WO2015071739A1 - A molecular complex of hexaconazole and imidacloprid and a process for production thereof - Google Patents
A molecular complex of hexaconazole and imidacloprid and a process for production thereof Download PDFInfo
- Publication number
- WO2015071739A1 WO2015071739A1 PCT/IB2014/002438 IB2014002438W WO2015071739A1 WO 2015071739 A1 WO2015071739 A1 WO 2015071739A1 IB 2014002438 W IB2014002438 W IB 2014002438W WO 2015071739 A1 WO2015071739 A1 WO 2015071739A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- imidacloprid
- hexaconazole
- molecular complex
- mixture
- grinding
- Prior art date
Links
- 239000005906 Imidacloprid Substances 0.000 title claims abstract description 106
- 229940056881 imidacloprid Drugs 0.000 title claims abstract description 106
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 title claims abstract description 104
- STMIIPIFODONDC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 31
- 238000009472 formulation Methods 0.000 claims abstract description 17
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 12
- 230000000361 pesticidal effect Effects 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000238631 Hexapoda Species 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000002538 fungal effect Effects 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 241000235349 Ascomycota Species 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001414825 Miridae Species 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- 241001466030 Psylloidea Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000008686 ergosterol biosynthesis Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 231100000618 neurotoxin Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Definitions
- a MOLECULAR COMPLEX OF HEXACONAZOLE AND IMIDACLOPRID AND A PROCESS FOR PRODUCTION THEREOF The present disclosure relates to a molecular complex of hexaconazole and imidacloprid and a process for production thereof.
- Hexaconazole is a white to off-white crystalline powder having a broad-spectrum fungicidal activity. It is a systemic fungicide that particularly controls ascomycetes and basidiomycetes by inhibiting ergosterol biosynthesis. Hexaconazole rapidly degrades in soil.
- Imidacloprid is a systemic insecticide which serves as an insect neurotoxin. This insecticide is effective for controlling aphids, whiteflies, thrips, scales, psyllids, plant bugs and various other harmful pest species in a variety of different crops.
- Imidacloprid is colorless crystalline solid with a weak characteristic odor and high water solubility.
- imidacloprid goes through a series of cycles of solubilization and re-crystallization leading to the generation of large and undesirable particles. These particles cause problems such as blockage of spray nozzles during application of the product.
- solubilization and recrystallisation it is difficult to maintain imidacloprid products as a homogeneous formulation that leads to issues during transfer to dilution tanks and in ensuring correct concentration of imidacloprid on dilution.
- a pesticidal formulation comprises a molecular complex of hexaconazole and imidacloprid, having a melting point of around 105°C measured as a single melting endotherm by differential scanning calorimetry.
- a process for preparing a molecular complex of hexaconazole and imidacloprid comprises mixing hexaconazole and imidacloprid in a stoichiometric ratio in a range of 1 :20 to 20: 1 , followed by grinding to obtain a dry mixture; melting the dry mixture; and cooling the melted mixture followed by grinding to obtain a molecular complex of hexaconazole and imidacloprid having a melting point of around 105°C measured as a single melting endotherm by differential scanning calorimetry.
- a process for preparing a molecular complex of hexaconazole and imidacloprid is also disclosed in accordance with another embodiment.
- the process comprises mixing hexaconazole and imidacloprid in a stoichiometric ratio in a range of 1 :20 to 20: 1, followed by grinding to obtain a dry mixture; adding a solvent to the dry mixture followed by grinding to obtain a wet mixture; and air drying the wet mixture to obtain the molecular complex having a melting point of around 105°C measured as a single melting endotherm by differential scanning calorimetry.
- Figure 1 illustrates a comparison Powder X-ray Diffraction (PXRD) profile of various samples of molecular complex of hexaconazole and imidacloprid having different molar ratios of hexaconazole and imidacloprid.
- PXRD Powder X-ray Diffraction
- Figure 2 illustrates the comparison Differential Scanning Calorimetric (DSC) profile of various samples of molecular complex of hexaconazole and imidacloprid having different molar ratios of hexaconazole and imidacloprid.
- DSC Differential Scanning Calorimetric
- Figure 3 illustrates the comparison Fourier Transformed Infrared Spectra (FT-IR) profile of various samples of molecular complex of hexaconazole and imidacloprid having different molar ratios of hexaconazole and imidacloprid.
- FT-IR Fourier Transformed Infrared Spectra
- Figure 4 illustrates the solubility profile HPLC data of samples of imidacloprid, and molecular complex of hexaconazole and imidacloprid having different molar ratios of hexaconazole and imidacloprid.
- Figure 5 illustrates the degradation profile - HPLC data of samples of imidacloprid, and molecular complex of hexaconazole and imidacloprid having different molar ratios of hexaconazole and imidacloprid.
- the disclosure relates to a pesticidal formulation.
- the pesticidal formulation comprises a molecular complex of hexaconazole and imidacloprid.
- Molecular complex herein refers to a substance in a solid form or solid formulations, which comprises at least two pure substances which interact with each other through hydrogen bonding or any other non covalent interactions to form molecular complex including co-crystals, solvates, hydrates or eutectic combinations or solid solutions, in which at least one of the pure substance is present in the solid form.
- Hexaconazole refers to all polymorphs, solvates, and hydrates of the substance having the formula (I):
- Imidacloprid refers to all polymorphs, solvates, and hydrates of the substance having the formula (II):
- the melting point of the molecular complex of hexaconazole and imidacloprid measured as a single melting endotherm by differential scanning calorimetry is around 105 °C.
- the molar ratio of imidacloprid to hexaconazole in the molecular complex of hexaconazole and imidacloprid is in a range of 1 :20 to 20: 1 and preferably in a range of 2: 1 to 8: 1.
- suitable amounts of hexaconazole and imidacloprid may be added to the pesticidal formulation.
- the present disclosure also provides a method for producing the molecular complex of hexaconazole and imidacloprid.
- the process comprises of preparing a mixture of hexaconazole and imidacloprid in required stoichiometric ratios, grinding the mixture, melting the ground mixture by heating, cooling the melted mixture and grinding it to obtain molecular complex of hexaconazole and imidacloprid.
- the ground mixture is melted by heating it at 100 to 1 10°C.
- the melting may be carried out under an inert atmosphere.
- the process comprises of admixing hexaconazole and imidacloprid to form a dry mixture, grinding said dry mixture for a predetermined period of time, adding to the ground dry mixture a solvent to obtain a wet mixture, grinding the wet mixture and air drying the same to obtain the molecular complex of hexaconazole with imidacloprid.
- the grinding of the dry mixture may be carried out for 15 to 20 minutes.
- the process comprises of admixing hexaconazole and imidacloprid to form a dry mixture, grinding said dry mixture for a predetermined period of time, adding to the ground dry mixture a solvent and grinding the same to obtain a wet mixture, heating the wet mixture, transferring the heated wet mixture to a glass vessel and air drying to obtain molecular complex of hexaconazole with imidacloprid.
- the heating may be carried out at a temperature around 100°C for 10 minutes.
- the heating may be carried out under nitrogen atmosphere.
- the grinding of the dry mixture may be carried out for 15 to 20 minutes.
- the grinding of the wet mixture may be carried out for 30 minutes.
- the grinding may be carried out in any suitable apparatus for grinding solids.
- Such apparatus includes but is not limited to mortar mills, vibrator mills or ball mills.
- the solvent is any suitable solvent including but not limited to acetonitrile, ethanol, methanol, ethyl acetate, acetone or their mixture.
- the amount of solvent added is in a range of 0.1 ml to 5 ml per 1 gram of combined weight of hexaconazole and imidacloprid.
- hexaconazole and imidacloprid are mixed in a molar ratio of 1 :20 to 20: 1 and preferably in a ratio of 2: 1 to 8: 1.
- Hexaconazole and imidacloprid are weighed in a 2: 1 to 8: 1 molar ratios for different experiments and ground using mortar pestle for 15 minutes followed melting under inert atmosphere at around 100 to 1 10°C and subsequently cooled to room temperature and ground to finer particles to obtain molecular complex of hexaconazole and imidacloprid.
- Powder X-ray Diffraction (PXRD) profiles were obtained from 5 to 10 mg of lightly ground samples obtained from Example 1 placed over Zero background silica flat sample stage.
- X-ray diffraction data was collected on a PANalytical "X"pertPRO diffractometer on a Copper source ( a - 1.5418) powered by 40kV and 30mA with a proportional counter radiation detector.
- Samples include molecular complex of hexaconazole and imidacloprid having hexaconazole and imidacloprid in molar ratios of 2: 1, 4: 1 , 6: 1 and 8: 1.
- Data collection was done with step size 0.020°, 0.50 second per step over 5-70 ° 2 ⁇ .
- Data was analyzed using Xpert Viewer software.
- PXRD profile data presented for the region where significant peaks were observed.
- DSC Differential Scanning Calorimetric
- FT-IR Fourier transformed infrared spectra
- Figure 3 illustrates the comparison IR profile of various samples of molecular complex of hexaconazole and imidacloprid having different molar ratios of hexaconazole and imidacloprid along with pure hexaconazole and imidaclopnd.
- H denotes Hexaconazole and I denotes Imidacloprid in figure 3.
- FT-IR spectra of various molecular complex obtained from examples 1 were compared with hexaconazole and imidacloprid individually and it was found that there are significant changes in IR spectral band of functional group regions to confirm the formation novel molecular complex.
- HPLC method A Waters 717plus autosampler with UV-2487 detector system was used. Experimental conditions used were Column: C-18 (30X2.1 mm); particle size: 1.5 ⁇ ; (Merck, Purospher); flow rate: 1ml per minute; mobile phase: Water: Acetonitrile (60:40), injection volume: ⁇ 0 ⁇ L ⁇ A binary gradient system was used as the elution for imidacloprid was obtained on time gradient method. A UV-Vis detector was used on dual wavelength at 270nm and 230nm. Samples were run for 10 minutes as Imidacloprid has retention time in the time window of 5,6-5.9 minutes.
- HPLC profile of solubility of Imidacloprid of individual molecular complexes is as follows-
- a pesticidal formulation comprising a molecular complex of hexaconazole and imidacloprid, having a melting point of around 105°C measured as a single melting endotherm by differential scanning calorimetry.
- a process for preparing a molecular complex of hexaconazole and imidacloprid comprising: mixing hexaconazole and imidacloprid in a stoichiometric ratio in a range of 1 :20 to 20: 1 , followed by grinding to obtain a dry mixture; melting the dry mixture; and cooling the melted mixture followed by grinding to obtain a molecular complex of hexaconazole and imidacloprid having a melting point of around 105°C measured as a single melting endotherm by differential scanning calorimetry. Further specific embodiments are disclosed below:
- a process for preparing a molecular complex of hexaconazole and imidacloprid comprising mixing hexaconazole and imidacloprid in a stoichiometric ratio in a range of 1 :20 to 20:1 , followed by grinding to obtain a dry mixture; adding a solvent to the dry mixture followed by grinding to obtain a wet mixture; and air drying the wet mixture to obtain the molecular complex having a melting point of around 105°C measured as a single melting endotherm by differential scanning calorimetry.
- the molecular complex of hexaconazole and imidacloprid as disclosed provide broad spectrum of control on both insect and fungal for a longer duration. Additionally, the molecular complexes of hexaconazole and imidacloprid have better hydrolytic stability as compared to commercially available versions of hexaconazole and imidacloprid.
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- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN3575/MUM/2013 | 2013-11-14 | ||
| IN3575MU2013 IN2013MU03575A (enrdf_load_stackoverflow) | 2013-11-14 | 2014-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015071739A1 true WO2015071739A1 (en) | 2015-05-21 |
Family
ID=53056852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2014/002438 WO2015071739A1 (en) | 2013-11-14 | 2014-11-14 | A molecular complex of hexaconazole and imidacloprid and a process for production thereof |
Country Status (2)
| Country | Link |
|---|---|
| IN (1) | IN2013MU03575A (enrdf_load_stackoverflow) |
| WO (1) | WO2015071739A1 (enrdf_load_stackoverflow) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972971A (en) * | 1993-06-21 | 1999-10-26 | Bayer Aktiengesellschaft | Fungicidal active compound combinations |
| WO2008003738A1 (en) * | 2006-07-06 | 2008-01-10 | Bayer Cropscience Ag | Pesticidal composition comprising a pyridylethylbenzamide derivative and an insecticide compound |
| US20080274882A1 (en) * | 2004-12-24 | 2008-11-06 | Bayer Cropscience Ag | Insecticides Based on Selected Neonicotinoids and Strobilurins |
-
2014
- 2014-11-14 WO PCT/IB2014/002438 patent/WO2015071739A1/en active Application Filing
- 2014-11-14 IN IN3575MU2013 patent/IN2013MU03575A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972971A (en) * | 1993-06-21 | 1999-10-26 | Bayer Aktiengesellschaft | Fungicidal active compound combinations |
| US20080274882A1 (en) * | 2004-12-24 | 2008-11-06 | Bayer Cropscience Ag | Insecticides Based on Selected Neonicotinoids and Strobilurins |
| WO2008003738A1 (en) * | 2006-07-06 | 2008-01-10 | Bayer Cropscience Ag | Pesticidal composition comprising a pyridylethylbenzamide derivative and an insecticide compound |
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| Publication number | Publication date |
|---|---|
| IN2013MU03575A (enrdf_load_stackoverflow) | 2015-07-31 |
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