AU2017202401B2 - A novel crystalline form of spirotetramat, a process for its preparation and use of the same - Google Patents
A novel crystalline form of spirotetramat, a process for its preparation and use of the same Download PDFInfo
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- AU2017202401B2 AU2017202401B2 AU2017202401A AU2017202401A AU2017202401B2 AU 2017202401 B2 AU2017202401 B2 AU 2017202401B2 AU 2017202401 A AU2017202401 A AU 2017202401A AU 2017202401 A AU2017202401 A AU 2017202401A AU 2017202401 B2 AU2017202401 B2 AU 2017202401B2
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- spirotetramat
- crystalline modification
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- plant
- composition
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VGHOWOWLIXPTOA-UHFFFAOYSA-N cyclohexane;toluene Chemical compound C1CCCCC1.CC1=CC=CC=C1 VGHOWOWLIXPTOA-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- XTXPYKFYYOFDLR-UHFFFAOYSA-N ethyl 1-[[2-(2,5-dimethylphenyl)acetyl]amino]-4-methoxycyclohexane-1-carboxylate Chemical compound C=1C(C)=CC=C(C)C=1CC(=O)NC1(C(=O)OCC)CCC(OC)CC1 XTXPYKFYYOFDLR-UHFFFAOYSA-N 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JPXGPRBLTIYFQG-UHFFFAOYSA-N heptan-4-yl acetate Chemical compound CCCC(CCC)OC(C)=O JPXGPRBLTIYFQG-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- UKJFVOWPUXSBOM-UHFFFAOYSA-N hexane;oxolane Chemical compound C1CCOC1.CCCCCC UKJFVOWPUXSBOM-UHFFFAOYSA-N 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 230000004132 lipogenesis Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical compound CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000016804 zinc Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/38—2-Pyrrolones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention describes a crystalline form of spirotetramat of formula (I), a crystal preparation process, the analyses of the crystal through various analytical methods and using the crystalline form to prepare a stable agrochemical formulation. The invention also describes the use of various solvents towards the crystalline form preparation conditions. -/zi NH
Description
A NOVEL CRYSTALLINE FORM OF SPIROTETRAMAT, A PROCESS FOR ITS PREPARATION AND USE OF THE SAME
Field of the Invention
The present invention relates to a crystalline form of cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (spirotetramat), to its preparation processes and to its use in agrochemical preparations.
Description of Related Art
Cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate, having common name of spirotetramat , is a member of the ketoenol /tetronic acid chemistry class. Spirotetramat has insecticidal activity for the control of a wide range of sucking insects on various crops and belongs to the chemical class of cyclic ketoenols. Its mode of action is through disruption of lipogenesis which leads to the inhibition of acetyl CoA carboxylase, a key enzyme in fatty acid biosynthesis. It shows insecticidal activity towards a wide spectrum of pest species such as aphids, thrips, mites, whiteflies, scales, and mealybugs on a wide range of fruits, vegetables and other plantations.
Spirotetramat has a molecular formula of C2iH27N05. Its chemical structure is:
The commercially available spirotetramat, which is usually manufactured by the process described in US PAT. NO. 6,114,374, is present in an amorphous state having a melting point of 128 °C. It has been found that spirotetramat in an amorphous state is not suitable for being prepared as compositions or formulations due to its high tendency of aggregation, in particular after prolonged storage. Therefore, there is a need to develop a novel form of spirotetramat exhibiting one or more improved properties, such as, for example, improved storage stability.
Summary of the Invention
In attempt to resolve some or all of the problems with existing amorphous form of spirotetramat, a new and stable crystalline form of spirotetramat has been prepared.
In a first aspect, the present invention provides a crystalline modification I of cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (spirotetramat), termed “crystalline modification I”, exhibiting at least five of the following reflexes, in any combination, as 20±O.2O degree in an X-ray powder diffractogram (X-RPD) recorded using Cu—Ka radiation at 25°C: 20 = 8.36 ±0.20 (1) 20= 11.42 ±0.20 (2) 20= 11.61 ±0.20 (3) 20= 13.59 ±0.20 (4) 20= 15.13 ±0.20 (5) 20= 16.79 ±0.20 (6) 20= 19.35 ±0.20 (7) 20 = 20.29 ± 0.20 (8) 20 = 20.80 ±0.20 (9) 20 = 22.42 ± 0.20 (10) 20 = 22.72 ± 0.20 (11) 20 = 24.38 ±0.20 (12) 20 = 24.62 ± 0.20 (13) 20 = 25.72 ± 0.20 (14) 20 = 25.92 ±0.20 (15) 20 = 27.36 ±0.20 (16) 20 = 29.34 ±0.20 (17) 20 = 29.57 ± 0.20 (18).
In an embodiment, the crystalline modification I of spirotetramat according to the first aspect of the invention, exhibiting at least 5, 6, 7, 8 or all of the following reflexes, in any combination, as 20±O.2O degree in an X-ray powder diffractogram recorded using Cu—Ka radiation at 25°C: 20 = 8.36 ±0.20 (1) 20= 13.59 ±0.20 (4) 20= 15.13 ±0.20 (5) 20= 16.79 ±0.20 (6) 20 = 20.29 ± 0.20 (8) 20 = 20.80 ± 0.20 (9) 20 = 22.42 ± 0.20 (10) 20 = 22.72 ± 0.20 (11) 20 = 24.38 ±0.20 (12) 20 = 24.62 ± 0.20 (13) 20 = 29.57 ± 0.20 (18).
In a second aspect, the present invention provides a crystalline modification I of spirotetramat according to the first aspect of the invention, exhibiting an infrared (IR) spectrum with characteristic functional group vibration peaks at wavenumbers (cm-1, ±0.2%) of one or more of about 2947, 1782, 1688, 1499, 1448, 1210 and 1094 cm'1 .
In a third aspect, the present invention provides a crystalline modification I of spirotetramat according to the first or second aspect of the invention, exhibiting a melting point of 145°C.
In a fourth aspect, the present invention provides a crystalline modification I of spirotetramat according to any one of the first to third aspects of the invention, exhibiting a differential scanning calorimetry (DSC) profile having an endothermic melting peak at 145 °C, preferably with a melting enthalpy of 91 J/g.
In a fifth aspect, the present invention provides a crystalline modification I of spirotetramat according to any one of the first to fourth aspects of the invention, characterized by X-ray powder diffraction pattern substantially as shown in Figure 2, and/or characterized by an IR spectrum substantially as shown in Figure 1, and/or characterized by a DSC thermogram substantially as shown in Figure 3.
In a sixth aspect, the present invention provides a crystalline modification I of spirotetramat according to any one of the first to fifth aspects of the invention, obtainable by the process substantially as described in Example 2 or 3.
In a seventh aspect, the present invention provides a crystalline modification I of spirotetramat according to any one of the first to sixth aspects of the invention, obtainable by the process of the eighth aspect of the invention.
It has been found that the crystalline modification I of spirotetramat may show a significant improvement in its storage stability, which may significantly reduce the aggregation problem encountered with current commercially available formulations. The crystalline modification I exists as a crystalline solid having a needle shape and is easy to filter without any breakage. In addition, it has been found that the crystalline modification I of spirotetramat may exhibit a high degree of stability when formulated compared to amorphous spirotetramat prepared in accordance with the disclosure of US PAT. NO. 6,114,374. In particular, the crystalline modification may exhibit a very low tendency to aggregate when formulated. This may allow the preparation of commercial formulations such as suspension concentrates (SC). Further, by virtue of good stability properties, the crystalline modification I of spirotetramat may provide a desirable long storage period for formulations.
Methods for preparing amorphous spirotetramat are well known in the art. Amorphous spirotetramat is manufactured and available on a commercial scale. A particularly suitable method for preparing amorphous spirotetramat is described in US PAT. NO. 6,114,374.
In an eighth aspect, the present invention provides a process for preparing a crystalline modification I of spirotetramat comprising the steps of: i) dissolving spirotetramat in a solvent or mixture of solvents; ii) precipitating the dissolved compound into crystalline modification I of spirotetramat; and iii) isolating the precipitated crystalline modification I.
In an embodiment of the eighth aspect of the invention, the spirotetramat in step i) is amorphous spirotetramat.
In an embodiment of the eighth aspect of the invention, the solvent is selected from the group consisting of isopropyl alcohol, n-propyl alcohol, ethyl acetate, toluene, xylene, benzene, chlorobenzene, ether, ethyl benzene, trifluoro methyl benzene, mesitylene, methanol, ethanol, or mixture of toluene-hexane, toluene-cyclohexane, THF-hexane, ethyl acetate-hexane, dichloromethane-hexane, dichloromethane-methanol, THF-water, DMF-water, and methanol-water.
In an embodiment of the eighth aspect of the invention, the solvent is selected from the group consisting of isopropyl alcohol, n-propyl alcohol, ethyl acetate, toluene, xylene, methanol and ethanol, methanol-water or a mixture thereof.
In an embodiment of the eighth aspect of the invention, the solvent is selected from the group consisting of toluene and methanol or a mixtures thereof.
In an embodiment of the eighth aspect of the invention, spirotetramat is dissolved in a solvent or a solvent mixture in step (i) as a concentrated solution by heating from room temperature to reflux temperature or below the reflux temperature of the solvent or the solvent mixture. Preferably, the concentrated solutions can be prepared at the reflux temperature of the solvents. The concentration of the solution depends on the solubility of spirotetramat in the corresponding solvent or solvent mixture.
In an embodiment of the eighth aspect of the invention, the concentrated homogeneous solution prepared in step (i) is then cooled to a temperature of about 0°C to 20°C to crystallize the desired crystalline form from the solvent. The crystalline modification I of spirotetramat can also be crystallized out by concentrating the homogeneous solution by removing the solvent or solvent mixture to a certain volume with or without applying vacuum and cooling to below the reflux temperature of the solvent or the solvent mixture.
In an embodiment of the eighth aspect of the invention, crystalline modification I of spirotetramat can also be effected by adding seed crystals of the desired crystalline form during crystallization into a solution prepared in step (i), which can promote or accelerate the crystallization.
The seed crystal amount added to the concentrated solution is typically in the range of 0.001% to 10% by weight, optionally 0.001% to 2.5% by weight, further optionally 0.005 to 0.5% by weight based on the weight of spirotetramat used for the preparation of concentrated solution in step (i). Optionally, the seed crystals are added to the concentrated solution at the temperature below the boiling point of the corresponding solvent or the solvent mixture.
In an embodiment of the eighth aspect of the invention, the precipitated crystalline modification I of spirotetramat obtained from step (ii) is isolated by the usual solid component separation techniques from solutions, such as filtration, centrifugation or decantation. Then, the isolated solid is washed with solvent one or more times. Preferably, the solvent employed in the washing stage consists of one or more components of the solvent or solvent mixture employed for preparation of concentrated solution in step (i), as described hereinbefore. The washing is usually carried out using the corresponding solvent or solvent mixture between room temperature and 0°C, depending on the solubility of the crystal, in order to minimize the loss of crystalline material in the corresponding washing solvent as much as possible. In an embodiment of the eighth aspect of the invention, crystalline modification I of spirotetramat is dissolved and recrystallized. The washings and/or the solvent of crystallization in any of the methods may be concentrated to obtain solid spirotetramat which may be recycled.
In a ninth aspect, the invention provides a crystalline material comprising the crystalline modification I of spirotetramat obtained according to the eighth aspect of the invention, having a content of a crystalline modification I of spirotetramat of at least 98% by weight.
In a tenth aspect, the present invention provides a composition comprising the crystalline modification I of spirotetramat according to any one of the first to seventh and ninth aspects of the invention, and at least one auxiliary.
In an eleventh aspect, the present invention provides a use of the crystalline modification I of spirotetramat according to any one of the first to seventh and ninth aspects of the invention, or a composition according to the tenth aspect of the invention for control of insects.
In an embodiment of the tenth aspect of the invention, the amount of the crystalline modification I of spirotetramat is less than 75% by weight of the composition, preferably less than 50% by weight of the composition.
In one particular embodiment of the tenth aspect of the invention, the amount of the crystalline modification I of spirotetramat is 24% by weight of the composition.
The use of spirotetramat as an insecticide is well known in the art and is used on a commercial scale. It has been found that the crystalline modification I of spirotetramat is also active in controlling pests. As a result, the techniques of formulating and applying spirotetramat known in the art with respect to amorphous spirotetramat, for example as disclosed in the prior art documents described hereinbefore, can also be applied in an analogous manner to spirotetramat in the crystalline modification I of the invention.
Accordingly, the present invention provides an insecticide composition comprising spirotetramat in the crystalline modification I as defined hereinbefore.
The present invention furthermore provides processes for preparing compositions for controlling pests using the crystalline modification I of spirotetramat.
The invention also provides a method for controlling pests, comprising applying to the plant, plant part, or surroundings of the plant, an insecticidally effective amount of crystalline modification I of spirotetramat according to any one of the first to seventh and ninth aspects of the invention, or a composition according to the tenth aspect of the invention. Accordingly, this provides for controlling insects in plants, plant parts, and/or their surroundings, comprising applying to the foliage or fruit of the plant, plant part, or surroundings of the plant, an effective amount of crystalline modification I of spirotetramat.
In an embodiment of the tenth aspect of the invention, the composition is in the form of a suspension concentrate (SC), soluble concentrate (SL), oil-based suspension concentrate (OD), water-soluble granule (SG), dispersible concentrate (DC), emulsifiable concentrate (EC), emulsion seed dressing, suspension seed dressing, granule (GR), microgranule (MG), suspoemulsion (SE) and water-dispersible granule (WG) using suitable auxiliaries, carriers and solvents.
In an embodiment of the tenth aspect of the invention, the composition is in the form of a suspension concentrate (SC).
In an embodiment of the tenth aspect of the invention, the crystalline modification I of spirotetramat may be present in a concentration sufficient to achieve the required dosage when applied to plants or the loci thereof, desirably in a concentration of about 1 to about 75% by weight of the total mixture. The formulations are prepared, for example, by extending the crystalline modification I of spirotetramat with water, solvents and carriers, using, if appropriate, emulsifiers and/or dispersants, and/or other auxiliaries.
These formulations are prepared by mixing the crystalline modification I of spirotetramat with at least one auxiliary, for example, surfactants, liquid diluents, solid diluents, wetting agents, dispersants, thickening agents, anti-freezing agents, biocides and any necessary adjuvants and other formulation ingredients.
Surfactants can be an emulsifier, dispersant or wetting agent of ionic or nonionic type. Examples which may be used include, but are not limited to, salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulphosuccinic ester salts, taurine derivatives, especially alkyltaurates, or phosphoric esters of polyethoxylated phenols or alcohols.
Liquid diluents include, but are not limited to, water, Ν,Ν-dimethylamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffines, alkylbenzenes, alkyl naphthalenes, glycerine, triacetine, oils of olive, castor, linseed, sesame, com, peanut, cotton-seed, soybean, rape-seed and coconut, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as hexyl acetate, heptyl acetate and octyl acetate, water and alcohols such methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol and mixtures thereof.
Solid diluents can be water-soluble or water-insoluble. Water-soluble solid diluents include, but are not limited to, salts such as alkali metal phosphates (e.g., sodium dihydrogen phosphate), alkaline earth phosphates, sulfates of sodium, potassium, magnesium and zinc, sodium and potassium chloride, sodium acetate, sodium carbonate and sodium benzoate, and sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol. Examples of water-insoluble solid diluents include, but are not limited to clays, synthetic and diatomaceous silicas, calcium and magnesium silicates, titanium dioxide, aluminum, calcium and zinc oxide and mixtures thereof.
Wetting agents include, but are not limited to, alkyl sulfosuccinates, laureates, alkyl sulfates, phosphate esters, acetylenic diols, ethoxyfluorinated alcohols, ethoxylated silicones, alkyl phenol ethyoxylates, benzene sulfonates, alkyl-substituted benzene sulfonates, alkyl a-olefin sulfonates, naphthalene sulfonates, alkyl-substituted napthalene sulfonates, condensates of naphthalene sulfonates and alkyl-substituted naphthalene sulfonates with formaldehyde, and alcohol ethoxylates. Polyalkylene glycol ether is particularly useful for the composition of the invention.
Dispersants include, but are not limited to, sodium, calcium and ammonium salts of ligninsulfonates (optionally polyethoxylated); sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; and naphthalene sulfonate-formaldehyde condensates. Of note are compositions comprising up to 10% by weight of dispersant. Ligninsulfonates such as sodium ligninsulfonates are particularly useful for the composition of the invention. Sodium alkyl naphthalene sulfonate -formaldehyde condensate is particularly useful for the composition of the invention.
Thickening agents include, but are not limited to, guar gum, pectin, casein, carrageenan, xanthan gum, alginates, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose. Synthetic thickeners include derivatives of the former categories, and also polyvinyl alcohols, polyacrylamides, polyvinylpyrrolidones, various polyethers, their copolymers as well as polyacrylic acids and their salts. Xanthan gum is particularly useful for the composition of the invention
Suitable anti-freezing agents are liquid polyols, for example ethylene glycol, propylene glycol or glycerol. The amount of antifreeze agents is generally from about 1% to about 20% by weight, in particular from about 5 to about 10% by weight, based on the total weight of the composition.
Biocides may also be added to the composition according to the invention. Suitable Biocides are those based on isothiazolones, for example Proxel® from ICI or Acticide® RS from Thor Chemie or Kathon® MK from Rohm & Haas. The amount of biocides is typically from 0.05% to 0.5% by weight, based on the total weight of composition.
Antifoaming agents include all substances which can normally be used for this purpose in agrochemical compositions. Suitable anti-foam agents are known in the art and are available commercially. Particularly preferred antifoam agents are mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids, such as the silicone antifoaming agents available from GE or Compton.
Antioxidants include all substances which can normally be used for this purpose in agrochemical compositions, as is known in the art. Preference is given to butylated hydroxytoluene (BHT).
Other formulation ingredients can also be used in the present invention, such as dyes, drying agents, and the like. These ingredients are known to one skilled in the art.
In an embodiment of the tenth aspect of the invention, the crystalline modification I of spirotetramat according to the invention can be present in its commercially available formulations and in its use forms, prepared from these formulations, and as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners and fertilizers.
All plants and plant parts can be treated in accordance with the invention. In the present context, plants are to be understood as meaning all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods, by biotechnological and genetic engineering methods, or by combinations of these methods, including the transgenic plants and the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. Harvested materials, and vegetative and generative propagation materials, for example, cutting, tubers, meristem tissue, rhizomes, offsets, seeds, single and multiple plant cells and any other plant tissues, are also included.
As used herein, the term “about,” when used in connection with a numerical amount or range, means somewhat more or somewhat less than the stated numerical amount or range, to a deviation of ± 10% of the stated numerical amount or endpoint of the range. “Surrounding,” as used herein, refers to the place on which the plants are growing, the place on which the plant propagation materials of the plants are sown or the place on which the plant propagation materials of the plants will be sown. "Precipitation" as used herein, refers to the sedimentation of a solid material (a precipitate), including the sedimentation of a crystalline material, from a liquid solution in which the solid material is present in amounts greater than its solubility in the amount of liquid solution.
Treatment of the plants and plant parts with the compositions or formulations of the inventions is carried out directly or by allowing the compositions or formulations to act on their surroundings, habitat or storage space by the customary treatment methods. Examples of these customary treatment methods include dipping, spraying, vaporizing, fogging, broadcasting, painting on in the case of propagation material, and applying one or more coats particularly in the case of seed.
The benefits of the invention are seen most when the composition is applied to kill sucking pests, such as aphids, thrips, mites, whiteflies, scales, mealybugs, in growing crops of useful plants: such as cotton, potato, ornamentals, fruit trees, vegetables, cucurbits, beet, bananas, apples, carrots, celery, citrus, pineapples and vines.
Throughout the description and claims of this specification, the words “comprise” and variations of the words, for example “comprising” and “comprises”, mean “including but not limited to”, and do not exclude other moieties, additives, components, integers or steps. Moreover the singular encompasses the plural unless the context otherwise requires: in particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.
Preferred features of each aspect of the invention may be as described in connection with any of the other aspects. Other features of the invention will become apparent from the following examples. Generally speaking the invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims and drawings). Thus features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. Moreover unless stated otherwise, any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
Where upper and lower limits are quoted for a property then a range of values defined by a combination of any of the upper limits with any of the lower limits may also be implied.
In this specification, references to properties are - unless stated otherwise - to properties measured under ambient conditions, i.e. at atmospheric pressure and at a temperature of about As used herein the term “room temperature” refers to a temperature range of from about 20 °C -26°C.
The term “crystalline”, as used herein, refers to a solid state form wherein molecules are arranged to form a crystal lattice comprising distinguishable unit cells. In general, crystalline material may, for example, be identified by yielding diffraction peaks when subjected to X-ray radiation and/or exhibiting an endothermic melting peak profile with a characteristic sharp peak under differential scanning calorimetry (DSC).
All percentages are given in weight % unless otherwise indicated.
The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement of any form of suggestion that such prior art forms part of the common general knowledge.
Brief Description of Drawings
Various features and aspects of the embodiments of the invention disclosed herein can be more clearly understood by reference to the drawings, which are intended to exemplify and illustrate, but not to limit, the scope of the invention, and wherein: FIG 1. is an infrared (IR) spectrum of an embodiment of crystalline modification I of spirotetramat. FIG 2. is a X-ray powder diffractogram (X-RPD) of the crystalline modification I of spirotetramat. FIG 3.is a Differential Scanning Calorimetry (DSC) thermogram of crystalline modification I of spirotetramat. FIG 4.is a X-ray powder diffractogram of amorphous spirotetramat.
Detailed Description
The present invention will now be described by the following examples, and in which the following measurement techniques have been employed, and which the examples are provided for illustrative purposes only, and not intended to limit the scope of the disclosure.
All X-ray diffractograms were determined using powder diffractometer in reflection geometry at 25° C, using the following acquisition parameters:
The IR spectrum was measured with the resolution of 4 cm’1 and with the number of scans of 16 for the crystallized samples. The crystalline modification I of spirotetramat can be identified by its characteristic functional group vibration peaks at wavenumbers (cm \ ±0.2%) of one or more of 2946.95, 1782.29, 1688.23, 1498.50, 1448.18, 1210.47 and 1094.09 cm’1 as shown in Figure 1.
All IR spectra were obtained using the following acquisition parameters:
All DSC thermograms were obtained using the following acquisition parameters:
Examples
Example 1: Preparation of amorphous spirotetramat in accordance with the disclosure of US PAT. NO. 6,114,374 with modification to Example (II-l), Example (I-l-a-1) and Example I-l-c-1.
There are several synthetic processes reported about the preparation of spirotetramat in the prior-art and hence, it can be either manufactured using one of the reported processes on a commercial scale or can be purchased in bulk quantity through various manufacturing industries. Spirotetramat can be conveniently prepared by using one of the procedures which is reported in US PAT. NO. 6,114,374 starting lfom 2,5-dimethylphenylacetyl chloride and ethyl l-amino-4-methoxylcyclohexanecarboxylate (as shown in Scheme 1).
At 0-10° C, 16.9 g of 2,5-dimethylphenylacetyl chloride in 20 ml of anhydrous tetrahydrofuran (THF) are added dropwise to 20.8 g of ethyl l-amino-4- methoxylcyclohexanecarboxylate and 29.4 ml of triethylamine in 200 ml of anhydrous THF, and the mixture is stirred at room temperature. After the reaction has ended (control by thin-layer chromatography (TLC)), the mixture is concentrated, taken up in a mixture of 0.5N HCl/methylene chloride and the organic phase is dried and concentrated. The residue, ethyl 1-(2-(2,5-dimethylphenyl)acetamido)-4-methoxycyclo hexanecarboxylate, is precipitated from MTBE/n-hexane.
At 80°C, 17.9 g of the above resulting compound in 36 ml of anhydrous dimethylformamide (DMF) are added dropwise to 14.94 g (0.128 mol) of potassium tert-butoxide in 51 ml of anhydrous DMF, and the mixture is stirred at room temperature for 1.5 hours. 440 ml of ice-water are then added and the mixture is acidified to pH 1 at 0-20° C. using concentrated HC1 and the precipitate is filtered off with suction and dried. The crude product is stirred with methyl tert-butyl ether (MTBE)/n-hexane, filtered off with suction and dried. 2.3 g (8 mmol) of the above resulting compound are precharged in 50 ml of anhydrous methylene chloride and admixed with 1.12 ml (8 mmol) of triethylamine, and 0.8 ml (8 mmol) of ethyl chioroformate in 5 ml of anhydrous methylene chloride are added dropwise at 0-10° C. Stirring is continued at room temperature and the reaction is monitored by TLC. The mixture is then washed twice with 50 ml of 0.5N NaOH each time, dried and evaporated, and the residue is precipitated from MTB ether/n-hexane.
Scheme 1. Synthesis of Spirotetramat
As shown in Figure 4, the X-ray powder diffraction pattern of the resulting spirotetramat product has no significant signals, which indicates the spirotetramat product prepared in accordance with the disclosure of US PAT. NO. 6,114,374 is amorphous.
Example 2: Preparation of crystalline modification I of spirotetramat.
Crystallization from toluene 10 g of spirotetramat amorphous sample prepared in Example 1 was taken in a 3 neck round bottom flask along with 100 mL of toluene and the resulting slurry was heated to 70 °C to get a homogeneous solution. The homogeneous solution was stirred at 70 °C for 2h and the insoluble particles, if any, were filtered. The resultant solution was slowly cooled to 20-25°C. Upon cooling, fine crystals were formed and the resulting heterogeneous mixture was stirred between 10 °C to 20 °C for 2h. Then, the slurry was filtered and washed with 10 mL of chilled toluene. The filtered crystals were dried under vacuum at 50 °C. The crystal product obtained had a purity of >98% and the recovered product as crystal was found to be about 85% yield.
The obtained crystals were analyzed by IR spectrometry, X-RPD and DSC and found out to be crystalline modification I of spirotetramat as shown in Figure 1 and 2, respectively.
The IR spectrum of the crystalline modification I of spirotetramat is set out Figure 1. The IR spectrum of spirotetramat exhibited the functional group characteristic vibrations peaks at wavenumbers of one or more 2946.95, 1782.29, 1688.23, 1498.50, 1448.18, 1210.47 and 1094.09 cm"1.
The DSC thermogram of spirotetramat exhibited an endothermic melting peak at 144.6 °C and a melting enthalpy of 144.6 J/g as shown in Figure 3.
The X-ray powder diffractogram of the crystals exhibited the reflexes in Figure 2 and the values are summarized in Table 1.
Table 1. X-ray powder diffractogram reflexes of crystalline modification I of spirotetramat
Example 3: Preparation of crystalline modification I of spirotetramat
Crystallization from methanol 10 g of spirotetramat amorphous sample prepared in Example 1 was taken in a 3 neck round bottom flask along with 100 mL of methanol and the resulting slurry was heated to 63-65 °C to get a homogeneous solution. The resultant hot solution was stirred at 63-65 °C for 2h and the insoluble if any, were filtered. The resultant solution was slowly cooled to 20-25°C. Upon cooling, fine crystals were formed and the resulting heterogeneous mixture was stirred between 10 to 20 °C for 2h. Then, the slurry was filtered and washed with 10 mL of hilled methanol. The filtered crystals were dried under vacuum at 45 °C. The crystal product obtained had a purity of >98% and the recovered product as crystal was found to be about 85%.
Formulation examples
Example 4: Preparation of suspension concentrate (SC) of amorphous spirotetramat
All of the components listed in Table 2 below were mixed uniformly and the resulting mixture was ground with a Dyno-Mill (manufactured by Willy A. Bachofen AG) to obtain a suspension concentrate.
Table 2
Example 5: Preparation of Suspension Concentrate (SC) of spirotetramat crystalline modification I
All of the components listed in Table 3 below were mixed uniformly and the resulting mixture was ground with a Dyno-Mill (manufactured by Willy A. Bachofen AG) to obtain a suspension concentrate.
Table 3
Example 6: Comparison of the storage stability
Samples prepared in Examples 4 and 5 were stored at 54 °C in heated ovens having the same atmosphere for 1 month, 3 months and 6 months. The procedures followed were according to CIPAC MT 46.3. The concentration of spirotetramat was measured at the end of each storage time by high pressure liquid chromatography (HPLC). The aggregation was measured by observation. The original concentration of spirotetramat in each formulation was 24 %. The results are listed in Table 4.
Table 4
Remark: “+” means small amount of aggregation. “++++” means a lot of aggregation. means no aggregation.
Claims (23)
- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:1. A crystalline modification I of cis-3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (spirotetramat) exhibiting at least 5 of the following reflexes in any combination, as 2Θ ± 0.20 degree in X-ray powder diffractogram (X-RPD) recorded using Cu—Ka radiation at 25°C: 20 = 8.36 ±0.20 (1) 20= 11.42 ±0.20 (2) 20= 11.61 ±0.20 (3) 20= 13.59 ±0.20 (4) 20= 15.13 ±0.20 (5) 20= 16.79 ±0.20 (6) 20= 19.35 ±0.20 (7) 20 = 20.29 ± 0.20 (8) 20 = 20.80 ± 0.20 (9) 20 = 22.42 ± 0.20 (10) 20 = 22.72 ± 0.20 (11) 20 = 24.38 ±0.20 (12) 20 = 24.62 ± 0.20 (13) 20 = 25.72 ± 0.20 (14) 20 = 25.92 ±0.20 (15) 20 = 27.36 ±0.20 (16) 20 = 29.34 ±0.20 (17) 20 = 29.57 ±0.20 (18).
- 2. The crystalline modification I of spirotetramat according to claim 1, exhibiting at least 5 of the following reflexes, in any combination, as 2Θ ± 0.20 degree in an X-ray powder diffractogram recorded using Cu—Ka radiation at 25 °C: 2Θ = 8.36 ±0.20 (1) 20= 13.59 ±0.20 (4) 20= 15.13 ±0.20 (5) 20= 16.79 ±0.20 (6) 2Θ = 20.29 ± 0.20 (8) 2Θ = 20.80 ± 0.20 (9) 20 = 22.42 ± 0.20 (10) 20 = 22.72 ± 0.20 (11) 20 = 24.38 ±0.20 (12) 20 = 24.62 ± 0.20 (13) 2Θ = 29.57 ±0.20 (18).
- 3. A crystalline modification I of spirotetramat according to claim 1, exhibiting all of the following reflexes, in any combination, as 20 ± 0.20 degree in an X-ray powder diffractogram recorded using Cu—Ka radiation at 25 °C: 20 = 8.36 ±0.20 (1) 20= 11.42 ±0.20 (2) 20= 11.61 ±0.20 (3) 20= 13.59 ±0.20 (4) 20= 15.13 ±0.20 (5) 20= 16.79 ±0.20 (6) 20= 19.35 ±0.20 (7) 2Θ = 20.29 ± 0.20 (8) 2Θ = 20.80 ± 0.20 (9) 2Θ = 22.42 ± 0.20 (10) 2Θ = 22.72 ± 0.20 (11) 20 = 24.38 ±0.20 (12) 2Θ = 24.62 ± 0.20 (13) 2Θ = 25.72 ± 0.20 (14) 2Θ = 25.92 ± 0.20 (15) 20 = 27.36 ±0.20 (16) 20 = 29.34 ±0.20 (17) 20 = 29.57 ±0.20 (18).
- 4. A crystalline modification I of spirotetramat according to any one of claims 1 to 3, exhibiting an IR spectrum with characteristic functional group vibration peaks at wavenumbers (cm-1, ± 0.2%) of one or more of about 2947, 1782, 1688, 1499, 1448, 1210 and 1094 cm-1.
- 5. A crystalline modification I of spirotetramat according to any one of claims 1 to 4, exhibiting a melting point of 145°C.
- 6. A crystalline modification I of spirotetramat according to any one of claims 1 to 5, exhibiting a differential scanning calorimetry (DSC) profile having an endothermic melting peak at 145°C.
- 7. A crystalline modification I of spirotetramat according to any one of claims 1 to 6, characterized by X-ray powder diffraction pattern substantially as shown in Figure 2, and/or characterized by an IR spectrum substantially as shown in Figure 1, and/or characterized by a DSC thermogram substantially as shown in Figure 3.
- 8. A process for the preparation of a crystalline modification I of spirotetramat according to any one of the preceding claims, comprising: the steps of i) dissolving spirotetramat in a solvent, or mixture of solvents; ii) precipitating the dissolved compound into crystalline modification I of spirotetramat; and iii) isolating the precipitated crystalline modification I.
- 9. The process according to claim 8, where the spirotetramat in step i) is amorphous spirotetramat.
- 10. The process according to claim 8 or 9, wherein the solvent is selected from the group consisting of isopropyl alcohol, n-propyl alcohol, ethyl acetate, toluene, xylene, methanol, ethanol, methanol-water and mixtures thereof.
- 11. The process according to any one of claims 8 to 10, where the solvent is selected from the group consisting of toluene, methanol and mixtures thereof.
- 12. The process according to any one of claims 8 to 11, wherein step ii) comprises concentrating the solution and/or by cooling and/or by the addition of a solubility reducing solvent and/or by adding a seed crystal of the crystalline modification I of spirotetramat.
- 13. The process according to claim 12, wherein step ii) is effected by cooling to about 0 °C to 20 °C.
- 14. A crystalline modification I of spirotetramat according to any one of claims 1 to 7, obtainable by the process of any one of claims 8 to 13.
- 15. A crystalline modification I of spirotetramat obtained by a process according to any one of claims 8 to 13 and having a content of crystalline modification I of spirotetramat of at least 98% by weight.
- 16. A composition comprising the crystalline modification I of spirotetramat according to any one of claims 1 to 7 and 15 and at least one auxiliary selected from one or more of a surfactant, a liquid diluent, a solid diluent, a wetting agent, a dispersant, a thickening agent, an antifreezing agent and a biocide.
- 17. The composition according to claim 16, which is in form of a suspension concentrate (SC), an oil-based suspension concentrate (OD), an soluble concentrate (SL), a water-soluble granule (SG), a dispersible concentrate (DC), an emulsifiable concentrate (EC), an emulsion seed dressing, a suspension seed dressing, a granule (GR), a microgranule (MG), a suspoemulsion (SE) or a water-dispersible granule (WG).
- 18. The composition according to claim 17, which is in form of a suspension concentrate (SC).
- 19. The composition according to any one of claims 16 to 18, which comprises the crystalline modification I of spirotetramat in an amount of less than 75 % by weight.
- 20. The composition according to any one of claims 16 to 19, which comprises the crystalline modification I of spirotetramat in an amount of 24 % by weight.
- 21. A method of controlling pests, comprising applying to a plant, plant part or surroundings of a plant, an insecticidally effective amount of the crystalline modification I of spirotetramat of any one of claims 1 to 7 and 15 or the composition of any one of claims 16 to 20.
- 22. A method of controlling a pest selected from the group consisting of aphids, thrips, mites, whiteflies, scales and mealybugs, comprising applying to a plant, plant part or surroundings of a plant, an insecticidally effective amount of the crystalline modification I of spirotetramat of any one of claims 1 to 7 and 15 or the composition of any one of claims 16 to 20.
- 23. A method according to claim 21 or 22, wherein the pest is present on cotton, potato, ornamentals, fruit trees, vegetables, cucurbits, beet, bananas, apples, carrots, celery, citrus, pineapples or vines.
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| AU2017202401A AU2017202401B2 (en) | 2017-04-11 | 2017-04-11 | A novel crystalline form of spirotetramat, a process for its preparation and use of the same |
| AU2017100455A AU2017100455B4 (en) | 2017-04-11 | 2017-04-26 | A novel crystalline form of spirotetramat, a process for its preparation and use of the same |
| BR102017023296-4A BR102017023296A2 (en) | 2017-04-11 | 2017-10-27 | INNOVATIVE CRYSTALLINE FORM OF SPIROTETRAMATE, PROCESS FOR THEIR PREPARATION AND USE OF THE SAME |
| PCT/CN2017/114412 WO2018188356A1 (en) | 2017-04-11 | 2017-12-04 | Crystalline form of spirotetramat, process for preparation and use thereof |
| CN201780058577.XA CN109790115B (en) | 2017-04-11 | 2017-12-04 | Crystal form of spirotetramat, preparation method and application thereof |
| TW107112158A TW201837019A (en) | 2017-04-11 | 2018-04-09 | A novel crystalline form of spirotetramat, a process for its preparation and use of the same |
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| Title |
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| Fischer R. et al., Spirotetramet (Movento®)-discovery, synthesis and physico-chemical properties, Bayer CropScience Journal, 2008, 61(2), pages 127-139 * |
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| AU2017100455B4 (en) | 2024-03-28 |
| TW201837019A (en) | 2018-10-16 |
| CN109790115A (en) | 2019-05-21 |
| CN109790115B (en) | 2022-06-07 |
| AU2017202401A1 (en) | 2018-03-08 |
| AU2017100455A4 (en) | 2017-05-25 |
| BR102017023296A2 (en) | 2017-12-26 |
| WO2018188356A1 (en) | 2018-10-18 |
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