TREA

INSECTICIDAL COMPOSITIONS WITH IMPROVED EFFECT

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Information

  • Patent Application
  • 20090149506
  • Publication Number
    20090149506
  • Date Filed
    November 30, 2006
    18 years ago
  • Date Published
    June 11, 2009
    16 years ago
Information
Abstract
The present invention relates to increasing the activity of crop protection compositions comprising anthranilic acid diamides through the addition of ammonium salts and/or phosphonium salts or through the addition of ammonium or phosphonium salts and penetrants, to the corresponding compositions, to processes for preparing them and to their use in crop protection.
Description

The present invention relates to increasing the activity of crop protection compositions comprising anthranilic acid diamides (anthranilamides) through the addition of ammonium salts and/or phosphonium salts or through the addition of ammonium or phosphonium salts and penetrants, to the corresponding compositions, to processes for preparing them and to their use in crop protection.


All inhibitors according to the invention of the nicotinic acetylcholine receptor are already known as agents for controlling animal pests, in particular insects, and can be prepared by processes described in the prior art. The activity of these compounds is good; however, in particular at low application rates and concentrations, it is not always entirely satisfactory. Furthermore, the compatibility of these compounds with plants is not always sufficient. There is therefore a need for increasing the activity of the crop protection compositions comprising the compounds.


The anthranilic acid diamides of the formula (I) are likewise known compounds which are known from the following publications, or comprised by them:


NL-A 9202078, WO 01/70671, WO 02/094791, JP-A 2003-212834, WO 03/015519, WO 03/016284, WO 03/015518, WO 03/015519, WO 03/024222, WO 03/016282, WO 03/016283, WO 03/062226, WO 03/027099, WO 04/027042, WO 04/033468.


Mixtures of anthranilic acid diamides with other active compounds are known from WO 05/107468. This publication also described mixtures with petroleum oils.


The anthranilic acid diamides can by summarized by the formula (I):







in which

  • A1 and A2 independently of one another represent oxygen or sulphur,
  • X1 represents N or CR10,
  • R1 represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl, where the substituents independently of one another may be selected from the group consisting of R6, halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C2-C4-alkoxycarbonyl, C1-C4-alkylamino, C2-C8-dialkylamino, C3-C6-cycloalkylamino, (C1-C4-alkyl)C3-C6-cycloalkylamino and R11,
  • R2 represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4-alkylamino, C2-C8-dialkylamino, C3-C6-cycloalkylamino, C2-C6-alkoxycarbonyl or C2-C6-alkylcarbonyl,
  • R3 represents hydrogen, R11 or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, where the substituents independently of one another may be selected from the group consisting of R6, halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl, C3-C6-trialkylsilyl, R11, phenyl, phenoxy or a 5- or 6-membered heteroaromatic ring, where each phenyl, phenoxy and 5- or 6-membered heteroaromatic ring may optionally be substituted and where the substituents independently of one another may be selected from the group consisting of one to three radicals W and one or more radicals R12, or
  • R2 and R3 may be attached to one another and form the ring M,
  • R4 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, cyano, nitro, hydroxyl, 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, C2-C8-dialkylamino, C3-C6-cycloalkylamino, C3-C6-trialkylsilyl or represents in each case optionally mono- or polysubstituted phenyl, benzyl or phenoxy, where the substituents independently of one another may be selected from the group consisting of C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cyclalkyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-halocycloalkyl, halogen, cyano, nitro, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, C2-C8-dialkylamino, C3-C6-cycloalkylamino, C3-C6-(alkyl)cycloalkylamino, C2-C4-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylaminocarbonyl, C3-C8-dialkylaminocarbonyl and C3-C6-trialkylsilyl,
  • R5 and R8 each independently of one another represent hydrogen, cyano, halogen or represent in each case optionally substituted C1-C4-alkyl, C1-C4-haloalkyl, R12, G, J, —OJ, —OG, —S(O)p-J, —S(O)p-G, —S(O)p-phenyl, where the substituents independently of one another may be selected from the group consisting of one to three radicals W or of R2, C1-C10-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C4-alkoxy or C1-C4-alkylhio, where each substituent may be substituted by one or more substituents independently of one another selected from the group consisting of G, J, R6, halogen, cyano, nitro, amino, hydroxyl, 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, C2-C8-dialkylamino, C3-C6-trialkylsilyl, phenyl and phenoxy, where each phenyl or phenoxy ring may optionally be substituted and where the substituents independently of one another may be selected from the group consisting of one to three radicals W and one or more radicals R12,
  • G in each case independently represents a 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring which may optionally contain one or two ring members from the group consisting of C(═O), SO and S(═O)2 and which may optionally be substituted by one to four substituents independently of one another selected from the group consisting of C1-C2-alkyl, halogen, cyano, nitro and C1-C2-alkoxy, or independently represents C2-C6-alkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, (cyano)C3-C7-cycloalkyl, (C1-C4-alkyl)C3-C6-cycloalkyl, (C3-C6-cycloalkyl)C1-C4-alkyl, where each cycloalkyl, (alkyl)cycloalkyl and (cycloalkyl)alkyl may optionally be substituted by one or more halogen atoms,
  • J in each case independently represents an optionally substituted 5- or 6-membered heteroaromatic ring, where the substituents independently of one another may be selected from the group consisting of one to three radicals W and one or more radicals R12,
  • R6 independently represents —C(=E1)R19, -LC(=E1)R19, —C(=E1)LR19, -LC(=E1)LR19, —OP(═O)(OR19)2, —SO2LR18 or -LSO2LR19, where each E1 independently represents O, S, N—R15, N—OR15, N—N(R15)2, N—S═O, N—CN or N—NO2,
  • R7 represents hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, halogen, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkyl-sulphinyl, C1-C4-haloalkylsulphonyl,
  • R9 represents C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylsulphinyl or halogen,
  • R10 represents hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, halogen, cyano or C1-C4-haloalkoxy,
  • R11 in each case independently represents in each case optionally mono- to trisubstituted C1-C6-alkylthio, C1-C6-alkylsulphenyl, C1-C6-haloalkylhio, C1-C6-haloalkylsulphenyl, phenylthio or phenylsulphenyl, where the substituents independently of one another may be selected from the list W, —S(O)nN(R6)2, —C(═O)R13, -L(C═O)R14, —S(C═O)LR14, —C(═O)LR13, —S(O)nNR13C(═O)R13, —S(O)nNR13C(═O)LR14 and —S(O)nNR13S(O)2LR94,
  • L in each case independently represents O, NR18 or S,
  • R12 in each case independently represents —B(OR17)2, amino, SH, thiocyanato, C3-C8-trialkylsilyloxy, C1-C4-alkyl disulphide, —SF5, —C(=E1)R19, -LC(=E1)R19, —C(=E1)LR19, -LC(=E1)LR19, —OP(═O)(OR19)2, —SO2LR19 or -LSO2LR19,
  • Q represents O or S,
  • R13 in each case independently represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C6-cycloalkyl, where the substituents independently of one another may be selected from the group consisting of R6, halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, C2-C8-dialkylamino, C3-C6-cycloalkylamino and (C1-C4-alkyl)C3-C6-cycloalkylamino,
  • R14 in each case independently represents in each case optionally mono- or polysubstituted C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl or C3-C6-cycloalkyl, where the substituents independently of one another may be selected from the group consisting of R6, halogen, cyano, nitro, hydroxyl, C1-C4-alkoxy, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, C2-C8-dialkylamino, C3-C6-cycloalkylamino and (C1-C4-alkyl)C3-C6-cycloalkylamino or represents optionally substituted phenyl, where the substituents independently of one another may be selected from the group consisting of one to three radicals W and one or more radicals R12,
  • R15 in each case independently represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-haloalkyl or C1-C6-alkyl, where the substituents independently of one another may be selected from the group consisting of cyano, nitro, hydroxyl, 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, C2-C8-dialkylamino, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl, C3-C6-trialkylsilyl and optionally substituted phenyl, where the substituents independently of one another may be selected from the group consisting of one to three radicals W and one or more radicals R12, or N(R5)2 represents a cycle which forms the ring M,
  • R16 represents C1-C12-alkyl or C1-C12-haloalkyl, or N(R16)2 represents a cycle which forms the ring M,
  • R17 in each case independently represents hydrogen or C1-C4-alkyl, or B(OR17)2 represents a ring in which the two oxygen atoms are linked via a chain of two or three carbon atoms which are optionally substituted by one or two substituents independently of one another selected from the group consisting of methyl and C2-C6-alkoxycarbonyl,
  • R18 in each case independently represents hydrogen, C1-C6-alkyl or C1-C6-haloalkyl, or N(R13)(R18) represents a cycle which forms the ring M,
  • R19 in each case independently of one another represents hydrogen or represents in each case optionally mono- or polysubstituted C1-C6-alkyl, where the substituents independently of one another may be selected from the group consisting of cyano, nitro, hydroxyl, 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, C2-C8-dialkylamino, CO2H, C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl, C3-C6-trialkylsilyl and optionally substituted phenyl, where the substituents independently of one another may be selected from the group consisting of one to three radicals W, C1-C6-haloalkyl, C3-C6-cycloalkyl and phenyl or pyridyl, each of which is optionally mono- to trisubstituted by W,
  • M represents in each case an optionally mono- to tetrasubstituted ring which, in addition to the nitrogen atom attached to the substituent pair R13 and R18, (R15)2 or (R16)2 contains two to six carbon atoms and optionally additionally a further nitrogen, sulphur or oxygen atom and where the substituents independently of one another may be selected from the group consisting of C1-C2-alkyl, halogen, cyano, nitro and C1-C2-alkoxy,
  • W in each case independently represents C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, C3-C6-halocycloalkyl, halogen, cyano, nitro, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, C2-C8-dialkylamino, C3-C6-cycloalkylamino, (C1-C4-alkyl)C3-C6-cycloalkylamino, C2-C4-alkylcarbonyl, C2-C6-alkoxycarbonyl, CO2H, C2-C6-alkylaminocarbonyl, C3-C8-dialkylaminocarbonyl or C3-C6-trialkylsilyl,
  • n in each case independently represents 0 or 1,
  • p in each case independently represents 0, 1 or 2.


If (a) R5 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio or halogen and (b) R8 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio, halogen, C2-C4-alkylcarbonyl, C2-C6-alkoxycarbonyl, C2-C6-alkylaminocarbonyl or C3-C8-dialkylaminocarbonyl, then (c) at least one substituent selected from the group consisting of R6, R11 and R12 is present and (d), if R12 is not present, at least one R6 or R11 is different from C2-C6-alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6-alkylaminocarbonyl and C3-C8-dialkylaminocarbonyl.


The compounds according to the general formula (I) include N-oxides and salts.


Depending inter alia on the nature of the substituents, the compounds of the formula (I) can be present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if appropriate, can be separated in a customary manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use and compositions comprising them. However, for the sake of simplicity, hereinbelow only compounds of the formula (I) are referred to, although what is meant is both the pure compounds and, if appropriate, mixtures having various proportions of isomeric compounds.


Preference is given to compounds of the formula (I-1)







in which

  • R2 represents hydrogen or C1-C6-alkyl,
  • R3 represents C1-C6-alkyl which is optionally substituted by one R6,
  • R4 represents C1-C4-alkyl, C1-C2-haloalkyl, C1-C2-haloalkoxy or halogen,
  • R5 represents hydrogen, C1-C4-alkyl, C1-C2-haloalkyl, C1-C2-haloalkoxy, cyano or halogen,
  • R6 represents —C(=E2)R19, -LC(=E2)R19, —C(=E2)LR19 or -LC(=E2)LR19, where each E2 independently represents O, S, N—R15, N—OR15, N—N(R5)2, and each L independently represents O or NR18,
  • R7 represents C1-C4-haloalkyl or halogen,
  • R9 represents C1-C2-haloalkyl, C1-C2-haloalkoxy, S(O)pC1-C2-haloalkyl or halogen,
  • R15 in each case independently represents hydrogen or represents in each case optionally substituted C1-C6-haloalkyl or C1-C6-alkyl, where the substituents independently of one another may be selected from the group consisting of cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl and C1-C4-haloalkylsulphonyl,
  • R18 represents in each case hydrogen or C1-C4-alkyl,
  • R19 in each case independently represents hydrogen or C1-C6-alkyl,
  • p independently represents 0, 1, 2.


In the radical definitions mentioned as being preferred, halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.


Particular preference is given to compounds of the formula (I-1) in which

  • R2 represents hydrogen or methyl,
  • R3 represents C1-C4-alkyl (in particular methyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl),
  • R4 represents methyl, trifluoromethyl, trifluoromethoxy, fluorine, chlorine, bromine or iodine,
  • R5 represents hydrogen, cyano, fluorine, chlorine, bromine, iodine, trifluoromethyl or trifluoromethoxy,
  • R7 represents chlorine or bromine,
  • R9 represents trifluoromethyl, chlorine, bromine, difluoromethoxy or trifluoroethoxy.


Very particular preference is given to the following compounds of the formula














(I-1)
























Example









No.
R2
R3
R4
R5
R7
R9
m.p.(° C.)





I-1-1
H
Me
Me
Cl
Cl
CF3
185-186


I-1-2
H
Me
Me
Cl
Cl
Cl
225-226


I-1-3
H
Me
Me
Cl
Cl
Br
162-164


I-1-4
H
i-Pr
Me
Cl
Cl
CF3
195-196


I-1-5
H
i-Pr
Me
Cl
Cl
Cl
173-175


I-1-6
H
i-Pr
Me
Cl
Cl
Br
159-161


I-1-7
H
Me
Me
Br
Cl
CF3
222-223


I-1-8
H
i-Pr
Me
Br
Cl
CF3
197-198


I-1-9
H
Me
Me
Br
Cl
Cl
140-141


I-1-10
H
i-Pr
Me
Br
Cl
Cl
152-153


I-1-11
H
Me
Me
Br
Cl
Br
147-149


I-1-12
H
i-Pr
Me
Br
Cl
Br
185-187


I-1-13
H
Me
Me
I
Cl
CF3
199-200


I-1-14
H
i-Pr
Me
I
Cl
CF3
188-189


I-1-15
H
Me
Me
I
Cl
Cl
233-234


I-1-16
H
i-Pr
Me
I
Cl
Cl
189-190


I-1-17
H
Me
Me
I
Cl
Br
229-230


I-1-18
H
i-Pr
Me
I
Cl
Br
191-192


I-1-19
H
i-Pr
Me
CN
Cl
CF3
>250


I-1-20
H
Me
Me
CN
Cl
CF3
214-216


I-1-21
H
i-Pr
Me
CN
Cl
Br
*


I-1-22
H
Me
Me
CN
Cl
Br
*


I-1-23
H
i-Pr
Me
CN
Cl
Cl
*


I-1-24
H
Me
Me
CN
Cl
Cl
*





* = 1H-NMR data (CDCl3):






  • I-1-80: 10.60 (s, 1H), 8.47 (s, 1H), 7.85 (dd, 1H), 7.56 (s, 2H), 7.39 (dd, 1H), 7.06 (s, 1H), 6.04 (b d, 1H), 4.20 (m, 1H), 2.24 (s, 3H), 1.26 (s, 6H).

  • I-1-81: 10.55 (s, 1H), 8.45 (s, 1H), 7.85 (dd, 1H), 7.57 (m, 2H), 7.37 (dd, 1H), 7.05 (s, 1H), 6.30 (b q, 1H), 2.98 (d, 3H), 2.24 (s, 3H).

  • I-1-82: 10.12 (s, 1H), 8.56 (d, 1H), 7.85 (d, 1H), 7.58 (m, 2H), 7.40 (dd, 1H), 6.97 (s, 1H), 6.00 (b d, 1H), 4.22 (m, 1H), 2.25 (s, 3H), 1.26 (d, 6H).

  • I-1-83: 10.55 (s, 1H), 8.45 (s, 1H), 7.85 (dd, 1H), 7.55 (s, 2H), 7.40 (dd, 1H), 6.97 (s, 1H), 6.30 (b q, 1H), 2.98 (d, 3H), 2.24 (s, 3H).



Especially preferred are the following compounds:



















Phthalic acid diamides have a broad insecticidal action; however, in individual cases the activity is unsatisfactory.


Descriptions have already been given in the literature to the effect that the activity of various active compounds can be increased through addition of ammonium or phosphonium salts. The salts in question, however, are salts with a detergent effect (for example WO 95/017817) and/or salts having relatively long alkyl and/or aryl substituents, which have a permeabilizing effect or which increase the solubility of the active compound (for example EP-A 0 453 086, EP-A 0 664 081, FR-A 2 600 494, U.S. Pat. No. 4,844,734, U.S. Pat. No. 5,462,912, U.S. Pat. No. 5,538,937, Ser. No. 03/0224939, Ser. No. 05/0009880, Ser. No. 05/0096386). Furthermore, the prior art describes the activity only for certain active compounds and/or certain applications of the composition in question. In still other cases, they are salts of sulphonic acids where the acids for their part have a paralysing action on insects (U.S. Pat. No. 2,842,476). An activity increase through ammonium sulphate is described for the herbicides glyphosate and phosphinothricin (U.S. Pat. No. 6,645,914, EP-A 0 036 106). However, this prior art neither discloses nor suggests a corresponding activity for insecticides.


Also, the use of ammonium sulphate as a formulating auxiliary has been described for certain active compounds and applications (WO 92/16108), but it is used there for the purpose of stabilizing the formulation, not for increasing activity.


It has now been found, entirely surprisingly, that the activity of insecticides from the class of the anthranilic acid diamides can be increased significantly through the addition of ammonium salts and/or phosphonium salts to the as-used solution (tank mix application) or through the incorporation of these salts into a formulation comprising such insecticides. Accordingly, the present invention provides the use of ammonium salts and/or phosphonium salts for increasing the activity of crop protection compositions comprising insecticidally active inhibitors of the nicotinic acetylcholine receptor as active compound. The invention also provides compositions comprising such insecticides and activity-increasing ammonium salts and/or phosphonium salts, specifically including not only formulated active compounds but also ready-to-use compositions (spray liquors). Finally, the invention also provides the use of these compositions for controlling harmful insects.


Ammonium salts and phosphonium salts which, according to the invention, increase the activity of crop protection compositions comprising anthranilic acid diamides are defined by formula (II)







in which

  • D represents nitrogen or phosphorus,
  • D preferably represents nitrogen,
  • R20, R21, R22 and R23 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,
  • R20, R21, R22 and R23 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,
  • R20, R21, R22 and R23 particularly preferably independently of one another represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl,
  • R20, R21, R22 and R23 very particularly preferably represent hydrogen,
  • R20, R21, R22 and R23 furthermore very particularly preferably both represent methyl or both represent ethyl,
  • n represents 1, 2, 3 or 4,
  • n preferably represents 1 or 2,
  • R24 represents an inorganic or organic anion,
  • R24 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,
  • R24 furthermore preferably represents carbonate, pentaborate, sulphite, benzoate, hydrogenoxalate, hydrogencitrate, methylsulphate or tetrafluoroborate,
  • R24 particularly preferably represents lactate, sulphate, nitrate, thiosulphate, thiocyanate, citrate, oxalate or formate,
  • R24 furthermore particularly preferably represents monohydrogenphosphate or dihydrogenphosphate and
  • R24 very particularly preferably represents sulphate.


The ammonium salts and phosphonium salts of the formula (II) can be used in a broad concentration range to increase the activity of crop protection compositions comprising anthranilamides. 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 from 0.75 to 37.5 mmol/l, particularly preferably from 1.5 to 25 mmol/l. In the case of a formulated product, the ammonium salt concentration and/or phosphonium salt concentration in the formulation is chosen such that it is within these stated general, preferred or very preferred ranges after the formulation has been diluted to the desired active compound concentration. The concentration of the salt in the formulation here is typically 1-50% by weight.


In a preferred embodiment of the invention, the activity is increased by adding to the crop protection compositions not only an ammonium salt and/or phosphonium salt but also, additionally, a penetrant. It is considered entirely surprising that even in these cases an even greater activity increase is observed. The present invention therefore likewise provides the use of a combination of penetrant and ammonium salts and/or phosphonium salts for increasing the activity of crop protection compositions comprising insecticidally active inhibitors of the nicotinic acetylcholine receptor as active compound. The invention likewise provides compositions which comprise insecticidally active inhibitors of the nicotinic acetylcholine receptor, penetrants and ammonium salts and/or phosphonium salts, including specifically not only formulated active compounds but also ready-to-use compositions (spray liquors). The invention additionally provides, finally, for the use of these compositions for controlling harmful insects.


Suitable penetrants in the present context include all those substances which are typically used to enhance the penetration of agrochemically 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 to 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 in order to determine 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′  (III)


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, t-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 numbers from 2 to 30.


A preferred group of penetrants are alkanol alkoxylates of the formula





R—O-(-EO—)w—R′  (III-a)


in which

    • R is as defined above,
    • R′ is as defined above,
    • EO represents —CH2—CH2—O— and
    • w represents numbers from 2 to 20.


A further preferred group of penetrants are alkanol alkoxylates of the formula





R—O-(-EO—)b—(—PO—)q—R′  (III-b)


in which

    • R is as defined above,
    • R′ is as defined above,
    • EO represents —CH2—CH2—O—,
    • PO represents









    • b represents numbers from 1 to 10 and

    • q represents numbers from 1 to 10.





A further preferred group of penetrants are alkanol alkoxylates of the formula





R—O—(—PO—)r-(EO—)s—R  (III-c)


in which

    • R is as defined above,
    • R′ is as defined above,
    • EO represents —CH2—CH2—O—,
    • PO represents









    • r represents numbers from 1 to 10 and

    • s represents numbers from 1 to 10.





A further preferred group of penetrants are alkanol alkoxylates of the formula





R—O-(-EO—)b—(—BO—)q—R′  (III-d)


in which

    • R and R′ are as defined above,
    • EO represents CH2—CH2—O—,
    • BO represents









    • b represents numbers from 1 to 10 and

    • q represents numbers from 1 to 10.





A further preferred group of penetrants are alkanol alkoxylates of the formula





R—O—(—BO—)r-(-EO—)s—R′  (III-e)


in which

    • R and R′ are as defined above,
    • BO represents









    • EO represents CH2—CH2—O—,

    • r represents numbers from 1 to 10 and

    • s represents numbers from 1 to 10.





A further preferred group of penetrants are alkanol alkoxylates of the formula





CH3—(CH2)r—CH2—O—(—CH2—CH2—O—)u—R′  (III-f)


in which

    • R′ is as defined above,
    • t represents numbers from 8 to 13 and
    • u represents numbers 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.


An example which may be mentioned of an alkanol alkoxylate of the formula (III-c) is 2-ethylhexyl alkoxylate of the formula







in which

    • EO represents —CH2—CH2—O—,
    • PO represents







the numbers 8 and 6 are average values.


An example which may be mentioned of an alkanol alkoxylate of the formula (III-d) is the formula





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


in which

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









    • the numbers 10, 6 and 2 are average values.





Particularly preferred alkanol alkoxylates of the formula (I-f) are compounds of this formula in which

    • t represents numbers from 9 to 12 and
    • u represents numbers from 7 to 9.


The alkanol alkoxylate of the formula (III-f-1)





CH3—(CH2)t—CH2—O-(—CH2—CH2—O—)u—H  (III-f-1)


in which

    • t represents the average value 10.5 and
    • u represents the average value 8.4


      may be mentioned as being very particularly preferred.


The above formulae provide a general definition of the alkanol alkoxylates. These substances are mixtures of substances of the stated type with different chain lengths. The indices therefore have average values which may also deviate from whole numbers.


The alkanol alkoxylates of the formulae stated are known and in some cases are available commercially 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 a spray coating. These include, for example, mineral and vegetable oils. Suitable oils are all mineral or vegetable oils—modified or otherwise—which can typically be used in agrochemical compositions. Mention may be made by way of example of sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maizeseed 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 penetrants in the compositions according to the invention can be varied within a wide range. In the case of a formulated crop protection composition, it is generally from 1 to 95% by weight, preferably from 1 to 55% by weight, particularly preferably from 15 to 40% by weight. In the ready-to-use compositions (spray liquors), the concentration is 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, “as per test” means that any compound that acts as a penetrant in the cuticle penetration test (Baur et al., 1997, Pesticide Science 51, 131-152) is suitable.
















Active





com-


#
pound
Salt
Penetrant


















1
(I-1-1)
ammonium sulphate
as per test


2
(I-1-1)
ammonium lactate
as per test


3
(I-1-1)
ammonium nitrate
as per test


4
(I-1-1)
ammonium thiosulphate
as per test


5
(I-1-1)
ammonium thiocyanate
as per test


6
(I-1-1)
ammonium citrate
as per test


7
(I-1-1)
ammonium oxalate
as per test


8
(I-1-1)
ammonium formate
as per test


9
(I-1-1)
ammonium hydrogenphosphate
as per test


10
(I-1-1)
ammonium dihydrogenphosphate
as per test


11
(I-1-1)
ammonium carbonate
as per test


12
(I-1-1)
ammonium benzoate
as per test


13
(I-1-1)
ammonium sulphite
as per test


14
(I-1-1)
ammonium benzoate
as per test


15
(I-1-1)
ammonium hydrogenoxalate
as per test


16
(I-1-1)
ammonium hydrogencitrate
as per test


17
(I-1-1)
tetramethylammonium sulphate
as per test


18
(I-1-1)
tetramethylammonium lactate
as per test


19
(I-1-1)
tetramethylammonium nitrate
as per test


20
(I-1-1)
tetramethylammonium thiosulphate
as per test


21
(I-1-1)
tetramethylammonium thiocyanate
as per test


22
(I-1-1)
tetramethylammonium citrate
as per test


23
(I-1-1)
tetramethylammonium oxalate
as per test


24
(I-1-1)
tetramethylammonium formate
as per test


25
(I-1-1)
tetramethylammonium hydrogenphosphate
as per test


26
(I-1-1)
tetramethylammonium dihydrogenphosphate
as per test


27
(I-1-1)
tetraethylammonium sulphate
as per test


28
(I-1-1)
tetraethylammonium lactate
as per test


29
(I-1-1)
tetraethylammonium nitrate
as per test


30
(I-1-1)
tetraethylammonium thiosulphate
as per test


31
(I-1-1)
tetraethylammonium thiocyanate
as per test


32
(I-1-1)
tetraethylammonium citrate
as per test


33
(I-1-1)
tetraethylammonium oxalate
as per test


34
(I-1-1)
tetraethylammonium formate
as per test


35
(I-1-1)
tetraethylammonium hydrogenphosphate
as per test


36
(I-1-1)
tetraethylammonium dihydrogenphosphate
as per test


37
(I-1-2)
ammonium sulphate
as per test


38
(I-1-2)
ammonium lactate
as per test


39
(I-1-2)
ammonium nitrate
as per test


40
(I-1-2)
ammonium thiosulphate
as per test


41
(I-1-2)
ammonium thiocyanate
as per test


42
(I-1-2)
ammonium citrate
as per test


43
(I-1-2)
ammonium oxalate
as per test


44
(I-1-2)
ammonium formate
as per test


45
(I-1-2)
ammonium hydrogenphosphate
as per test


46
(I-1-2)
ammonium dihydrogenphosphate
as per test


47
(I-1-2)
ammonium carbonate
as per test


48
(I-1-2)
ammonium benzoate
as per test


49
(I-1-2)
ammonium sulphite
as per test


50
(I-1-2)
ammonium benzoate
as per test


51
(I-1-2)
ammonium hydrogenoxalate
as per test


52
(I-1-2)
ammonium hydrogencitrate
as per test


53
(I-1-2)
tetramethylammonium sulphate
as per test


54
(I-1-2)
tetramethylammonium lactate
as per test


55
(I-1-2)
tetramethylammonium nitrate
as per test


56
(I-1-2)
tetramethylammonium thiosulphate
as per test


57
(I-1-2)
tetramethylammonium thiocyanate
as per test


58
(I-1-2)
tetramethylammonium citrate
as per test


59
(I-1-2)
tetramethylammonium oxalate
as per test


60
(I-1-2)
tetramethylammonium formate
as per test


61
(I-1-2)
tetramethylammonium hydrogenphosphate
as per test


62
(I-1-2)
tetramethylammonium dihydrogenphosphate
as per test


63
(I-1-2)
tetraethylammonium sulphate
as per test


64
(I-1-2)
tetraethylammonium lactate
as per test


65
(I-1-2)
tetraethylammonium nitrate
as per test


66
(I-1-2)
tetraethylammonium thiosulphate
as per test


67
(I-1-2)
tetraethylammonium thiocyanate
as per test


68
(I-1-2)
tetraethylammonium citrate
as per test


69
(I-1-2)
tetraethylammonium oxalate
as per test


70
(I-1-2)
tetraethylammonium formate
as per test


71
(I-1-2)
tetraethylammonium hydrogenphosphate
as per test


72
(I-1-2)
tetraethylammonium dihydrogenphosphate
as per test


73
(I-1-3)
ammonium sulphate
as per test


74
(I-1-3)
ammonium lactate
as per test


75
(I-1-3)
ammonium nitrate
as per test


76
(I-1-3)
ammonium thiosulphate
as per test


77
(I-1-3)
ammonium thiocyanate
as per test


78
(I-1-3)
ammonium citrate
as per test


79
(I-1-3)
ammonium oxalate
as per test


80
(I-1-3)
ammonium formate
as per test


81
(I-1-3)
ammonium hydrogenphosphate
as per test


82
(I-1-3)
ammonium dihydrogenphosphate
as per test


83
(I-1-3)
ammonium carbonate
as per test


84
(I-1-3)
ammonium benzoate
as per test


85
(I-1-3)
ammonium sulphite
as per test


86
(I-1-3)
ammonium benzoate
as per test


87
(I-1-3)
ammonium hydrogenoxalate
as per test


88
(I-1-3)
ammonium hydrogencitrate
as per test


89
(I-1-3)
tetramethylammonium sulphate
as per test


90
(I-1-3)
tetramethylammonium lactate
as per test


91
(I-1-3)
tetramethylammonium nitrate
as per test


92
(I-1-3)
tetramethylammonium thiosulphate
as per test


93
(I-1-3)
tetramethylammonium thiocyanate
as per test


94
(I-1-3)
tetramethylammonium citrate
as per test


95
(I-1-3)
tetramethylammonium oxalate
as per test


96
(I-1-3)
tetramethylammonium formate
as per test


97
(I-1-3)
tetramethylammonium hydrogenphosphate
as per test


98
(I-1-3)
tetramethylammonium dihydrogenphosphate
as per test


99
(I-1-3)
tetraethylammonium sulphate
as per test


100
(I-1-3)
tetraethylammonium lactate
as per test


101
(I-1-3)
tetraethylammonium nitrate
as per test


102
(I-1-3)
tetraethylammonium thiosulphate
as per test


103
(I-1-3)
tetraethylammonium thiocyanate
as per test


104
(I-1-3)
tetraethylammonium citrate
as per test


105
(I-1-3)
tetraethylammonium oxalate
as per test


106
(I-1-3)
tetraethylammonium formate
as per test


107
(I-1-3)
tetraethylammonium hydrogenphosphate
as per test


108
(I-1-3)
tetraethylammonium dihydrogenphosphate
as per test


109
(I-1-4)
ammonium sulphate
as per test


110
(I-1-4)
ammonium lactate
as per test


111
(I-1-4)
ammonium nitrate
as per test


112
(I-1-4)
ammonium thiosulphate
as per test


113
(I-1-4)
ammonium thiocyanate
as per test


114
(I-1-4)
ammonium citrate
as per test


115
(I-1-4)
ammonium oxalate
as per test


116
(I-1-4)
ammonium formate
as per test


117
(I-1-4)
ammonium hydrogenphosphate
as per test


118
(I-1-4)
ammonium dihydrogenphosphate
as per test


119
(I-1-4)
ammonium carbonate
as per test


120
(I-1-4)
ammonium benzoate
as per test


121
(I-1-4)
ammonium sulphite
as per test


122
(I-1-4)
ammonium benzoate
as per test


123
(I-1-4)
ammonium hydrogenoxalate
as per test


124
(I-1-4)
ammonium hydrogencitrate
as per test


125
(I-1-4)
tetramethylammonium sulphate
as per test


126
(I-1-4)
tetramethylammonium lactate
as per test


127
(I-1-4)
tetramethylammonium nitrate
as per test


128
(I-1-4)
tetramethylammonium thiosulphate
as per test


129
(I-1-4)
tetramethylammonium thiocyanate
as per test


130
(I-1-4)
tetramethylammonium citrate
as per test


131
(I-1-4)
tetramethylammonium oxalate
as per test


132
(I-1-4)
tetramethylammonium formate
as per test


133
(I-1-4)
tetramethylammonium hydrogenphosphate
as per test


134
(I-1-4)
tetramethylammonium dihydrogenphosphate
as per test


135
(I-1-4)
tetraethylammonium sulphate
as per test


136
(I-1-4)
tetraethylammonium lactate
as per test


137
(I-1-4)
tetraethylammonium nitrate
as per test


138
(I-1-4)
tetraethylammonium thiosulphate
as per test


139
(I-1-4)
tetraethylammonium thiocyanate
as per test


140
(I-1-4)
tetraethylammonium citrate
as per test


141
(I-1-4)
tetraethylammonium oxalate
as per test


142
(I-1-4)
tetraethylammonium formate
as per test


143
(I-1-4)
tetraethylammonium hydrogenphosphate
as per test


144
(I-1-4)
tetraethylammonium dihydrogenphosphate
as per test


145
(I-1-5)
ammonium sulphate
as per test


146
(I-1-5)
ammonium lactate
as per test


147
(I-1-5)
ammonium nitrate
as per test


148
(I-1-5)
ammonium thiosulphate
as per test


149
(I-1-5)
ammonium thiocyanate
as per test


150
(I-1-5)
ammonium citrate
as per test


151
(I-1-5)
ammonium oxalate
as per test


152
(I-1-5)
ammonium formate
as per test


153
(I-1-5)
ammonium hydrogenphosphate
as per test


154
(I-1-5)
ammonium dihydrogenphosphate
as per test


155
(I-1-5)
ammonium carbonate
as per test


156
(I-1-5)
ammonium benzoate
as per test


157
(I-1-5)
ammonium sulphite
as per test


158
(I-1-5)
ammonium benzoate
as per test


159
(I-1-5)
ammonium hydrogenoxalate
as per test


160
(I-1-5)
ammonium hydrogencitrate
as per test


161
(I-1-5)
tetramethylammonium sulphate
as per test


162
(I-1-5)
tetramethylammonium lactate
as per test


163
(I-1-5)
tetramethylammonium nitrate
as per test


164
(I-1-5)
tetramethylammonium thiosulphate
as per test


165
(I-1-5)
tetramethylammonium thiocyanate
as per test


166
(I-1-5)
tetramethylammonium citrate
as per test


167
(I-1-5)
tetramethylammonium oxalate
as per test


168
(I-1-5)
tetramethylammonium formate
as per test


169
(I-1-5)
tetramethylammonium hydrogenphosphate
as per test


170
(I-1-5)
tetramethylammonium dihydrogenphosphate
as per test


171
(I-1-5)
tetraethylammonium sulphate
as per test


172
(I-1-5)
tetraethylammonium lactate
as per test


173
(I-1-5)
tetraethylammonium nitrate
as per test


174
(I-1-5)
tetraethylammonium thiosulphate
as per test


175
(I-1-5)
tetraethylammonium thiocyanate
as per test


176
(I-1-5)
tetraethylammonium citrate
as per test


177
(I-1-5)
tetraethylammonium oxalate
as per test


178
(I-1-5)
tetraethylammonium formate
as per test


179
(I-1-5)
tetraethylammonium hydrogenphosphate
as per test


180
(I-1-5)
tetraethylammonium dihydrogenphosphate
as per test


181
(I-1-6)
ammonium sulphate
as per test


182
(I-1-6)
ammonium lactate
as per test


183
(I-1-6)
ammonium nitrate
as per test


184
(I-1-6)
ammonium thiosulphate
as per test


185
(I-1-6)
ammonium thiocyanate
as per test


186
(I-1-6)
ammonium citrate
as per test


187
(I-1-6)
ammonium oxalate
as per test


188
(I-1-6)
ammonium formate
as per test


189
(I-1-6)
ammonium hydrogenphosphate
as per test


190
(I-1-6)
ammonium dihydrogenphosphate
as per test


191
(I-1-6)
ammonium carbonate
as per test


192
(I-1-6)
ammonium benzoate
as per test


193
(I-1-6)
ammonium sulphite
as per test


194
(I-1-6)
ammonium benzoate
as per test


195
(I-1-6)
ammonium hydrogenoxalate
as per test


196
(I-1-6)
ammonium hydrogencitrate
as per test


197
(I-1-6)
tetramethylammonium sulphate
as per test


198
(I-1-6)
tetramethylammonium lactate
as per test


199
(I-1-6)
tetramethylammonium nitrate
as per test


200
(I-1-6)
tetramethylammonium thiosulphate
as per test


201
(I-1-6)
tetramethylammonium thiocyanate
as per test


202
(I-1-6)
tetramethylammonium citrate
as per test


203
(I-1-6)
tetramethylammonium oxalate
as per test


204
(I-1-6)
tetramethylammonium formate
as per test


205
(I-1-6)
tetramethylammonium hydrogenphosphate
as per test


206
(I-1-6)
tetramethylammonium dihydrogenphosphate
as per test


207
(I-1-6)
tetraethylammonium sulphate
as per test


208
(I-1-6)
tetraethylammonium lactate
as per test


209
(I-1-6)
tetraethylammonium nitrate
as per test


210
(I-1-6)
tetraethylammonium thiosulphate
as per test


211
(I-1-6)
tetraethylammonium thiocyanate
as per test


212
(I-1-6)
tetraethylammonium citrate
as per test


213
(I-1-6)
tetraethylammonium oxalate
as per test


214
(I-1-6)
tetraethylammonium formate
as per test


215
(I-1-6)
tetraethylammonium hydrogenphosphate
as per test


216
(I-1-6)
tetraethylammonium dihydrogenphosphate
as per test


217
(I-1-7)
ammonium sulphate
as per test


218
(I-1-7)
ammonium lactate
as per test


219
(I-1-7)
ammonium nitrate
as per test


220
(I-1-7)
ammonium thiosulphate
as per test


221
(I-1-7)
ammonium thiocyanate
as per test


222
(I-1-7)
ammonium citrate
as per test


223
(I-1-7)
ammonium oxalate
as per test


224
(I-1-7)
ammonium formate
as per test


225
(I-1-7)
ammonium hydrogenphosphate
as per test


226
(I-1-7)
ammonium dihydrogenphosphate
as per test


227
(I-1-7)
ammonium carbonate
as per test


228
(I-1-7)
ammonium benzoate
as per test


229
(I-1-7)
ammonium sulphite
as per test


230
(I-1-7)
ammonium benzoate
as per test


231
(I-1-7)
ammonium hydrogenoxalate
as per test


232
(I-1-7)
ammonium hydrogencitrate
as per test


233
(I-1-7)
tetramethylammonium sulphate
as per test


234
(I-1-7)
tetramethylammonium lactate
as per test


235
(I-1-7)
tetramethylammonium nitrate
as per test


236
(I-1-7)
tetramethylammonium thiosulphate
as per test


237
(I-1-7)
tetramethylammonium thiocyanate
as per test


238
(I-1-7)
tetramethylammonium citrate
as per test


239
(I-1-7)
tetramethylammonium oxalate
as per test


240
(I-1-7)
tetramethylammonium formate
as per test


241
(I-1-7)
tetramethylammonium hydrogenphosphate
as per test


242
(I-1-7)
tetramethylammonium dihydrogenphosphate
as per test


243
(I-1-7)
tetraethylammonium sulphate
as per test


244
(I-1-7)
tetraethylammonium lactate
as per test


245
(I-1-7)
tetraethylammonium nitrate
as per test


246
(I-1-7)
tetraethylammonium thiosulphate
as per test


247
(I-1-7)
tetraethylammonium thiocyanate
as per test


248
(I-1-7)
tetraethylammonium citrate
as per test


249
(I-1-7)
tetraethylammonium oxalate
as per test


250
(I-1-7)
tetraethylammonium formate
as per test


251
(I-1-7)
tetraethylammonium hydrogenphosphate
as per test


252
(I-1-7)
tetraethylammonium dihydrogenphosphate
as per test


253
(I-1-8)
ammonium sulphate
as per test


254
(I-1-8)
ammonium lactate
as per test


255
(I-1-8)
ammonium nitrate
as per test


256
(I-1-8)
ammonium thiosulphate
as per test


257
(I-1-8)
ammonium thiocyanate
as per test


258
(I-1-8)
ammonium citrate
as per test


259
(I-1-8)
ammonium oxalate
as per test


260
(I-1-8)
ammonium formate
as per test


261
(I-1-8)
ammonium hydrogenphosphate
as per test


262
(I-1-8)
ammonium dihydrogenphosphate
as per test


263
(I-1-8)
ammonium carbonate
as per test


264
(I-1-8)
ammonium benzoate
as per test


265
(I-1-8)
ammonium sulphite
as per test


266
(I-1-8)
ammonium benzoate
as per test


267
(I-1-8)
ammonium hydrogenoxalate
as per test


268
(I-1-8)
ammonium hydrogencitrate
as per test


269
(I-1-8)
tetramethylammonium sulphate
as per test


270
(I-1-8)
tetramethylammonium lactate
as per test


271
(I-1-8)
tetramethylammonium nitrate
as per test


272
(I-1-8)
tetramethylammonium thiosulphate
as per test


273
(I-1-8)
tetramethylammonium thiocyanate
as per test


274
(I-1-8)
tetramethylammonium citrate
as per test


275
(I-1-8)
tetramethylammonium oxalate
as per test


276
(I-1-8)
tetramethylammonium formate
as per test


277
(I-1-8)
tetramethylammonium hydrogenphosphate
as per test


278
(I-1-8)
tetramethylammonium dihydrogenphosphate
as per test


279
(I-1-8)
tetraethylammonium sulphate
as per test


280
(I-1-8)
tetraethylammonium lactate
as per test


281
(I-1-8)
tetraethylammonium nitrate
as per test


282
(I-1-8)
tetraethylammonium thiosulphate
as per test


283
(I-1-8)
tetraethylammonium thiocyanate
as per test


284
(I-1-8)
tetraethylammonium citrate
as per test


285
(I-1-8)
tetraethylammonium oxalate
as per test


286
(I-1-8)
tetraethylammonium formate
as per test


287
(I-1-8)
tetraethylammonium hydrogenphosphate
as per test


288
(I-1-8)
tetraethylammonium dihydrogenphosphate
as per test


289
(I-1-11)
ammonium sulphate
as per test


290
(I-1-11)
ammonium lactate
as per test


291
(I-1-11)
ammonium nitrate
as per test


292
(I-1-11)
ammonium thiosulphate
as per test


293
(I-1-11)
ammonium thiocyanate
as per test


294
(I-1-11)
ammonium citrate
as per test


295
(I-1-11)
ammonium oxalate
as per test


296
(I-1-11)
ammonium formate
as per test


297
(I-1-11)
ammonium hydrogenphosphate
as per test


298
(I-1-11)
ammonium dihydrogenphosphate
as per test


299
(I-1-11)
ammonium carbonate
as per test


300
(I-1-11)
ammonium benzoate
as per test


301
(I-1-11)
ammonium sulphite
as per test


302
(I-1-11)
ammonium benzoate
as per test


303
(I-1-11)
ammonium hydrogenoxalate
as per test


304
(I-1-11)
ammonium hydrogencitrate
as per test


305
(I-1-11)
tetramethylammonium sulphate
as per test


306
(I-1-11)
tetramethylammonium lactate
as per test


307
(I-1-11)
tetramethylammonium nitrate
as per test


308
(I-1-11)
tetramethylammonium thiosulphate
as per test


309
(I-1-11)
tetramethylammonium thiocyanate
as per test


310
(I-1-11)
tetramethylammonium citrate
as per test


311
(I-1-11)
tetramethylammonium oxalate
as per test


312
(I-1-11)
tetramethylammonium formate
as per test


313
(I-1-11)
tetramethylammonium hydrogenphosphate
as per test


314
(I-1-11)
tetramethylammonium dihydrogenphosphate
as per test


315
(I-1-11)
tetraethylammonium sulphate
as per test


316
(I-1-11)
tetraethylammonium lactate
as per test


317
(I-1-11)
tetraethylammonium nitrate
as per test


318
(I-1-11)
tetraethylammonium thiosulphate
as per test


319
(I-1-11)
tetraethylammonium thiocyanate
as per test


320
(I-1-11)
tetraethylammonium citrate
as per test


321
(I-1-11)
tetraethylammonium oxalate
as per test


322
(I-1-11)
tetraethylammonium formate
as per test


323
(I-1-11)
tetraethylammonium hydrogenphosphate
as per test


324
(I-1-11)
tetraethylammonium dihydrogenphosphate
as per test


325
(I-1-12)
ammonium sulphate
as per test


326
(I-1-12)
ammonium lactate
as per test


327
(I-1-12)
ammonium nitrate
as per test


328
(I-1-12)
ammonium thiosulphate
as per test


329
(I-1-12)
ammonium thiocyanate
as per test


330
(I-1-12)
ammonium citrate
as per test


331
(I-1-12)
ammonium oxalate
as per test


332
(I-1-12)
ammonium formate
as per test


333
(I-1-12)
ammonium hydrogenphosphate
as per test


334
(I-1-12)
ammonium dihydrogenphosphate
as per test


335
(I-1-12)
ammonium carbonate
as per test


336
(I-1-12)
ammonium benzoate
as per test


337
(I-1-12)
ammonium sulphite
as per test


338
(I-1-12)
ammonium benzoate
as per test


339
(I-1-12)
ammonium hydrogenoxalate
as per test


340
(I-1-12)
ammonium hydrogencitrate
as per test


341
(I-1-12)
tetramethylammonium sulphate
as per test


342
(I-1-12)
tetramethylammonium lactate
as per test


343
(I-1-12)
tetramethylammonium nitrate
as per test


344
(I-1-12)
tetramethylammonium thiosulphate
as per test


345
(I-1-12)
tetramethylammonium thiocyanate
as per test


346
(I-1-12)
tetramethylammonium citrate
as per test


347
(I-1-12)
tetramethylammonium oxalate
as per test


348
(I-1-12)
tetramethylammonium formate
as per test


349
(I-1-12)
tetramethylammonium hydrogenphosphate
as per test


350
(I-1-12)
tetramethylammonium dihydrogenphosphate
as per test


351
(I-1-12)
tetraethylammonium sulphate
as per test


352
(I-1-12)
tetraethylammonium lactate
as per test


353
(I-1-12)
tetraethylammonium nitrate
as per test


354
(I-1-12)
tetraethylammonium thiosulphate
as per test


355
(I-1-12)
tetraethylammonium thiocyanate
as per test


356
(I-1-12)
tetraethylammonium citrate
as per test


357
(I-1-12)
tetraethylammonium oxalate
as per test


358
(I-1-12)
tetraethylammonium formate
as per test


359
(I-1-12)
tetraethylammonium hydrogenphosphate
as per test


360
(I-1-12)
tetraethylammonium dihydrogenphosphate
as per test


361
(I-1-13)
ammonium sulphate
as per test


362
(I-1-13)
ammonium lactate
as per test


363
(I-1-13)
ammonium nitrate
as per test


364
(I-1-13)
ammonium thiosulphate
as per test


365
(I-1-13)
ammonium thiocyanate
as per test


366
(I-1-13)
ammonium citrate
as per test


367
(I-1-13)
ammonium oxalate
as per test


368
(I-1-13)
ammonium formate
as per test


369
(I-1-13)
ammonium hydrogenphosphate
as per test


370
(I-1-13)
ammonium dihydrogenphosphate
as per test


371
(I-1-13)
ammonium carbonate
as per test


372
(I-1-13)
ammonium benzoate
as per test


373
(I-1-13)
ammonium sulphite
as per test


374
(I-1-13)
ammonium benzoate
as per test


375
(I-1-13)
ammonium hydrogenoxalate
as per test


376
(I-1-13)
ammonium hydrogencitrate
as per test


377
(I-1-13)
tetramethylammonium sulphate
as per test


378
(I-1-13)
tetramethylammonium lactate
as per test


379
(I-1-13)
tetramethylammonium nitrate
as per test


380
(I-1-13)
tetramethylammonium thiosulphate
as per test


381
(I-1-13)
tetramethylammonium thiocyanate
as per test


382
(I-1-13)
tetramethylammonium citrate
as per test


383
(I-1-13)
tetramethylammonium oxalate
as per test


384
(I-1-13)
tetramethylammonium formate
as per test


385
(I-1-13)
tetramethylammonium hydrogenphosphate
as per test


386
(I-1-13)
tetramethylammonium dihydrogenphosphate
as per test


387
(I-1-13)
tetraethylammonium sulphate
as per test


388
(I-1-13)
tetraethylammonium lactate
as per test


389
(I-1-13)
tetraethylammonium nitrate
as per test


390
(I-1-13)
tetraethylammonium thiosulphate
as per test


391
(I-1-13)
tetraethylammonium thiocyanate
as per test


392
(I-1-13)
tetraethylammonium citrate
as per test


393
(I-1-13)
tetraethylammonium oxalate
as per test


394
(I-1-13)
tetraethylammonium formate
as per test


395
(I-1-13)
tetraethylammonium hydrogenphosphate
as per test


396
(I-1-13)
tetraethylammonium dihydrogenphosphate
as per test


397
(I-1-14)
ammonium sulphate
as per test


398
(I-1-14)
ammonium lactate
as per test


399
(I-1-14)
ammonium nitrate
as per test


400
(I-1-14)
ammonium thiosulphate
as per test


401
(I-1-14)
ammonium thiocyanate
as per test


402
(I-1-14)
ammonium citrate
as per test


403
(I-1-14)
ammonium oxalate
as per test


404
(I-1-14)
ammonium formate
as per test


405
(I-1-14)
ammonium hydrogenphosphate
as per test


406
(I-1-14)
ammonium dihydrogenphosphate
as per test


407
(I-1-14)
ammonium carbonate
as per test


408
(I-1-14)
ammonium benzoate
as per test


409
(I-1-14)
ammonium sulphite
as per test


410
(I-1-14)
ammonium benzoate
as per test


411
(I-1-14)
ammonium hydrogenoxalate
as per test


412
(I-1-14)
ammonium hydrogencitrate
as per test


413
(I-1-14)
tetramethylammonium sulphate
as per test


414
(I-1-14)
tetramethylammonium lactate
as per test


415
(I-1-14)
tetramethylammonium nitrate
as per test


416
(I-1-14)
tetramethylammonium thiosulphate
as per test


417
(I-1-14)
tetramethylammonium thiocyanate
as per test


418
(I-1-14)
tetramethylammonium citrate
as per test


419
(I-1-14)
tetramethylammonium oxalate
as per test


420
(I-1-14)
tetramethylammonium formate
as per test


421
(I-1-14)
tetramethylammonium hydrogenphosphate
as per test


422
(I-1-14)
tetramethylammonium dihydrogenphosphate
as per test


423
(I-1-14)
tetraethylammonium sulphate
as per test


424
(I-1-14)
tetraethylammonium lactate
as per test


425
(I-1-14)
tetraethylammonium nitrate
as per test


426
(I-1-14)
tetraethylammonium thiosulphate
as per test


427
(I-1-14)
tetraethylammonium thiocyanate
as per test


428
(I-1-14)
tetraethylammonium citrate
as per test


429
(I-1-14)
tetraethylammonium oxalate
as per test


430
(I-1-14)
tetraethylammonium formate
as per test


431
(I-1-14)
tetraethylammonium hydrogenphosphate
as per test


432
(I-1-14)
tetraethylammonium dihydrogenphosphate
as per test


433
(I-1-18)
ammonium sulphate
as per test


434
(I-1-18)
ammonium lactate
as per test


435
(I-1-18)
ammonium nitrate
as per test


436
(I-1-18)
ammonium thiosulphate
as per test


437
(I-1-18)
ammonium thiocyanate
as per test


438
(I-1-18)
ammonium citrate
as per test


439
(I-1-18)
ammonium oxalate
as per test


440
(I-1-18)
ammonium formate
as per test


441
(I-1-18)
ammonium hydrogenphosphate
as per test


442
(I-1-18)
ammonium dihydrogenphosphate
as per test


443
(I-1-18)
ammonium carbonate
as per test


444
(I-1-18)
ammonium benzoate
as per test


445
(I-1-18)
ammonium sulphite
as per test


446
(I-1-18)
ammonium benzoate
as per test


447
(I-1-18)
ammonium hydrogenoxalate
as per test


448
(I-1-18)
ammonium hydrogencitrate
as per test


449
(I-1-18)
tetramethylammonium sulphate
as per test


450
(I-1-18)
tetramethylammonium lactate
as per test


451
(I-1-18)
tetramethylammonium nitrate
as per test


452
(I-1-18)
tetramethylammonium thiosulphate
as per test


453
(I-1-18)
tetramethylammonium thiocyanate
as per test


454
(I-1-18)
tetramethylammonium citrate
as per test


455
(I-1-18)
tetramethylammonium oxalate
as per test


456
(I-1-18)
tetramethylammonium formate
as per test


457
(I-1-18)
tetramethylammonium hydrogenphosphate
as per test


458
(I-1-18)
tetramethylammonium dihydrogenphosphate
as per test


459
(I-1-18)
tetraethylammonium sulphate
as per test


460
(I-1-18)
tetraethylammonium lactate
as per test


461
(I-1-18)
tetraethylammonium nitrate
as per test


462
(I-1-18)
tetraethylammonium thiosulphate
as per test


463
(I-1-18)
tetraethylammonium thiocyanate
as per test


464
(I-1-18)
tetraethylammonium citrate
as per test


465
(I-1-18)
tetraethylammonium oxalate
as per test


466
(I-1-18)
tetraethylammonium formate
as per test


467
(I-1-18)
tetraethylammonium hydrogenphosphate
as per test


468
(I-1-18)
tetraethylammonium dihydrogenphosphate
as per test


469
(I-1-19)
ammonium sulphate
as per test


470
(I-1-19)
ammonium lactate
as per test


471
(I-1-19)
ammonium nitrate
as per test


472
(I-1-19)
ammonium thiosulphate
as per test


473
(I-1-19)
ammonium thiocyanate
as per test


474
(I-1-19)
ammonium citrate
as per test


475
(I-1-19)
ammonium oxalate
as per test


476
(I-1-19)
ammonium formate
as per test


477
(I-1-19)
ammonium hydrogenphosphate
as per test


478
(I-1-19)
ammonium dihydrogenphosphate
as per test


479
(I-1-19)
ammonium carbonate
as per test


480
(I-1-19)
ammonium benzoate
as per test


481
(I-1-19)
ammonium sulphite
as per test


482
(I-1-19)
ammonium benzoate
as per test


483
(I-1-19)
ammonium hydrogenoxalate
as per test


484
(I-1-19)
ammonium hydrogencitrate
as per test


485
(I-1-19)
tetramethylammonium sulphate
as per test


486
(I-1-19)
tetramethylammonium lactate
as per test


487
(I-1-19)
tetramethylammonium nitrate
as per test


488
(I-1-19)
tetramethylammonium thiosulphate
as per test


489
(I-1-19)
tetramethylammonium thiocyanate
as per test


490
(I-1-19)
tetramethylammonium citrate
as per test


491
(I-1-19)
tetramethylammonium oxalate
as per test


492
(I-1-19)
tetramethylammonium formate
as per test


493
(I-1-19)
tetramethylammonium hydrogenphosphate
as per test


494
(I-1-19)
tetramethylammonium dihydrogenphosphate
as per test


495
(I-1-19)
tetraethylammonium sulphate
as per test


496
(I-1-19)
tetraethylammonium lactate
as per test


497
(I-1-19)
tetraethylammonium nitrate
as per test


498
(I-1-19)
tetraethylammonium thiosulphate
as per test


499
(I-1-19)
tetraethylammonium thiocyanate
as per test


500
(I-1-19)
tetraethylammonium citrate
as per test


501
(I-1-19)
tetraethylammonium oxalate
as per test


502
(I-1-19)
tetraethylammonium formate
as per test


503
(I-1-19)
tetraethylammonium hydrogenphosphate
as per test


504
(I-1-19)
tetraethylammonium dihydrogenphosphate
as per test


505
(I-1-20)
ammonium sulphate
as per test


506
(I-1-20)
ammonium lactate
as per test


507
(I-1-20)
ammonium nitrate
as per test


508
(I-1-20)
ammonium thiosulphate
as per test


509
(I-1-20)
ammonium thiocyanate
as per test


510
(I-1-20)
ammonium citrate
as per test


511
(I-1-20)
ammonium oxalate
as per test


512
(I-1-20)
ammonium formate
as per test


513
(I-1-20)
ammonium hydrogenphosphate
as per test


514
(I-1-20)
ammonium dihydrogenphosphate
as per test


515
(I-1-20)
ammonium carbonate
as per test


516
(I-1-20)
ammonium benzoate
as per test


517
(I-1-20)
ammonium sulphite
as per test


518
(I-1-20)
ammonium benzoate
as per test


519
(I-1-20)
ammonium hydrogenoxalate
as per test


520
(I-1-20)
ammonium hydrogencitrate
as per test


521
(I-1-20)
tetramethylammonium sulphate
as per test


522
(I-1-20)
tetramethylammonium lactate
as per test


523
(I-1-20)
tetramethylammonium nitrate
as per test


524
(I-1-20)
tetramethylammonium thiosulphate
as per test


525
(I-1-20)
tetramethylammonium thiocyanate
as per test


526
(I-1-20)
tetramethylammonium citrate
as per test


527
(I-1-20)
tetramethylammonium oxalate
as per test


528
(I-1-20)
tetramethylammonium formate
as per test


529
(I-1-20)
tetramethylammonium hydrogenphosphate
as per test


530
(I-1-20)
tetramethylammonium dihydrogenphosphate
as per test


531
(I-1-20)
tetraethylammonium sulphate
as per test


532
(I-1-20)
tetraethylammonium lactate
as per test


533
(I-1-20)
tetraethylammonium nitrate
as per test


534
(I-1-20)
tetraethylammonium thiosulphate
as per test


535
(I-1-20)
tetraethylammonium thiocyanate
as per test


536
(I-1-20)
tetraethylammonium citrate
as per test


537
(I-1-20)
tetraethylammonium oxalate
as per test


538
(I-1-20)
tetraethylammonium formate
as per test


539
(I-1-20)
tetraethylammonium hydrogenphosphate
as per test


540
(I-1-20)
tetraethylammonium dihydrogenphosphate
as per test


541
(I-1-21)
ammonium sulphate
as per test


542
(I-1-21)
ammonium lactate
as per test


543
(I-1-21)
ammonium nitrate
as per test


544
(I-1-21)
ammonium thiosulphate
as per test


545
(I-1-21)
ammonium thiocyanate
as per test


546
(I-1-21)
ammonium citrate
as per test


547
(I-1-21)
ammonium oxalate
as per test


548
(I-1-21)
ammonium formate
as per test


549
(I-1-21)
ammonium hydrogenphosphate
as per test


550
(I-1-21)
ammonium dihydrogenphosphate
as per test


551
(I-1-21)
ammonium carbonate
as per test


552
(I-1-21)
ammonium benzoate
as per test


553
(I-1-21)
ammonium sulphite
as per test


554
(I-1-21)
ammonium benzoate
as per test


555
(I-1-21)
ammonium hydrogenoxalate
as per test


556
(I-1-21)
ammonium hydrogencitrate
as per test


557
(I-1-21)
tetramethylammonium sulphate
as per test


558
(I-1-21)
tetramethylammonium lactate
as per test


559
(I-1-21)
tetramethylammonium nitrate
as per test


560
(I-1-21)
tetramethylammonium thiosulphate
as per test


561
(I-1-21)
tetramethylammonium thiocyanate
as per test


562
(I-1-21)
tetramethylammonium citrate
as per test


563
(I-1-21)
tetramethylammonium oxalate
as per test


564
(I-1-21)
tetramethylammonium formate
as per test


565
(I-1-21)
tetramethylammonium hydrogenphosphate
as per test


566
(I-1-21)
tetramethylammonium dihydrogenphosphate
as per test


567
(I-1-21)
tetraethylammonium sulphate
as per test


568
(I-1-21)
tetraethylammonium lactate
as per test


569
(I-1-21)
tetraethylammonium nitrate
as per test


570
(I-1-21)
tetraethylammonium thiosulphate
as per test


571
(I-1-21)
tetraethylammonium thiocyanate
as per test


572
(I-1-21)
tetraethylammonium citrate
as per test


573
(I-1-21)
tetraethylammonium oxalate
as per test


574
(I-1-21)
tetraethylammonium formate
as per test


575
(I-1-21)
tetraethylammonium hydrogenphosphate
as per test


576
(I-1-21)
tetraethylammonium dihydrogenphosphate
as per test


577
(I-1-22)
ammonium sulphate
as per test


578
(I-1-22)
ammonium lactate
as per test


579
(I-1-22)
ammonium nitrate
as per test


580
(I-1-22)
ammonium thiosulphate
as per test


581
(I-1-22)
ammonium thiocyanate
as per test


582
(I-1-22)
ammonium citrate
as per test


583
(I-1-22)
ammonium oxalate
as per test


584
(I-1-22)
ammonium formate
as per test


585
(I-1-22)
ammonium hydrogenphosphate
as per test


586
(I-1-22)
ammonium dihydrogenphosphate
as per test


587
(I-1-22)
ammonium carbonate
as per test


588
(I-1-22)
ammonium benzoate
as per test


589
(I-1-22)
ammonium sulphite
as per test


590
(I-1-22)
ammonium benzoate
as per test


591
(I-1-22)
ammonium hydrogenoxalate
as per test


592
(I-1-22)
ammonium hydrogencitrate
as per test


593
(I-1-22)
tetramethylammonium sulphate
as per test


594
(I-1-22)
tetramethylammonium lactate
as per test


595
(I-1-22)
tetramethylammonium nitrate
as per test


596
(I-1-22)
tetramethylammonium thiosulphate
as per test


597
(I-1-22)
tetramethylammonium thiocyanate
as per test


598
(I-1-22)
tetramethylammonium citrate
as per test


599
(I-1-22)
tetramethylammonium oxalate
as per test


600
(I-1-22)
tetramethylammonium formate
as per test


601
(I-1-22)
tetramethylammonium hydrogenphosphate
as per test


602
(I-1-22)
tetramethylammonium dihydrogenphosphate
as per test


603
(I-1-22)
tetraethylammonium sulphate
as per test


604
(I-1-22)
tetraethylammonium lactate
as per test


605
(I-1-22)
tetraethylammonium nitrate
as per test


606
(I-1-22)
tetraethylammonium thiosulphate
as per test


607
(I-1-22)
tetraethylammonium thiocyanate
as per test


608
(I-1-22)
tetraethylammonium citrate
as per test


609
(I-1-22)
tetraethylammonium oxalate
as per test


610
(I-1-22)
tetraethylammonium formate
as per test


611
(I-1-22)
tetraethylammonium hydrogenphosphate
as per test


612
(I-1-22)
tetraethylammonium dihydrogenphosphate
as per test


613
(I-1-23)
ammonium sulphate
as per test


614
(I-1-23)
ammonium lactate
as per test


615
(I-1-23)
ammonium nitrate
as per test


616
(I-1-23)
ammonium thiosulphate
as per test


617
(I-1-23)
ammonium thiocyanate
as per test


618
(I-1-23)
ammonium citrate
as per test


619
(I-1-23)
ammonium oxalate
as per test


620
(I-1-23)
ammonium formate
as per test


621
(I-1-23)
ammonium hydrogenphosphate
as per test


622
(I-1-23)
ammonium dihydrogenphosphate
as per test


623
(I-1-23)
ammonium carbonate
as per test


624
(I-1-23)
ammonium benzoate
as per test


625
(I-1-23)
ammonium sulphite
as per test


626
(I-1-23)
ammonium benzoate
as per test


627
(I-1-23)
ammonium hydrogenoxalate
as per test


628
(I-1-23)
ammonium hydrogencitrate
as per test


629
(I-1-23)
tetramethylammonium sulphate
as per test


630
(I-1-23)
tetramethylammonium lactate
as per test


631
(I-1-23)
tetramethylammonium nitrate
as per test


632
(I-1-23)
tetramethylammonium thiosulphate
as per test


633
(I-1-23)
tetramethylammonium thiocyanate
as per test


634
(I-1-23)
tetramethylammonium citrate
as per test


635
(I-1-23)
tetramethylammonium oxalate
as per test


636
(I-1-23)
tetramethylammonium formate
as per test


637
(I-1-23)
tetramethylammonium hydrogenphosphate
as per test


638
(I-1-23)
tetramethylammonium dihydrogenphosphate
as per test


639
(I-1-23)
tetraethylammonium sulphate
as per test


640
(I-1-23)
tetraethylammonium lactate
as per test


641
(I-1-23)
tetraethylammonium nitrate
as per test


642
(I-1-23)
tetraethylammonium thiosulphate
as per test


643
(I-1-23)
tetraethylammonium thiocyanate
as per test


644
(I-1-23)
tetraethylammonium citrate
as per test


645
(I-1-23)
tetraethylammonium oxalate
as per test


646
(I-1-23)
tetraethylammonium formate
as per test


647
(I-1-23)
tetraethylammonium hydrogenphosphate
as per test


648
(I-1-23)
tetraethylammonium dihydrogenphosphate
as per test


649
(I-1-24)
ammonium sulphate
as per test


650
(I-1-24)
ammonium lactate
as per test


651
(I-1-24)
ammonium nitrate
as per test


652
(I-1-24)
ammonium thiosulphate
as per test


653
(I-1-24)
ammonium thiocyanate
as per test


654
(I-1-24)
ammonium citrate
as per test


655
(I-1-24)
ammonium oxalate
as per test


656
(I-1-24)
ammonium formate
as per test


657
(I-1-24)
ammonium hydrogenphosphate
as per test


658
(I-1-24)
ammonium dihydrogenphosphate
as per test


659
(I-1-24)
ammonium carbonate
as per test


660
(I-1-24)
ammonium benzoate
as per test


661
(I-1-24)
ammonium sulphite
as per test


662
(I-1-24)
ammonium benzoate
as per test


663
(I-1-24)
ammonium hydrogenoxalate
as per test


664
(I-1-24)
ammonium hydrogencitrate
as per test


665
(I-1-24)
tetramethylammonium sulphate
as per test


666
(I-1-24)
tetramethylammonium lactate
as per test


667
(I-1-24)
tetramethylammonium nitrate
as per test


668
(I-1-24)
tetramethylammonium thiosulphate
as per test


669
(I-1-24)
tetramethylammonium thiocyanate
as per test


670
(I-1-24)
tetramethylammonium citrate
as per test


671
(I-1-24)
tetramethylammonium oxalate
as per test


672
(I-1-24)
tetramethylammonium formate
as per test


673
(I-1-24)
tetramethylammonium hydrogenphosphate
as per test


674
(I-1-24)
tetramethylammonium dihydrogenphosphate
as per test


675
(I-1-24)
tetraethylammonium sulphate
as per test


676
(I-1-24)
tetraethylammonium lactate
as per test


677
(I-1-24)
tetraethylammonium nitrate
as per test


678
(I-1-24)
tetraethylammonium thiosulphate
as per test


679
(I-1-24)
tetraethylammonium thiocyanate
as per test


680
(I-1-24)
tetraethylammonium citrate
as per test


681
(I-1-24)
tetraethylammonium oxalate
as per test


682
(I-1-24)
tetraethylammonium formate
as per test


683
(I-1-24)
tetraethylammonium hydrogenphosphate
as per test


684
(I-1-24)
tetraethylammonium dihydrogenphosphate
as per test









Crop protection compositions according to the invention may also comprise further components, for example, surfactants and/or dispersing auxiliaries or emulsifiers.


Suitable nonionic surfactants and/or dispersing auxiliaries include all substances of this type that can usually be used in agrochemical compositions. Polyethylene oxide/polypropylene oxide block copolymers, polyethylene glycol ethers of straight-chain alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, furthermore polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol and polyvinyl pyrrolidone and copolymers of (meth)acrylic acid and (meth)acrylic esters, and additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may be phosphated and optionally may be neutralized with bases, examples of which that may be mentioned being sorbitol ethoxylates, and also polyoxyalkyleneamine derivatives may be mentioned as being preferred.


Suitable anionic surfactants are all substances of this type that can usually be used in agrochemical compositions. Preference is given to alkali metal salts and alkaline earth metal salts of alkylsulphonic acids or alkylarylsulphonic acids.


A further preferred group of anionic surfactants and/or dispersing auxiliaries are the following salts that are of low solubility in plant oil: salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid/formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.


Suitable additives which may be included in the formulations according to the invention are emulsifiers, foam inhibitors, preservatives, antioxidants, colorants and inert filling materials.


Preferred emulsifiers are ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, and also ethoxylated and propoxylated arylalkylphenols, and also sulphated or phosphated arylalkyl ethoxylates and/or arylalkyl ethoxypropoxylates, mention being made by way of example of sorbitan derivatives, such as polyethylene oxide sorbitan fatty acid esters and sorbitan fatty acid esters.







EXAMPLES

Myzus persicae Test (MYZUPE)


















Solvent:
7 parts by weight of dimethylformamide



Emulsifier:
2 parts 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 amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution.


Bell pepper plants (Capsicum annuum) which are heavily infested by the Green peach aphid (Myzus persicaei) are treated by spraying with the active compound preparation of the desired concentration.


After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.


In this test, for example, the following embodiments of the invention show good activity: see table below
















MYZUPE












Compound
ppm
% 6 d







(I-1-20) + AS
—
—



according to the invention



(I-1-20) + AS + penetrant
0.8
95



according to the invention



(I-1-20)
0.8
 0



prior art



(I-1-3) + AS + penetrant
0.8
70



according to the invention



(I-1-3)
0.8
 0



prior art











Aphis gossypii Test (APHIGO)


















Solvent:
7 parts by weight of dimethylformamide



Emulsifier:
2 parts 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 amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution.


Cotton leaves (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are sprayed with an active compound preparation of the desired concentration.


After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.


In this test, for example, the following embodiments of the invention show good activity: see table below
















APHIGO












Compound
ppm
% 6 d







(I-1-20) + AS
0.8
95



according to the invention



(I-1-20) + AS + penetrant
0.8
95



according to the invention



(I-1-20)
0.8
 0



prior art



(I-1-3) + AS + penetrant
0.8
80



according to the invention



(I-1-3)
0.8
 0



prior art









Claims
  • 1. Composition comprising at least one insecticidally or acaricidally active compound from the class of the anthranilamidesat least one salt of formula (II)
  • 2. Composition according to claim 1, wherein the active compound is a compound of the formula (I)
  • 3. Composition according to claim 1, wherein the active compound is present in an amount from 0.5 to 50% by weight.
  • 4. Composition according to claim 1, wherein D represents nitrogen.
  • 5. Composition according to claim 4, wherein R24 represents bicarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate, sulphate, nitrate, thiosulphate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate, citrate or oxalate.
  • 6. Composition according to claim 4, wherein R24 represents carbonate, pentaborate, sulphite, benzoate, hydrogenoxalate, hydrogencitrate, methylsulphate or tetrafluoroborate.
  • 7. Composition according to one or more of claim 1, further comprising at least one penetrant.
  • 8. Composition according to claim 7, wherein the penetrant is i) a fatty alcohol alkoxylate of the formula (III) R—O-(-AO)v—R′  (III)in whichR represents straight-chain or branched alkyl having 4 to 20 carbon atoms,R′ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-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 andv represents a numbers from 2 to 30,and/or ii) a mineral or vegetable oil and/or iii) ester of a mineral or vegetable oil.
  • 9. Composition according to claim 7, wherein the penetrant is an ester of a vegetable oil.
  • 10. Composition according to claim 7, wherein the penetrant is rapeseed oil methyl ester.
  • 11. Composition according to one or more of claim 7, wherein the penetrant is present in an amount from 1 to 95% by weight.
  • 12. Method of controlling harmful insects, comprising applying a composition according to claim 1, diluted or undiluted to an insect or a habitat thereof in such an amount that an effective amount of the insecticidally active compounds contained therein is permitted to act on the insects or said habitat.
  • 13. Method of increasing the activity of crop protection of an anthranilic acid diamide, comprising forming a ready-to-use spray liquor comprising a composition according to claim 1.
  • 14. Method according to claim 12, wherein the spray liquor is prepared using a penetrant.
  • 15. Method according to claim 13, wherein the salt of the formula (II) is present in a concentration of from 0.5 to 80 mmol/l.
  • 16. Method according to claim 14, wherein the penetrant is present in a concentration of from 0.1 to 10 g/l.
  • 17. Method according to claim 14, wherein the penetrant is present in a concentration of from 0.1 to 10 g/l and the salt of the formula (II) is present in a concentration of from 0.5 to 80 mmol/l.
  • 18. A composition of claim 1, that is capable of increasing the activity of a crop protection comprising an anthranilic acid diamide compound wherein said composition comprises a ready-to-use crop protection spray liquor.
  • 19. A composition according to claim 18, wherein the salt of the formula (II) is present in the ready-to-use crop protection spray liquor in a concentration of from 0.5 to 80 mmol/l.
  • 20. A composition according to claim 18, further comprising a penetrant.
Priority Claims (1)
Number Date Country Kind
102005059470.0 Dec 2005 DE national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2006/011471 11/30/2006 WO 00 9/19/2008