53; 2.970), (8.53; 2.810), (8.18; 2.660), (8.18; 2.660), (8.16; 2.970), (8.16; 2.800), (8.05; 0.810), (7.97; 0.380), (7.80; 2.170), (7.74; 3.030), (7.65; 2.730), (7.64; 2.720), (7.63; 2.630), (7.62; 2.510), (7.43; 2.610), (7.43; 2.910), (7.35; 3.130), (7.35; 2.770), (3.62; 1.650), (3.62; 1.220), (3.61; 1.160), (3.61; 1.600), (3.60; 3.920), (3.60; 1.570), (3.59; 1.120), (3.59; 1.240), (3.59; 1.640), (3.40; 0.940), (3.38; 0.940), (3.18; 0.560), (3.17; 0.740), (3.16; 1.220), (3.16; 1.080), (3.12; 410.100), (3.07; 0.530), (2.70; 9.830), (2.68; 9.710), (2.66; 0.440), (2.66; 0.530), (2.53; 3.700), (2.51; 1.790), (2.50; 26.970), (2.49; 53.120), (2.49; 73.150), (2.48; 52.040), (2.48; 25.710), (2.32; 0.430), (2.18; 16.000), (2.04; 0.570), (1.78; 1.660), (1.77; 1.760), (1.76; 4.610), (1.75; 1.720), (1.75; 1.550), (1.11; 0.930), (1.09; 1.860), (1.07; 0.940), (0.01; 0.410), (−0.00; 8.710)


 


7




4.62

(10.93; 0.320), (8.61; 4.920), (8.54; 1.860), (8.53; 1.980), (8.52; 2.030), (8.52; 1.950), (8.17; 1.860), (8.17; 1.880), (8.15; 2.090), (8.15; 1.970), (7.85; 0.600), (7.82; 1.960), (7.74; 2.160), (7.65; 1.900), (7.64; 1.920), (7.63; 1.860), (7.62; 1.780), (7.43; 1.990), (7.42; 2.210), (7.32; 2.200), (7.32; 2.000), (3.97; 0.580), (3.95; 0.880), (3.93; 0.850), (3.92; 0.580), (3.62; 2.200), (3.62; 1.650), (3.61; 1.610), (3.61; 2.180), (3.60; 5.260), (3.60; 2.180), (3.59; 1.540), (3.59; 2.180), (3.58; 0.620), (3.42; 0.970), (3.40; 2.810), (3.39; 2.840), (3.37; 0.980), (3.19; 0.320), (3.18; 0.290), (3.18; 0.340), (3.16; 0.760), (3.13; 146.780), (3.08; 0.310), (2.53; 1.040), (2.50; 7.750), (2.49; 15.060), (2.49; 20.530), (2.49; 14.510), (2.48; 7.110), (2.19; 11.060), (2.04; 0.280), (1.78; 2.280), (1.77; 2.440), (1.77; 1.900), (1.76; 6.210), (1.76; 1.860), (1.75; 2.320), (1.75; 2.060), (1.11; 3.080), (1.09; 6.150), (1.07; 16.000), (1.06; 14.370), (0.00; 1.420)


 


8




3.11
525
(10.499; 1.75), (8.513; 1.32), (8.509; 1.42), (8.501; 1.44), (8.498; 1.39), (8.347; 0.68), (8.335; 0.69), (8.188; 1.32), (8.184; 1.32), (8.167; 1.49), (8.164; 1.38), (7.872; 1.44), (7.869; 1.54), (7.766; 1.66), (7.762; 1.56), (7.629; 1.40), (7.618; 1.36), (7.609; 1.33), (7.597; 1.34), (7.585; 0.37), (7.578; 2.89), (7.573; 0.96), (7.561; 1.00), (7.556; 3.19), (7.549; 0.38), (7.462; 2.05), (7.042; 0.39), (7.035; 3.11), (7.030; 0.98), (7.018; 0.95), (7.013; 2.83), (7.005; 0.30), (3.815; 15.00), (3.295; 242.65), (2.689; 4.62), (2.678; 4.68), (2.668; 0.42), (2.538; 0.40), (2.522; 0.85), (2.517; 1.42), (2.508; 15.41), (2.504; 31.19), (2.499; 42.19), (2.495; 29.65), (2.490; 13.57), (2.224; 7.06), (2.067; 0.49), (−0.000; 0.42)


 


9




3.94
574
(10.299; 3.51), (8.523; 2.80), (8.519; 3.03), (8.511; 3.07), (8.508; 3.02), (8.192; 2.69), (8.188; 2.73), (8.172; 3.01), (8.168; 2.83), (7.792; 0.74), (7.786; 5.70), (7.780; 2.00), (7.769; 2.18), (7.764; 6.68), (7.757; 0.91), (7.728; 1.62), (7.635; 2.97), (7.623; 2.88), (7.615; 2.80), (7.603; 2.81), (7.491; 7.72), (7.476; 7.01), (7.470; 4.64), (7.457; 3.54), (7.419; 3.57), (7.413; 3.00), (3.412; 0.94), (3.394; 2.82), (3.377; 2.90), (3.359; 1.03), (3.297; 356.18), (3.273; 2.36), (2.669; 0.38), (2.539; 0.49), (2.522; 1.07), (2.509; 20.00), (2.504; 40.68), (2.500; 55.33), (2.495; 39.05), (2.490; 18.02), (2.326; 0.39), (2.322; 0.31), (2.164; 15.00), (2.067; 0.49), (1.109; 2.92), (1.091; 5.88), (1.074; 2.81), (−0.000; 0.57)


 


10




4.29
588
(10.260; 3.62), (8.516; 2.72), (8.512; 2.92), (8.504; 2.93), (8.500; 2.87), (8.227; 1.44), (8.216; 1.43), (8.205; 0.53), (8.191; 2.65), (8.187; 2.66), (8.170; 2.93), (8.167; 2.74), (7.796; 0.72), (7.789; 5.45), (7.784; 1.92), (7.772; 2.09), (7.767; 6.29), (7.760; 0.82), (7.634; 2.84), (7.623; 2.72), (7.614; 2.67), (7.602; 2.67), (7.502; 7.15), (7.477; 4.03), (7.472; 3.93), (7.465; 3.88), (7.457; 3.51), (7.352; 3.25), (7.346; 2.98), (3.412; 0.52), (3.394; 1.44), (3.377; 1.50), (3.359; 0.65), (3.336; 0.36), (3.296; 388.43), (3.273; 2.27), (2.678; 9.46), (2.667; 9.46), (2.539; 0.55), (2.522; 1.22), (2.509; 21.90), (2.504; 44.19), (2.500; 59.82), (2.495; 42.06), (2.490; 19.33), (2.331; 0.34), (2.326; 0.37), (2.173; 15.00), (2.067; 0.47), (1.109; 1.44), (1.091; 2.92), (1.074; 1.43), (−0.000; 0.64)


 


11




4.79
616
(10.218; 2.55), (8.502; 2.02), (8.498; 2.13), (8.490; 2.19), (8.486; 2.08), (8.177; 1.91), (8.174; 1.89), (8.157; 2.14), (8.153; 1.96), (8.060; 1.02), (8.040; 1.02), (7.796; 0.59), (7.789; 4.12), (7.784; 1.45), (7.773; 1.66), (7.767; 4.72), (7.761; 0.63), (7.629; 2.04), (7.617; 2.00), (7.609; 1.92), (7.597; 1.92), (7.517; 5.01), (7.476; 2.93), (7.461; 3.23), (7.456; 4.78), (7.312; 2.40), (7.306; 2.22), (3.948; 0.58), (3.931; 0.90), (3.912; 0.87), (3.896; 0.58), (3.301; 175.99), (3.277; 1.68), (2.539; 0.44), (2.523; 0.70), (2.509; 10.95), (2.505; 21.48), (2.500; 28.55), (2.496; 20.02), (2.491; 9.24), (2.178; 11.07), (1.055; 15.00), (1.038; 14.81), (−0.000; 0.48)


 


12




3.58
565
(10.593; 2.79), (8.528; 2.87), (8.524; 3.01), (8.516; 3.11), (8.512; 2.96), (8.197; 2.75), (8.193; 2.76), (8.177; 3.10), (8.173; 2.86), (7.872; 3.85), (7.844; 4.04), (7.840; 3.32), (7.795; 0.87), (7.788; 6.27), (7.783; 2.12), (7.771; 2.43), (7.766; 7.18), (7.759; 0.92), (7.640; 2.93), (7.628; 2.88), (7.620; 2.80), (7.608; 2.95), (7.588; 1.81), (7.511; 3.61), (7.480; 3.75), (7.478; 4.13), (7.458; 3.65), (3.301; 260.31), (3.278; 2.37), (2.539; 0.61), (2.523; 1.02), (2.510; 15.65), (2.505; 30.88), (2.500; 41.22), (2.496; 29.01), (2.491; 13.42), (2.210; 15.00), (2.068; 1.64), (−0.000; 0.61)


 


13




3.88
579
(10.529; 2.62), (8.520; 2.86), (8.516; 3.02), (8.508; 3.10), (8.505; 2.97), (8.360; 0.72), (8.196; 2.71), (8.192; 2.70), (8.176; 3.03), (8.172; 2.81), (7.867; 2.85), (7.798; 0.84), (7.791; 6.18), (7.786; 2.22), (7.769; 10.05), (7.639; 2.82), (7.627; 2.75), (7.619; 2.65), (7.607; 2.62), (7.523; 3.05), (7.479; 4.14), (7.459; 3.67), (3.299; 249.99), (3.276; 2.46), (2.691; 10.00), (2.679; 10.01), (2.665; 0.39), (2.539; 0.63), (2.523; 1.03), (2.509; 16.11), (2.505; 31.86), (2.500; 42.61), (2.496; 30.03), (2.491; 14.04), (2.224; 15.00), (2.068; 0.34), (−0.000; 0.43)


 


14




3.57
616
(10.676; 0.76), (8.975; 1.15), (8.548; 0.62), (8.545; 0.65), (8.537; 0.67), (8.533; 0.64), (8.245; 0.60), (8.242; 0.59), (8.225; 0.67), (8.222; 0.63), (8.193; 1.06), (7.846; 0.74), (7.843; 0.77), (7.766; 0.95), (7.712; 0.83), (7.707; 0.79), (7.691; 0.63), (7.679; 0.60), (7.671; 0.58), (7.659; 0.57), (3.290; 61.94), (2.539; 0.46), (2.522; 0.42), (2.509; 5.91), (2.504; 11.51), (2.500; 15.28), (2.495; 10.83), (2.491; 5.11), (2.234; 3.36), (1.260; 15.00), (−0.000; 1.04)


 


15




2.89
573
(10.637; 0.74), (8.568; 3.45), (8.565; 3.56), (8.557; 3.59), (8.553; 3.30), (8.533; 0.43), (8.524; 0.38), (8.343; 0.92), (8.335; 0.85), (8.317; 0.62), (8.238; 1.91), (8.219; 1.95), (7.869; 1.86), (7.770; 1.75), (7.692; 1.57), (7.681; 1.75), (7.673; 1.69), (7.662; 1.41), (7.229; 0.55), (7.210; 0.76), (7.190; 0.59), (6.694; 13.03), (6.489; 0.66), (6.327; 0.97), (6.306; 0.86), (5.746; 6.51), (5.344; 1.14), (3.755; 0.48), (3.451; 0.49), (3.393; 1.00), (3.379; 1.36), (3.308; 1853.88), (3.284; 52.64), (3.225; 0.83), (3.222; 0.77), (3.192; 0.50), (3.184; 0.42), (3.177; 0.42), (2.859; 2.41), (2.731; 0.44), (2.677; 8.46), (2.669; 9.78), (2.621; 0.60), (2.581; 1.67), (2.565; 15.00), (2.539; 3.75), (2.522; 8.30), (2.509; 118.29), (2.505; 222.13), (2.500; 290.90), (2.496; 201.03), (2.491; 96.93), (2.405; 0.94), (2.384; 0.42), (2.358; 0.41), (2.332; 1.62), (2.327; 2.10), (2.322; 1.72), (2.290; 0.42), (2.276; 0.78), (2.214; 6.07), (2.132; 0.84), (2.096; 0.44), (2.069; 0.86), (2.060; 0.60), (2.056; 0.68), (1.987; 1.06), (1.979; 3.77), (1.974; 3.78), (1.942; 1.04), (1.937; 1.21), (1.908; 0.68), (1.398; 1.10), (1.235; 0.89), (1.193; 0.36), (1.175; 0.50), (0.890; 0.79), (0.859; 2.38), (−0.000; 18.75), (−0.008; 0.80)


 


16




3.66
615
(10.559; 0.88), (8.557; 0.59), (8.554; 0.62), (8.546; 0.68), (8.542; 0.60), (8.245; 0.56), (8.241; 0.59), (8.224; 0.62), (8.220; 0.57), (7.891; 1.23), (7.841; 0.78), (7.793; 0.93), (7.699; 1.35), (7.687; 0.62), (7.678; 0.62), (7.666; 0.58), (6.698; 2.39), (3.382; 0.61), (3.303; 675.53), (3.280; 8.35), (2.673; 0.79), (2.669; 1.03), (2.664; 0.81), (2.539; 2.14), (2.508; 62.10), (2.504; 110.51), (2.500; 139.90), (2.495; 95.96), (2.491; 46.52), (2.331; 0.78), (2.327; 0.98), (2.322; 0.74), (2.220; 3.38), (2.069; 1.19), (1.241; 15.00), (1.222; 0.51), (−0.000; 18.33), (−0.008; 0.76)


 


17




2.99
544
(10.639; 4.11), (10.175; 0.52), (9.119; 4.43), (9.113; 4.56), (8.551; 3.44), (8.542; 3.34), (8.539; 3.45), (8.462; 2.82), (8.456; 2.78), (8.440; 2.96), (8.434; 2.98), (8.412; 0.37), (8.339; 1.38), (8.235; 2.93), (8.215; 3.10), (7.994; 0.66), (7.911; 2.56), (7.877; 3.03), (7.801; 0.76), (7.798; 0.77), (7.764; 4.04), (7.677; 2.51), (7.666; 2.59), (7.657; 2.53), (7.646; 2.30), (7.512; 0.60), (6.983; 4.84), (6.962; 4.97), (5.747; 0.42), (4.445; 2.46), (4.428; 7.40), (4.410; 7.46), (4.392; 2.45), (3.957; 0.69), (3.427; 0.47), (3.304; 457.99), (3.234; 0.43), (3.231; 0.39), (2.859; 0.35), (2.742; 0.41), (2.732; 0.61), (2.686; 13.10), (2.675; 12.24), (2.634; 0.47), (2.619; 0.45), (2.580; 0.79), (2.539; 6.39), (2.501; 135.51), (2.327; 0.95), (2.277; 2.77), (2.239; 14.53), (2.132; 2.49), (2.070; 1.41), (2.049; 0.30), (1.987; 0.51), (1.360; 7.59), (1.342; 15.00), (1.325; 7.28), (1.293; 0.41), (1.236; 1.22), (1.175; 0.40), (−0.000; 6.60)


 


18




3.01
568
(10.676; 3.73), (9.398; 2.95), (8.763; 1.83), (8.744; 1.84), (8.739; 1.68), (8.548; 2.82), (8.544; 2.84), (8.536; 2.89), (8.532; 2.58), (8.354; 1.76), (8.342; 1.72), (8.239; 2.72), (8.235; 2.54), (8.219; 2.95), (8.215; 2.55), (8.156; 3.18), (8.136; 2.88), (8.005; 4.39), (7.889; 3.43), (7.886; 3.40), (7.769; 3.80), (7.766; 3.38), (7.679; 2.62), (7.668; 2.56), (7.659; 2.42), (7.647; 2.32), (5.746; 1.06), (3.305; 946.34), (2.687; 9.85), (2.676; 10.12), (2.628; 0.31), (2.539; 2.95), (2.505; 136.08), (2.500; 169.46), (2.496; 119.21), (2.383; 0.37), (2.332; 1.05), (2.327; 1.31), (2.322; 1.04), (2.291; 0.33), (2.278; 0.86), (2.245; 15.00), (2.132; 0.66), (2.069; 0.59), (1.987; 0.73), (1.398; 1.26), (1.236; 1.18), (1.175; 0.43), (0.008; 0.44), (−0.000; 8.71)


 


19




3.85
610
(10.616; 0.74), (9.388; 0.64), (8.757; 0.35), (8.754; 0.36), (8.744; 0.38), (8.741; 0.39), (8.532; 0.45), (8.530; 0.51), (8.524; 0.50), (8.522; 0.51), (8.239; 0.33), (8.225; 0.36), (8.156; 0.69), (8.143; 0.66), (8.026; 0.66), (7.867; 0.83), (7.715; 0.53), (7.669; 0.28), (7.663; 0.29), (5.761; 0.43), (3.568; 0.45), (3.386; 0.93), (3.360; 342.69), (3.336; 5.04), (3.329; 0.30), (2.616; 0.34), (2.525; 0.94), (2.522; 1.17), (2.519; 1.27), (2.510; 17.53), (2.507; 37.51), (2.504; 51.34), (2.501; 37.25), (2.498; 17.32), (2.388; 0.32), (2.240; 1.86), (2.077; 0.46), (1.910; 0.32), (1.255; 13.50), (−0.000; 0.77)


 


20




2.77
574
(10.775; 2.80), (8.973; 4.95), (8.972; 4.87), (8.563; 2.74), (8.560; 3.00), (8.552; 3.00), (8.548; 2.89), (8.341; 1.39), (8.329; 1.40), (8.318; 0.49), (8.252; 2.75), (8.248; 2.77), (8.231; 3.09), (8.228; 2.87), (8.168; 3.59), (7.882; 3.15), (7.879; 3.31), (7.765; 3.57), (7.761; 3.27), (7.694; 2.91), (7.682; 2.81), (7.673; 2.74), (7.661; 2.72), (4.058; 0.70), (4.040; 2.11), (4.022; 2.12), (4.004; 0.74), (3.622; 0.34), (3.340; 0.35), (3.290; 320.52), (2.691; 9.32), (2.679; 9.81), (2.668; 0.96), (2.664; 0.62), (2.538; 0.71), (2.522; 2.52), (2.517; 4.04), (2.508; 38.37), (2.504; 76.37), (2.499; 102.94), (2.495; 72.38), (2.490; 33.42), (2.330; 0.50), (2.326; 0.66), (2.321; 0.45), (2.241; 15.00), (2.068; 0.83), (1.986; 9.51), (1.399; 3.66), (1.237; 0.41), (1.193; 2.64), (1.175; 5.37), (1.157; 2.56), (−0.000; 6.67)


 


21




3.24
602
(10.727; 2.06), (8.974; 3.48), (8.973; 3.39), (8.545; 1.91), (8.542; 2.06), (8.534; 2.10), (8.530; 2.02), (8.236; 1.94), (8.232; 1.93), (8.215; 2.32), (8.212; 2.32), (8.203; 2.91), (8.173; 1.28), (8.154; 1.28), (7.874; 2.25), (7.871; 2.36), (7.731; 2.50), (7.727; 2.31), (7.686; 2.01), (7.675; 1.96), (7.666; 1.87), (7.654; 1.88), (4.040; 0.49), (4.022; 0.49), (3.948; 0.57), (3.932; 0.87), (3.913; 0.83), (3.897; 0.59), (3.300; 108.65), (2.673; 0.33), (2.668; 0.44), (2.664; 0.31), (2.538; 0.43), (2.522; 1.59), (2.517; 2.52), (2.508; 24.74), (2.504; 49.28), (2.499; 66.35), (2.495; 46.51), (2.490; 21.53), (2.326; 0.42), (2.249; 10.36), (2.068; 0.52), (1.986; 2.16), (1.399; 3.12), (1.193; 0.63), (1.175; 1.21), (1.158; 0.61), (1.061; 15.00), (1.044; 14.84), (−0.000; 5.15)


 


22




4.43
700
(10.271; 1.47), (8.493; 3.21), (8.489; 3.38), (8.481; 3.52), (8.477; 3.35), (8.340; 7.59), (8.185; 1.40), (8.174; 1.38), (8.137; 3.12), (8.133; 3.08), (8.117; 3.47), (8.113; 3.16), (7.771; 3.64), (7.758; 5.94), (7.585; 3.27), (7.573; 3.10), (7.564; 2.99), (7.553; 3.09), (7.455; 2.82), (7.450; 3.09), (7.332; 3.39), (7.326; 3.14), (4.208; 1.45), (4.190; 2.64), (4.181; 1.84), (4.168; 2.44), (4.051; 2.36), (4.037; 2.09), (4.028; 2.63), (4.022; 1.03), (4.010; 1.32), (3.303; 943.61), (3.282; 3.11), (2.679; 11.18), (2.668; 11.68), (2.539; 2.21), (2.522; 4.95), (2.517; 7.51), (2.509; 75.70), (2.504; 144.01), (2.500; 190.84), (2.495; 129.18), (2.491; 59.60), (2.336; 0.44), (2.331; 0.95), (2.327; 1.34), (2.322; 0.90), (2.318; 0.41), (2.169; 16.00), (2.069; 1.06), (1.987; 1.20), (1.398; 0.41), (1.237; 2.53), (1.193; 0.36), (1.175; 0.70), (1.157; 0.37), (0.008; 0.91), (−0.000; 24.12), (−0.009; 0.76)


 


23




4.08
691
(10.535; 4.53), (8.503; 0.50), (8.497; 3.16), (8.493; 3.40), (8.485; 3.42), (8.481; 3.22), (8.341; 8.02), (8.324; 1.36), (8.315; 1.91), (8.302; 1.79), (8.142; 3.22), (8.139; 3.20), (8.122; 3.57), (8.118; 3.16), (7.860; 3.47), (7.857; 3.63), (7.787;  7.64), (7.773; 3.75), (7.749; 3.99), (7.745; 3.71), (7.590; 3.33), (7.578; 3.12), (7.570; 3.15), (7.558; 3.09), (7.552; 1.12), (4.211; 1.59), (4.194; 3.01), (4.184; 1.97), (4.171; 2.52), (4.140; 0.68), (4.134; 0.55), (4.056; 2.82), (4.039; 4.96), (4.032; 2.87), (4.021; 3.81), (4.013; 1.62), (4.003; 1.30), (3.756; 0.67), (3.361; 0.68), (3.354; 0.84), (3.300; 1105.50), (2.689; 10.86), (2.677; 11.26), (2.669; 2.75), (2.664; 2.45), (2.652; 1.02), (2.539; 3.57), (2.522; 8.46), (2.517; 13.57), (2.509; 123.25), (2.504; 229.19), (2.500; 299.50), (2.495; 201.66), (2.491; 92.17), (2.336; 0.74), (2.331; 1.51), (2.326; 1.93), (2.322; 1.39), (2.317; 0.60), (2.221; 16.00), (2.069; 1.67), (1.987; 13.51), (1.837; 0.50), (1.831; 0.93), (1.398; 1.03), (1.237; 1.32), (1.193; 3.86), (1.175; 7.67), (1.157; 3.84), (0.008; 1.21), (−0.000; 28.43), (−0.008; 0.85)


 


24




5.29
742
(10.218; 0.94), (8.483; 0.67), (8.479; 0.70), (8.471; 0.73), (8.467; 0.71), (8.336; 1.74), (8.139; 0.67), (8.135; 0.67), (8.118; 0.75), (8.115; 0.68), (7.801; 2.10), (7.769; 0.78), (7.587; 0.69), (7.575; 0.66), (7.566; 0.66), (7.555; 0.65), (7.489; 1.02), (7.426; 0.70), (7.420; 0.76), (7.254; 0.79), (7.247; 0.74), (4.202; 0.33), (4.185; 0.60), (4.176; 0.42), (4.163; 0.55), (4.049; 0.52), (4.036; 0.48), (4.027; 0.60), (3.305; 134.81), (2.522; 0.90), (2.518; 1.40), (2.509; 13.53), (2.505; 25.66), (2.500; 33.89), (2.496; 23.38), (2.491; 11.06), (2.165; 3.53), (1.987; 0.55), (1.254; 16.00), (1.175; 0.32), (−0.000; 2.12)


 


25




4.84
733
(10.443; 1.00), (8.484; 0.64), (8.480; 0.69), (8.472; 0.70), (8.468; 0.67), (8.338; 1.84), (8.138; 0.62), (8.134; 0.61), (8.118; 0.67), (8.114; 0.64), (7.820; 1.89), (7.770; 0.82), (7.689; 1.86), (7.587; 0.62), (7.575; 0.60), (7.566; 0.59), (7.555; 0.59), (4.205; 0.35), (4.188; 0.62), (4.179; 0.46), (4.165; 0.58), (4.052; 0.56), (4.039; 0.62), (4.030; 0.64), (4.021; 0.33), (4.012; 0.33), (3.304; 203.13), (3.280; 2.47), (2.539; 0.36), (2.522; 1.18), (2.518; 1.85), (2.509; 17.61), (2.505; 33.34), (2.500; 44.02), (2.496; 30.12), (2.491; 14.11), (2.222; 3.43), (1.987; 0.59), (1.290; 0.66), (1.259; 16.00), (1.175; 0.35), (1.107; 0.57), (−0.000; 3.10)


 


26




4.97
728
(10.236; 2.96), (8.480; 2.20), (8.476; 2.35), (8.469; 2.41), (8.465; 2.30), (8.340; 5.46), (8.127; 2.19), (8.123; 2.17), (8.107; 2.44), (8.103; 2.25), (7.984; 1.56), (7.965; 1.58), (7.788; 6.09), (7.770; 2.51), (7.582; 2.29), (7.570; 2.16), (7.562; 2.10), (7.550; 2.16), (7.449; 2.21), (7.447; 2.23), (7.443; 2.40), (7.292; 2.54), (7.286; 2.37), (5.747; 0.91), (4.206; 1.04), (4.188; 1.89), (4.179; 1.31), (4.165; 1.71), (4.049; 1.66), (4.036; 1.49), (4.027; 1.87), (4.009; 0.91), (3.950; 0.64), (3.933; 0.96), (3.914; 0.93), (3.898; 0.63), (3.310; 241.62), (2.540; 0.36), (2.523; 1.14), (2.510; 15.41), (2.505; 28.56), (2.501; 37.18), (2.496; 25.31), (2.492; 11.74), (2.176; 11.11), (1.236; 0.83), (1.059; 16.00), (1.043; 15.80), (−0.000; 1.92)


 


27




4.55
719
(10.493; 3.34), (8.482; 2.09), (8.478; 2.18), (8.470; 2.26), (8.467; 2.14), (8.341; 6.10), (8.129; 2.88), (8.126; 3.63), (8.109; 3.35), (8.106; 3.55), (7.853; 2.59), (7.850; 2.68), (7.814; 5.39), (7.772; 2.78), (7.715; 2.84), (7.711; 2.71), (7.584; 2.08), (7.573; 2.00), (7.564; 1.90), (7.552; 1.90), (5.747; 3.75), (4.209; 1.12), (4.191; 2.05), (4.182; 1.45), (4.169; 1.91), (4.053; 1.82), (4.039; 1.62), (4.031; 2.04), (4.012; 1.03), (3.948; 0.70), (3.931; 1.07), (3.913; 1.05), (3.896; 0.68), (3.305; 178.70), (2.670; 0.33), (2.540; 0.41), (2.523; 1.29), (2.509; 18.63), (2.505; 34.66), (2.501; 45.04), (2.496; 31.34), (2.492; 14.92), (2.233; 11.39), (1.477; 0.40), (1.264; 0.44), (1.248; 0.51), (1.236; 0.69), (1.120; 0.32), (1.103; 0.34), (1.063; 16.00), (1.046; 15.82), (−0.000; 2.14)


 


28




2.64
613
(10.262; 4.03), (8.466; 3.17), (8.462; 3.37), (8.455; 3.48), (8.451; 3.32), (8.415; 3.19), (8.410; 3.24), (8.188; 0.62), (8.177; 1.74), (8.166; 1.72), (8.155; 0.59), (8.108; 3.14), (8.105; 3.16), (8.088; 3.55), (8.084; 3.28), (7.847; 2.12), (7.841; 2.04), (7.827; 2.39), (7.820; 2.33), (7.586; 7.90), (7.554; 3.45), (7.543; 6.99), (7.534; 3.31), (7.522; 6.54), (7.447; 3.07), (7.446; 3.11), (7.441; 3.43), (7.326; 3.68), (7.319; 3.39), (5.747; 1.72), (4.482; 8.54), (4.039; 0.51), (4.021; 0.55), (3.850; 1.87), (3.832; 2.94), (3.826; 2.24), (3.810; 2.25), (3.485; 2.35), (3.464; 2.88), (3.445; 1.84), (3.305; 325.95), (2.678; 11.00), (2.666; 10.90), (2.539; 0.66), (2.522; 1.96), (2.517; 3.05), (2.509; 28.85), (2.504; 54.37), (2.500; 71.65), (2.496; 48.90), (2.491; 22.92), (2.331; 0.37), (2.327; 0.50), (2.322; 0.37), (2.158; 16.00), (2.070; 0.39), (1.987; 2.37), (1.193; 0.69), (1.175; 1.37), (1.157; 0.67), (−0.000; 3.04)


 


29




2.31
604
(10.538; 4.58), (8.470; 2.83), (8.466; 2.98), (8.458; 3.06), (8.455; 2.94), (8.416; 3.57), (8.410; 3.59), (8.322; 0.72), (8.311; 1.83), (8.300; 1.84), (8.113; 2.74), (8.110; 2.72), (8.093; 3.04), (8.090; 2.82), (7.848; 5.79), (7.827; 2.46), (7.821; 2.34), (7.743; 3.98), (7.739; 3.78), (7.613; 7.31), (7.559; 2.91), (7.548;  3.33), (7.543; 4.87), (7.527; 3.11), (7.523; 3.94), (7.445; 0.70), (5.747; 2.64), (4.484; 9.31), (3.854; 2.00), (3.836; 3.18), (3.814; 2.43), (3.714; 1.34), (3.518; 0.33), (3.488; 2.60), (3.468; 3.25), (3.449; 2.08), (3.420; 0.33), (3.401; 0.38), (3.309; 952.42), (3.252; 0.56), (2.687; 10.28), (2.675; 10.79), (2.539; 1.35), (2.523; 4.50), (2.509; 64.64), (2.505; 120.25), (2.500; 156.42), (2.496; 108.56), (2.492; 51.43), (2.332; 0.78), (2.327; 1.03), (2.322; 0.75), (2.210; 16.00), (1.987; 0.53), (1.941; 0.96), (1.236; 0.74), (1.175; 0.36), (−0.000; 7.18)


 


30




3.02
646
(10.424; 1.01), (8.458; 0.70), (8.455; 0.75), (8.447; 0.77), (8.443; 0.74), (8.413; 0.74), (8.408; 0.74), (8.109; 0.69), (8.105; 0.70), (8.089; 0.78), (8.085; 0.72), (7.846; 0.49), (7.840; 0.48), (7.825; 0.64), (7.819; 1.24), (7.815; 0.88), (7.682; 1.71), (7.638; 1.81), (7.556; 0.74), (7.544; 0.85), (7.541; 1.00), (7.536; 0.77), (7.524; 0.79), (7.521; 0.83), (4.481; 1.94), (3.852; 0.43), (3.834; 0.67), (3.828; 0.51), (3.812; 0.51), (3.483; 0.53), (3.463; 0.65), (3.443; 0.42), (3.305; 88.33), (2.522; 0.49), (2.518; 0.78), (2.509; 7.18), (2.505; 13.53), (2.500; 17.82), (2.496; 12.20), (2.491; 5.72), (2.209; 3.49), (1.987; 1.20), (1.257; 16.00), (1.193; 0.36), (1.175; 0.70), (1.157; 0.34), (−0.000; 0.53)


 


31




3.51
591
(7.96; 0.180), (7.94; 0240), (7.81; 0.160), (7.61; 0.180), (7.43; 0.180), (7.42; 0.210), (5.69; 0.310), (3.16; 0.540), (3.11; 332.660), (3.06; 0.260), (3.05; 0.190), (2.66; 0.230), (2.66; 0.310), (2.65; 0.190), (2.53; 0.700), (2.51; 0.940), (2.50; 16.140), (2.49; 32.390), (2.49; 45.170), (2.48; 32.230), (2.48; 16.000), (2.32; 0.200), (2.31; 0.300), (2.31; 0.190), (2.17; 0.750), (1.36; 0.250), (1.24; 0.300), (0.01; 0.190), (−0.00; 5.170), (−0.01; 0.220)


 


32




2.09
630
(8.68; 2.520), (8.54; 1.080), (8.54; 1.150), (8.54; 1.170), (8.53; 1.150), (8.52; 2.450), (8.52; 2.530), (8.51; 2.640), (8.51; 2.530), (8.30; 7.120), (8.27; 1.120), (8.26; 1.120), (8.19; 1.080), (8.19; 1.150), (8.18; 1.120), (8.17; 1.060), (8.16; 2.440), (8.16; 2.410), (8.15; 2.640), (8.15; 2.480), (8.03; 15.520), (7.71; 0.950), (7.70; 0.940), (7.69; 0.990), (7.69; 0.950), (7.66; 1.980), (7.66; 1.990), (7.64; 2.440), (7.64; 3.110), (7.63; 1.080), (7.63; 1.080), (7.62; 1.100), (7.62; 2.460), (7.61; 2.410), (7.60; 2.350), (7.60; 2.330), (7.47; 3.870), (7.47; 3.790), (7.47; 3.430), (7.46; 1.550), (7.45; 1.230), (7.45; 3.650), (7.44; 2.960), (7.43; 0.940), (7.43; 0.960), (7.42; 1.730), (7.40; 0.950), (7.40; 0.940), (7.37; 1.080), (7.37; 2.310), (7.32; 4.160), (7.32; 1.790), (7.32; 1.700), (7.30; 2.090), (7.30; 1.970), (7.21; 1.210), (7.21; 0.930), (7.20; 1.740), (5.03; 5.430), (3.52; 13.060), (3.17; 15.000), (3.08; 9.160), (2.95; 17.820), (2.92; 9.200), (2.92; 18.680), (2.92; 25.870), (2.91; 18.280), (2.91; 8.810), (2.81; 12.810), (2.81; 12.790), (2.79; 17.540), (2.75; 10.300), (2.75; 20.340), (2.75; 28.540), (2.74; 20.370), (2.74; 9.890), (2.40; 1.820), (2.25; 16.000), (2.24; 6.720), (0.00; 7.860)


 


33




2.49
664



 


34




4.38
763
(10.03; 0.330), (8.40; 1.120), (8.40; 1.120), (8.39; 1.150), (8.38; 1.070), (8.36; 2.910), (8.29; 1.240), (8.03; 1.010), (8.03; 0.930), (8.01; 1.080), (8.01; 1.010), (7.97; 0.280), (7.95; 0.570), (7.93; 0.540), (7.53; 1.030), (7.52; 0.990), (7.51; 0.940), (7.49; 0.880), (7.41; 1.140), (7.41; 1.210), (7.32; 1.240), (7.31; 1.050), (7.14; 1.840), (4.26; 4.280), (3.39; 0.340), (3.38; 0.550), (3.36; 0.540), (3.34; 0.330), (3.21; 0.320), (3.19; 0.530), (3.12; 195.600), (3.07; 0.390), (2.66; 0.300), (2.53; 2.450), (2.50; 17.530), (2.49; 33.800), (2.49; 45.830), (2.48; 32.500), (2.48; 16.000), (2.32; 0.280), (2.31; 0.320), (2.13; 6.220), (2.04; 0.260), (1.36; 0.280), (1.23; 1.040), (1.22; 1.010), (1.10; 3.630), (1.08; 3.580), (0.89; 0.300), (0.88; 0.320), (0.87; 0.600), (0.86; 0.430), (0.85; 0.560), (0.84; 0.340), (0.83; 0.260), (0.54; 0.330), (0.52; 0.330), (0.40; 0.330), (0.39; 0.520), (0.38; 0.510), (0.37; 0.530), (0.36; 0.330), (0.35; 0.230), (0.31; 0.260), (0.30; 0.410), (0.28; 0.440), (0.28; 0.520), (0.26; 0.510), (0.26; 0.250), (0.24; 0.320), (0.23; 0.320), (0.22; 0.460), (0.21; 0.580), (0.19; 0.470), (0.17; 0.290), (0.16; 0.500), (0.15; 0.570), (0.13; 0.440), (0.12; 0.270), (−0.00; 5.860)


 


35




4.1
737
(10.03; 0.800), (8.56; 0.170), (8.40; 1.620), (8.39; 1.620), (8.39; 1.630), (8.38; 1.490), (8.35; 4.440), (8.29; 1.850), (8.03; 1.470), (8.03; 1.400), (8.01; 1.560), (8.01; 1.430), (7.88; 0.190), (7.87; 0.820), (7.85; 0.810), (7.53; 1.550), (7.51; 1.490), (7.51; 1.430), (7.49; 1.310), (7.40; 1.790), (7.40; 1.900), (7.31; 2.020), (7.31; 1.670), (7.14; 2.720), (4.27; 6.340), (4.20; 0.170), (3.97; 0.180), (3.96; 0.530), (3.94; 0.770), (3.92; 0.760), (3.90; 0.520), (3.89; 0.190), (3.29; 0.160), (3.16; 0.600), (3.12; 134.430), (2.66; 0.280), (2.53; 2.240), (2.52; 0.540), (2.50; 17.440), (2.49; 33.400), (2.49; 45.180), (2.48; 32.220), (2.48; 16.000), (2.31; 0.330), (2.29; 0.290), (2.13; 9.990), (1.36; 0.770), (1.24; 0.240), (1.19; 0.860), (1.17; 0.810), (1.11; 0.170), (1.10; 0.330), (1.07; 12.150), (1.05; 12.140), (0.86; 0.260), (0.84; 0.260), (0.83; 0.260), (0.81; 0.200), (−0.00; 7.970)


 


36




3.62
709
(10.07; 0.570), (8.41; 0.690), (8.40; 0.720), (8.40; 0.750), (8.39; 0.710), (8.35; 1.880), (8.29; 0.800), (8.04; 0.960), (8.04; 0.880), (8.02; 0.810), (8.02; 0.780), (7.53; 0.730), (7.52; 0.750), (7.51; 0.690), (7.50; 0.680), (7.41; 0.720), (7.40; 0.830), (7.34; 0.870), (7.34; 0.790), (7.12; 1.220), (4.27; 2.120), (3.25; 0.170), (3.18; 0.500), (3.17; 0.690), (3.12; 238.920), (3.08; 0.270), (3.08; 0.300), (3.06; 0.200), (2.69; 2.760), (2.68; 2.700), (2.66; 0.270), (2.66; 0.330), (2.53; 2.650), (2.51; 1.200), (2.50; 17.760), (2.49; 34.530), (2.49; 47.050), (2.48; 33.050), (2.48; 16.000), (2.32; 0.200), (2.32; 0.260), (2.31; 0.320), (2.13; 4.390), (1.36; 0.300), (1.24; 0.170), (−0.00; 5.680)


 


37




2.58
607
(8.44; 0.850), (8.44; 0.870), (8.43; 0.910), (8.42; 0.810), (8.06; 0.960), (8.06; 0.960), (8.04; 1.140), (8.04; 1.110), (7.99; 0.830), (7.99; 0.790), (7.98; 0.900), (7.97; 0.890), (7.94; 0.210), (7.61; 0.320), (7.60; 0.440), (7.59; 1.270), (7.58; 1.380), (7.58; 0.780), (7.56; 1.090), (7.56; 0.850), (7.54; 0.510), (7.54; 1.020), (7.52; 0.960), (7.51; 0.860), (7.50; 0.930), (7.50; 0.720), (7.50; 0.590), (7.48; 0.800), (7.46; 0.470), (7.46; 0.470), (7.41; 0.980), (7.40; 1.050), (7.35; 1.210), (7.34; 1.000), (7.09; 1.670), (6.87; 0.830), (6.39; 0.320), (4.22; 3.860), (4.18; 0.490), (3.60; 0.190), (3.31; 0.160), (3.29; 0.180), (3.27; 0.210), (3.22; 0.340), (3.11; 125.070), (2.73; 0.240), (2.71; 3.270), (2.70; 3.260), (2.66; 0.400), (2.65; 0.300), (2.53; 1.070), (2.50; 20.220), (2.49; 36.300), (2.49; 46.540), (2.48; 32.590), (2.48; 16.000), (2.45; 0.210), (2.38; 3.210), (2.32; 0.250), (2.31; 0.280), (2.29; 0.930), (2.18; 1.360), (2.14; 5.700), (2.04; 0.190), (1.76; 0.180), (1.36; 10.740), (1.25; 0.200), (1.19; 0.210), (1.17; 0.190), (−0.00; 9.080)


 


38




3.06
635
(8.43; 1.010), (8.42; 1.000), (8.41; 1.030), (8.41; 0.960), (8.05; 0.970), (8.05; 0.900), (8.03; 1.010), (8.03; 0.950), (8.02; 0.260), (7.99; 1.000), (7.97; 1.290), (7.97; 1.060), (7.96; 0.290), (7.84; 0.590), (7.82; 0.570), (7.60; 0.420), (7.59; 1.520), (7.58; 2.010), (7.56; 1.050), (7.56; 0.870), (7.55; 0.420), (7.54; 0.420), (7.53; 1.000), (7.52; 1.000), (7.51; 0.960), (7.50; 1.390), (7.49; 0.680), (7.48; 0.850), (7.48; 0.910), (7.46; 0.570), (7.46; 0.460), (7.40; 1.190), (7.40; 1.210), (7.32; 1.250), (7.31; 1.090), (7.12; 1.750), (6.87; 1.000), (6.39; 0.380), (4.22; 4.450), (4.14; 0.600), (3.98; 0.330), (3.96; 0.500), (3.94; 0.470), (3.93; 0.380), (3.93; 0.340), (3.31; 0.240), (3.31; 0.210), (3.30; 0.490), (3.28; 0.570), (3.26; 0.510), (3.25; 0.350), (3.11; 127.470), (3.01; 0.320), (2.99; 0.230), (2.66; 0.330), (2.53; 1.020), (2.50; 21.310), (2.49; 37.380), (2.49; 46.790), (2.48; 32.700), (2.48; 16.000), (2.32; 0.260), (2.31; 0.310), (2.30; 1.120), (2.18; 1.580), (2.17; 0.370), (2.15; 6.170), (2.04; 0.310), (1.36; 12.100), (1.31; 0.270), (1.25; 0.300), (1.19; 4.470), (1.17; 4.250), (1.12; 0.190), (1.11; 0.230), (1.08; 7.300), (1.06; 7.150), (0.86; 0.200), (0.84; 0.240), (−0.00; 3.990)


 


39




2.8
633
(10.01; 0.620), (8.44; 1.540), (8.44; 1.350), (8.43; 1.570), (8.42; 1.230), (8.10; 0.440), (8.08; 0.910), (8.06; 1.570), (8.06; 1.290), (8.04; 1.530), (8.04; 1.270), (8.00; 1.310), (7.99; 1.280), (7.98; 1.430), (7.97; 1.250), (7.97; 1.310), (7.61; 0.730), (7.59; 2.140), (7.59; 2.450), (7.58; 1.520), (7.57; 1.660), (7.57; 1.550), (7.55; 0.760), (7.54; 1.500), (7.52; 1.450), (7.52; 1.400), (7.50; 2.050), (7.48; 1.190), (7.47; 0.630), (7.46; 0.630), (7.40; 1.470), (7.40; 1.530), (7.30; 1.780), (7.29; 1.550), (7.12; 2.430), (7.07; 0.430), (6.76; 0.510), (4.25; 0.610), (4.23; 5.170), (4.20; 1.100), (3.81; 0.430), (3.80; 0.530), (3.47; 0.470), (3.12; 36.230), (2.75; 0.530), (2.74; 0.690), (2.73; 0.650), (2.73; 0.510), (2.57; 0.440), (2.55; 0.480), (2.54; 0.580), (2.53; 1.200), (2.50; 20.470), (2.49; 36.240), (2.49; 46.040), (2.48; 32.380), (2.48; 16.000), (2.41; 0.430), (2.30; 2.070), (2.18; 0.520), (2.14; 8.360), (2.12; 1.510), (1.74; 0.450), (1.36; 1.120), (1.19; 1.010), (1.17; 0.610), (0.70; 0.580), (0.69; 0.560), (0.68; 0.890), (0.66; 1.090), (0.66; 1.100), (0.64; 1.620), (0.63; 1.600), (0.61; 0.630), (0.50; 0.700), (0.49; 1.780), (0.48; 1.790), (0.48; 1.440), (0.46; 0.520), (−0.00; 1.720)


 


40




3.84
737
(8.41; 2.35), (8.41; 2.93), (8.40; 4.77), (8.40; 3.73), (8.38; 0.47), (8.38; 0.45), (8.37; 0.42), (8.37; 0.41), (8.14; 0.60), (8.12; 3.82), (8.12; 2.77), (8.10; 0.85), (8.10; 0.87), (8.04; 2.26), (8.04; 2.29), (8.02; 2.42), (8.02; 2.31), (7.96; 0.23), (7.96; 0.22), (7.94; 0.25), (7.94; 0.26), (7.85; 0.92), (7.83; 0.95), (7.53; 2.37), (7.52; 2.34), (7.51; 2.22), (7.50; 2.16), (7.46; 0.24), (7.45; 0.23), (7.44; 0.23), (7.43; 0.22), (7.40; 2.01), (7.40; 2.07), (7.39; 2.40), (7.39; 2.27), (7.31; 2.30), (7.31; 2.11), (7.14; 3.27), (6.87; 0.57), (6.46; 0.24), (4.57; 0.24), (4.33; 0.32), (4.31; 8.42), (4.20; 1.24), (3.96; 0.61), (3.95; 0.93), (3.93; 0.93), (3.91; 0.65), (3.89; 0.26), (3.28; 0.32), (3.26; 0.45), (3.24; 0.37), (3.11; 6.59), (2.86; 0.46), (2.53; 0.70), (2.51; 0.57), (2.50; 9.40), (2.49; 18.80), (2.49; 26.12), (2.48; 18.49), (2.48; 9.13), (2.30; 0.60), (2.18; 0.89), (2.13; 12.54), (1.36; 7.82), (1.19; 0.27), (1.17; 4.37), (1.15; 4.29), (1.13; 0.49), (1.12; 0.49), (1.10; 0.28), (1.10; 0.31), (1.07; 16.00), (1.05; 15.86), (1.02; 0.63), (1.01; 0.57), (0.84; 0.80), (0.83; 0.27), (0.81; 0.25), (−0.00; 4.34)


 


41




3.63
737
(8.41; 2.11), (8.41; 2.24), (8.40; 2.23), (8.40; 2.17), (8.19; 4.54), (8.17; 5.37), (8.16; 0.67), (8.14; 0.21), (8.04; 2.36), (8.04; 2.45), (8.02; 2.69), (8.02; 2.58), (8.00; 0.42), (7.99; 0.40), (7.97; 0.44), (7.97; 0.43), (7.96; 0.43), (7.95; 0.43), (7.93; 1.21), (7.91; 1.72), (7.89; 0.87), (7.82; 1.00), (7.81; 1.00), (7.53; 2.36), (7.51; 2.33), (7.51; 2.30), (7.49; 2.19), (7.40; 1.98), (7.40; 2.05), (7.39; 2.31), (7.39; 2.16), (7.30; 2.29), (7.30; 2.05), (7.13; 3.15), (6.88; 0.27), (4.31; 7.85), (4.24; 0.53), (3.98; 0.23), (3.96; 0.59), (3.94; 0.92), (3.92; 0.89), (3.91; 0.63), (3.89; 0.22), (3.68; 0.90), (3.31; 0.49), (3.30; 1.20), (3.28; 1.63), (3.26; 1.27), (3.25; 0.57), (3.11; 18.81), (2.86; 0.43), (2.66; 0.22), (2.53; 0.93), (2.51; 0.76), (2.50; 12.11), (2.49; 24.22), (2.49; 33.58), (2.48; 23.79), (2.48; 11.70), (2.31; 0.22), (2.30; 0.64), (2.18; 0.24), (2.14; 12.16), (1.36; 1.61), (1.22; 0.22), (1.20; 15.72), (1.18; 15.43), (1.13; 0.45), (1.12; 0.46), (1.10; 0.28), (1.09; 0.41), (1.07; 16.00), (1.05; 15.80), (0.86; 0.52), (0.84; 0.74), (0.84; 0.53), (0.83; 0.30), (0.83; 0.31), (0.81; 0.29), (−0.00; 3.99)


 


42




3.94
737
(8.41; 2.09), (8.41; 2.27), (8.40; 2.42), (8.40; 2.44), (8.39; 0.39), (8.39; 0.34), (8.37; 0.17), (8.34; 1.43), (8.32; 1.91), (8.28; 0.32), (8.19; 1.37), (8.17; 1.08), (8.14; 0.21), (8.12; 2.26), (8.10; 0.38), (8.05; 2.13), (8.04; 2.19), (8.03; 2.38), (8.02; 2.25), (7.97; 0.23), (7.97; 0.20), (7.85; 0.91), (7.83; 0.95), (7.53; 2.32), (7.52; 2.28), (7.51; 2.20), (7.50; 2.17), (7.49; 0.17), (7.40; 1.97), (7.40; 2.07), (7.40; 2.37), (7.40; 2.22), (7.32; 2.26), (7.31; 2.12), (7.14; 3.07), (6.87; 0.51), (6.50; 0.17), (6.40; 0.21), (4.33; 8.28), (4.23; 0.88), (3.98; 0.21), (3.96; 0.60), (3.95; 0.91), (3.93; 0.92), (3.91; 0.62), (3.89; 0.24), (3.29; 0.27), (3.27; 0.35), (3.26; 0.29), (3.11; 6.39), (3.03; 0.18), (2.86; 0.56), (2.53; 0.64), (2.51; 0.50), (2.50; 8.44), (2.49; 16.91), (2.49; 23.45), (2.48; 16.58), (2.48; 8.16), (2.30; 0.62), (2.18; 0.92), (2.13; 12.32), (1.36; 8.50), (1.21; 0.20), (1.19; 0.39), (1.18; 3.60), (1.16; 3.53), (1.13; 0.57), (1.12; 0.59), (1.10; 0.28), (1.07; 16.00), (1.05; 15.84), (1.03; 0.25), (1.01; 0.20), (0.86; 0.35), (0.84; 0.81), (0.83; 0.23), (0.83; 0.29), (0.81; 0.25), (−0.00; 4.06)


 


43




3.25
635
(10.01; 0.39), (8.43; 0.50), (8.43; 0.51), (8.42; 0.52), (8.41; 0.52), (8.06; 0.51), (8.06; 0.52), (8.04; 0.54), (8.04; 0.54), (7.84; 0.59), (7.83; 0.86), (7.83; 0.58), (7.82; 0.25), (7.80; 0.33), (7.79; 0.41), (7.79; 0.27), (7.78; 0.37), (7.77; 0.44), (7.77; 0.31), (7.67; 0.25), (7.66; 0.20), (7.65; 0.36), (7.65; 0.41), (7.65; 0.41), (7.64; 0.36), (7.61; 0.54), (7.59; 0.69), (7.57; 0.26), (7.54; 0.53), (7.52; 0.54), (7.52; 0.52), (7.50; 0.49), (7.40; 0.52), (7.40; 0.55), (7.31; 0.57), (7.31; 0.52), (7.14; 0.78), (4.15; 1.12), (3.95; 0.23), (3.93; 0.25), (3.11; 127.21), (2.86; 0.18), (2.66; 0.24), (2.66; 0.29), (2.65; 0.22), (2.56; 0.17), (2.53; 0.58), (2.51; 1.33), (2.50; 16.85), (2.49; 33.02), (2.49; 45.40), (2.48; 32.33), (2.48; 16.00), (2.33; 0.17), (2.32; 0.21), (2.31; 0.29), (2.31; 0.22), (2.29; 0.19), (2.18; 0.17), (2.15; 2.92), (1.36; 1.49), (1.19; 0.36), (1.17; 0.33), (1.13; 0.17), (1.11; 0.21), (1.07; 3.82), (1.06; 3.73), (0.01; 0.24), (−0.00; 4.95), (−0.01; 0.28)


 


44




2.84
601
(10.01; 0.35), (8.43; 0.35), (8.43; 0.39), (8.42; 0.34), (8.42; 0.35), (8.13; 0.21), (8.06; 0.38), (8.06; 0.38), (8.04; 0.42), (8.04; 0.40), (7.86; 0.50), (7.85; 0.54), (7.84; 0.27), (7.84; 0.66), (7.83; 0.69), (7.81; 0.20), (7.61; 0.26), (7.60; 0.30), (7.60; 0.52), (7.59; 0.66), (7.59; 0.33), (7.57; 0.61), (7.56; 0.19), (7.55; 0.18), (7.54; 0.39), (7.52; 0.39), (7.52; 0.38), (7.50; 0.37), (7.41; 0.37), (7.40; 0.39), (7.31; 0.41), (7.31; 0.39), (7.13; 0.57), (6.87; 0.18), (4.11; 0.57), (4.09; 0.55), (3.96; 0.18), (3.94; 0.18), (3.19; 0.26), (3.11; 146.20), (3.05; 0.17), (2.66; 0.21), (2.66; 0.29), (2.65; 0.22), (2.53; 0.54), (2.51; 1.22), (2.50; 16.79), (2.49; 32.94), (2.49; 45.26), (2.48; 32.20), (2.48; 16.00), (2.32; 0.20), (2.31; 0.29), (2.31; 0.20), (2.18; 0.31), (2.15; 2.13), (1.36; 2.74), (1.19; 0.17), (1.08; 2.78), (1.06; 2.75), (0.01; 0.20), (−0.00; 5.00)


 


45




3.26
669
(10.02; 0.45), (8.45; 0.19), (8.44; 0.63), (8.43; 0.63), (8.42; 0.61), (8.42; 0.62), (8.14; 0.40), (8.11; 0.46), (8.06; 0.52), (8.06; 0.56), (8.04; 0.59), (8.04; 0.52), (7.93; 0.36), (7.91; 0.45), (7.85; 0.22), (7.83; 0.56), (7.81; 0.46), (7.79; 0.37), (7.77; 0.40), (7.76; 0.17), (7.54; 0.62), (7.53; 0.61), (7.52; 0.61), (7.51; 0.60), (7.40; 0.54), (7.40; 0.60), (7.31; 0.61), (7.31; 0.54), (7.14; 0.86), (6.87; 0.18), (4.26; 1.02), (3.97; 0.17), (3.95; 0.27), (3.94; 0.26), (3.35; 0.21), (3.11; 66.87), (2.86; 0.19), (2.66; 0.21), (2.66; 0.31), (2.65; 0.23), (2.57; 0.18), (2.54; 0.22), (2.53; 0.50), (2.50; 16.63), (2.49; 32.76), (2.49; 45.15), (2.48; 32.21), (2.48; 16.00), (2.32; 0.20), (2.31; 0.31), (2.31; 0.20), (2.29; 0.32), (2.18; 0.29), (2.16; 0.20), (2.14; 3.07), (2.04; 0.18), (1.40; 0.24), (1.36; 2.52), (1.19; 0.64), (1.18; 0.60), (1.13; 0.19), (1.11; 0.22), (1.07; 4.05), (1.06; 4.01), (1.03; 0.16), (0.01; 0.29), (−0.00; 6.56), (−0.01; 0.29)


 


46




3.47
669
(8.42; 2.05), (8.41; 2.17), (8.41; 2.18), (8.40; 2.16), (8.39; 0.47), (8.38; 0.46), (8.37; 0.47), (8.37; 0.46), (8.05; 2.49), (8.05; 3.09), (8.04; 2.93), (8.03; 2.95), (8.03; 3.68), (8.02; 3.97), (8.00; 0.89), (7.97; 0.24), (7.96; 0.43), (7.96; 0.45), (7.94; 0.45), (7.94; 0.45), (7.92; 3.85), (7.89; 3.22), (7.88; 0.79), (7.86; 1.02), (7.84; 0.99), (7.53; 2.26), (7.52; 2.22), (7.51; 2.14), (7.50; 2.08), (7.46; 0.38), (7.44; 0.40), (7.44; 0.40), (7.42; 0.39), (7.40; 2.06), (7.40; 2.15), (7.40; 2.47), (7.40; 2.30), (7.32; 2.39), (7.31; 2.18), (7.15; 3.28), (6.87; 0.70), (6.42; 0.67), (6.40; 0.25), (4.19; 8.85), (4.07; 2.01), (3.98; 0.24), (3.97; 0.60), (3.95; 0.93), (3.93; 0.95), (3.91; 0.63), (3.90; 0.25), (3.27; 0.34), (3.25; 0.48), (3.23; 0.41), (3.22; 0.27), (3.11; 6.03), (2.86; 0.34), (2.53; 0.49), (2.50; 10.41), (2.49; 20.76), (2.49; 28.77), (2.48; 20.60), (2.48; 10.32), (2.30; 0.77), (2.18; 1.23), (2.14; 12.70), (1.36; 11.04), (1.19; 0.29), (1.16; 4.48), (1.15; 4.39), (1.13; 0.40), (1.12; 0.37), (1.10; 0.26), (1.07; 16.00), (1.05; 15.90), (0.86; 0.23), (0.84; 0.49), (0.83; 0.22), (0.83; 0.21), (−0.00; 1.35)


 


47




3.25
635
(8.43; 1.93), (8.43; 2.16), (8.42; 2.14), (8.42; 2.15), (8.40; 0.26), (8.40; 0.29), (8.39; 0.25), (8.06; 2.09), (8.05; 2.21), (8.04; 2.42), (8.03; 2.38), (7.97; 0.34), (7.96; 0.28), (7.96; 0.28), (7.85; 1.00), (7.84; 1.26), (7.83; 5.57), (7.83; 2.29), (7.82; 2.13), (7.81; 6.40), (7.80; 1.16), (7.79; 0.82), (7.62; 0.84), (7.61; 5.73), (7.61; 2.05), (7.59; 2.35), (7.59; 4.84), (7.58; 0.81), (7.58; 0.40), (7.57; 0.68), (7.53; 2.26), (7.52; 2.26), (7.51; 2.17), (7.50; 2.14), (7.45; 0.22), (7.41; 2.03), (7.40; 2.12), (7.40; 2.46), (7.40; 2.33), (7.32; 2.36), (7.31; 2.17), (7.13; 3.33), (4.14; 8.77), (4.03; 1.03), (3.99; 0.22), (3.97; 0.63), (3.96; 0.96), (3.94; 0.94), (3.92; 0.62), (3.90; 0.25), (3.28; 0.36), (3.26; 0.46), (3.25; 0.39), (3.23; 0.23), (3.18; 0.30), (3.16; 0.55), (3.11; 22.16), (2.86; 0.61), (2.66; 0.27), (2.53; 0.70), (2.50; 13.66), (2.49; 26.76), (2.49; 36.81), (2.48; 26.15), (2.48; 12.98), (2.31; 0.23), (2.31; 0.24), (2.30; 1.32), (2.15; 12.57), (1.17; 4.36), (1.16; 4.25), (1.13; 0.68), (1.11; 0.67), (1.11; 0.31), (1.07; 16.00), (1.06; 15.68), (0.86; 0.31), (0.84; 0.46), (0.83; 0.30), (−0.00; 1.78)


 


48




3.43
669
(8.42; 0.93), (8.42; 1.05), (8.41; 1.05), (8.41; 1.05), (8.13; 0.64), (8.11; 1.65), (8.05; 1.03), (8.05; 1.07), (8.03; 1.15), (8.03; 1.14), (7.97; 0.57), (7.95; 0.78), (7.92; 0.16), (7.86; 0.43), (7.84; 0.46), (7.83; 0.69), (7.81; 0.98), (7.79; 0.49), (7.53; 1.09), (7.52; 1.09), (7.51; 1.04), (7.50; 1.02), (7.40; 1.08), (7.40; 1.09), (7.40; 1.22), (7.40; 1.18), (7.32; 1.17), (7.31; 1.08), (7.14; 1.67), (6.87; 1.03), (6.40; 0.21), (6.34; 0.20), (4.17; 4.41), (4.03; 0.49), (3.97; 0.31), (3.95; 0.46), (3.93; 0.46), (3.91; 0.32), (3.60; 0.26), (3.19; 0.16), (3.11; 5.61), (2.53; 0.25), (2.51; 0.33), (2.50; 5.14), (2.49; 10.15), (2.49; 13.98), (2.48; 9.96), (2.48; 4.97), (2.30; 0.43), (2.18; 1.84), (2.14; 6.19), (1.76; 0.31), (1.36; 16.00), (1.19; 0.26), (1.13; 1.19), (1.12; 1.18), (1.07; 7.85), (1.06; 7.72), (0.86; 0.18), (0.84; 0.39), (0.83; 0.16), (−0.00; 0.69)


 


49




2.62
683
(8.44; 1.00), (8.44; 1.03), (8.43; 1.02), (8.42; 0.97), (8.07; 1.00), (8.07; 0.98), (8.05; 1.08), (8.05; 0.99), (7.82; 0.51), (7.80; 0.50), (7.76; 0.76), (7.74; 0.97), (7.73; 0.50), (7.71; 1.05), (7.71; 0.74), (7.69; 0.75), (7.59; 0.43), (7.57; 0.66), (7.55; 1.16), (7.53; 1.05), (7.53; 0.97), (7.51; 0.93), (7.40; 0.98), (7.40; 1.07), (7.31; 1.10), (7.30; 0.96), (7.24; 1.43), (6.87; 1.02), (6.40; 0.41), (4.54; 3.03), (4.28; 3.50), (3.93; 0.44), (3.91; 0.42), (3.11; 22.82), (2.86; 0.41), (2.53; 0.45), (2.51; 0.53), (2.50; 7.94), (2.49; 15.67), (2.49; 21.60), (2.48; 15.37), (2.48; 7.68), (2.30; 0.73), (2.18; 1.77), (2.15; 5.77), (1.36; 16.00), (1.19; 1.87), (1.17; 0.47), (1.17; 1.81), (1.13; 0.42), (1.12; 0.41), (1.05; 7.41), (1.04; 7.39), (−0.00; 0.65)


 


50




2.28
683
(8.45; 0.99), (8.44; 1.01), (8.44; 1.02), (8.43; 0.93), (8.08; 1.01), (8.08; 0.99), (8.06; 1.09), (8.06; 0.99), (7.84; 0.53), (7.82; 0.53), (7.73; 1.95), (7.71; 2.47), (7.61; 1.02), (7.60; 1.89), (7.58; 1.22), (7.55; 1.09), (7.54; 1.04), (7.53; 0.98), (7.52; 0.95), (7.41; 1.04), (7.40; 1.14), (7.31; 1.16), (7.31; 1.01), (7.24; 1.49), (6.87; 1.06), (6.40; 0.40), (4.47; 3.48), (4.38; 2.21), (4.26; 3.02), (3.93; 0.47), (3.91; 0.45), (3.11; 53.00), (2.53; 0.45), (2.51; 0.56), (2.50; 7.77), (2.49; 15.18), (2.49; 20.82), (2.48; 14.79), (2.48; 7.36), (2.30; 1.05), (2.18; 1.83), (2.16; 5.99), (1.36; 16.00), (1.19; 1.55), (1.17; 1.70), (1.05; 7.68), (1.04; 7.54), (−0.00; 0.61)


 


51




3.42
683
(8.44; 0.51), (8.44; 0.53), (8.43; 0.51), (8.43; 0.51), (8.08; 0.55), (8.07; 0.58), (8.06; 0.59), (8.05; 0.54), (7.74; 0.63), (7.70; 0.33), (7.68; 0.75), (7.66; 0.63), (7.62; 0.50), (7.60; 0.50), (7.55; 0.62), (7.54; 0.56), (7.53; 0.56), (7.52; 0.52), (7.40; 0.56), (7.40; 0.61), (7.31; 0.61), (7.30; 0.57), (7.23; 0.80), (6.87; 1.05), (4.49; 2.10), (4.48; 0.35), (4.25; 0.35), (4.24; 1.98), (3.11; 39.96), (2.53; 1.56), (2.51; 0.77), (2.50; 10.02), (2.49; 19.40), (2.49; 26.51), (2.48; 18.82), (2.48; 9.31), (2.30; 0.77), (2.18; 1.84), (2.15; 3.16), (2.06; 0.40), (2.04; 0.37), (1.39; 0.87), (1.36; 16.00), (1.19; 0.56), (1.18; 1.70), (1.17; 0.62), (1.17; 1.59), (1.13; 0.32), (1.05; 4.10), (1.04; 3.97), (−0.00; 1.05)


 


52




3.92
751
(8.44; 1.24), (8.44; 1.31), (8.43; 1.27), (8.43; 1.25), (8.11; 0.76), (8.08; 1.05), (8.08; 1.48), (8.07; 1.42), (8.06; 1.44), (8.05; 1.34), (8.02; 1.46), (7.97; 1.20), (7.95; 0.90), (7.83; 0.69), (7.81; 0.69), (7.55; 1.40), (7.54; 1.39), (7.53; 1.28), (7.52; 1.22), (7.40; 1.33), (7.40; 1.45), (7.31; 1.51), (7.30; 1.39), (7.25; 1.89), (6.87; 1.02), (6.40; 0.43), (4.65; 3.74), (4.59; 0.37), (4.33; 4.83), (3.94; 0.39), (3.92; 0.58), (3.90; 0.59), (3.89; 0.38), (3.31; 0.35), (3.29; 0.43), (3.27; 0.35), (3.11; 85.64), (2.86; 1.12), (2.53; 2.14), (2.51; 1.10), (2.50; 13.76), (2.49; 26.62), (2.49; 36.29), (2.48; 25.64), (2.48; 12.62), (2.30; 1.23), (2.18; 1.84), (2.15; 7.58), (2.07; 0.42), (1.36; 16.00), (1.19; 3.75), (1.18; 3.69), (1.13; 1.08), (1.12; 1.09), (1.08; 0.33), (1.07; 0.62), (1.05; 9.89), (1.03; 9.55), (−0.00; 1.13)


 


53




3.95
751
(8.43; 1.23), (8.43; 1.29), (8.42; 1.31), (8.42; 1.25), (8.08; 3.31), (8.08; 2.38), (8.07; 1.69), (8.06; 1.46), (8.05; 1.38), (8.03; 1.38), (7.84; 0.67), (7.82; 0.68), (7.55; 1.36), (7.54; 1.35), (7.53; 1.26), (7.52; 1.22), (7.40; 1.30), (7.40; 1.33), (7.40; 1.48), (7.31; 1.51), (7.31; 1.34), (7.23; 1.93), (6.87; 1.06), (6.40; 0.33), (4.65; 4.68), (4.31; 0.44), (4.29; 4.89), (3.95; 0.40), (3.93; 0.59), (3.91; 0.57), (3.89; 0.39), (3.12; 19.42), (2.87; 0.47), (2.53; 0.70), (2.51; 0.33), (2.50; 4.61), (2.49; 8.99), (2.49; 12.28), (2.48; 8.72), (2.48; 4.34), (2.18; 1.87), (2.16; 7.61), (2.07; 0.42), (1.37; 16.00), (1.19; 1.61), (1.17; 1.43), (1.13; 0.48), (1.12; 0.47), (1.06; 9.74), (1.04; 9.58), (−0.00; 0.40)


 


54




4
737
(8.40; 2.23), (8.39; 2.27), (8.38; 2.40), (8.38; 2.34), (8.31; 2.57), (8.31; 3.53), (8.30; 1.96), (8.28; 2.73), (8.28; 1.80), (8.26; 0.35), (8.22; 0.38), (8.20; 2.98), (8.18; 1.99), (8.17; 0.38), (8.03; 2.03), (8.03; 1.97), (8.01; 2.23), (8.01; 2.04), (7.86; 0.99), (7.84; 0.97), (7.53; 2.14), (7.51; 2.09), (7.51; 1.99), (7.49; 1.91), (7.40; 2.15), (7.40; 2.40), (7.32; 2.39), (7.31; 2.14), (7.14; 3.14), (6.87; 1.04), (6.40; 0.41), (4.27; 8.30), (4.20; 0.40), (3.96; 0.64), (3.95; 0.98), (3.93; 0.94), (3.91; 0.63), (3.29; 0.40), (3.27; 0.37), (3.12; 45.65), (3.04; 0.39), (2.87; 0.60), (2.53; 1.90), (2.51; 1.01), (2.50; 12.65), (2.49; 24.51), (2.49; 33.42), (2.48; 23.74), (2.48; 11.77), (2.30; 0.56), (2.18; 1.85), (2.16; 0.33), (2.13; 12.21), (2.04; 0.65), (1.36; 16.00), (1.19; 3.42), (1.17; 3.19), (1.13; 0.65), (1.12; 0.63), (1.09; 0.46), (1.07; 15.56), (1.05; 15.36), (−0.00; 0.99)”


 


55




4.5
751
(10.027; 1.76), (8.412; 2.10), (8.408; 2.21), (8.401; 2.26), (8.397; 2.19), (8.350; 4.70), (8.313; 1.94), (8.045; 2.11), (8.041; 2.16), (8.025; 2.37), (8.021; 2.26), (7.809; 0.83), (7.790; 0.82), (7.542; 2.41), (7.530; 2.34), (7.522; 2.25), (7.510; 2.22), (7.403; 1.84), (7.402; 1.88), (7.397; 2.12), (7.396; 1.97), (7.304; 2.12), (7.299; 1.93), (7.203; 2.29), (4.559; 7.07), (3.955; 0.59), (3.939; 0.88), (3.920; 0.86), (3.903; 0.59), (3.117; 123.19), (2.875; 15.99), (2.527; 0.86), (2.511; 0.58), (2.506; 0.83), (2.498; 11.27), (2.493; 23.13), (2.488; 32.43), (2.484; 22.67), (2.479; 10.86), (2.146; 11.38), (1.364; 0.75), (1.060; 16.00), (1.044; 15.82), (−0.000; 0.50)


 


56




4.37
765
(10.060; 1.09), (8.446; 1.41), (8.442; 1.51), (8.434; 1.54), (8.430; 1.48), (8.140; 3.02), (8.091; 1.49), (8.087; 1.53), (8.071; 2.81), (8.067; 2.14), (7.795; 0.57), (7.776; 0.58), (7.562; 1.66), (7.550; 1.60), (7.542; 1.55), (7.530; 1.55), (7.405; 1.24), (7.403; 1.28), (7.398; 1.43), (7.397; 1.34), (7.300; 1.45), (7.294; 1.31), (7.259; 1.51), (6.873; 0.89), (6.405; 0.47), (4.762; 4.77), (4.422; 4.54), (3.934; 0.38), (3.917; 0.59), (3.898; 0.58), (3.882; 0.39), (3.118; 123.30), (2.824; 10.81), (2.527; 0.87), (2.511; 0.56), (2.506; 0.81), (2.498; 11.01), (2.493; 22.59), (2.488; 31.67), (2.484; 22.09), (2.479; 10.51), (2.183; 1.50), (2.158; 7.62), (1.364; 16.00), (1.045; 10.82), (1.029; 10.70)


 


57




4.26
765
(10.025; 1.71), (8.415; 2.08), (8.412; 2.15), (8.404; 2.22), (8.400; 2.22), (8.058; 2.20), (8.054; 2.04), (8.038; 2.33), (8.034; 2.28), (7.975; 0.77), (7.941; 4.38), (7.891; 1.86), (7.808; 0.81), (7.790; 0.77), (7.540; 2.55), (7.528; 2.41), (7.520; 2.27), (7.508; 2.16), (7.406; 1.92), (7.400; 2.07), (7.309; 2.18), (7.302; 1.95), (7.224; 2.20), (5.689; 0.97), (4.635; 5.70), (4.521; 6.95), (4.047; 0.58), (4.029; 0.54), (3.952; 0.61), (3.935; 0.88), (3.917; 0.95), (3.900; 0.60), (3.609; 0.37), (3.602; 0.47), (3.352; 0.36), (3.206; 0.34), (3.189; 0.47), (3.174; 0.68), (3.112; 1092.94), (3.093; 24.71), (3.043; 0.36), (2.666; 0.64), (2.662; 1.51), (2.657; 2.00), (2.652; 1.40), (2.647; 0.67), (2.558; 0.43), (2.526; 1.93), (2.510; 4.94), (2.505; 7.03), (2.497; 106.03), (2.493; 219.75), (2.488; 310.47), (2.483; 217.21), (2.478; 104.28), (2.324; 0.68), (2.319; 1.34), (2.315; 1.88), (2.310; 1.26), (2.305; 0.68), (2.140; 11.24), (2.040; 1.67), (1.974; 2.71), (1.901; 0.40), (1.771; 0.34), (1.762; 0.72), (1.419; 0.39), (1.404; 1.27), (1.363; 1.67), (1.245; 0.53), (1.195; 0.75), (1.177; 1.62), (1.159; 0.72), (1.059; 16.00), (1.042; 15.78), (0.895; 0.49), (−0.000; 8.56)


 


58




4.54
791
(10.032; 2.34), (8.417; 3.05), (8.413; 3.24), (8.405; 3.35), (8.401; 3.22), (8.059; 3.10), (8.055; 3.13), (8.038; 3.52), (8.035; 3.24), (7.943; 6.51), (7.894; 3.71), (7.876; 1.34), (7.541; 3.51), (7.529; 3.36), (7.521; 3.26), (7.509; 3.19), (7.415; 2.66), (7.414; 2.73), (7.409; 3.06), (7.314; 3.11), (7.309; 2.79), (7.226; 3.31), (4.632; 8.35), (4.518; 10.12), (3.392; 0.64), (3.372; 1.26), (3.355; 1.29), (3.335; 0.67), (3.115; 162.24), (3.092; 26.49), (2.510; 0.95), (2.506; 1.40), (2.497; 19.29), (2.493; 39.54), (2.488; 55.40), (2.483; 38.66), (2.479; 18.44), (2.142; 16.00), (1.404; 1.95), (1.092; 10.11), (1.076; 9.97), (0.885; 0.45), (0.877; 0.67), (0.865; 1.30), (0.857; 0.83), (0.853; 0.88), (0.844; 1.35), (0.832; 0.77), (0.824; 0.55), (0.395; 0.49), (0.391; 0.54), (0.382; 1.04), (0.373; 1.01), (0.369; 1.00), (0.360; 1.15), (0.352; 0.66), (0.348; 0.73), (0.338; 0.64), (0.299; 0.57), (0.288; 0.81), (0.285; 0.78), (0.278; 0.74), (0.275; 1.01), (0.267; 1.03), (0.254; 1.12), (0.247; 0.56), (0.243; 0.55), (0.238; 0.59), (0.232; 0.72), (0.225; 0.82), (0.215; 1.16), (0.203; 1.44), (0.192; 1.13), (0.179; 0.54), (0.162; 0.72), (0.150; 1.16), (0.140; 1.35), (0.127; 1.07), (0.117; 0.60), (−0.000; 1.51)


 


59




4.05
763
(12.543; 1.97), (11.209; 0.83), (10.018; 3.12), (8.425; 2.59), (8.414; 2.60), (8.084; 0.89), (8.082; 0.94), (8.062; 3.85), (8.060; 3.46), (8.043; 3.38), (7.949; 7.54), (7.894; 3.31), (7.829; 1.72), (7.542; 2.03), (7.532; 2.06), (7.522; 1.85), (7.512; 1.94), (7.400; 2.91), (7.293; 3.52), (7.227; 3.58), (4.946; 0.83), (4.643; 8.95), (4.527; 9.55), (3.651; 0.91), (3.449; 0.87), (3.410; 0.84), (3.389; 1.09), (3.364; 1.00), (3.358; 0.99), (3.284; 1.22), (3.262; 1.15), (3.239; 1.63), (3.214; 1.98), (3.116; 1733.15), (3.113; 1640.53), (3.091; 31.11), (3.053; 1.27), (3.050; 1.14), (2.711; 1.44), (2.701; 1.66), (2.657; 3.08), (2.560; 1.17), (2.524; 3.80), (2.497; 167.94), (2.493; 345.71), (2.488; 495.50), (2.486; 456.28), (2.484; 388.70), (2.481; 312.40), (2.417; 1.10), (2.407; 0.97), (2.395; 0.92), (2.313; 2.88), (2.134; 16.00), (2.040; 1.23), (1.404; 12.37), (1.402; 11.71), (1.244; 1.46), (1.045; 0.81), (0.943; 0.98), (0.632; 0.91), (0.614; 2.89), (0.601; 3.06), (0.475; 1.26), (0.457; 3.46), (0.451; 3.24), (−0.000; 15.31), (−0.002; 14.21)


 


60




3.91
757
(10.330; 1.09), (8.418; 1.84), (8.414; 2.00), (8.406; 2.04), (8.402; 1.96), (8.061; 1.81), (8.058; 1.90), (8.041; 2.07), (8.037; 1.99), (7.987; 0.54), (7.981; 0.59), (7.974; 0.51), (7.958; 0.73), (7.941; 4.10), (7.888; 1.68), (7.791; 1.66), (7.724; 1.86), (7.720; 1.73), (7.543; 2.05), (7.531; 1.96), (7.523; 1.92), (7.511; 1.90), (7.243; 3.01), (6.873; 0.87), (6.401; 0.45), (4.640; 5.20), (4.531; 6.22), (4.368; 0.34), (3.961; 0.51), (3.945; 0.81), (3.926; 0.78), (3.910; 0.56), (3.113; 307.41), (3.099; 20.73), (3.016; 0.92), (2.662; 0.42), (2.657; 0.67), (2.652; 0.44), (2.526; 0.61), (2.510; 1.68), (2.506; 2.33), (2.497; 33.91), (2.493; 70.02), (2.488; 98.68), (2.483; 69.12), (2.478; 33.18), (2.319; 0.40), (2.315; 0.62), (2.310; 0.41), (2.286; 0.74), (2.189; 9.57), (2.137; 0.81), (1.510; 0.47), (1.404; 0.55), (1.364; 16.00), (1.228; 0.65), (1.211; 0.64), (1.092; 1.15), (1.073; 14.69), (1.057; 14.36), (−0.000; 3.83)


 


61




4.12
783
(8.419; 3.13), (8.416; 3.39), (8.408; 3.46), (8.404; 3.32), (8.062; 3.68), (8.058; 3.75), (8.042; 3.68), (8.038; 3.46), (7.942; 6.69), (7.890; 2.76), (7.801; 2.73), (7.799; 2.97), (7.727; 3.26), (7.723; 3.00), (7.544; 3.49), (7.532; 3.34), (7.524; 3.25), (7.512; 3.28), (7.239; 5.92), (5.688; 0.54), (4.638; 8.59), (4.528; 10.47), (3.401; 0.67), (3.381; 1.31), (3.364; 1.35), (3.344; 0.67), (3.119; 211.31), (3.098; 29.20), (3.010; 1.23), (2.511; 1.05), (2.506; 1.47), (2.498; 22.54), (2.494; 46.59), (2.489; 65.64), (2.484; 45.93), (2.480; 22.04), (2.287; 1.18), (2.190; 16.00), (2.136; 1.15), (1.404; 5.15), (1.364; 2.27), (1.132; 0.83), (1.115; 1.12), (1.106; 10.41), (1.089; 10.33), (0.899; 0.53), (0.891; 0.71), (0.878; 1.38), (0.871; 0.84), (0.866; 0.92), (0.858; 1.51), (0.846; 0.81), (0.838; 0.57), (0.403; 0.61), (0.395; 1.10), (0.386; 1.06), (0.382; 1.11), (0.373; 1.25), (0.365; 0.72), (0.361; 0.83), (0.351; 0.74), (0.317; 0.58), (0.306; 0.83), (0.303; 0.82), (0.292; 1.04), (0.286; 1.09), (0.272; 1.17), (0.264; 0.58), (0.251; 0.85), (0.240; 0.89), (0.230; 1.22), (0.217; 1.50), (0.206; 1.24), (0.193; 0.56), (0.177; 0.78), (0.164; 1.25), (0.154; 1.43), (0.141; 1.16), (0.132; 0.67), (0.000; 1.48)


 


62




3.64
755
(10.329; 1.95), (8.431; 3.12), (8.427; 3.40), (8.419; 3.43), (8.415; 3.28), (8.283; 0.47), (8.278; 0.53), (8.260; 0.50), (8.217; 0.76), (8.214; 1.03), (8.208; 1.17), (8.197; 1.54), (8.193; 1.18), (8.071; 2.94), (8.067; 3.08), (8.051; 3.38), (8.047; 3.17), (7.995; 0.88), (7.986; 0.47), (7.949; 6.60), (7.890; 2.98), (7.789; 2.78), (7.704; 2.89), (7.701; 2.71), (7.548; 3.37), (7.537; 3.16), (7.528; 3.13), (7.516; 3.05), (7.507; 0.47), (7.269; 1.20), (7.251; 5.42), (4.672; 1.11), (4.648; 8.69), (4.570; 1.43), (4.539; 9.71), (3.115; 585.74), (3.109; 56.53), (3.039; 1.04), (2.743; 0.60), (2.734; 0.89), (2.725; 1.26), (2.716; 1.25), (2.707; 0.94), (2.701; 0.89), (2.697; 0.72), (2.690; 0.64), (2.662; 0.74), (2.657; 1.07), (2.653; 0.71), (2.527; 1.10), (2.510; 2.86), (2.506; 4.13), (2.498; 56.93), (2.493; 116.98), (2.488; 164.48), (2.484; 114.57), (2.479; 54.47), (2.320; 0.67), (2.315; 0.98), (2.310; 0.68), (2.283; 1.31), (2.184; 16.00), (2.146; 1.22), (2.040; 0.96), (1.974; 0.49), (1.894; 1.96), (1.404; 2.56), (1.363; 0.67), (0.650; 0.83), (0.637; 2.22), (0.631; 2.95), (0.619; 2.90), (0.613; 2.35), (0.602; 1.08), (0.496; 1.30), (0.486; 3.12), (0.479; 2.87), (0.470; 2.41), (0.458; 0.78), (−0.000; 5.29)


 


63




2.01 2.27
575



 


64




3.17 3.49
557
(8.496; 0.37), (8.494; 0.38), (8.488; 0.37), (8.486; 0.37), (8.410; 1.59), (8.386; 2.20), (8.383; 0.97), (8.378; 0.97), (8.375; 0.96), (8.369; 0.83), (8.368; 0.87), (8.366; 0.89), (8.365; 0.86), (8.355; 0.59), (8.331; 0.66), (8.011; 0.96), (8.008; 1.21), (8.005; 0.42), (7.997; 1.00), (7.995; 1.22), (7.992; 0.43), (7.819; 1.32), (7.795; 1.20), (7.782; 0.53), (7.775; 0.34), (7.774; 0.35), (7.772; 0.38), (7.771; 0.38), (7.758; 0.49), (7.750; 0.79), (7.748; 0.99), (7.747; 0.97), (7.745; 0.81), (7.663; 0.30), (7.662; 0.33), (7.660; 0.31), (7.527; 0.40), (7.519; 0.39), (7.513; 0.39), (7.505; 0.37), (7.468; 1.07), (7.460; 1.30), (7.455; 0.99), (7.447; 1.06), (7.430; 2.62), (6.974; 0.67), (6.973; 0.67), (4.064; 0.67), (4.053; 0.67), (3.757; 9.31), (3.653; 0.31), (3.642; 0.78), (3.631; 0.35), (3.483; 0.30), (2.823; 0.64), (2.817; 0.64), (2.646; 0.46), (2.638; 0.46), (2.222; 0.90), (2.221; 1.42), (2.220; 0.86), (2.198; 2.12), (2.177; 0.30), (1.974; 5.29), (1.973; 6.30), (1.951; 3.45), (1.947; 6.63), (1.943; 10.02), (1.939; 6.85), (1.935; 3.31), (1.812; 0.33), (1.801; 0.97), (1.795; 0.29), (1.790; 0.33), (1.386; 13.50), (1.216; 0.93), (1.204; 1.74), (1.199; 0.46), (1.192; 0.93), (−0.000; 7.90)


 


65




3.71
597
(10.549; 3.82), (10.396; 4.84), (8.540; 2.80), (8.483; 2.94), (8.479; 3.07), (8.471; 3.12), (8.468; 2.95), (8.357; 0.70), (8.348; 1.72), (8.337; 1.67), (8.326; 0.62), (8.144; 2.95), (8.140; 2.79), (8.123; 3.22), (8.120; 2.91), (7.975; 1.73), (7.969; 1.65), (7.953; 1.88), (7.947; 1.74), (7.866; 3.54), (7.863; 3.70), (7.761; 4.03), (7.756; 3.58), (7.569; 2.95), (7.557; 2.90), (7.549; 2.79), (7.537; 2.77), (7.494; 3.97), (7.371; 2.43), (7.349; 2.29), (4.057; 0.69), (4.039; 1.82), (4.021; 1.86), (4.003; 0.72), (3.652; 0.39), (3.618; 0.41), (3.559; 0.50), (3.552; 0.52), (3.546; 0.53), (3.434; 1.29), (3.312; 2504.39), (2.700; 10.34), (2.689; 10.41), (2.679; 1.79), (2.674; 2.62), (2.670; 3.33), (2.665; 2.44), (2.660; 1.31), (2.628; 0.47), (2.619; 0.54), (2.539; 4.05), (2.523; 15.97), (2.509; 188.46), (2.505; 339.59), (2.500; 433.23), (2.496; 296.11), (2.492; 138.38), (2.332; 2.10), (2.327; 2.83), (2.323; 1.99), (2.318; 0.89), (2.231; 16.00), (2.085; 2.72), (2.069; 2.88), (1.987; 7.32), (1.908; 0.49), (1.237; 0.69), (1.193; 2.05), (1.175; 4.04), (1.157; 2.03), (0.890; 1.13), (−0.000; 6.89)


 


66




2.84
555
(10.417; 1.62), (8.507; 0.67), (8.474; 0.62), (8.470; 0.69), (8.462; 0.67), (8.458; 0.63), (8.145; 0.60), (8.141; 0.61), (8.125; 0.69), (8.121; 0.62), (7.972; 0.37), (7.967; 0.39), (7.950; 0.39), (7.944; 0.43), (7.831; 0.81), (7.828; 0.81), (7.758; 0.94), (7.706; 0.87), (7.702; 0.82), (7.569; 0.63), (7.557; 0.64), (7.549; 0.62), (7.537; 0.94), (7.533; 1.03), (7.353; 0.55), (7.331; 0.53), (4.039; 0.38), (4.021; 0.41), (3.381; 0.44), (3.305; 691.37), (3.282; 14.43), (2.678; 0.42), (2.674; 0.78), (2.669; 1.02), (2.664; 0.74), (2.539; 1.56), (2.522; 4.28), (2.509; 57.37), (2.505; 107.43), (2.500; 140.94), (2.496; 98.10), (2.491; 46.94), (2.332; 0.68), (2.327; 0.93), (2.322; 0.67), (2.229; 3.47), (2.085; 0.55), (2.069; 1.91), (1.987; 1.75), (1.285; 16.00), (1.193; 0.49), (1.175; 0.95), (1.157; 0.52), (1.046; 0.34), (1.030; 0.33), (0.008; 0.54), (−0.000; 12.25), (−0.009; 0.46)


 


67




3.31
493
(10.486; 2.72), (10.400; 3.40), (8.527; 1.91), (8.524; 1.91), (8.522; 1.84), (8.470; 2.23), (8.467; 2.32), (8.459; 2.40), (8.455; 2.25), (8.175; 1.44), (8.156; 1.48), (8.132; 2.24), (8.128; 2.22), (8.112; 2.49), (8.108; 2.26), (7.994; 0.84), (7.989; 0.84), (7.974; 1.21), (7.967; 1.19), (7.951; 1.26), (7.945; 1.25), (7.859; 2.32), (7.857; 2.46), (7.854; 2.56), (7.784; 0.53), (7.779; 0.50), (7.763; 0.79), (7.758; 0.75), (7.728; 2.75), (7.725; 2.54), (7.675; 1.57), (7.654; 1.07), (7.565; 2.33), (7.553; 2.27), (7.544; 2.26), (7.533; 2.97), (7.527; 3.14), (7.360; 1.68), (7.338; 1.60), (4.039; 1.09), (4.021; 1.10), (4.003; 0.39), (3.957; 0.63), (3.940; 0.95), (3.922; 0.92), (3.905; 0.62), (3.305; 407.19), (2.678; 0.44), (2.674; 0.86), (2.669; 1.10), (2.664; 0.80), (2.660; 0.43), (2.539; 1.33), (2.522; 4.99), (2.509; 62.36), (2.505; 115.15), (2.500; 149.52), (2.496; 102.45), (2.491; 48.17), (2.332; 0.78), (2.327; 1.02), (2.322; 0.73), (2.237; 11.04), (2.069; 1.78), (1.987; 4.83), (1.245; 3.18), (1.193; 1.42), (1.175; 2.84), (1.157; 1.39), (1.080; 16.00), (1.063; 15.77), (−0.000; 5.36)


 


65




3.71
597.2
(10.42; 1.62), (8.51; 0.67), (8.47; 0.62), (8.47; 0.69), (8.46; 0.67), (8.46; 0.63), (8.15; 0.60), (8.14; 0.61), (8.13; 0.69), (8.12; 0.62), (7.97; 0.37), (7.97; 0.39), (7.95; 0.39), (7.94; 0.43), (7.83; 0.81), (7.83; 0.81), (7.76; 0.94), (7.71; 0.87), (7.70; 0.82), (7.57; 0.63), (7.56; 0.64), (7.55; 0.62), (7.54; 0.94), (7.53; 1.03), (7.35; 0.55), (7.33; 0.53), (4.04; 0.38), (4.02; 0.41), (3.38; 0.44), (3.31; 691.37), (3.28; 14.43), (2.68; 0.42), (2.67; 0.78), (2.67; 1.02), (2.66; 0.74), (2.54; 1.56), (2.52; 4.28), (2.51; 57.37), (2.50; 107.43), (2.50; 140.94), (2.50; 98.10), (2.49; 46.94), (2.33; 0.68), (2.33; 0.93), (2.32; 0.67), (2.23; 3.47), (2.08; 0.55), (2.07; 1.91), (1.99; 1.75), (1.29; 16.00), (1.19; 0.49), (1.17; 0.95), (1.16; 0.52), (1.05; 0.34), (1.03; 0.33), (0.01; 0.54), (0.00; 12.25), (−0.01; 0.46)


 


66




2.84
555.1
(10.55; 3.82), (10.40; 4.84), (8.54; 2.80), (8.48; 2.94), (8.48; 3.07), (8.47; 3.12), (8.47; 2.95), (8.36; 0.70), (8.35; 1.72), (8.34; 1.67), (8.33; 0.62), (8.14; 2.95), (8.14; 2.79), (8.12; 3.22), (8.12; 2.91), (7.98; 1.73), (7.97; 1.65), (7.95; 1.88), (7.95; 1.74), (7.87; 3.54), (7.86; 3.70), (7.76; 4.03), (7.76; 3.58), (7.57; 2.95), (7.56; 2.90), (7.55; 2.79), (7.54; 2.77), (7.49; 3.97), (7.37; 2.43), (7.35; 2.29), (4.06; 0.69), (4.04; 1.82), (4.02; 1.86), (4.00; 0.72), (3.67; 0.35), (3.65; 0.39), (3.62; 0.41), (3.56; 0.50), (3.55; 0.52), (3.55; 0.53), (3.43; 1.29), (3.31; 2504.39), (2.70; 10.34), (2.69; 10.41), (2.68; 1.79), (2.67; 2.62), (2.67; 3.33), (2.67; 2.44), (2.66; 1.31), (2.63; 0.47), (2.62; 0.54), (2.54; 4.05), (2.52; 15.97), (2.51; 188.46), (2.51; 339.59), (2.50; 433.23), (2.50; 296.11), (2.49; 138.38), (2.33; 2.10), (2.33; 2.83), (2.32; 1.99), (2.32; 0.89), (2.23; 16.00), (2.08; 2.72), (2.07; 2.88), (1.99; 7.32), (1.91; 0.49), (1.24; 0.69), (1.19; 2.05), (1.17; 4.04), (1.16; 2.03), (0.89; 1.13), (0.00; 6.89)


 


67





583.1
(10.49; 2.72), (10.40; 3.40), (8.53; 1.91), (8.52; 1.91), (8.52; 1.84), (8.47; 2.23), (8.47; 2.32), (8.46; 2.40), (8.45; 2.25), (8.18; 1.44), (8.16; 1.48), (8.13; 2.24), (8.13; 2.22), (8.11; 2.49), (8.11; 2.26), (7.99; 0.84), (7.99; 0.84), (7.97; 1.21), (7.97; 1.19), (7.95; 1.26), (7.95; 1.25), (7.86; 2.32), (7.86; 2.46), (7.85; 2.56), (7.78; 0.53), (7.78; 0.50), (7.76; 0.79), (7.76; 0.75), (7.73; 2.75), (7.72; 2.54), (7.68; 1.57), (7.65; 1.07), (7.56; 2.33), (7.55; 2.27), (7.54; 2.26), (7.53; 2.97), (7.53; 3.14), (7.36; 1.68), (7.34; 1.60), (4.06; 0.37), (4.04; 1.09), (4.02; 1.10), (4.00; 0.39), (3.96; 0.63), (3.94; 0.95), (3.92; 0.92), (3.91; 0.62), (3.30; 407.19), (2.68; 0.44), (2.67; 0.86), (2.67; 1.10), (2.66; 0.80), (2.66; 0.43), (2.54; 1.33), (2.52; 4.99), (2.51; 62.36), (2.50; 115.15), (2.50; 149.52), (2.50; 102.45), (2.49; 48.17), (2.34; 0.37), (2.33; 0.78), (2.33; 1.02), (2.32; 0.73), (2.24; 11.04), (2.07; 1.78), (1.99; 4.83), (1.25; 3.18), (1.19; 1.42), (1.17; 2.84), (1.16; 1.39), (1.08; 16.00), (1.06; 15.77), (0.00; 5.36)


 


68




3.66
655.1
(10.16; 2.23), (8.47; 3.24), (8.46; 3.13), (8.45; 3.24), (8.45; 3.02), (7.99; 3.07), (7.99; 2.92), (7.97; 3.37), (7.97; 3.23), (7.74; 3.92), (7.73; 4.86), (7.72; 5.87), (7.70; 7.23), (7.70; 4.98), (7.50; 3.48), (7.49; 3.40), (7.48; 3.17), (7.47; 3.19), (7.43; 8.19), (7.43; 2.47), (7.41; 2.41), (7.41; 6.43), (7.08; 0.39), (7.06; 8.17), (7.04; 0.99), (7.03; 1.15), (7.02; 1.12), (5.52; 0.51), (5.45; 1.90), (4.55; 2.61), (4.51; 5.94), (4.46; 5.86), (4.44; 0.92), (4.44; 0.98), (4.42; 3.22), (4.42; 1.43), (4.41; 1.04), (4.39; 0.98), (4.39; 0.82), (4.37; 0.32), (4.07; 0.53), (4.05; 0.47), (3.89; 2.06), (3.88; 2.02), (3.86; 2.29), (3.85; 2.24), (3.48; 1.94), (3.47; 0.47), (3.45; 3.29), (3.43; 1.53), (3.34; 0.35), (3.32; 0.49), (3.31; 0.46), (2.94; 0.33), (2.83; 0.35), (2.82; 0.38), (2.78; 0.96), (2.77; 16.00), (2.76; 15.62), (2.73; 1.46), (2.68; 0.34), (2.62; 0.39), (2.60; 0.36), (2.58; 0.40), (2.58; 0.37), (2.55; 0.42), (2.53; 0.42), (2.52; 0.42), (2.51; 0.38), (2.50; 0.44), (2.47; 0.67), (2.46; 0.77), (2.46; 0.75), (2.45; 0.50), (2.43; 0.54), (2.42; 0.48), (2.40; 0.50), (2.40; 0.56), (2.38; 0.57), (2.38; 0.55), (2.36; 0.66), (2.30; 0.94), (2.28; 0.96), (2.20; 24.46), (2.14; 2463.28), (2.12; 5.91), (2.11; 5.80), (2.11; 6.05), (2.10; 4.22), (2.09; 2.45), (2.07; 0.97), (2.07; 0.96), (2.05; 0.97), (2.04; 1.07), (2.01; 1.76), (1.96; 481.38), (1.96; 44.49), (1.95; 265.53), (1.95; 491.65), (1.94; 697.21), (1.93; 475.63), (1.93; 239.61), (1.79; 2.48), (1.78; 1.34), (1.77; 2.58), (1.77; 3.85), (1.76; 2.51), (1.76; 1.25), (1.39; 1.02), (1.27; 1.58), (1.22; 0.53), (1.20; 1.01), (1.19; 0.52), (1.13; 0.59), (1.11; 1.06), (1.10; 0.48), (0.91; 2.89), (0.88; 0.35), (0.15; 0.33), (0.01; 3.88), (0.00; 79.00), (−0.01; 2.79), (−0.15; 0.37)


 


69




2.89
555.1
(10.62; 0.92), (10.29; 1.27), (8.48; 0.72), (8.48; 0.78), (8.47; 0.80), (8.47; 0.73), (8.37; 0.42), (8.36; 0.45), (8.15; 0.72), (8.15; 0.69), (8.13; 0.78), (8.13; 0.71), (7.90; 0.36), (7.88; 0.61), (7.86; 1.31), (7.78; 0.96), (7.77; 0.89), (7.63; 0.62), (7.61; 0.56), (7.57; 0.74), (7.56; 0.72), (7.55; 0.67), (7.54; 0.67), (7.27; 1.45), (7.25; 0.84), (4.04; 0.43), (4.02; 0.42), (3.43; 0.36), (3.41; 0.41), (3.30; 559.69), (3.28; 4.39), (2.71; 2.60), (2.70; 2.60), (2.68; 0.47), (2.67; 0.74), (2.67; 0.94), (2.66; 0.74), (2.54; 2.17), (2.52; 4.91), (2.51; 52.99), (2.50; 95.66), (2.50; 122.72), (2.50; 84.65), (2.49; 40.48), (2.33; 0.58), (2.33; 0.75), (2.32; 0.56), (2.23; 3.86), (2.07; 16.00), (1.99; 1.63), (1.19; 0.47), (1.17; 0.95), (1.16; 0.48), (0.01; 0.76), (0.00; 14.81), (−0.01; 0.59)


 


70




2.76
555.1
(10.55; 4.54), (10.25; 5.08), (8.47; 6.02), (8.47; 4.83), (8.46; 7.29), (8.46; 4.74), (8.34; 1.93), (8.33; 1.90), (8.15; 2.61), (8.13; 2.77), (8.13; 2.69), (7.86; 3.98), (7.76; 4.37), (7.56; 3.10), (7.55; 7.06), (7.54; 2.96), (7.53; 2.47), (7.47; 4.39), (7.32; 0.33), (7.11; 2.79), (7.10; 2.71), (4.06; 0.37), (4.04; 1.03), (4.02; 1.16), (4.00; 0.43), (3.71; 0.41), (3.58; 0.38), (3.56; 0.41), (3.51; 0.52), (3.50; 0.57), (3.48; 0.87), (3.45; 1.05), (3.32; 3880.78), (3.23; 3.74), (3.18; 1.90), (3.15; 1.41), (3.14; 1.34), (3.11; 1.10), (3.10; 1.08), (3.09; 1.03), (3.07; 0.88), (3.05; 0.84), (3.01; 0.71), (3.00; 0.72), (2.99; 0.68), (2.96; 0.64), (2.92; 0.55), (2.90; 0.54), (2.87; 0.55), (2.84; 0.53), (2.83; 0.49), (2.80; 0.51), (2.75; 0.56), (2.71; 10.73), (2.69; 11.29), (2.68; 2.26), (2.67; 3.42), (2.67; 4.17), (2.67; 3.15), (2.64; 0.58), (2.58; 1.25), (2.54; 8.31), (2.52; 18.72), (2.51; 228.93), (2.51; 420.15), (2.50; 544.13), (2.50; 380.45), (2.49; 185.40), (2.41; 1.26), (2.40; 1.07), (2.33; 3.19), (2.33; 4.05), (2.32; 3.01), (2.31; 0.74), (2.30; 0.68), (2.28; 0.71), (2.24; 16.00), (2.20; 0.71), (2.18; 0.68), (2.16; 0.60), (2.12; 0.44), (2.07; 2.43), (2.05; 0.55), (2.00; 0.78), (1.99; 5.11), (1.96; 0.41), (1.91; 0.55), (1.88; 0.40), (1.87; 0.34), (1.82; 0.33), (1.65; 0.37), (1.49; 0.38), (1.43; 0.35), (1.33; 0.33), (1.29; 0.37), (1.24; 1.78), (1.19; 1.47), (1.18; 2.81), (1.16; 1.51), (1.02; 0.32), (0.89; 0.38), (0.87; 0.34), (0.85; 0.34), (0.00; 12.92)


 


71




3.5
623.0
(18.86; 1.01), (17.46; 0.96), (17.01; 1.02), (15.71; 0.95), (14.61; 1.05), (13.00; 1.03), (11.91; 1.00), (10.93; 3.03), (10.58; 2.80), (8.76; 3.72), (8.49; 2.38), (8.48; 2.07), (8.47; 1.92), (8.35; 1.36), (8.34; 1.59), (8.18; 0.92), (8.16; 2.12), (8.14; 1.96), (7.87; 2.80), (7.76; 3.12), (7.75; 0.99), (7.71; 1.11), (7.58; 2.38), (7.57; 2.78), (7.56; 2.69), (7.55; 2.06), (7.43; 0.93), (5.86; 0.94), (4.97; 1.08), (4.52; 0.99), (4.48; 0.96), (4.43; 1.07), (4.42; 1.00), (4.41; 0.99), (4.32; 0.99), (4.20; 1.11), (4.18; 1.12), (4.13; 1.10), (4.12; 1.09), (4.09; 1.09), (4.04; 1.05), (4.03; 1.02), (4.00; 0.96), (3.94; 1.09), (3.92; 1.57), (3.90; 1.31), (3.88; 1.43), (3.86; 1.49), (3.84; 1.51), (3.81; 1.61), (3.77; 1.56), (3.76; 1.68), (3.74; 1.65), (3.70; 1.63), (3.68; 1.67), (3.65; 1.89), (3.64; 1.99), (3.63; 2.16), (3.62; 2.09), (3.57; 2.37), (3.56; 2.47), (3.54; 2.72), (3.49; 3.73), (3.46; 4.33), (3.45; 4.70), (3.44; 4.56), (3.30; 9797.66), (3.28; 116.36), (3.18; 1.04), (3.05; 1.03), (3.01; 0.98), (2.97; 1.23), (2.89; 1.24), (2.84; 1.03), (2.78; 1.29), (2.77; 1.22), (2.76; 1.35), (2.75; 1.58), (2.74; 1.79), (2.70; 8.90), (2.70; 8.25), (2.69; 8.62), (2.68; 7.04), (2.67; 11.13), (2.67; 14.20), (2.66; 10.83), (2.54; 33.75), (2.51; 808.06), (2.50; 1441.06), (2.50; 1834.67), (2.50; 1264.22), (2.49; 600.71), (2.33; 9.02), (2.33; 11.60), (2.32; 8.09), (2.23; 10.45), (2.08; 1.04), (2.07; 16.00), (1.24; 1.87), (0.89; 1.00), (0.00; 41.23)


 


72




3.91
650.2



 


73





650.2



 


74




3.7
582.1
(10.46; 2.01), (9.55; 2.34), (8.47; 1.84), (8.47; 1.94), (8.46; 1.98), (8.46; 1.92), (8.25; 1.18), (8.24; 1.21), (8.14; 1.45), (8.13; 1.47), (8.12; 1.57), (8.12; 1.50), (7.88; 1.82), (7.88; 1.89), (7.74; 1.97), (7.74; 1.90), (7.58; 16.00), (7.56; 1.62), (7.55; 1.50), (7.55; 1.47), (7.54; 1.45), (6.90; 2.40), (4.03; 0.34), (4.02; 0.35), (3.95; 0.54), (3.94; 0.80), (3.93; 0.78), (3.91; 0.53), (3.38; 0.38), (3.35; 482.12), (3.33; 1.69), (2.62; 0.33), (2.62; 0.47), (2.61; 0.34), (2.52; 0.73), (2.52; 0.95), (2.52; 1.02), (2.51; 24.51), (2.51; 53.11), (2.50; 73.79), (2.50; 52.16), (2.50; 23.35), (2.39; 0.32), (2.39; 0.44), (2.24; 8.36), (2.08; 0.65), (1.99; 1.61), (1.26; 0.44), (1.23; 1.08), (1.19; 0.46), (1.17; 0.94), (1.16; 0.50), (1.07; 12.75), (1.06; 12.70), (0.01; 0.52), (0.00; 18.11), (−0.01; 0.48)


 


75




3.66
582.1



 


76




3.4
584.1
(8.72; 1.96), (8.67; 0.37), (8.47; 2.09), (8.47; 2.32), (8.46; 2.26), (8.46; 2.35), (8.40; 0.37), (8.40; 0.37), (8.37; 1.38), (8.36; 1.37), (8.35; 1.40), (8.35; 1.40), (8.13; 1.32), (8.12; 1.38), (8.05; 0.39), (7.81; 0.35), (7.76; 0.70), (7.58; 1.20), (7.57; 1.25), (7.57; 1.23), (7.56; 1.15), (7.44; 1.34), (7.43; 1.33), (6.87; 0.46), (4.03; 0.53), (4.02; 0.54), (3.93; 0.69), (3.92; 1.04), (3.91; 1.09), (3.90; 0.72), (3.80; 0.89), (3.45; 0.63), (3.44; 0.72), (3.44; 0.74), (3.43; 0.81), (3.36; 296.43), (3.36; 339.87), (3.33; 3.15), (3.29; 0.34), (3.28; 0.38), (2.62; 0.64), (2.62; 0.88), (2.61; 0.62), (2.54; 0.54), (2.52; 1.70), (2.52; 2.28), (2.52; 2.82), (2.51; 45.87), (2.51; 96.06), (2.50; 130.59), (2.50; 92.75), (2.50; 41.57), (2.39; 0.58), (2.39; 0.80), (2.38; 0.57), (2.37; 0.50), (2.21; 3.38), (2.18; 0.90), (2.08; 8.16), (2.06; 0.36), (1.99; 2.30), (1.76; 0.34), (1.65; 0.45), (1.64; 0.44), (1.46; 0.37), (1.35; 5.10), (1.26; 0.56), (1.24; 1.86), (1.19; 0.74), (1.17; 1.36), (1.16; 4.29), (1.15; 3.69), (1.07; 1.74), (1.06; 16.00), (1.06; 4.61), (1.05; 15.74), (0.01; 1.30), (0.00; 34.71), (−0.01; 0.91)


 


77




2.89
555.9
(10.51; 4.01), (8.74; 3.43), (8.74; 3.46), (8.74; 3.52), (8.73; 3.58), (8.72; 0.55), (8.49; 4.25), (8.49; 4.61), (8.48; 4.68), (8.48; 4.54), (8.42; 0.57), (8.42; 0.63), (8.41; 0.67), (8.41; 0.68), (8.37; 4.57), (8.37; 4.19), (8.35; 3.44), (8.35; 2.82), (8.22; 0.54), (8.22; 0.56), (8.20; 0.60), (8.20; 0.56), (8.17; 3.12), (8.16; 3.15), (8.15; 3.48), (8.14; 3.33), (8.03; 0.32), (7.97; 0.54), (7.97; 0.63), (7.97; 0.63), (7.97; 0.53), (7.88; 3.32), (7.76; 3.87), (7.75; 3.80), (7.60; 3.22), (7.59; 3.19), (7.58; 3.12), (7.57; 3.32), (7.56; 0.67), (7.55; 0.57), (7.54; 0.55), (7.50; 0.53), (7.48; 0.76), (7.46; 3.51), (7.44; 3.37), (7.28; 2.22), (7.19; 3.52), (6.87; 0.79), (6.82; 0.50), (6.64; 0.45), (4.06; 0.70), (4.04; 2.10), (4.02; 2.12), (4.00; 0.73), (3.80; 1.77), (3.75; 4.28), (3.60; 0.40), (3.48; 0.32), (3.45; 0.49), (3.44; 0.49), (3.43; 0.52), (3.40; 0.94), (3.39; 1.16), (3.33; 1664.42), (2.68; 12.71), (2.67; 13.48), (2.54; 1.97), (2.52; 6.88), (2.51; 109.35), (2.51; 217.70), (2.50; 288.68), (2.50; 206.24), (2.49; 98.56), (2.37; 0.92), (2.34; 0.65), (2.33; 1.36), (2.33; 1.85), (2.32; 1.31), (2.32; 0.62), (2.22; 16.00), (2.18; 1.33), (2.07; 7.26), (1.99; 9.43), (1.94; 2.79), (1.91; 0.68), (1.76; 0.36), (1.40; 0.71), (1.36; 10.48), (1.30; 0.63), (1.26; 1.05), (1.24; 3.32), (1.19; 2.75), (1.17; 5.45), (1.16; 2.66), (0.85; 0.48), (0.01; 2.21), (0.00; 54.87), (−0.01; 1.98)









Analytical Methods:

The logP values reported in the table above and in the Preparation Examples were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed-phase columns (C18), with the following methods:
The LC-MS determination in the acidic range is carried out at pH 2.7 using the mobile phases 0.1% aqueous formic acid and acetonitrile (contains 0.1% formic acid), linear gradient from 10% acetonitrile to 95% acetonitrile
Calibration was carried out using unbranched alkan-2-ones (having from 3 to 16 carbon atoms) with known logP values (the logP values were determined by the retention times using linear interpolation between two successive alkanones).
The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
The MH+ signals were determined using an Agilent MSD system with ESI and positive or negative ionisation.
The NMR spectra were determined using a Bruker Avance 400 fitted with a flow probe head (volume 60 μl). The solvent used was d6-DMSO, with tetramethylsilane (0.00 ppm) being employed as reference. The examples in the table above were recorded in d6-DMSO as solvent, with the exception of Example No. 64, which was recorded in CD3CN as solvent. The measuring temperature is 303K when the solvent used is d6-DMSO and 298K when the solvent used is CD3CN.
In individual cases, the samples were measured using a Bruker Avance II 600 or III 600.
USE EXAMPLES
Example 1
Myzus Test
MYZUPE Spray Treatment


    Solvents: 78 parts by weight of acetone
    
        1.5 parts by weight of dimethylformamide
    
    
    Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether


To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Discs of Chinese cabbage (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration.
After 6 days, the effect in % is determined 100% means that all of the aphids have been killed; 0% means that none of the aphids have been killed.
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of 80%: 32, 63
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of 90%: 15, 21, 33
Example 2
Phaedon Test
PHAECO Spray Treatment


    Solvents: 78.0 parts by weight of acetone
    
        1.5 parts by weight of dimethylformamide
    
    
    Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether


To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Discs of Chinese cabbage (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).
After 7 days, the activity in % is determined 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 500 g/ha, an activity of 100%: 19, 20
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of 83%: 1
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of 100%: 3, 10, 11, 13, 14, 15, 17, 18, 21, 22, 64, 65, 67, 68, 71, 73, 74, 76, 77
Example 3
Spodoptera frugiperda Test
SPODFR Spray Treatment


    Solvents: 78.0 parts by weight of acetone
    
        1.5 parts by weight of dimethylformamide
    
    
    Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether


To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Discs of maize leaves (Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).
After 7 days, the effect in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 500 g/ha, an activity of 100%: 19, 20
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of 83%: 4, 46, 52
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of 100%: 1, 10, 11, 12, 14, 17, 21, 22, 33, 55, 56, 59, 63, 64, 65, 66, 67, 68, 71, 73, 74, 76, 77
In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 g/ha, an activity of 100%: 15
Example 4
Boophilus microplus Test
BOOPMI Injection
Solvent: dimethyl sulphoxide
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.
The active compound solution is injected into the abdomen (Boophilus microplus), and the animals are transferred into dishes and stored in a climate-controlled room.
After 7 days, the activity in % is determined. The activity is assessed by position of fertile eggs. 100% means that none of the ticks has laid any fertile eggs.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 20 μg/animal: 15, 22, 63
Example 5
Lucilia cuprina Test
LUCICU
Solvent: dimethyl sulphoxide
To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulphoxide and the concentrate is diluted with water to the desired concentration.
Vessels containing horse meat treated with the active compound preparation of the desired concentration are populated with about 20 Lucilia cuprina larvae.
After 48 h, the kill in % is determined 100% means that all of the larvae have been killed; 0% means that none of the larvae have been killed.
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 90% at an application rate of 100 ppm: 11, 12
In this test, for example, the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 100 ppm: 15, 21, 22
Example 6
Phaedon cochleariae Test
PHAECO Spray Treatment


    
    
        Solvents: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
        Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
    
    


To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Discs of Chinese cabbage (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).
After the desired period of time, the activity in % is determined 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
In this test, for example, the following compounds of the Preparation Examples show an efficacy which is superior to the prior art: see table
Spodoptera frugiperda Test (SPODFR Spray Treatment)

    
    
        Solvents: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
        Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
    
    


To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Discs of maize leaves (Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).
After the desired period of time, the activity in % is determined 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
In this test, for example, the following compounds of the Preparation Examples show an efficacy which is superior to the prior art: see table














Substance
Structure
Object
Concentration
% Activity







Example 18: according to the invention




PHAECO SPODFR
100 g/ha 100 g/ha
100 7 d 100 7 d


 


No. 1 known WO 2007/144100




PHAECO SPODFR
100 g/ha 100 g/ha
 0 7 d  0 7 d

## Claims

1. A compound of formula (I)



or an N-oxide and/or salt thereof,
in which
R1 represents hydrogen, amino, or hydroxyl; or represents C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents that independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, (C1-C4-alkoxy)carbonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino and (C1-C4-alkyl)-C3-C6-cycloalkylamino,
R2 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino, C1-C6-alkoxycarbonyl or C1-C6-alkylcarbonyl, and
R3 represents hydrogen; or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, or C2-C6-alkynyl, where the substituents are identical or different and independently of one another and are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkyl-sulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkyl-carbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C1-C6-alkoxycarbonyl, C1-C6-alkylcarbonyl, C3-C6-trialkylsilyl, amino, C3-C6-cycloalkylamino and a 5- or 6-membered heteroaromatic ring; or represents optionally mono- or polysubstituted C3-C12-cycloalkyl, C3-C12-cyclo-alkyl-C1-C6-alkyl or C4-C12-bicycloalkyl, where the substituents independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, amino, C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C1-C6-alkoxycarbonyl, C1-C6-alkylcarbonyl, C3-C6-trialkylsilyl and a 5- or 6-membered heteroaromatic ring, or
R2 and R3 are joined to one another via two to six carbon atoms and form a ring which optionally additionally contains a further ring nitrogen, sulphur or oxygen atom and are optionally mono- to tetrasubstituted by C1-C2-alkyl, halogen, cyano, amino or C1-C2-alkoxy, or R2 and R3 together represent ═S(C1-C4-alkyl)2 or ═S(O)(C1-C4-alkyl)2,
R4 represents hydrogen, halogen, cyano, nitro, hydroxyl, amino, (C═O)OH, OCN, SCN, C1-C4-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy, SF5, C1-C4-alkylthio, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkyl-sulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylcarbonylamino, N-methoxy-N-methylamino, C1-C4-alkoxycarbonyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, aminothiocarbonyl, C1-C4-alkylaminothiocarbonyl, C1-C4-dialkylaminothiocarbonyl, C3-C6-cycloalkylamino, (C1-C4-alkoxy)imino, (C1-C4-alkyl)(C1-C4-alkoxy)imino, (C1-C4-haloalkyl)(C1-C4-alkoxy)imino, C1-C4-alkyl-sulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl, C1-C4-dialkylamino-sulphonyl, C1-C4-alkylsulphoximino, or C3-C6-trialkylsilyl; or represents a 3- to 6-membered saturated, partially saturated or aromatic ring that optionally contains one to three heteroatoms selected from the group consisting of O, S and N and that is optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of halogen, cyano, nitro, hydroxyl, amino, carboxyl, C1-C4-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkyl-sulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylcarbonylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, aminothiocarbonyl, C1-C4-alkyl-aminothiocarbonyl, C1-C4-dialkylaminothiocarbonyl, C3-C6-cycloalkylamino, C1-C4-alkylsulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl and C1-C4-dialkylaminosulphonyl, or
two radicals R4, via adjacent carbon atoms, form a ring and together represent —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH═CH—)2—, —OCH2O—, —O(CH2)2O—, —OCF2O—, —(CF2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—, or two radicals R4, via adjacent carbon atoms, together form a fused ring selected from the rings below that are optionally mono- or polysubstituted by identical or different substituents that independently of one another are selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C3-C6-halocycloalkyl, halogen, C1-C6-alkoxy, C1-C4-alkylthio(C1-C6-alkyl), C1-C4-alkylsulphinyl(C1-C6-alkyl), C1-C4-alkylsulphonyl(C1-C6-alkyl), C1-C4-alkylamino, di-(C1-C4-alkyl)amino and C3-C6-cycloalkylamino,




n represents 0 to 3,
R5 represents C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, halogen, cyano, nitro or C3-C6-trialkylsilyl,
A represents —(C2-C6-alkenylene)-, —(C2-C6-alkynylene)-, —R8—C(═O)—R8—, —R8—NHS(═O)2—R8, R8—C(═O)—C(═O)—R8, —R8—N(C1-C6-alkyl)S(═O)2—R8, phenyl, furan, thiophene, imidazole, thiazole, oxazole, pyridine, pyrimidine, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline, imidazolidine, imidazoline, isoxazoline, piperidine, piperazine, pyrrolidone, pyrrolidinone, imidazolidone, imidazolidinone, triazolinone, triazolidinone, thiazolone, thiazolidinone, oxazolone, or oxazolidinone; or represents —(C1-C6)alkylene- that is mono- or polysubstituted independently by halogen or hydroxyl,
R8 represents straight-chain or branched —(C1-C6-alkylene)- or represents a direct bond,
Q represents phenyl that is mono- or polysubstituted by R10, or represents a 5- or 6-membered partially saturated or saturated heterocyclic or heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, where the ring or the ring system is optionally mono- or polysubstituted by identical or different R10,
R10 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, CO2H, CO2NH2, NO2, OH, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C3-C6-cycloalkylamino, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)aminocarbonyl, di-(C1-C4-alkyl)aminocarbonyl, tri-(C1-C2)alkylsilyl, or (C1-C4-alkyl)(C1-C4-alkoxy)-imino or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the ring are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, NO2, OH, C1-C4-alkoxy, and C1-C4-haloalkoxy,
with the proviso that R10 does not represent hydrogen if A represents —R8—C(═O)—R8 and Q represents phenyl,

R6 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C6-cycloalkoxy or




R7 independently represents hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, halogen, cyano, nitro, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio,
P represents 0 to 4, and
Z represents N, CH, CF, CCl, CBr or CI.

2. A compound according to claim 1 in which
R1 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, cyano(C1-C6-alkyl), C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylsulphinyl-C1-C4-alkyl or C1-C4-alkylsulphonyl-C1-C4-alkyl,
R2 represents hydrogen or C1-C6-alkyl,
R3 represents hydrogen; or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, where the substituents are identical or different and independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkyl-carbonyl and C3-C6-trialkylsilyl; or represents C3-C12-cycloalkyl or C4-C10-bicycloalkyl, where the substituents independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R4 represents hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, halogen, cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, nitro, hydroxyl, amino, (C═O)OH, C1-C4-alkylsulphonyloxy, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, C1-C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkylcarbonylamino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, aminocarbonyl, C1-C4-alkylaminocarbonyl, C1-C4-dialkylaminocarbonyl, aminothiocarbonyl, C1-C4-alkylaminothiocarbonyl, C1-C4-dialkylaminothiocarbonyl, C1-C4-alkylsulphonylamino, aminosulphonyl, C1-C4-alkylaminosulphonyl or C1-C4-dialkylaminosulphonyl, or
two adjacent radicals R4 form a ring and together represent —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH═CH—)2—, —OCH2O—, —O(CH2)2O—, —OCF2O—, —(CF2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,
R5 represents C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, halogen, cyano, nitro or C3-C6-trialkylsilyl,
A represents —(C2-C4-alkenylene)-, —(C2-C4-alkynylene), —R8—C(═O)—R8, —R8—NHS(═O)2—R8, —R8—N(C1-C4-alkyl)S(═O)2—R8, R8—C(═O)—C(═O)—R8, phenyl, furan, thiophene, imidazole, thiazole, oxazole, pyridine, pyrimidine, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline, imidazolidine, imidazoline, isoxazoline, piperidine, piperazine, pyrrolidone, pyrrolidinone, imidazolidone, imidazolidinone, triazolinone, triazolidinone, thiazolone, thiazolidinone, oxazolone, or oxazolidinone; or represents —(C1-C6)alkylene- that is mono- or polysubstituted independently by halogen, C1-C4-alkyoxy, halo-C1-C4-alkyl, halo-C1-C6-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl or C1-C4-haloalkylsulphonyl,
R6 represents C1-C6-alkyl, C3-C6-cycloalkoxy, or




R7 independently represents hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylsulphonyl or (C1-C4-alkyl)-C1-C4-alkoxyimino,
p represents 1, 2 or 3,
Z represents N, CH, CF, CCl, CBr or CI,
R8 represents straight-chain or branched —(C1-C4-alkylene)- or represents a direct bond,
R10 represents hydrogen, C1-C3-alkyl, C1-C3-haloalkyl, C1-C2-alkoxy, halogen, cyano, hydroxyl, nitro, C1-C2-haloalkoxy; or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the heteroaromatic ring are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-halocycloalkyl, halogen, CN, NO2, OH, C1-C4-alkoxy and C1-C4-haloalkoxy,
with the proviso that R10 does not represent hydrogen if A represents —R8—C(═O)—R8 and Q represents phenyl, and

Q represents phenyl that is mono- or polysubstituted by R10 or represents a 5- or 6-membered partially saturated or saturated heterocyclic or heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, where the heteroatoms are selected from the group consisting of N, S, and O, where the ring or the ring system is optionally mono- or polysubstituted by identical or different R10.

3. A compound according to claim 1 in which
A represents —C(═O)—, —CH2(CO)—, CH2CH(OH)—, —C(═O)—C(═O)—, —CH═CH—, —C≡C—, isoxazoline, imidazolidone, —CH2NHSO2CH2—, —CH2NMeSO2CH2—, —(CO)CH2—, —CHCl—, —CCl2—, —CHF—, or —CF2—.

4. A compound according to claim 1 in which
R1 represents hydrogen, methyl, cyclopropyl, cyanomethyl, methoxymethyl, methylthiomethyl, methylsulphinylmethyl or methylsulphonylmethyl,
R2 represents hydrogen or methyl,
R3 represents hydrogen; or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, or C1-C6-alkoxy, where the substituents are identical or different and independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl; or represents optionally mono- or polysubstituted C3-C6-cycloalkyl, where the substituents are identical or different and independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R4 represents hydrogen, C1-C4-alkyl, C1-C2-haloalkyl, halogen, cyano or C1-C2-haloalkoxy, or
two adjacent radicals R4 form a ring and together represent —(CH2)4—, —(CH═CH—)2—, —O(CH2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,
R5 represents C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro or C3-C6-trialkylsilyl,
A represents —CH(Hal)-, —C(Hal)2-, —C(═O)—, —CH2(CO)—, —(CO)CH2—, —C(═O)—C(═O)—, CH2(CS)—, CH2CH(OH)—, —CH2NHSO2—, —CH2NMeSO2—, —CH2NHSO2CH2—, —CH2NMeSO2CH2—, —CH2N(SO2Me)CH2—, -cyclopropyl-, cyclobutyl, CH2(CO)CH2—, —CH═CH—, —C≡C—, phenyl, furan, thiophene, imidazole, thiazole, oxazole, pyridine, pyrimidine, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline, imidazolidine, imidazoline, isoxazoline, piperidine, piperazine, pyrrolidone, pyrrolidinone, imidazolidone, imidazolidinone, triazolinone, triazolidinone, thiazolone, thiazolidinone, oxazolone, or oxazolidinone,
R6 represents methyl or




R7 independently represents hydrogen, halogen or C1-C4-haloalkyl,
P represents 1 or 2,
Z represents N, CH, CF, CCl or CBr,
R8 represents methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or isobutyl or a direct bond,
R10 represents hydrogen, C1-C3-alkyl, C1-C3-haloalkyl, C1-C2-alkoxy, halogen, cyano, hydroxyl, C1-C2-haloalkoxy; or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the heteroaromatic ring are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of C1-C3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C3-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-halocycloalkyl, halogen, cyano, C1-C4-alkoxy, and C1-C4-haloalkoxy,
with the proviso that R10 does not represent hydrogen if A represents —R8—C(═O)—R8 and Q represents phenyl, and

Q represents phenyl that is mono- or polysubstituted by R10; or represents a 5- or 6-membered heteroaromatic ring selected from the group consisting of Q-1 to Q-53 and Q-58 to Q-59, and Q62 to Q63 that is optionally mono- or polysubstituted by R10 or an aromatic 9-membered fused heterobicyclic ring system Q-54 to Q-56; or represents a 5-membered heterocyclic ring Q-60 to Q-61,

5. A mixture of compounds according to claim 4, in which Q is Q58 and Q59, the ratio of a compound of the formula (I) in which Q is Q58 to a compound of the formula (I) in which Q is Q59 being 60:40 to 99:1.

6. A mixture of compounds of formula (I)



or an N-oxide and/or salt thereof,
in which
R1 represents hydrogen, methyl, cyclopropyl, cyanomethyl, methoxymethyl, methylthiomethyl, methylsulphinylmethyl or methylsulphonylmethyl,
R2 represents hydrogen or methyl,
R3 represents hydrogen; or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, or C1-C6-alkoxy, where the substituents are identical or different and independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl; or represents optionally mono- or polysubstituted C3-C6-cycloalkyl, where the substituents are identical or different and independently of one another are selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylsulphimino, C1-C4-alkylsulphimino-C1-C4-alkyl, C1-C4-alkylsulphimino-C2-C5-alkylcarbonyl, C1-C4-alkylsulphoximino, C1-C4-alkylsulphoximino-C1-C4-alkyl, C1-C4-alkylsulphoximino-C2-C5-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl and C3-C6-trialkylsilyl,
R4 represents hydrogen, C1-C4-alkyl, C1-C2-haloalkyl, halogen, cyano or C1-C2-haloalkoxy, or
two adjacent radicals R4 form a ring and together represent —(CH2)4—, —(CH═CH—)2—, —O(CH2)2O—, —O(CF2)2O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,
R5 represents C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C6-halocycloalkyl, C2-C6-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C1-C4-alkoxy, C1-C4-haloalkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro or C3-C6-trialkylsilyl,
A represents —CH(Hal)-, —C(Hal)2-, —C(═O)—, —CH2(CO)—, —(CO)CH2—, —C(═O)—C(═O)—, CH2(CS)—, CH2CH(OH)—, —CH2NHSO2— —CH2NMeSO2— —CH2NHSO2CH2—, —CH2NMeSO2CH2— —CH2N(SO2Me)CH2—, -cyclopropyl-, cyclobutyl, CH2(CO)CH2—, —CH═CH—, —C≡C—, phenyl, furan, thiophene, imidazole, thiazole, oxazole, pyridine, pyrimidine, azetidine, oxetane, thietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline, imidazolidine, imidazoline, isoxazoline, piperidine, piperazine, pyrrolidone, pyrrolidinone, imidazolidone, imidazolidinone, triazolinone, triazolidinone, thiazolone, thiazolidinone, oxazolone, or oxazolidinone,
R6 represents methyl or




R7 independently represents hydrogen, halogen or C1-C4-haloalkyl,
p represents 1 or 2,
Z represents N, CH, CF, CCl or CBr,
R10 represents hydrogen, C1-C3-alkyl, C1-C3-haloalkyl, C1-C2-alkoxy, halogen, cyano, hydroxyl, C1-C2-haloalkoxy; or represents phenyl or a 5- or 6-membered heteroaromatic ring, where phenyl or the heteroaromatic ring are optionally mono- or polysubstituted by identical or different substituents selected from the group consisting of C1-C3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C3-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-halocycloalkyl, halogen, cyano, C1-C4-alkoxy, and C1-C4-haloalkoxy, and
Q represents




wherein the ratio of a compound of the formula (I) in which Q is Q62 to a compound of the formula (I) in which Q is Q63 is 60:40 to 99:1.

7. A composition comprising at least one compound according to claim 1 and at least one salt of the formula (XXIV)



in which
D represents nitrogen or phosphorus,
R11, R12, R13 and R14 independently of one another represent hydrogen or in each case optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally substituted C1-C8-alkylene where the substituents are selected from the group consisting of halogen, nitro and cyano,
m represents 1, 2, 3 or 4, and
R15 represents an inorganic or organic anion.

8. A composition comprising at least one compound according to claim 1 and at least one penetrant of formula (XXV)


R—O-(-AO)V—R′  (XXV)

in which
R represents straight-chain or branched alkyl having 4 to 20 carbon atoms,
R′ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl,
AO represents an ethylene oxide radical, a propylene oxide radical, or a butylene oxide radical or represents a mixture of ethylene oxide and propylene oxide radicals or butylene oxide radicals and
V represents a number from 2 to 30.

9. An agrochemical composition comprising at least one compound according to claim 1 and at least one extender and/or surfactant.

10. A process for producing an agrochemical composition comprising mixing at least one compound according to claim 1 with at least one extender and/or surfactant.

11. A method for controlling animal pests comprising applying at least one compound according to claim 1 to animal pests and/or phytopathogenic fungi and/or their habitat and/or seed.