WO2017219768A1 - Polymorphe de chlorantraniliprole et son procédé de préparation - Google Patents

Polymorphe de chlorantraniliprole et son procédé de préparation Download PDF

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WO2017219768A1
WO2017219768A1 PCT/CN2017/083516 CN2017083516W WO2017219768A1 WO 2017219768 A1 WO2017219768 A1 WO 2017219768A1 CN 2017083516 W CN2017083516 W CN 2017083516W WO 2017219768 A1 WO2017219768 A1 WO 2017219768A1
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crystal
chlorantraniliprole
group
ether
add
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PCT/CN2017/083516
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English (en)
Chinese (zh)
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徐晓勇
任国宾
李忠
齐明辉
杜丹
刘鹏建
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华东理工大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the present invention is in the field of medicinal chemistry, and in particular, the present invention relates to polymorphs of chlorantraniliprole, their use and methods of preparation.
  • Invertebrate pests such as arthropods are important for achieving efficient agricultural production. Invertebrate pests can cause serious crop damage to growing and stored crops, especially forests, greenhouse crops, ornamental plants, nursery crops, and stored foods. And fiber products, livestock, households, and public health and animal health.
  • Chlorantranyl benzamide (compound of formula I), ie
  • the chemical name is 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloropyridin-2-yl)-1H-pyrazole- 5-carboxamide, which is a broad-spectrum efficient and broad-spectrum, has a very broad spectrum of Lepidoptera, Lepidoptera, Capsule, Moth, Moth, Moth, Moth, Moth, etc. Good control effect, can also control a variety of non-Lepidoptera pests such as Coleoptera, Aphididae, Hymenoptera, Diptera, and B.
  • the crystal is selected from the group consisting of Form A, Form B, and Form F.
  • the X-ray powder diffraction pattern of the crystalline form A includes 3 or more selected from the group consisting of 2 ⁇ values of the group: 8.7 ⁇ 0.2°, 11.5 ⁇ 0.2°, 17.3 ⁇ 0.2°, 20.5 ⁇ 0.2°, 21.3 ⁇ 0.2°, 21.8 ⁇ 0.2°, 22.7 ⁇ 0.2°, 25.0 ⁇ 0.2°, 25.6 ⁇ 0.2°, 27.3 ⁇ 0.2 °, 28.4 ⁇ 0.2 °, 29.0 ⁇ 0.2 ° and 30.2 ⁇ 0.2 °.
  • the X-ray powder diffraction pattern of the Form A may further include 3 or more 2 ⁇ values selected from the group consisting of: 8.7 ⁇ 0.2°, 10.0 ⁇ 0.2°, 11.5 ⁇ 0.2°, 12.3 ⁇ 0.2°, 17.3 ⁇ 0.2°, 20.5 ⁇ 0.2°, 21.3 ⁇ 0.2°, 21.8 ⁇ 0.2°, 22.7 ⁇ 0.2°, 25.0 ⁇ 0.2°, 25.6 ⁇ 0.2°, 27.3 ⁇ 0.2°, 28.4 ⁇ 0.2°, 29.0 ⁇ 0.2°, 30.2 ⁇ 0.2°, 32.1 ⁇ 0.2°, 32.8 ⁇ 0.2°, 35.9 ⁇ 0.2°, 37.3 ⁇ 0.2°, 38.3 ⁇ 0.2°, 39.1 ⁇ 0.2°, 39.6 ⁇ 0.2°, 40.3 ⁇ 0.2° and 43.4 ⁇ 0.2 °.
  • the X-ray powder diffraction pattern of Form A is substantially characterized as in Figure 15.
  • the TG map of Form A is substantially characterized as in Figure 17.
  • the DSC pattern of Form A has an endothermic peak in the range of 222-227 °C.
  • the DSC pattern of Form A is substantially as characterized in FIG.
  • the Form A purity is greater than 95%, preferably, the purity is greater than 97%, more preferably, the purity is greater than 99%, and most preferably, the purity is greater than 99.5%.
  • the X-ray powder diffraction pattern of Form B comprises 3 or more 2 ⁇ values selected from the group consisting of: 7.3 ⁇ 0.2°, 9.6 ⁇ 0.2°, 13.4 ⁇ 0.2°, 18.6 ⁇ 0.2°, 19.3 ⁇ 0.2°, 21.3 ⁇ 0.2°, 21.9 ⁇ 0.2°, 23.8 ⁇ 0.2°, 25.8 ⁇ 0.2°, 26.2 ⁇ 0.2°, and 26.6 ⁇ 0.2°.
  • the X-ray powder diffraction pattern of the Form B may further include 3 or more 2 ⁇ values selected from the group consisting of: 7.3 ⁇ 0.2°, 9.6 ⁇ 0.2°, 10.0 ⁇ 0.2°, 13.4 ⁇ 0.2°, 13.9 ⁇ 0.2°, 14.9 ⁇ 0.2°, 16.6 ⁇ 0.2°, 17.0 ⁇ 0.2°, 17.8 ⁇ 0.2°, 18.6 ⁇ 0.2°, 19.3 ⁇ 0.2°, 20.9 ⁇ 0.2°, 21.3 ⁇ 0.2°, 21.9 ⁇ 0.2°, 23.5 ⁇ 0.2°, 23.8 ⁇ 0.2°, 24.5 ⁇ 0.2°, 25.0 ⁇ 0.2°, 25.8 ⁇ 0.2°, 26.2 ⁇ 0.2°, 26.6 ⁇ 0.2°, 28.4 ⁇ 0.2°, 29.0 ⁇ 0.2°, 30.4 ⁇ 0.2 °, 33.6 ⁇ 0.2 °, 34.5 ⁇ 0.2 °, 35.0 ⁇ 0.2 °, 36.2 ⁇ 0.2 °, 37.2 ⁇ 0.2 °, 38.4 ⁇ 0.2 ° and 38.8 ⁇ 0.2 °.
  • the X-ray powder diffraction pattern of Form B is substantially characterized as in Figure 1.
  • the TG map of Form B is substantially characterized as in Figure 3.
  • the DSC pattern of Form B has an endothermic peak in the range of 155-160 ° C and/or 242-247 ° C.
  • the DSC pattern of Form B is substantially as characterized in FIG.
  • the Form B purity is greater than 95%, preferably, the purity is greater than 97%, more preferably, the purity is greater than 99%, and most preferably, the purity is greater than 99.5%.
  • the crystalline form B is a solvate of ethylene glycol dimethyl ether, preferably a hemiethylene glycol dimethyl ether solvate.
  • the X-ray powder diffraction pattern of the Form F comprises 3 or more 2 ⁇ values selected from the group consisting of: 8.4 ⁇ 0.2°, 16.2 ⁇ 0.2°, 16.7 ⁇ 0.2°, 17.0 ⁇ 0.2°, 18.6 ⁇ 0.2°, 19.2 ⁇ 0.2°, 20.0 ⁇ 0.2°, 20.6 ⁇ 0.2°, 21.3 ⁇ 0.2°, 22.2 ⁇ 0.2°, 23.8 ⁇ 0.2°, 24.6 ⁇ 0.2°, 25.2 ⁇ 0.2°, 28.2 ⁇ 0.2°, 28.8 ⁇ 0.2°, 29.2 ⁇ 0.2°, 32.7 ⁇ 0.2°, and 33.8 ⁇ 0.2°.
  • the X-ray powder diffraction pattern of the Form F may further include 3 or more 2 ⁇ values selected from the group consisting of 8.4 ⁇ 0.2°, 9.4 ⁇ 0.2°, 10.3 ⁇ 0.2°, 13.4 ⁇ 0.2°, 15.2 ⁇ 0.2°, 16.2 ⁇ 0.2°, 16.7 ⁇ 0.2°, 17.0 ⁇ 0.2°, 17.4 ⁇ 0.2°, 18.6 ⁇ 0.2°, 19.2 ⁇ 0.2°, 20.0 ⁇ 0.2°, 20.6 ⁇ 0.2°, 21.3 ⁇ 0.2°, 22.2 ⁇ 0.2°, 22.6 ⁇ 0.2°, 23.8 ⁇ 0.2°, 24.6 ⁇ 0.2°, 25.2 ⁇ 0.2°, 26.9 ⁇ 0.2°, 27.4 ⁇ 0.2°, 28.2 ⁇ 0.2°, 28.8 ⁇ 0.2°, 29.2 ⁇ 0.2 °, 29.6 ⁇ 0.2 °, 32.7 ⁇ 0.2 ° and 33.8 ⁇ 0.2 °.
  • the X-ray powder diffraction pattern of Form F is substantially as characterized in FIG.
  • the TG map of Form F is substantially characterized as in Figure 14.
  • the DSC pattern of Form F has an endothermic peak in the range of 129-134 ° C and/or 237-242 ° C.
  • the DSC pattern of Form F is substantially as characterized in FIG.
  • the Form F purity is greater than 95%, preferably, the purity is greater than 97%, more preferably, the purity is greater than 99%, and most preferably, the purity is greater than 99.5%.
  • the Form F is a solvate of pyridine, preferably a monopyridine solvate.
  • a pesticidal composition comprising:
  • a method of preparing the crystalline form A of the first aspect of the invention comprising the steps of:
  • organic solvent A1 selected from the group consisting of substituted or unsubstituted C1-C9 alcohols, polyethylene glycol-200, substituted or unsubstituted benzenes, ethers, Substituted or unsubstituted C1-C7 alkyl, ester, substituted or unsubstituted C1-C6 ketone, 2-methyltetrahydrofuran, acetonitrile, 1,4-dioxane, acetic acid, water, N,N-di Methylformamide, N-methylpyrrolidone, sulfolane, diethylamine, sulfolane, or a combination thereof;
  • substitution is selected from the group consisting of C1-C3 alkoxy, C1-C6 alkyl, halogen, nitro;
  • the weight-to-volume ratio of the compound of the formula I to the organic solvent A1 is 50 mg: 0.1-20 mL, preferably 50 mg: 1.0-15 mL.
  • the weight-to-volume ratio of the compound of the formula I to the organic solvent A2 is 100 mg: 0.1-10 mL, preferably 100 mg: 1.0-6.0 mL, more preferably 100 mg. : 1.3-5 mL.
  • the C1-C9 alcohol is selected from the group consisting of 2-ethoxyethanol, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, uncle Butanol, 3-methyl-1-butanol, n-octanol, cyclopentanol, benzyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, triethylene glycol , 2,2,2-trifluoroethanol, or a combination thereof.
  • the substituted or unsubstituted benzene is selected from the group consisting of toluene, trifluorotoluene, cumene, p-xylene, mesitylene, chlorobenzene, or a combination thereof.
  • the ether is selected from the group consisting of isopropyl ether, n-butyl ether, diphenyl ether, dibenzyl ether, anisole, phenethyl ether, m-xylylene ether, diethyl ether, and methyl ring.
  • the C1-C7 alkyl group is selected from the group consisting of nitromethane, 2-nitropropane, dichloromethane, chloroform, 1,2-dichloroethane, n-heptane, n-hexane. , cyclohexane, n-pentane, or a combination thereof.
  • the ester is selected from the group consisting of ethyl formate, ethyl acetate, butyl acetate, ethyl lactate, ethyl cyanoacetate, diethyl oxalate, diethyl malonate, and lemon.
  • the substituted or unsubstituted C1-C6 ketone is selected from the group consisting of acetone, 2-butanone, 3-pentanone, cyclohexanone, 4-methyl-2-pentanone, acetone Or a combination thereof.
  • a fourth aspect of the invention there is provided a method of preparing the crystalline form B of the first aspect of the invention, comprising the steps of:
  • the weight to volume ratio of the compound of formula I to the organic solvent B1 is 5-20 mg: 0.5-2 mL, preferably 10-15 mg: 1-1.5 mL.
  • the frequency of the ultrasonic treatment is from 20 kHz to 500 MHz.
  • step (ii) the sonication time is from 30 min to 90 min.
  • the weight-to-volume ratio of the compound of the formula I to the organic solvent B2 is from 0.1 to 1.0 g: 0.4 to 5 mL, preferably from 0.2 to 0.5 g: from 0.8 to 2 mL. .
  • the dissolution is carried out under heating, and the heating temperature is from 35 ° C to 60 ° C, preferably from 40 to 55 ° C.
  • the temperature is lowered to 3 ° C to 5 ° C, preferably 3.5 to 4.5 ° C.
  • step (b) crystallization is carried out using ethylene glycol dimethyl ether.
  • a filtration and drying step is further included.
  • a method of preparing the crystalline form F of the first aspect of the invention comprising the steps of:
  • the weight to volume ratio of the compound of formula I to the organic solvent F is from 5 to 50 mg: 1 mL, preferably from 10 to 30 mg: 1 mL.
  • the dissolution is carried out under heating, and the heating temperature is from 30 ° C to 50 ° C, preferably from 40 to 50 ° C.
  • the temperature is lowered to 10 ° C to 25 ° C, preferably 10 to 20 ° C.
  • the solvent is selected by using a solvent selected from the group consisting of n-butyl ether, diethyl ether, diisopropyl ether, methyl tert-butyl ether, n-pentane, n-hexane, Cyclohexane, n-heptane, or a combination thereof.
  • a filtration and drying step is further included.
  • a use of the crystal of the first aspect of the invention or the pesticidal composition of the second aspect of the invention for preventing or controlling a pest for preventing or controlling a pest.
  • the pest is selected from the group consisting of Lepidoptera, Coleoptera, Non-Lepidoptera, and Diptera.
  • the lepidoptera is selected from the group consisting of the genus Noctuidae, the genus Coleoptera, the genus Corydalis, the genus Corydalis, the genus Mothidae, the genus Hymenoptera, the genus Mothidae, and the genus Mothidae.
  • the coleoptera is selected from the group consisting of the family A. and the family A.
  • the Diptera is a genus Lepidoptera.
  • the non-Lepidoptera is Bemisia tabaci.
  • the prevention or control is to prevent or control pests in agriculture, forestry or horticulture.
  • Figure 1 shows the XRD pattern of Form B.
  • Figure 2 shows a DSC chart of Form B.
  • Figure 3 shows a TG map of Form B.
  • Figure 4 shows a molecular stereostructure projection of Form B.
  • Figure 5 shows a cell stack projection of Form B.
  • Figure 6 shows a five-day high temperature stability XRD pattern of Form B.
  • Figure 7 shows a 10-day high temperature stability XRD pattern of Form B.
  • Figure 8 shows a five-day high wet stability XRD pattern of Form B.
  • Figure 9 shows a 10-day high humidity stability XRD pattern of Form B.
  • Figure 10 shows a five-day light stability XRD pattern of Form B.
  • Figure 11 shows the X-ray pattern of Form B light stability for ten days.
  • Figure 12 shows the XRD pattern of Form F.
  • Figure 13 shows a DSC chart of Form F.
  • Figure 14 shows a TG map of Form F.
  • Figure 15 shows the XRD pattern of Form A.
  • Figure 16 shows a DSC chart of Form A.
  • Figure 17 shows a TG map of Form A.
  • Figure 18 shows a molecular stereostructure projection of Form F.
  • Figure 19 shows a cell stack projection of Form F.
  • the present inventors have unexpectedly discovered, for the first time, a polymorph of chlorantraniliprole, its application and a preparation method through extensive and intensive research.
  • the present invention has been completed on this basis.
  • the term “about” means that the value can vary by no more than 1% from the recited value.
  • the expression “about 100” includes all values between 99 and 101 and (eg, 99.1, 99.2, 99.3, 99.4, etc.).
  • the terms "containing” or “including” may be open, semi-closed, and closed. In other words, the terms also include “consisting essentially of,” or “consisting of.”
  • n or n or more selected from the group of 2 refers to any positive integer (eg, n, n+1, . . . ) comprising n and greater than n, wherein the upper limit Nup is the group The number of all 2 ⁇ peaks in the middle. For example, “3 or more” includes not only 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, .. upper limit Nup each positive integer, also includes “4 or more", “5 or more", “6 or more” and the like.
  • the compound of the formula I of the present invention is chlorantraniliprole, and the structural formula is
  • the chemical name is 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloropyridin-2-yl)-1H-pyrazole- 5-carboxamide, which is a broad-spectrum efficient and broad-spectrum, has a very broad spectrum of Lepidoptera, Lepidoptera, Capsule, Moth, Moth, Moth, Moth, Moth, etc. Good control effect, can also control a variety of non-Lepidoptera pests such as Coleoptera, Aphididae, Hymenoptera, Diptera, and B.
  • the polymorphic form of the compound can exhibit different melting points, hygroscopicity, stability, solubility, bioavailability, and fluidity, etc., which are important factors influencing the drug-forming properties.
  • the crystal of the present invention comprises a crystal form selected from the group consisting of Form A, Form B and Form F.
  • solvate a substance formed after the drug and the solvent are crystallized.
  • the solvent species which readily form a solvate with an organic compound are water, methanol, benzene, ethanol, ether, aromatic hydrocarbon, heterocyclic aromatic hydrocarbon, and the like.
  • Hydrate is a special solvate.
  • hydrates have a separately discussed value for their specificity in the synthesis of drug substances, pharmaceutical preparations, drug storage, and drug activity evaluation.
  • the crystal of the compound represented by the formula (I) may be an unsolvated compound or a solvate.
  • the "active ingredient" in the pesticidal composition of the present invention means a compound of the formula (I) according to the present invention.
  • the "active ingredient” and the pesticidal composition of the present invention can be used as a preventive or control pest.
  • the present invention provides the use of crystal forms A, B, F and a pesticidal composition thereof, which is highly efficient and broad-spectrum, and belongs to the family Lepidoptera, Scorpionidae, Capsae, Mothaceae, Mothidae
  • the Phytophthora, the genus Mothidae, the Mothidae, etc. have good control effects, and can also control a variety of non-Lepidoptera pests such as Coleoptera, Aphididae, Diptera, and Diptera .
  • the crystalline forms of the compounds of the present invention all have good thermal stability and non-hygroscopicity.
  • the crystal form of the present invention can effectively prevent or control harmful organisms.
  • Normal temperature or room temperature means 4 ° C to 25 ° C, preferably 15 to 25 ° C.
  • XRD X-ray powder diffraction
  • Instrument model Rigaku Ultima IV
  • target Cu-K ⁇ (40 kV, 40 mA)
  • D/tex Ultra detector using a D/tex Ultra detector at room temperature.
  • the scanning range is from 3° to 45° in the 2 ⁇ range and the scanning speed is 20°/min.
  • Measurement differences associated with such X-ray powder diffraction analysis results are produced by a variety of factors including: (a) errors in sample preparation (eg, sample height), (b) instrument error, (c) calibration differences, ( d) operator error (including errors that occur when determining peak position), and (e) properties of the substance (eg, preferred orientation error). Calibration errors and sample height errors often result in displacement of all peaks in the same direction. When a flat stent is used, a small difference in sample height will result in a large displacement of the XRD peak position. Systematic studies have shown that a 1 mm sample height difference can result in a 2[Theta] peak shift of up to 1[deg.].
  • displacements can be identified from the X-ray diffraction pattern, And the displacement can be eliminated by compensating for the displacement (using a system calibration factor for all peak position values) or recalibrating the instrument. As described above, measurement errors from different instruments can be corrected by applying a system calibration factor to make the peak positions consistent.
  • TG (thermogravimetric analysis) method Instrument model: TA Q500 thermogravimetric analyzer, using N 2 atmosphere, heating rate is 10 ° C / min
  • 1.66 weigh 500mg chlorantraniliprole amorphous in the container, adding a total volume of 50mL, volume ratio Is 1:1 tetrahydrofuran and water, anhydrous methanol, absolute ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, ethyl acetate, butyl acetate, isopropyl acetate, n-Heptane, n-hexane, cyclohexane, dichloromethane, 1,2-dichloroethane, nitromethane, acetonitrile, acetone, 2-butanone, 4-methyl-2-pentanone, anhydrous ether Methyl tert-butyl ether, ethylene glycol dimethyl ether, toluene, p-xylene, or a combination thereof, dissolved, and allowed to volatilize, and dried under vacuum to
  • chlorantraniliprole 1.73 100 mg was crystallized in 1.3 mL of pyridine, and steamed to obtain a solid, which was dried under vacuum to give chlorantraniliprole crystal form A.
  • the XRD pattern of the obtained Form A is shown in Fig. 15, and the diffraction angle data is basically as shown in Table 1 below.
  • the DSC spectrum of Form A is substantially as shown in Figure 16, wherein the endothermic peak corresponds to the melt decomposition process.
  • the TG spectrum of Form A is basically as shown in Figure 17, and there is substantially no weight loss before decomposition.
  • form B was a semi-glycol dimethyl ether solvate.
  • the XRD pattern of the obtained Form B is shown in Fig. 1, and the diffraction angle data is basically as shown in Table 2 below.
  • the DSC spectrum of Form B is basically as shown in Figure 2, in which the first endothermic peak corresponds to the solvent loss process and the second endothermic peak corresponds to the melt decomposition process.
  • the TG spectrum of Form B is substantially as shown in Figure 3, wherein about 9% of the weight loss before 160 °C corresponds to the solvent loss process.
  • Example 2 The Form B sample of Example 2 was placed in an oven at 60 ⁇ 2 ° C. After 5 and 10 days, the sample was taken out for XRD testing to examine the crystal stability of the sample to temperature. The results are shown in Figures 6 and 7. Under this condition, the Form B sample was stable.
  • the Form B sample of Example 2 was placed under 90 ⁇ 5% humidity conditions, and after 5 days and 10 days, the sample was taken out for XRD test to examine the crystal form stability of the sample against humidity. The results are shown in Figures 8 and 9, under which the Form B sample was stable.
  • the Form B sample of Example 2 was placed at 4500 ⁇ 500 lux light intensity, and after 5 and 10 days, the sample was taken out for XRD testing to examine the crystal stability of the sample to light. The results are shown in Figures 10 and 11, under which the Form B sample was stable.
  • a certain amount of water-dispersible granules WDG was weighed by an analytical balance (0.0001 g), and dissolved in distilled water to prepare a 500 mg/L mother liquor.
  • Dipping method The mother liquor was diluted to 5 mg/L with distilled water and diluted to a test concentration with distilled water containing 0.1% Tween-80.
  • the target of the test is the armyworm.
  • the appropriate amount of corn leaves is fully infiltrated in the prepared liquid, and then placed in a petri dish with a filter paper. It is naturally dried and dried, and the 3rd instar larvae of the armyworm are 8 heads/dish, placed in 24- The culture was observed at 27 ° C, and the results were investigated after 4 days.
  • the insect is touched by a brush, and severe poisoning is regarded as a dead insect.
  • the test concentrations were 0.3, 0.1, 0.03, 0.01, and 0.003 mg/L, respectively.
  • Spray method The mother liquor was diluted with distilled water to the test concentration.
  • the target of the test is the armyworm, which is to spray the corn leaves. After spraying, the appropriate amount of corn leaves is cut into the petri dish with filter paper and dried naturally.
  • the 3rd instar larvae of the armyworm are 8 heads/dish, placed in 24-27.
  • the indoor culture was observed at °C, and the results were investigated after 4 days.
  • the insect is touched by a brush, and severe poisoning is regarded as a dead insect.
  • the test concentrations were 0.5, 0.135, 0.045, 0.015, and 0.005 mg/L, respectively.
  • the test results of the insecticidal activity of Form A and Form B showed (Table 5) that after the spray treatment, the mortality of the test insects treated with Form B and Form A was 43.75% and 37.5% at 0.03 mg/L, respectively; After the leaf leaching treatment, the mortality of the test insects treated with Form B and Form A was 93.7% and 87.5%, respectively, at 0.3 mg/L.
  • Form F is a monopyridine solvate.
  • the XRD pattern of the obtained Form F is shown in Fig. 12, and the diffraction angle data is basically as shown in Table 6 below.
  • the DSC spectrum of Form F is basically as shown in Figure 13, in which the first endothermic peak corresponds to the solvent loss process and the second endothermic peak corresponds to the melt decomposition process.
  • the TG spectrum of Form F is substantially as shown in Figure 14, wherein about 13.96% of the weight loss before 160 °C is the solvent loss process. It can be judged that the form F is a pyridine solvate.
  • SXRD single crystal X-ray diffraction

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Abstract

L'invention concerne un polymorphe de chlorantraniliprole, son utilisation et son procédé de préparation. En particulier, la présente invention concerne un polymorphe de 3-bromo-N- [4-chloro-2-méthyl-6-[(méthylamino) carbonyl] phényl]-1-(3-chloropyridin-2-yl) -1 H-pyrazole-5-formamide, son procédé de préparation et son utilisation.
PCT/CN2017/083516 2016-06-21 2017-05-08 Polymorphe de chlorantraniliprole et son procédé de préparation WO2017219768A1 (fr)

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CN201610453174.2A CN107522689B (zh) 2016-06-21 2016-06-21 氯虫苯甲酰胺的多晶型及其制备方法
CN201610453174.2 2016-06-21

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