TW200811092A - Novel crystalline modifications of 3-chloro-N2-[(1S)-1-methyl-2-(methylsulphonyl)ethyl]-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}phthalamide - Google Patents

Abstract

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

Description

200811092 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to novel 3-chloro-N2-[(1S)-1-indolyl-2-(indolyl)ethylmethyl-4- [l,2,2,2-tetrafluorosuccinyl (trifluoromethyl)ethyl]benzene 5 yl 5 decylamine (refer to the following CMP, cf. formula (A)) crystal modification, preparation method thereof and Used as an agricultural chemical. [Prior Art]

The CMP is disclosed as a racemate in EP-A 1 006 107, and is a pure image isomer of Japanese Patent Application No. 2005-239974, which is incorporated herein by reference. CMP can be synthesized by the methods described there. Further methods are described in International Patent Application PCT/EP05/00894. In the foregoing synthetic method, the CMP of the crystalline variant IV (for further naming and characterization, see further description below). The crystal modification is metastable. B The appearance of various crystalline variants (polymorphic forms) of active substances is important for the preparation of the preparation methods and the development of the formulations. Thus, the various crystallization variants of the compound differ not only in appearance (crystallinity) and hardness, but also in many more intensive physicochemical properties. Stability, filtration, properties, solubility, moisture absorption, melting point, solid density and fluidity will have a considerable impact on the quality and efficiency of crop processing formulations. It is currently not possible to expect the presence and amount of crystalline variants, including their physicochemical properties. In particular, the thermodynamic stability and its different performance after being administered to living organisms cannot be pre-measured 5 200811092. SUMMARY OF THE INVENTION The purpose of Yuhuan is to provide a novel crystalline variant of c Mp which can be mastered by the physicochemical properties of the chemical formula.

According to the invention, the object can be achieved by CM

10 15

Achieved for crystallized variants. The following is a crystallization of the CMp, which is characterized by having a U 1 2 fine a, > 2〇% relative intensity, and a 反射-ray end, & The powder X-ray diffraction pattern of the crystal modification 1 is also shown in the figure, ", the strongest signal of the x-ray powder diffraction pattern of the 曰曰 variant 1 (2 13.24, 14.76 ° and 18.81. appears (each item ± 〇 .2. The present invention is also directed to the CMP crystal modification π characterized by having a ray powder diffraction pattern at the reflection position of the following Table 2 (2 theta, > 20% relative intensity). The powder X-ray diffraction pattern of the body 11 is also corresponding to 19.42. 12.93. 19.91. 18,51. , 14 39. , shown in Figure 2. The crystallization of the crystalline variant n is the strongest signal (2 theta) corresponding to 14.74. 10.29. 16.43. 23.89. 15.28. , 11.6Γ, 15.84. And 18.50. Appears (±0.2 per item). The present invention is also directed to a CMP crystal modification ΙΠ characterized by having an X-ray powder diffraction pattern of the reflection position carried in Table 3 below (2 theta, > 20% relative intensity). The powder X-ray diffraction pattern of crystal modification III is also shown in Fig. 3. The strongest signal of the X-ray powder diffraction pattern of the crystal modification π (2 20 200811092 theta) corresponds to 21·84. 15.52. , 9.50. , 14.57. 13.43. , 20 25.79. 16.50. And 23.22. Appears (±0.2 per item). All powder X-ray diffraction data are obtained with the following parameters: Diffraction: Transmission 5

Spectrometer: Curve 锗 (Π1) (Curved Germanium (111)) Wavelength: 1.540598 Cu Detector: Linear PSD (Linear PSD) Scan Mode: Propagation / Mobile PSD / Fixed Omega Scanning Type: 2 theta : Omega 2 theta data: ±0·2ο 10 200811092 Table i

2 theta /° Relative strength 1 Relative strength 2 9.31 Weak 38 10.96 Weak 35 11.54 Weak 26 1L80 Weak 38 12.93 Extremely strong 95 13.24 Strong 62 14.39 Strong 67 14/76 Medium 59 15.44 Weak 21 16.09 Medium 44 16.75 Medium 51 16.94 Medium 48 17.46 Weak 26 17.79 of 41 8 200811092

17.96 Medium 44 18.51 Strong 80 18.81 Medium 56 19.42 Extremely strong 100 19.63 Medium 45 19.91 Extremely strong 89 20.78 Weak 37 20.99 Weak 25 21·88 Weak 37 22.26 Weak 35 22.74 Weak 23 23.47 Medium 43 23.89 Medium 44 24.23 Weak 28 25.20 Weak 28 26.24 Weak 28 9 200811092 26.96 Weak 36 2738 Weak 25 28.04 Weak 25 28.25 Weak 23 28.88 Weak 24 29.40 Weak. 21

^Signal intensity > 60 to 80%, "extremely strong" should be understood as >80 to 100% of the strongest signal strength in the spectrum. "Weak" is better understood as the intensity of the strongest signal in the spectrum of 20 to 40%. "Medium" should be understood as the strongest signal strength in the spectrum > 40 to 60%. 5 "Strong" should be understood as the strongest signal strength in the spectrum. >60 to 80%, "extremely strong" should be understood as >80 to 100% of the strongest signal strength in the spectrum. 2 The correlation strength of the strongest signal in the spectrum, which is arbitrarily defined as 100. 10 200811092

Table 2 2 theta /° relative intensity 1 relative intensity 2 6.34 weak 22 8.70 weak 33 10.29 strong 71 10.84 weak ' 39 11.61 weak 40 12.17 weak 30 13.70 weak 21 14.13 weak 32 14.74 extremely strong 100 15.28 medium 51 15.84 medium 42 16.43 medium 60 16.94 Weak 30 17.37 Weak 31 17.50 Weak 38 π 200811092

17.79 Weak 31 17.95 Weak 27 18.50 Medium 46 18.96 Weak 23 20.63 Weak 27 20.90 Weak 35 21.06 Weak 38 22.48 Weak 35 22.73 Weak 37 23.05 Weak 25 23.89 Of 53 24.17 Weak 25 25.57 Weak 25 Weakness is better understood as the strongest signal in the spectrum. 20 to 40% of the intensity, "middle" is understood to be 40 to 60% of the strongest signal strength in the spectrum, and "strong" is understood to be 60 to 80% of the strongest signal strength in the spectrum. "Extremely strong" is understood to be the strongest in the spectrum. Signal strength > 80 to 100%. 5 2 The correlation strength of the strongest signal in the spectrum, which is arbitrarily defined as 100. 12 200811092 Table 3

2 theta/. Relative strength 1 Relative intensity 2 9.50 Medium 58 13.43 Weak 20 14.57 Medium 44 15.52 Medium 46 1638 Strong 64 16.50 Weak 29 18.24 Weak 36 19.11 Weak 30 19.92 Weak 27 21,84 Weak 27 23.22 Extremely strong 100 23.88 Weak 32 2414 Weak 22 25.79 Weak 26 13 200811092 25.98 Weak 33 29.58 Weak 24 1 "Weak" is better understood as 20 to 40% of the strongest signal strength in the spectrum. "Medium" is understood as the strongest signal strength in the spectrum > 40 to 60%, "strong" understanding For the 60 to 80% of the strongest signal strength in the spectrum, "extremely strong" is understood to be >80 to 100% of the strongest signal strength in the spectrum. 2 The correlation strength of the strongest signal in the spectrum, which is arbitrarily defined as 100. The known CMP crystal modification IV is characterized by an X-ray powder diffraction pattern having reflection positions carried by the following Table 4 (2 theta, > 20% relative intensity). The powder X-ray diffraction pattern of crystal modification IV is also shown in FIG. Table 4 2 theta/0 relative intensity 1 relative intensity 2 5·16 medium 42 6.18 medium 52 6.52 strong 64 7.00 strong 64 7.37 medium 43 8.63 medium 57 14 200811092

9.00 weak 35 9.85 weak 39 10.34 weak 38 10.58 weak 39 11.59 weak 32 12.27 medium 48 1238 strong 63 12.84 weak 35 13.05 extremely strong 88 1339 weak 31 13.48 weak 37 13.66 medium 47 14.06 weak 31 14,57 medium 57 14.99 weak 38 15.97 pole Strong 100 15 200811092

16.32 Weak 37 16.59 Weak 37 16.85 Medium 44 17.28 Medium 42 17.46 Weak 37 17.75 Medium 52 18.23 Medium 50 18.64 Strong 70 18.86 Weak 29 19.77 Strong 66 20.19 Weak 34 20.54 Weak 38 21.03 Weak 30 2135 Medium 42 21.63 Weak 31 22.11 Weak 29 16 200811092

22.36 Weak 38 22.47 Medium 47 22.55 Weak 33 23.14 Weak 26 2336 Weak 26 23.93 Weak 24 24.30 Weak 32 24.88 Medium 41 25.09 Weak 22 25.50 Weak 20 25.95 Weak 22 26.20 Weak 22 26.58 Weak 28 27.16 Weak 26 28.87 Weak 21 Weak 21 It should be understood that the intensity of the strongest signal in the spectrum is 20 to 40%, "middle" should be understood as the highest signal intensity in the spectrum > 40 to 60%, and "strong" should be understood as 17 of the strongest signal strength in the spectrum of 200811092 > 60 To 80%, "extremely strong" should be understood as 80 to 100% of the strongest signal strength in the spectrum. 2 The correlation strength of the strongest signal in the spectrum, which is arbitrarily defined as 100. 5 The CMP crystal modification of the present invention also has IR spectroscopy properties. The IR spectrum contains the highest bands in Table 5 (Crystalline Variation I), Table 6 (Crystal Variation II) and Table 7 (Crystal Variation III) (in the FTIR section of the Brecker District of Bremen, Germany) Measurement (Tensor) 37 measurement, using the Golden Gate ATR unit for solid state): ίο Table 5 Wave number [cm1] Wave number [cm_1J Wave number [cm1] Wave number [cm1] 3268 1415 981 628 3022 1301 928 585 2937 1277 867 562 2839 1249 828 1630 1232 814 1591 1206 804 1568 1168 751 1529 1131 728 1506 1101 708 1442 1024 645 18 200811092 Table 6 Wave number [cm1] Wave number [em·1] Wave number [cm1] Wave number 丨cii 。 。 。 。 。 。 。 。 。 。 Μ Wavenumber 丨 cm1] Wavenumber 丨 cm Ί 3268 1381 1026 752 3024 1306 1007 728 2931 1276 979 707 1668 1251 906 660 1630 1219 884 640 1589 1204 875 604 19 200811092 1570 U71 860 588 1537 1134 831 1448 1113 820 1415 109 7 807 > The known CMP crystal modification IV can also characterize IR spectroscopy. The IR spectrum contains the highest point in the band below in Table 8 (measured in FTIR tensor (Tensor 37) in the Brooke district of Bremen, Germany, using the Golden Gate ATR unit for 5 solid state): Table 8 Wavenumber [cnf1 Wavenumber [em1] Wavenumber 丨 cm1] 3250 1210 830 2934 1167 814 1652 1137 762 1592 1101 752 1568 1029 728 1524 1012 709 1444 979 644 20 200811092 1417 929 625 1293 908 587 1278 859 562 The crystal variant of the invention is also Characteristics can be described by Raman spectroscopy. The highest point of the band (measured by Lehman, R100/S in Brooke, Bremen, Germany) is shown in Table 9 (Crystalline Variation I), Table 10 (Crystal Variation II) and Table 11 (Crystal Variation III): 5 Table 9 Wavenumber [cm 1 wave number [cm1] wave number 丨 cm 4 wave number [cm1] 3069 1296 802 393 3021 1264 765 357 2990 1238 752 346 2931 1223 740 330 2888 1205 728 306 2741 1197 709 284 2552 1171 702 259 1666 1157 688 230 1653 1141 645 217 21 200811092

1632 1132 627 209 1612 1108 590 194 1591 1063 568 155 1567 984 539 92 1532 963 530 1505 929 505 1453 897 487 1408 875 465 1386 853 445 1318 818 410 Table ίο Wavenumber [cm1] Wavenumber [cm1] Wavenumber [cm1 Wavenumber [cm1] 3077 1414 934 507 3007 1381 904 475 2978 1319 877 446 2932 1297 814 432 22 200811092

2890 1259 772 400 2752 1210 754 347 2557 1168 699 330 1650 1133 651 306 1614 1106 627 294 1589 1095 588 276 1569 1064 555 228 1514 984 541 181 1462 967 527 99 Table 11 Wavenumber [cm·1] Wavenumber 丨 cm 1 Wavenumber 丨 cm1] Wavenumber 丨cnf1] 3077 1455 1159 876 2986 1414 1136 852 2932 1401 1098 821 2743 1385 1070 806 2600 1365 1042 774 23 200811092 1669 1321 985 754 1641 1293 955 742 1617 1256 923 702 1589 1236 906 1541 1206 894 The known crystal modification IV can also characterize Raman spectroscopy. The highest point of the band (measured by Lehman R100/S in Brooke, Bremen, Germany) is shown in Table 12: Table 12 Wavenumber [cm 1 Wavenumber 丨 cm1] Wave Number 丨 cm1] Wave Number 丨 cm1] 3078 1321 908 445 2980 1298 875 419 2935 1264 810 399 1658 1211 765 346 1615 1172 753 292 1592 1135 740 224 1568 1107 700 178 24 200811092 1525 -—---- 1065 644 100 1455 ~——---- 1003 589 —--^ 1409 ——----- 953 534 —--—^1382 930 477 —------_ --- Han dynaming == The CMP of body 1 is unsatisfactorily stable, even if it is stored for a long time. For, 匕 crystallized variants. What's more, the crystal modification I is in the air = 2 knots; For these reasons, it is particularly suitable for solid clothes and clothing. 0. Due to its stability, its formulation has the required tolerance. Crystalline variant 1 was prepared in such a manner that the stabilized CMP S1 article was fixed in a fixed manner. The CMP of the crystal modification I can include the following methods:

Method A broadcasts J! junction body 11 or 1v^cmp _ at least - a kind of non-polar, sputum and heat. Alternatively, the CMP of the crystal modification II or IV is suspended in f^. a mixture of non-polar organic _ and at least a polar solvent and σ, , , , . After the recrystallization is completed, the precipitate is separated and dried. The preferred polar organic solvent is a branched or linear compound, which is more preferably a linear or cyclic hydrocarbon. It is preferably n-hexane, n-hexane, ortho-ruthenium, ring (10), positively pungent, positive It is burning or disagreeting. ^ 25 15 200811092 Esters (such as decyl acetate, ethyl acetate or propyl acetate), nitriles (such as acetonitrile, butyronitrile or benzonitrile), ethers (such as dimethoxyethane, diethylene glycol) Ether, THE, two, etc., alkane, NMP, sulfonane or oxime], an alcohol (such as decyl alcohol, ethanol or isopropanol) or acetic acid is a preferred polar solvent. Ethyl acetate or dimethoxyethane is preferred, and ethyl acetate is preferred. If 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 I 1000:1 to 30:1, more preferably 500:1. Up to 25:1, excellent for 400" to 20:1 and excellent for 300:1 to 15:1. 1〇 The crystallization of the crystal modification IV used has a preferred concentration of 10 to 500 g/l, a higher concentration of 25 to 300 g/Ι, and a superior concentration of 50 to 250 g/l. The duration of recrystallization is quite different. It is preferably from 1 to 24 hours, more preferably from 2 to 12 hours, and particularly preferably from 4 to 8 hours. Recrystallization can be carried out over a wide range of temperatures. It is preferred to have a boiling point reflux temperature of 80-150 in a solvent mixture. Under the €, the best is 9O-120QC, and the better is 100-120 °C. For example, the boiling point of the solvent mixture is below 100 ° C (hexane, cyclohexane), and recrystallization is carried out under pressure (1-8 bar). The CMP of the crystal modification I can be added to the reaction mixture as a seed material to increase its yield or shorten the required recrystallization time.

Method B Step 1 26 200811092 The CMP of the crystal modification ιν is heated in a mixture of a non-polar organic solvent and ethyl acetate. The preferred non-polar organic solvent is a branched, linear or cyclic hydrocarbon, more preferably a linear or cyclic hydrocarbon, especially excellent as a secret, a positive 5 burn, a cyclohexane, a positive > Geng is burning, it is burning, and it is extremely good for the ring to burn or to be dazzling. For example, a mixture of organic solvent (OS) and ethyl acetate (EA) is used for recrystallization. The preferred mixing ratio of the two solvents is (os: EA, v/v) to 1:2 and more preferably 500:1 to 1:1, the excellent is 200:1 to 1:1, and the excellent is 100:1 to 2.1. The crystal modification 1 obtained by the method B according to the present invention is preferably recrystallized in a mixture of n-hexane and ethyl acetate. The CMPis of the crystalline variant IV is preferably used at a concentration of from 1 to 500 § with a wave of 25 to 300 g/l and a very good concentration of 5 〇t 〇 2 〇〇 g/1. There are many differences in the duration of recrystallization. Preferably, it is 5 to 24 hours, more preferably 1 to 12 hours, and superior is 2 to 8 hours. 15. Step 1 of Method B of the present invention can be carried out over a wide temperature range. Preferably, the (four) point does not exceed 100 ° C, and the boiling point of the solvent mixture can be carried out at a reflux temperature, for example, the boiling point of the solvent mixture exceeds 1 Torr. 〇, can be carried out from 6 〇 to ^ (10), preferably 7 (TC to 100 art, and more preferably 7 (rc to 9 〇t.) Crystallization variant I CMP can be added to the reaction mixture as species 2 〇 increase its output or shorten the required recrystallization time. After crushing, the batch is cooled, and the product is filtered off and dried. 27 200811092 Step 2 The material obtained in step 1 is heated and stirred in water. Cooling and filtering out. The material is then dried. The material obtained in step 1 is introduced into water to a suspension having a concentration of 10 to 500 5 g/Ι, preferably 20 to 250 g/Ι, more preferably 50 to 200 g / Ι. Step 2 of the method B of the invention can be carried out in a wide temperature range (the upper limit is the boiling point of water), preferably above 70 ° C, more preferably above 80 ° C, and excellent For boiling water (l〇〇°C), the duration of step 2 varies greatly. Step 2 is better than 0.5 1〇 and 24 hours, more preferably between 1 and 12 hours, and excellent Between 2 and 6 hours. After step 2 has been carried out, the product is preferably filtered and subsequently dried (for example in a drying oven or using a desiccant) Dryer, such as P205, or CaCl2). 15

Method CMP of Crystalline Variant II can be obtained by the following method: CMP of Crystalline Variant IV is heated in water at reflux temperature. The material is then dried. 2〇 Recrystallization can be carried out over a wide temperature range (the upper limit depends on the boiling point of water). The recrystallization reaction is preferably carried out at 40 ° C or higher, more preferably at 60 ° C or higher, and particularly preferably at boiling water (100 ° C). 28 200811092 The duration of recrystallization is quite different. Step 俾 Between 24 hours, preferably i to 12 hours ^ 仃 between 0.5 hours. To the method of the present invention, the method C is carried out, and the crystal modification is made into a suspension having a concentration of ω to 500 g/1, which is preferably 50 to 200 g/l as compared with p. To 250g/l, more

10 15

20

Method D Crystallization of the ruthenium CMP can be obtained by the following method: CMP of the crystal modification IV is immersed; 13⁄4 士 n into your ... #,, placed in a mixture of organic solvents and alcohols, 'Aya The precipitate formed is separated by a suitable known method, such as filtration. A preferred non-polar organic solvent (os) can be used as a branched or linear carbonitride: more preferably a linear hydrocarbon, especially a positive, positive, n-heptane, n-octane, and Excellent is n-hexane. 1 Available alcohols (AL) are branched or linear alcohols having two to five carbon atoms, preferably ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tertiary butyl Alcohol, especially excellent in n-propanol. The recrystallization of more ic is carried out in a mixture of n-hexane and n-propanol. Solvents for recrystallization can be used with a preferred mixing ratio (OS:AL, v/v) of 200:1 to! · 2, better 100:1 to 1], excellent for 20:1 to I], and excellent for 5:1 to 1:1. Then = 曰 can be carried out in a wide temperature range, better than 70-130. €. Moreover, the length of the performance period of 、 曰 相 is quite different. Preferably, the heating initially acts 29 200811092 at the reflux temperature and then at the reflux temperature. The heating at the reflux temperature is usually carried out for 5 minutes to 6 hours, preferably 5 minutes to 2 hours, and more preferably 10 to 60 minutes. Subsequent heating without reflux temperature is generally carried out for 10 minutes to 6 hours, preferably 20 minutes to 3 hours, more preferably 30 minutes to 2 hours 5 hours. Thereafter, the crystallization solution is allowed to stand still without heating until the recrystallized material is precipitated. The resting state generally lasts from 1 to 48 hours, preferably from 3 to 24 hours, more preferably from 6 to 18 hours. • For the method D of the present invention, the crystallization of the crystal modification IV is carried out at a concentration of 10 to 500 g/Ι, preferably 20 to 250 §/1, more preferably 50 to 200 §/b 1 〇 The invention is not limited to this invention. The solvent system used in the following examples is a preferred one. [Examples] Preparation Example 1 (Method A) 15 CMP crystal modification I was obtained by suspending CMP of p crystal modification IV obtained by a known synthesis method in n-octane/ethyl acetate (100: Lv/v), concentration 165 g/l, and stirred at 115 to 120 QC for six hours. Thereafter, the product was separated by filtration and vacuum drying. A material having a melting point of 168-170 QC, containing 90 to 95% of the crystalline variant I, is obtained in a yield of 97 to 99%. 20 Preparation Example 2 (Method A) Crystallization variant I of CMP was obtained by suspending CMP of crystal modification IV obtained by a known synthesis method in n-octane at a concentration of 147 g/Ι and at 115 to 120 QC. Stir for six hours. Thereafter, the precipitate was separated by filtration and vacuum drying 30 200811092. The crystal modification I yield of the obtained clp of 168_17〇〇c was 97 to 99% (the ratio of crystal modification! 9〇 to 95%). Preparation of Example 3 (Method b) The crystallization of Crystallization I of CMP was obtained by a known synthesis method, and the CMP of the CMP was obtained from the known synthesis method (3: lv/v). , concentration 102 g / Ι ' at 80-90. Mix and smash for 3 hours. Thereafter, the batch was cooled and the product was filtered off with suction and dried. The obtained material was stirred at a concentration of 129 g/1 in water at reflux temperature for about 3 hours, cooled, filtered off with suction and moistened with water. Finally, it was dried in a dryer of P2〇5. A substance having a melting point of 171 ° C was obtained. Preparation Example 4 (Method B) The crystallization crystal modification j of CMP was obtained from the known synthesis method: CMP of body IV in hexane/acetate (3: lv/v), Concentration 83 15

G/1, stirred at reflux temperature for 2 hours. Thereafter, the batch was cooled and filtered to obtain a precipitate. The obtained material was stirred at reflux temperature of 172 g/m in water for 3 hours, and the obtained precipitate was collected by filtration. Finally,

The dryness of CaCU is dry and dry. The crystal modification I of the melting point i69〇c was obtained in a yield of 83%. Preparation Example 5 (Method d) The crystallization of crystal modification m of CMP was obtained by a known synthesis method. The crystal modification 1V < was transferred to the positive (four) and the positively mixed 彳V/V) 'concentration 50 g / 1 'and heat at reflux temperature for a few minutes. In contrast, Luo liquid does not rely on H degree heating _ hours, and then the mixture is allowed to stand for 1, 20 200811092 hours. The precipitate formed was filtered off. The melting point of 140-143 was obtained. . The CMP has a crystal modification with a yield of 48%. 5 Formulation Example 1 A formulation that dissolves concentrated CMP (SC) is prepared. The particle size after the preparation procedure was about 1.5 μm (Fig. 5a). It was then stored at 54 ° C for six weeks. Storage • After the active material was used to contain only about 50% of the formulation of Crystalline I, showing a specific crystal growth with an average particle size of 8 μm (Figure 5b). The formulation having a variant I 10 ratio of 80-85% had a particle size of about 6 μm (Fig. 5c). On the other hand, the formulation in which the active material has a variant I of 90% or more has almost no crystal growth, and the particle size at the same time is about 1.8 μm (Fig. 5d). 32

Claims (1)

200811092 X. Patent application scope: 1. A 3-chloro-N2-[(1S)-1-indolyl-2-(methylsulfonyl)ethyl]-#-{2-methyl-4-[l , Crystalline variant I of 2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}decylamine, characterized by the use of CuKa radiation, the X-ray powder diffraction 5 pattern At least the following reflection locations: • 2. 3-Chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethylmethyl-4-[l,2,2,2 according to the scope of patent application - Crystalline variant I of tetrafluoro-I.(trifluoromethyl)ethyl] ίο phenyl}decylamine, characterized by the use of Cu Ka radiation, the X-ray powder diffraction pattern having at least the following further reflection Location: 33 200811092 3. According to the scope of patent application, 3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-NM2-mercapto-4-[1,2, Crystalline variant I of 2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}decylamine, characterized by the use of Cu Κα radiation 5 lines, the X-ray powder diffraction pattern substantially conforms The spectrum of Figure 1. 4. A 3-chloro-N2-[(1S)-1-indolyl-2-(indolyl)ethyl]-indole 2-methyl | -4-[1,2,2,2·tetrafluoro Crystalline variant II of -1-(trifluoromethyl)ethyl]phenyl}3 melamine, characterized by the use of CuKa radiation having an X-ray powder diffraction pattern with at least the following further reflection positions: 34 200811092 5. 3-Chloro-N2-[(1S>1-methyl-2-(methylsulfonyl)ethylmethyl-4-[1,2,2,2-four according to item 4 of the scope of the patent application Crystalline variant II of fluoro small (trifluoromethyl)ethyl] phenyl} decylamine characterized by the use of Cu Κα radiation 5 lines, the X-ray powder diffraction pattern having at least the following further reflection positions: 2 theta/c 8.70 10.84 14.13 17.50 20.90 2L06 22.48 22.73 6. 3-Chloro-N, [(1S)-1-methyl ίο -2-(indolyl)ethyl]methyl-4-, according to Clause 4 or 5 of the scope of the patent application Crystalline variant II of [l,2,2,2-tetrafluorosuccinyl(trifluoromethyl)ethyl]phenyl}decylamine, characterized by the use of Cu 35 200811092 Κα radiation, X-ray powder diffraction The pattern roughly conforms to the frequency of Figure 2. A 3-chloro-indole ((5) small methyl-1·(methylsulfonyl)ethylmethyl-441,2,2,2-tetrafluoro(trifluoromethyl) Crystalline variant III of ethyl]phenyl]anthracene, characterized by the use of Cu Κα radiation, the X-ray powder diffraction pattern having at least the following further reflection positions: 2 theta/( 9.50 13.43 14.57 15.52 16.50 21.84 23.22 25.79 8' 3-Chloro-N1-[(1 S)-l-fluorenyl-2-(methylsulfonyl)ethyl according to item 7 of the scope of the patent application Crystalline variant 曱 of thiol-4-[l,2,2,2-tetrafluoro-i-(trifluoromethyl)ethyl]phenyl}decylamine, which is characterized by the use of CuKa radiation 'X- The ray powder diffraction pattern has at least the following further reflection positions: 36 1 theta/0 200811092 16.38 18,24 19.11 19,92 23.88 24,14 25.98 29.58 9. According to the scope of patent application No. 7 or 8 of 3_ gas·n2_[(is) small kefu-2-(methyl sulfonyl) ethyl {2•methyl, 2, 2, 2_ four Crystalline variant of fluoro]•(trimethyl)ethyl]phenyl}decylamine, its characteristics 5 10 Radiation, the diffraction pattern of the Χ·ray powder roughly conforms to the spectrum of Figure 3. 10. _N2-[(1S)小methyl-2_(methylsulfonyl)ethyl]_ν1_'{2_methyl, 2, 2, according to one or more of the items i to 3 of the scope of the patent application 2_tetrafluoro]-(trifluoromethyl)ethyl]phenyl-forming amine crystals I, which can be obtained from the following method: a) f2 ^43; a'N2-[(1SH-^-2 -(^^i group)ethyl]-N-{2-methyl-吼, such as fluorine small (three =] phenyl m amide suspended in at least one non-polar organic solvent soil and b or crystallized 3'-chlorine [(ls) small methyl) ethyl]-#{2-methyl-4-anthracene, 2,2,2-tetrafluorobenzene dish V-il methyl) 37 15 200811092 base]phenyl}guanamine, suspended in a mixture of at least one non-polar organic solvent and at least one polar solvent and heated, or C) crystallized variant IV 23|N2_[(1SHm) ^基]-Ν -{2-methyl-4_[1,2,2,2-tetrafluorosuccinyl(trifluoromethyl)ethyl]phenyl}decylamine precedes non-polar organic solvents and ethyl acetate The mixture is heated and then heated in water. • 11. (1 1〇S>1 monomethyl_2_(methyl sulphate)ethyl) according to one or more of the claims 4 to 6 of the patent application One N1♦ Crystalline variant of phenyl-4_[U,2,2-tetra-I-(difluoromethyl)ethyl]phenyl decylamine, which can be heated in water 1 3H[(1S)-1 -Methyl-2_(methylglycosyl)ethyl]-N-{L methyl is called n2,2,fluoro]fluoromethyl)ethyl]phenyl} decylamine crystal derivative IV. 12. Root 2 According to one or more of items 7 to 9 of the patent application scope, chloro-N-[(lS)-l-methyl-2_(methylsulfonyl)ethyl]methyl • 4 [I , 2,2,2 tetrafluoro]-(difluoroindolyl)ethyl]phenyl}decylamine crystal modification III 'which can be heated in a mixture of a non-polar organic solvent and an alcohol - 3-chloro- N2-[(10)·1_methyl_2_(methylsulfonyl)ethyl]_Nl methyl 20 -4-[1,2,2,2-tetrafluoro-1_(trifluoromethyl)ethyl] Stupid base} The crystallized variant IV of decylamine is obtained. !3·- The preparation of the scope of the patent application! To 3 items - or a plurality of "monochloro-N -[(1S)-:U methyl_2_ H of the crystalline variant I of (methanesulfonyl)ethyl]methyl-[ ', tetrafluoro 1 (monofluoromethyl)ethyl]phenyl}decylamine is included in a non-polar organic solvent or a non-polar solvent And B 38 200811092, suspension of ethyl vinegar mixture heated 3- -N2 - [(1 s) -l- methyl-2- (methanesulfonamide stuffed yl) ethyl] -Nl {2_ ice-yl methyl] phenyl} phthalocyanine crystal Amides of variant Π * Ιν. 14·Preparation of one or more of the scope of the patent application from “S1 to 3” [(1S) small methyl-2_(indolyl)ethyl]indolyl [,, '2 tetrafluoro-1-(II) The method of crystal modification I of fluoromethyl)ethyl]phenyl}decylamine includes the first crystallized variant 1V, 3-chloro-NM (1S> in a mixture of a non-polar organic solvent and ethyl acetate). ; 4-methyl-2-(methyl fluorenyl) ethyl hydrazine 1] 2-methyl ortho, 2, 2, 2, fluoro small (trifluoromethyl) ethyl] benzene 10 yl} decylamine heating, Then heated in water. 15.- The preparation of the patent range 4 i - called 〇SH.m (w-branched) E2: ^ 4 [1'2,2,2 tetrafluoro-1-(difluorofluorene) A method of crystallizing variant 11 of ethyl]phenyl decylamine comprising the step of capturing 3-chloro-N2-[(1S)small methyl-2-(methyl 15 sulphate)ethyl] in water { 2_曱基冰 [1,2,2,2-tetrafluoro+(trifluoromethylindenyl) _ethyl]phenyl}decylamine crystal modification IV heating. 16, ^ preparation (four) paste range 7 Up to 9 - or more than 3-gas-N -[(1S)-1-methyl_2-(methylsulfonyl)ethyl]_Ni-p-mercapto-4-[l,2,2' Crystallization of 2-tetrafluoro·1_(trifluoromethyl)ethyl]phenyl}decylamine The method 'includes 3-chloro-ice [(13) small methyl κ-methylsulfonyl) ethyl]-Νι_{2_mercapto-4-[1,2 in a mixture of a non-polar organic solvent and an alcohol. Crystalline variant IV of 2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}decylamine was heated. Π.—The composition, including one or more of the patent applications 丨 to 3, 39, 200811092, 3-chloro-N -{(is)-i-methylmethylsulfonyl)ethyl}_Νι_{2_ Crystalline variant I of mercapto-4-[l,2,2,2-tetrafluoro(trifluorodecyl)ethyl]phenyl}decylamine. 18·—Composition=, including one or more of the patent scopes 4 to 6 of 3 chloro N [(is) small methyl j (methionite) ethyl]_^1_{2_ fluorenyl The knot II of -4-[1,2,2,2-tetrafluoro(trifluoromethyl)ethyl]phenyl}decylamine. • I9 · A composition 1, including one or more of the patent applications in paragraphs 4 to 3, n2_[(ish_methyl_2_(methylsulfonyl)ethyl (tetra)methyl 10 -4-[ Crystalline variant of 1,2,2,2-tetrafluoro-4-(trifluoromethyl)ethyl]phenyl}decylamine III 〇2〇· One or more of the patent claims 1 i 3 3 residual N [(1S) small methyl-2-(indenyl)ethyl]_:^1-{2-methyl-4-[l,2,2,2-tetrafluoro(trifluorofluorene) The use of chloroformylamine as a pesticidal composition. 21. A 3-chloro-N2-{- (1S) bismuthyl-2-((methylsulfonyl)ethyl}·ν1_{2_methyl_4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl] The use of phenyl}guanamine crystal variant II as an insecticidal composition. 20 22.- One of the patent applications in the range of items 7 to 9 of 3_chloro-Ν-[(1S)-1 -mercapto-2-(methylsulfonyl)ethyl]_ν1_"2-methyl-4-[1,2,2,2-tetrafluoro-1·(trifluoromethyl)ethyl]phenyl} The use of phthalamide crystal modification III as an insecticidal composition. 23·-A method for controlling unwanted insects Characterized by the application of 3-chloro-N2-[(1S)-1-indolyl-2-(indolyl)ethyl]-NM2- comprising one or more of items 1 to 3 of the application specification 200811092 Formulation of crystalline variant I of mercapto-4-[l,2,2,2-tetrafluorosuccinyl(ethyl)phenyl]decylamine in insects and/or their habitat and/or Or a seed. 5 24 · A method for controlling an unwanted insect, characterized by applying 3-chloro-N2-[(1S)-1- comprising one or more of items 4 to 6 of the patent application scope Methyl-2-(methylsulfonyl)ethyl]-NM2-methyl-4-[l,2,2,2-tetrafluoros(trifluoro-methyl)ethyl]phenyl}decylamine The formulation of the crystal modification II is in insects and/or its habitat and/or seed. ίο 25 - A method of controlling an unwanted insect, characterized in that the application comprises one of items 7 to 9 of the scope of the patent application or 3-Chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1]]-mercapto-4-[l,2,2,2-tetrafluoro Formulation of crystalline variant III of -1-(trifluoromethyl)ethyl]phenyl}decylamine in insects and/or their habitat and/or seeds.