WO2007112844A1

WO2007112844A1 - Novel crystalline polymorphs of 3-chloro-n2-[(1s)-1-methyl-2-(methylsulfonyl)ethyl]-n1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}phthalamide

Info

Publication number: WO2007112844A1
Application number: PCT/EP2007/002388
Authority: WO
Inventors: Britta Olenik; Rüdiger Fischer; Christian Funke; Lorna Elisabeth Davies; Gerhard Thielking; Sergiy Pazenok; Hiroto Harayama; Hayami Nakao; Michihiko Kawaguchi; Masanori Tohnishi
Original assignee: Bayer Cropscience Ag
Priority date: 2006-03-29
Filing date: 2007-03-19
Publication date: 2007-10-11
Also published as: TW200811092A; AR060135A1

Abstract

The present invention relates to defined crystalline polymorphs of 3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}phthalamide of the formula (A), to processes for its preparation and to its use in agrochemical formulations.

Description

Novel crystalline modifications of 3-chloro-N ² -KlS) -l-methyl-2- (methylsulfonylmethyl-N'- (2-methyl-4- [l, 2,2,2-tetrafluoro-1- (trifluoromethyl ^" ) -ethvphenyl-phthalamide

The present invention relates to novel crystalline modifications of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N ¹ - {2-methyl-4-[1,2] 2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide (hereinafter referred to as CMP, see formula (A)), processes for their preparation and their use in agrochemical preparations.

CMP is known as a racemate from EP-A 1 006 107 and as a pure enantiomer from unpublished Japanese patent application JP 2005-239974. CMP can be synthesized by the methods described therein. Another method is described in International Patent Application PCT / EP05 / 00894.

In the above-described synthetic methods, CMP of the crystalline modification FV (for nomenclature and characterization, see below in the description) is obtained. This crystalline modification is metastable.

The occurrence of active ingredients in various crystalline modifications (= polymorphism) is of great importance both for the preparation of manufacturing processes and for the development of formulations. Thus, the various crystalline modifications of a chemical compound differ in appearance (crystal habit) and hardness in numerous other physico-chemical properties. Differences in stability, filterability, solubility, hygroscopicity, melting point, solids density, and flowability can exert a strong influence on the quality and efficacy of plant treatment agents. It has not been possible to predict the occurrence and number of crystalline modifications, including their physicochemical properties. Above all, the thermodynamic stability and the different behavior after administration in living organisms can not be determined in advance. It is therefore an object of the present invention to produce novel crystalline modifications of CMP which are easy to handle in formulations because of their physico-chemical properties.

This object is achieved according to the invention by novel crystalline modifications of CMP, which are referred to below as crystalline modifications I, II and III.

The invention therefore relates to the crystalline modification I of CMP, which is characterized in that it has an X-ray powder diffractogram with the reflective layers given in Table 1 (2 theta,> 20% relative intensity). The powder X-ray diffraction pattern of the crystalline modification I is also shown in FIG. The most intense signals (2 theta) of the X-ray powder diffraction pattern of the crystalline modification I are thus at 19.42 °, 12.93 °, 19.91 °, 18.51 °, 14.39 °, 13.24 °, 14.76 ° and 18.81 ° (each ± 0.2 °).

The invention likewise relates to the crystalline modification II of CMP, which is characterized in that it has an X-ray powder diffractogram with the reflective layers specified in Table 2 below (2 theta,> 20% relative intensity). The powder X-ray diffractogram of the crystalline modification II is also shown in FIG. The most intense signals (2 theta) of the X-ray powder diffraction pattern of the crystalline modification π are thus at 14.74 °, 10.29 °, 16.43 °, 23.89 °, 15.28 °, 11.61 °, 15.84 ° and 18.50 ° (each ± 0, 2 °).

The invention likewise provides the crystalline modification III of CMP, which is characterized in that it has an X-ray powder diffractogram with the reflective layers (2 theta,> 20% relative intensity) given in Table 3 below. The powder X-ray diffraction pattern of the crystalline modification III is also shown in FIG. The most intense signals (2 theta) of the X-ray powder diffraction pattern of the crystalline modification πi are therefore 21.84 °, 15.52 °, 9.50 °, 14.57 °, 13.43 °, 25.79 °, 16.50 ° and 23.22 ° (each ± 0.2 °).

All powder X-ray diffractometry data were obtained with the following acquisition parameters:

Diffractometer: Transmission

Monochromator: Curved germanium (111)

Wavelength: 1.540598 Cu Detector: Linear PSD

Scan Mode: Transmission / Moving PSD / Fixed omega

S can type: 2Theta: Omega

2Theta indication: ± 0.2 ° Table 1

By "weak" is preferably understood an intensity of 20 to 40% of the most intense signal in the spectrum, "medium" an intensity of> 40 to 60% of the most intense signal in the spectrum under "strong" an intensity of> 60 to 80 % of the most intense signal in the spectrum and under "very strong" an intensity of> 80 to 100% of the most intense signal in the spectrum

² Intensity relative to the most intense signal of the spectrum, which is arbitrarily defined as 100.

Table 2

Weak By "weak" is preferably understood an intensity of 20 to 40% of the most intense signal in the spectrum, "medium" an intensity of> 40 to 60% of the most intense signal in the spectrum under "strong" an intensity of> 60 to 80 % of the most intense signal in the spectrum and under "very strong" an intensity of> 80 to 100% of the most intense signal in the spectrum

Intensity relative to the most intense signal of the spectrum, which is arbitrarily defined as 100.

Table 3

The known crystalline modification IV of CMP is characterized in that it has an X-ray powder diffractogram with the reflective layers given in Table 4 below (2 theta,> 20% relative intensity). The powder X-ray diffraction pattern of the crystalline modification IV is also shown in FIG.

Table 4

The crystalline modifications of CMP according to the invention can also be characterized by BR spectroscopy. The ER spectra contain the following band maxima listed in Table 5 (crystalline modification I), Table 6 (crystalline modification II) and Table 7 (crystalline modification III) (measured on FTIR Tensor 37, Bruker, Bremen, Germany using a Golden Gate ATR unit for solids):

Table 5

Table 6

Table 7

The known crystalline modification IV of CMP can also be characterized by IR spectroscopy. The IR spectrum contains the following band maxima listed in Table 8 (measured on FTIR Tensor 37, Bruker, Bremen, Germany using a Golden Gate ATR unit for solids):

Table 8

The crystalline modifications of the invention can also be characterized by Raman spectroscopy. The band maxima (measured on a Raman R100 / S, Bruker, Breyer men, Germany) are listed in Table 9 (crystalline modification I), Table 10 (crystalline modification II) and Table 1 1 (crystalline modification HI):

Table 9

Table 10

Table 11

The known crystalline modification IV can also be characterized by Raman spectroscopy. The band maxima (measured on a Raman R100 / S, Bruker, Bremen, Germany) are listed in Table 12: Table 12

CMP of the crystalline modification I is surprisingly stable and does not convert to any other crystalline modifications even after prolonged storage. In addition, compared to other crystalline modifications, the crystalline modification I has a much lower tendency to absorb water from the air. For these reasons, it is excellently suitable for the production of solid formulations. Its stability gives these formulations the desired long-term storage stability. With the crystalline modification I can thus be defined and produced specifically stable solid preparations of CMP.

CMP of the crystalline modification I can be obtained by the following methods:

Method A

CMP of crystalline modification II or FV is suspended in at least one apolar organic solvent and heated. Alternatively, CMP of crystalline modification II or IV is suspended in a mixture of at least one apolar organic solvent and at least one polar solvent and heated. After recrystallization, the precipitate is isolated and dried.

As an apolar organic solvent is preferably a branched, unbranched or cyclic hydrocarbon, more preferably an unbranched or cyclic hydrocarbon, most preferably n-pentane, n-hexane, n-heptane, cyclohexane, n-octane, n-nonane or n Decane, and particularly preferably n-octane or heptane. Preferred polar solvents are esters (such as, for example, methyl acetate, ethyl acetates or propyl acetates), nitriles (such as, for example, acetonitrile, butyronitrile or benzonitrile), ethers (such as, for example, dimethoxoethanes, diglyme, THF, dioxanes, NMP, sulpholane or DMAA), Alcohols (such as methanol, ethanol or isopropanol) or acetic acid used. Particularly preferably, ethyl acetate or dimethoxymethane are used, very particularly preferably ethyl acetate.

When a mixture of at least one organic non-polar solvent and at least one polar solvent is used, the mixing ratio (organic solvent: polar solvent, v / v) is generally from 1000: 1 to 30: 1, more preferably 500: 1 to 25: 1, more preferably 400: 1 to 20: 1 and most preferably 300: 1 to 15: 1.

The CMP of the crystalline modification FV is preferably used in a concentration of 10 to 500 g / l, more preferably in a concentration of 25 to 300 g / l and particularly preferably in a concentration of 50 to 250 g / l.

The recrystallization time can be varied within a wide range. It is preferably 1 to 24 hours, more preferably 2 to 12 hours and most preferably 4 to 8 hours.

The recrystallization can be carried out in a wide temperature range. Preferably, it is at the boiling point of the solvent mixture under reflux at 80 - from 150 ⁰ C, preferably at 90 - 12O ⁰ C and most preferably at 100-120 ⁰ C.

In a solvent mixture having a boiling point below 100 ⁰ C (hexane, cyclohexane), the recrystallization under elevated pressure (1-8 bar) is performed.

The reaction mixture may be added with CMP of the crystalline modification I as a seed for improving the yield or shortening the necessary recrystallization time.

Method B

Shriek i

CMP of crystalline modification IV is heated in a mixture of apolar organic solvent and ethyl acetate.

As an apolar organic solvent is preferably a branched, unbranched or cyclic hydrocarbon, more preferably an unbranched or cyclic hydrocarbon, most preferably n-pentane, n-hexane, cyclohexane, n-heptane, n-octane and especially preferably cyclohexane or n -Hexan used.

If a mixture of an organic solvent (OLM) and ethyl acetate (EA) is used for the recrystallization, the two solvents are preferably in a mixing ratio (OLM: EA, v / v) of 1000: 1 to 1: 2, particularly preferred 500: 1 to 1: 1, most preferably 200: 1 to 1: 1 and particularly preferably 100: 1 to 2: 1 used.

The recrystallization for the preparation of the crystalline modification I by the process B according to the invention is preferably carried out in a mixture of n-hexane and ethyl acetate.

CMP of the crystalline modification IV is preferably used in a concentration of 10 to 500 g / l, more preferably in a concentration of 25 to 300 g / l and particularly preferably in a concentration of 50 to 200 g / l.

The recrystallization time can be varied within a wide range. It is preferably 0.5 to 24 hours, more preferably 1 to 12 hours and most preferably 2 to 8 hours.

Step 1 of the method B according to the invention can be carried out in a wide temperature range. It is preferably carried out under reflux at the boiling point of the solvent mixture, as long as the boiling point does not exceed 100 ^° C. In a solvent mixture having a boiling point of more than 100 ⁰ C, it is carried out at a temperature of 60 ⁰ C to 100 ⁰ C, preferably at 70 ⁰ C to 100 ⁰ C and particularly preferably at 70 to 90 ⁰ C.

The mixture is then cooled, the product is filtered off and dried. step 2

The Maieriai obtained from step 1 is stirred in water with heating, cooled abgeπitriert. Subsequently, the material is dried.

The material obtained from step 1 is introduced in water as suspension in a concentration of 10 to 500 g / l, preferably 20 to 250 g / l, particularly preferably 50 to 200 g / l.

Step 2 of the process B according to the invention can be carried out in a wide temperature range (bounded above by the boiling point of water). Preferably, it is carried out above 70 ⁰ C, more preferably above 8O ⁰ C and most preferably in boiling water (100 ⁰ C).

The duration of step 2 can be varied within a wide range. Preferably, step 2 is carried out between 0.5 and 24 hours, more preferably between 1 and 12 hours and most preferably between 2 and 6 hours.

The product is preferably obtained after the implementation of step 2 by filtration and then dried (for example in a drying oven or in a desiccator over a drying agent such as P ₂ O ₅ or CaCl ₂ ).

Method C

CMP of the crystalline modification II can be obtained by the following method:

CMP of the crystalline modification FV is refluxed in water. Subsequently, the material is dried.

The recrystallization can be carried out in a wide temperature range (limited above by the boiling point of water). The recrystallization reaction is preferably carried out above 40 ^° C., more preferably above 60 ^° C., and most preferably in boiling water (100 ^° C.).

The duration of the recrystallization can be varied within a wide range. Preferably, step 2 is carried out between 0.5 and 24 hours, more preferably between 1 and 12 hours, and most preferably between 1 and 6 hours.

CMP of the crystalline modification II is introduced for the process C according to the invention in water as a suspension in a concentration of 10 to 500 g / l, preferably 20 to 250 g / l, particularly preferably 50 to 200 g / l. Method D

CMP of the crystalline modification HI can be obtained by the following method:

CMP of crystalline modification IV is heated in a mixture of an apolar organic solvent and an alcohol, and the resulting precipitate formed by suitable known methods, e.g. Filtration, isolated.

The apolar organic solvent (OLM) used is preferably a branched or unbranched hydrocarbon, particularly preferably an unbranched hydrocarbon, very particularly preferably n-pentane, n-hexane, n-heptane, n-octane and particularly preferably n-hexane.

The alcohol (AL) used is preferably a branched or unbranched alcohol having two to five carbon atoms, particularly preferably ethanol, n-propanol, isopropanol, n-butanol, isobutanol or t-butanol, most preferably n-propanol.

Particularly preferably, the recrystallization is carried out in a mixture of n-hexane and n-propanol.

The solvents used for the recrystallization are preferably in a mixing ratio (OLM: AL, v / v) of 200: 1 to 1: 2, more preferably 100: 1 to 1: 1, most preferably 20: 1 to 1: 1 and more preferably 5: 1 to 1: 1 used.

The recrystallization can be carried out in a wide temperature range, preferably at 70-130 ^° C.

The duration of the recrystallization can be varied within a wide range. Preference is first heated under reflux, then without reflux. The heating under reflux is generally carried out for 5 minutes to 6 hours, preferably 5 minutes to 2 hours and particularly preferably 10 to 60 minutes. The subsequent heating without reflux is generally carried out for 10 minutes to 6 hours, preferably for 20 minutes to 3 hours, particularly preferably for 30 minutes to 2 hours. Subsequently, the recrystallization solution is left to stand without heating until the recrystallized material has precipitated. This resting phase generally lasts 1 to 48 hours, preferably 3 to 24 hours, more preferably 6 to 18 hours.

CMP of the crystalline modification IV is introduced for the process D according to the invention in a concentration of 10 to 500 g / l, preferably 20 to 250 g / l, particularly preferably 50 to 200 g / l. The following examples illustrate the invention without limiting it. The solvent systems used in the following examples are particularly preferred.

Examples

Production Example 1 (Method A)

The crystalline modification I of CMP was obtained by suspending CMP of crystalline modification IV, as obtained from the known synthesis process, in n-octane / ethyl acetate (100: 1 v / v) at a concentration of 165 g / l, and was stirred at 1 15 to 120 ⁰ C for six hours. Thereafter, the precipitate was isolated by filtration and dried in vacuo. It was obtained in a yield of 97 to 99%, a material having a melting point of 168 - 17O ⁰ C, which consisted of 90 to 95% of the crystalline modification I.

Production Example 2 (Method A)

The crystalline modification I of CMP was obtained by CMP fication of the crystalline medi- IV, as it is recovered from the known synthesis process, l suspended in n-octane in a concentration of 147 g / and six hours at 1 15 to 120 ⁰ C was stirred. Thereafter, the precipitate was isolated by filtration and dried in vacuo. There was a yield of 97 to 99%, the crystalline modification I of CMP with a melting point 168-170 ⁰ C. (proportion of crystal modification I 90 to 95%).

Production Example 3 (Method B)

The crystalline modification I of CMP was obtained by reacting CMP of the crystalline modification IV, as obtained from the known synthesis process, in hexane / ethyl acetate

(3: 1 v / v) in a concentration of 102 g / l for 3 hrs. At 80 - 90 ⁰ C was stirred. The mixture was then cooled, filtered off with suction and dried. The material obtained was in a

Concentration of 129 g / l in water for about 3 hrs. Stirred under reflux, cooled, filtered with suction and washed well with water. The desiccator was finally dried over P ₂ O 5. It wur- de a material with a melting point of 171 ⁰ C was obtained.

Production Example 4 (Method B)

The crystalline modification I of CMP was obtained by subjecting CMP of the crystalline modification rv, as obtained from the synthesis process described, in hexane / ethyl acetate (3: 1 v / v) in a concentration of 83 g / l for 2 hours Reflux was stirred. Subsequently, the batch was cooled and the precipitated material was recovered by filtration. The The material obtained was stirred at a concentration of 172 g / l in water for about 3 hours under reflux and the precipitated material was recovered by filtration. The desiccator was finally dried over CaCl ₂ . The crystalline modification I of CMP with a melting point of 169 ° C. was obtained with a yield of 83%.

Production Example 5 (Method D)

The crystalline modification IE of CMP was obtained by reacting CMP of the crystalline modification IV, as obtained from the described synthesis process, in a mixture of n-hexane and n-propanol (3: 1, v / v) in a concentration of 50 g / l was dissolved and heated under reflux for 20 minutes. The reaction solution was heated for a further hour without reflux and then allowed to stand for 12 hours without stirring. The formed precipitate was filtered off. There was a yield of 48%, the crystalline modification III of CMP with a melting point of 140 - 143 obtained ^0C.

Formulation Example 1

A formulation of CMP in the form of a soluble concentrate (SC) is prepared. In this case, the particle size immediately after production was about 1.5 μm (FIG. 5 a). It was then stored at 54 ° C for six weeks. After this storage, a formulation using only about 50% Modification I showed significant crystal growth and an average particle size of about 8 μm (Figure 5 b). A formulation containing about 80-85% of modification I showed particle sizes of about 6 μm (Figure 5 c). In contrast, formulations containing active ingredient> 90% Modification I showed almost no crystal growth at particle sizes of approximately 1.8 μm (Figure 5 d).

Claims

claims

1. Crystalline modification I of 3-chloro-N ² - [(1S) -1-methyl-2- (methyl-sulfonyi) ethyl-N ^! - {2-methyl-4- [l, 2,2,2-tetrafluoro-l- (trifluoromethyl) ethyl] phenyl} phthalamide, characterized in that their X-ray powder diffractogram using Cu Kα radiation having at least the following reflection layers

2Theta / °

12.93

13.24

14.39

14.76

18.51

18.81

19.42

19.91

Crystalline modification I of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-l- (trifluoromethyl) ethyl] phenyl} phthalamide according to claim 1, characterized in that its X-ray powder diffractogram using Cu Kα radiation has at least the following further reflective layers

2Theta / °

16.09

16.75

16.94

17.79

17.96

19.63

23.47

23,89

Crystalline modification I of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-l - (trifluoromethyl) ethyl] phenyl} phthalamide according to claim 1 or 2, characterized in that its X-ray powder diffraction pattern when using Cu Kα radiation substantially corresponds to the reproduced spectrum in Figure 1 spectrum.

4. Crystalline modification π of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, 2-tetrafluoro-l - (trifluoromethyl) ethyl] phenyl} phthalamide, characterized in that its X-ray powder diffractogram using Cu Kα radiation has at least the following reflection layers

2Theta / °

10.29

11, 61

14,74

15.28

15.84

16.43

18.50

23,89

Crystalline modification II of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N ¹ - {2-methyl-4-[l, 2,2,2- Tetrafluoro-l- (trifluoromethyl) ethyl] phenyl} phthalamide according to claim 4, characterized in that its X-ray powder diffractogram using Cu Kα radiation has at least the following further reflective layers

2Theta / °

8.70

10.84

14.13

17.50

20.90

21, 06

22.48

22.73

Crystalline modification II of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N - {2-methyl-4- [l, 2,2,2-tetrafluoro -l- (trifluoromethyl) ethyl] phenyl} phthalamide according to claim 4 or 5, characterized in that their X-ray powder diffraction pattern when using Cu Kα radiation substantially corresponds to the reproduced in Figure 2 spectrum.

7. Crystalline modification m of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N ¹ - {2-methyl-4- [1, 2,2, 2-tetrafluoro-1 - (trifluoromethyl) ethyl] phenyl} phthalamide, characterized in that its X-ray powder diffractogram using Cu Kα radiation has at least the following reflection layers

2Theta / °

9.50

13.43

14.57

15.52

16.50

21, 84

23.22

25.79

Crystalline modification III of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-l- (trifluoromethyl) ethyl] phenyl} phthalamide according to claim 7, characterized in that its X-ray powder diffractogram using Cu Kα radiation has at least the following further reflective layers

2Theta / °

16.38

18.24

19.1 1

19.92

ZJ ₁ OO

24.14

25,98

29.58

Crystalline modification III of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-l - (trifluoromethyl) ethyl] phenyl} phthalamide according to claim 7 or 8, characterized in that its X-ray powder diffraction pattern when using Cu Kα radiation substantially corresponds to the reproduced in Figure 3 spectrum.

10. Crystalline modification I of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, 2-tetrafluoro-1 - (trifluoromethyl) ethyl] phenyl} phthalamide according to one or more of claims 1 to 3, obtainable by:

a) 3-Chloro-N ² - [(1S) -I-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2-tetrafluoro- l - (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification II or IV is suspended and heated in at least one apolar organic solvent,

or

b) 3-Chloro-N ² - [(1S) -I-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2-tetrafluoro- l - (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification II or FV is suspended and heated in a mixture of at least one apolar organic solvent and at least one polar solvent,

or

c) 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N ¹ - {2-methyl-4- [l, 2,2,2-tetrafluoro- l- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification IV is first heated in a mixture of an apolar organic solvent and ethyl acetate and then in water.

1 1. Crystalline modification II of 3-chloro-N ² - [(IS) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, 2-tetrafluoro-1 - (trifluoromethyl) -ethyl] -phenyl} phthalamide according to one or more of claims 4 to 6, obtainable by reacting 3-chloro-N ² - [(1S) -l-methyl-2-

(Methyl-sulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2-tetrafluoro-l- (trifluoromethyl) ethyl] phenyl} - phthalamide of the crystalline modification FV is heated in water.

12. Crystalline modification III of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2 tetrafluoro-1- (trifluoromethyl) -ethyl] -phenyl} phthalamide according to one or more of claims 7 to 9, obtainable by reacting 3-chloro-N ² - [(1S) -l-methyl-2-

(methyl-sulfonyl) ethyl] -N ^l - {2-methyl-4- [l, ₂₎ 2,2-tetrafluoro-l- (trifluoromethyl) ethyl] phenyl} - phthalamide of the crystalline modification IV in a mixture of a is heated apolar organic solvent and an alcohol heated.

13. A process for the preparation of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline

Modification I according to one or more of claims 1 to 3, comprising the heating a suspension of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2-tetrafluoro- l- (trifluoromethyl) ethyl] phenyl} phthalamide of crystalline modification II or IV in an apolar organic solvent or in a mixture of an apolar solvent and ethyl acetate.

14. Process for the preparation of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, A 2-tetrafluoro-1 - (trifluoromethyl) -ethyl] phenyl} phthalamide of the crystalline modification I according to one or more of claims 1 to 3, comprising heating 3-chloro-N ² - [(1S) -l-methyl- 2- (methyl-sulfonyl) ethyl] -N ^I - {2-methyl-4- [l, 2,2,2-tetra- fluoro-l- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification FV initially in a mixture of apolar organic solvent and ethyl acetate and then heating in water.

15. A process for the preparation of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, 2-Tetrafluoro-1- (trifluoromethyl) -ethyl] phenyl} phthalamide of crystalline modification II according to one or more of claims 4 to 6, comprising heating 3-chloro-N ² - [(1S) -l-methyl-2 - (methylsulfonyl) ethyl] - N ^l - {2-methyl-4- [l, 2,2,2-tetrafluoro-l - (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification IV in water.

16. A process for the preparation of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2, 2-Tetrafluoro-1 - (trifluoromethyl) ethyl] phenyl} phthalamide of crystalline modification III according to one or more of claims 7 to 9, comprising heating 3-chloro-N ² - [(1S) -l-methyl- 2- (methyl-sulfonyl) ethyl] -N ^l - {2-methyl-4- [l, 2,2,2-tetrafluoro-l - (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification IV in a mixture from an apolar organic solvent and an alcohol.

17. A composition comprising 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline

Modification I according to one or more of claims 1 to 3.

18. A composition comprising 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification II according to one or more of Claims 4 to 6.

19. A composition comprising 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification III according to one or more of Claims 7 to 9.

20. Use of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N ¹ - {2-methyl-4- [1H 2] - tetrafluoro-1 Ctrifluoromethyl-ethyl-phenyl-phthalamide of the crystalline modification I according to one or more of Claims 1 to 3 for the preparation of insecticidally active compositions.

21. Use of 3-chloro-N ² - [(1S) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2- Tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification π according to one or more of Claims 4 to 6 for the preparation of insecticidally active compositions.

22. Use of 3-chloro-N ² - [(IS) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl-4- [l, 2,2,2-tetrafluoro -l- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline modification

III according to one or more of claims 7 to 9 for the preparation of insecticidally active compositions.

23. A method of controlling unwanted insects, characterized in that a composition comprising 3-chloro-N ² - [(IS) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl- 4- [l, 2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline

Modification I according to one or more of claims 1 to 3 is applied to the insects and / or their habitat and / or seed.

24. A method for controlling undesirable insects, characterized in that a composition comprising 3-chloro-N ² - [(IS) -l-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl- 4- [l, 2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline

Modification II according to one or more of claims 4 to 6 is applied to the insects and / or their habitat and / or seed.

25. A method of controlling unwanted insects, characterized in that a composition comprising 3-chloro-N ² - [(1S) -I-methyl-2- (methylsulfonyl) ethyl] -N '- {2-methyl -4- [l, 2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl} phthalamide of the crystalline

Modification III according to one or more of claims 7 to 9 is applied to the insects and / or their habitat and / or seed.