AU2017101360A4 - A novel crystalline form of cyflufenamid, a process for its preparation and use of the same - Google Patents
A novel crystalline form of cyflufenamid, a process for its preparation and use of the same Download PDFInfo
- Publication number
- AU2017101360A4 AU2017101360A4 AU2017101360A AU2017101360A AU2017101360A4 AU 2017101360 A4 AU2017101360 A4 AU 2017101360A4 AU 2017101360 A AU2017101360 A AU 2017101360A AU 2017101360 A AU2017101360 A AU 2017101360A AU 2017101360 A4 AU2017101360 A4 AU 2017101360A4
- Authority
- AU
- Australia
- Prior art keywords
- cyflufenamid
- crystalline modification
- composition
- solvent
- crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000005755 Cyflufenamid Substances 0.000 title claims abstract description 78
- ACMXQHFNODYQAT-UHFFFAOYSA-N cyflufenamid Chemical compound FC1=CC=C(C(F)(F)F)C(C(NOCC2CC2)=NC(=O)CC=2C=CC=CC=2)=C1F ACMXQHFNODYQAT-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 230000008569 process Effects 0.000 title description 8
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 230000004048 modification Effects 0.000 claims description 53
- 238000012986 modification Methods 0.000 claims description 53
- 241000196324 Embryophyta Species 0.000 claims description 27
- 230000000855 fungicidal effect Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 206010061217 Infestation Diseases 0.000 claims description 5
- 244000038559 crop plants Species 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 230000011514 reflex Effects 0.000 claims description 5
- 229910002483 Cu Ka Inorganic materials 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 230000002538 fungal effect Effects 0.000 claims description 3
- 241000219104 Cucurbitaceae Species 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims description 2
- 238000001757 thermogravimetry curve Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 24
- 239000002904 solvent Substances 0.000 abstract description 23
- 238000009472 formulation Methods 0.000 abstract description 16
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000004546 suspension concentrate Substances 0.000 description 15
- -1 aliphatic alcohols Chemical class 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000011877 solvent mixture Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000004562 water dispersible granule Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003139 biocide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000004507 flowable concentrates for seed treatment Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000219122 Cucurbita Species 0.000 description 2
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 241000896246 Golovinomyces cichoracearum Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000004491 dispersible concentrate Substances 0.000 description 2
- 239000004495 emulsifiable concentrate Substances 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- QODCSKFZMRDUMK-UHFFFAOYSA-N 2,3-difluoro-6-(trifluoromethyl)benzonitrile Chemical compound FC1=CC=C(C(F)(F)F)C(C#N)=C1F QODCSKFZMRDUMK-UHFFFAOYSA-N 0.000 description 1
- CXJOONIFSVSFAD-UHFFFAOYSA-N 2-(4-methoxyphenyl)acetyl chloride Chemical compound COC1=CC=C(CC(Cl)=O)C=C1 CXJOONIFSVSFAD-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000000832 Ayote Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000241235 Citrullus lanatus Species 0.000 description 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 241000221787 Erysiphe Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000002989 Euphorbia neriifolia Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 244000070406 Malus silvestris Species 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000896242 Podosphaera Species 0.000 description 1
- 241001337898 Podosphaera aphanis Species 0.000 description 1
- 241000317981 Podosphaera fuliginea Species 0.000 description 1
- 241001337928 Podosphaera leucotricha Species 0.000 description 1
- 241000951259 Podosphaera xanthii Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000040738 Sesamum orientale Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000019714 Triticale Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZCZSIDMEHXZRLG-UHFFFAOYSA-N acetic acid heptyl ester Natural products CCCCCCCOC(C)=O ZCZSIDMEHXZRLG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000010352 biotechnological method Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- AEILLAXRDHDKDY-UHFFFAOYSA-N bromomethylcyclopropane Chemical compound BrCC1CC1 AEILLAXRDHDKDY-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical class C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters 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
- 244000053095 fungal pathogen Species 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- 150000008282 halocarbons Chemical class 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008101 lactose Substances 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
- 238000004519 manufacturing process Methods 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
- 239000012046 mixed solvent Substances 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
- XARFYWLPWXJPAZ-UHFFFAOYSA-N n'-(cyclopropylmethoxy)-2-fluoro-6-(trifluoromethyl)benzenecarboximidamide Chemical compound FC=1C=CC=C(C(F)(F)F)C=1C(N)=NOCC1CC1 XARFYWLPWXJPAZ-UHFFFAOYSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 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
- 239000012044 organic layer Substances 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-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
- 235000021017 pears 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
- 239000003208 petroleum Substances 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
- 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
- 229920001296 polysiloxane 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
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 235000015136 pumpkin Nutrition 0.000 description 1
- 239000003620 semiochemical Substances 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
- 235000021012 strawberries Nutrition 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
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 241000228158 x Triticosecale Species 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
- C07C259/18—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines having carbon atoms of hydroxamidine groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention describes the crystalline form of cyflufenamid of formula (I), the crystal preparation process, and the analyses of the crystal through various analytical methods and using the crystal to prepare stable agrochemical formulation. The invention also describes the use of various solvent towards the crystalline form preparation conditions. CF3 NOCH2 -<
Description
A NOVEL CRYSTALLINE FORM OF CYFLUFENAMID, A PROCESS FOR ITS PREPARATION AND USE OF THE SAME
Technical Field
The present disclosure relates to a crystalline form of (Z)-N-[a-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoromethyl)benzyl]-2-phenylacetamide (cyflufenamid), to its preparation processes and to its use in agrochemical preparations.
Background
Cyflufenamid ((Z)-N-[a-(cyclopropylmethoxyimino)-2,3-difluoro-6- (trifluoromethyl)benzyl]-2-phenylacetamide) is a selective fungicide for the powdery mildew which belongs to a chemical class of amidoxime. It has translaminar and vapor action which improves control of diseases. Cyflufenamid’s chemical structure is:
(I) EP0805148B1 reports the process for the preparation of cyflufenamid and its derivatives. EP0805148B1 reports the melting point of cyflufenamid in the range of 61 °C to 62 °C. However, EP0805148B1 does not disclose the preparation and characterization of cyflufenamid crystalline forms.
It has been found that cyflufenamid as mentioned in EP0805148B1 is not suitable for being used in an economical formulation due to its high tendency to aggregate, in particular after prolonged storage. Therefore, there is a need to provide a novel form of cyflufenamid exhibiting improved properties, such as, for example, improved storage stability.
Summary of the Invention
In an attempt to resolve some or all of the problems with form of cyflufenamid, a new and stable crystalline form of cyflufenamid has been prepared.
The commercially available cyflufenamid can be manufactured by several synthetic processes. For example, EP0805148B1 teaches one of the processes starting from 2,3-difluoro-6-trifluoromethylbenzonitrile through oxime formation followed by condensation of the oxime group with (bromomethyl) cyclopropane and condensation of the amino group with phenylacetyl chloride (as shown in Scheme 1).
Scheme 1. Synthesis of Cyflufenamid
In a first aspect, the invention provides a crystalline modification I of cyflufenamid, termed “crystalline modification I”, exhibiting at least three of the following reflexes as 2Θ±0.20 degree in an X-ray powder diffractogram (X-RPD) recorded using Cu—Ka radiation at 25 °C: 20 = 11.19 ± 0.20 (1) 20= 12.98 ±0.20 (2) 20= 15.85 ±0.20 (3) 20= 18.63 ±0.20 (4) 20= 19.76 ±0.20 (5) 20 = 21.09 ±0.20 (6) 20 = 22.26 ± 0.20 (7) 2Θ = 23.32 ± 0.20 (8) 2Θ = 24.23 ± 0.20 (9) 20 = 25.41 ±0.20 (10) 20 = 28.07 ± 0.20 (11) 20 = 29.02 ± 0.20 (12) 20 = 30.35 ± 0.20 (13) 20 = 31.83 ±0.20 (14) 20 = 32.33 ± 0.20 (15) 20 = 34.04 ± 0.20 (16) 20 = 37.07 ± 0.20 (17) 20 = 38.66 ± 0.20 (18) 20 = 50.14 ±0.20 (19).
In an embodiment, the crystalline modification I of cyflufenamid according to the first aspect of the invention, exhibits at least 3, 4, 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 = 11.19 ± 0.20 (1) 20= 12.98 ±0.20 (2) 20= 15.85 ±0.20 (3) 20= 19.76 ±0.20 (5) 20 = 21.09 ±0.20 (6) 20 = 22.26 ± 0.20 (7) 20 = 23.32 ± 0.20 (8) 2Θ = 24.23 ± 0.20 (9) 20 = 25.41 ±0.20 (10) 20 = 28.07 ± 0.20 (11) 20 = 29.02± 0.20 (12) 20 = 31.83 ±0.20 (14) 20 = 32.33 ± 0.20 (15) 20 = 34.04 ± 0.20 (16).
In a second aspect, the present invention provides a crystalline modification I of cyflufenamid 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%) 3244, 3022, 2929, 2880, 2161, 1674, 1620, 1599, 1505, 1457, 1430, 1399, 1317, 1282, 1199, 1153, 1029, 956, 697 and 581 cm'1.
The crystalline modification I of cyflufenamid according to an embodiment of the invention may be further characterized by differential scanning calorimetry (DSC) and thermogravimetric (TGA). The DSC spectrum of the crystalline modification of I of cyflufenamid exhibits a melting point of 64 °C as shown in Figure 3. The melting point for crystalline modification I of cyflufenamid is higher than the melting point reported in EP0805148B1 as ranging from 61 °C to 62 °C.
In a third aspect, the present invention provides a crystalline modification I of cyflufenamid according to the first or second aspects of the invention, characterized by a X-ray powder diffraction pattern substantially as shown in Figure 2, and/or characterized by an IR spectrum substantially as shown in Figure 1.
In a fourth aspect, the present invention provides a crystalline modification I of cyflufenamid according to any one of the first to third aspects of the invention, obtainable by the process substantially as described in Example 1 or 2.
In a fifth aspect, the present invention provides a crystalline modification I of cyflufenamid according to any one of the first to fourth aspects of the invention, obtainable by the process of the sixth aspect of the invention.
It has been found that the present crystalline modification I of cyflufenamid may show a significant improvement in its storage stability, which may significantly reduce the aggregation problem encountered with current commercially available formulations. In addition, it has been found that the crystalline modification I of cyflufenamid may exhibit a high degree of stability when formulated compared to cyflufenamid prepared in accordance with the disclosure of EP0805148B1. In particular, the crystalline modification I may exhibit a very low tendency to aggregate when formulated. This may allow the preparation of commercial formulations such as suspension concentrates (SC), water-dispersible granules (WG) and flowable concentrate for seed treatment (FS). Further, by virtue of good stability properties, the crystalline modification I of cyflufenamid may provide a desirable long storage period for formulations.
In a sixth aspect, the present invention provides a process for preparing a crystalline modification I of cyflufenamid comprising the steps of: i) dissolving cyflufenamid in a solvent or mixture of solvents; ii) precipitating the dissolved compound into crystalline modification I of cyflufenamid; and iii) isolating the precipitated crystalline modification I.
In an embodiment of the sixth aspect of the invention, the cyflufenamid in step i) is amorphous cyflufenamid or a crystal form cyflufenamid.
In an embodiment of the sixth aspect of the invention, the solvent is selected from the group consisting of halogenated hydrocarbons (for example, trifluoro methyl benzene, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene and trichlorobenzene), nitrated hydrocarbons (for example, nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene and o-nitrotoluene), aliphatic, cycloaliphatic or aromatic hydrocarbons (for example, benzene, pentane, n-octane, nonane, ethyl benzene, mesitylene, xylene, toluene), cymene, petroleum fractions having a boiling range of from 70 °C to 190 °C, ligroin, methyl ethyl ketone and aliphatic alcohols (for example, methanol, isopropyl alcohol, n-propanol, n-butanol and tert-amyl alcohol) and mixtures thereof.
In an embodiment of the sixth aspect of the invention, the solvent is selected from the group consisting of aromatic hydrocarbons and aliphatic alcohols or a mixture thereof.
In an embodiment of the sixth aspect of the invention, the solvent is selected from the group consisting of xylene, methanol or a mixture thereof.
According to an embodiment of the sixth aspect of the present invention, step ii) is effected by concentration of the solvent 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 cyflufenamid.
According to an embodiment of the sixth aspect of the present invention, crystalline modification I of cyflufenamid is prepared by dissolving the cyflufenamid in a solvent or a solvent mixture as a concentrated solution by heating from ambient temperature to a temperature at or below the reflux temperature of the solvent or the solvent mixture. Optionally, the concentrated solutions can be prepared at the reflux temperature of the solvents. The concentration of the solution depends on the solubility of cyflufenamid in the corresponding solvent or solvent mixture.
In an embodiment of the sixth aspect of the invention, the concentrated homogeneous solution thus prepared as in step (i) is then cooled to ambient temperature or cooled to about 0 to 20 °C, preferably 10 °C to 20 °C, to crystallize the desired crystalline form from the solvent. The crystalline modification I of cyflufenamid 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 sixth aspect of the invention, crystallization of crystalline modification I of cyflufenamid can also be obtained by adding seed crystals of the desired crystalline form during crystallization into the 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, more particularly in the range of 0.005% to 0.5% by weight, based on the weight of cyflufenamid used for the preparation of concentrated solution in step (i). Optionally, the seed crystals are added to the concentrated solution at a temperature below the boiling point of the corresponding solvent or the solvent mixture.
In an embodiment of the sixth aspect of the invention, the precipitated crystalline modification I of cyflufenamid obtained from step (ii) is isolated by the usual solid component separating techniques from solutions, such as filtration, centrifugation or decantation. Then, the isolated solid will be washed with solvent one or more times. Optionally, the solvent employed in the washing stage consists of one or more components of the solvent or solvent mixture employed for the 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 avoid the loss of crystal as far as possible in the corresponding washing solvent.
In an embodiment of the sixth aspect of the invention, crystalline modification I of cyflufenamid is dissolved and recrystallized. The washings and/or the solvent of crystallization in any of the methods may be concentrated to obtain solid cyflufenamid which may be recycled.
In a seventh aspect, the present invention provides a crystalline modification I of cyflufenamid obtained according to the sixth aspect of the invention, having a crystalline modification I of cyflufenamid content of at least 98% by weight.
In an eighth aspect, the present invention provides a fungicidal composition comprising the crystalline modification I of cyflufenamid according to any one of the first to fifth and seventh aspects of the invention, and at least one auxiliary.
In a ninth aspect, the present invention provides a use of the crystalline modification I of cyflufenamid according to any one of the first to fifth and seventh aspects of the invention, or a composition according to the eighth aspect of the invention for the control of fungal infestations.
In an embodiment of the eighth aspect of the invention, the amount of the crystalline modification I of cyflufenamid is less than 75% by weight of the composition, preferably less than 50% by weight of the composition, more preferably less than 30% by weight of the composition, still more preferably less than 20% by weight of the composition, still more preferably less than 10% by weight of the composition, and still more preferably 10% by weight of the composition.
The use of cyflufenamid as a fungicide is well known in the art and is used on a commercial scale. The crystalline modification I of cyflufenamid is also active in controlling fungal infestations. As a result, the techniques of formulating and applying cyflufenamid can also be applied in an analogous manner to cyflufenamid in the crystalline modification I of the present invention.
Accordingly, the present invention provides a fungicidal composition comprising cyflufenamid in the crystalline modification I as defined hereinbefore.
Accordingly, the present invention furthermore provides processes for preparing compositions for controlling fungicidal infestations using the crystalline modification I of cyflufenamid.
In an embodiment of the eighth aspect of the invention, the crystalline modification I of cyflufenamid is in the form of suspension concentrates (SC), oil-based suspension concentrates (OD), water-soluble granules (SG), dispersible concentrates (DC), emulsifiable concentrates (EC), emulsion seed dressings, flowable concentrate for seed treatment (FS) , granules (GR), microgranules (MG), suspoemulsions (SE) and water-dispersible granules (WG). The crystalline modification I of cyflufenamid can be included into these customary formulations in a known manner using suitable auxiliaries, carriers and solvents and the like.
In an embodiment of the eighth aspect of the invention, the composition is in the form of a water-dispersible granules (SC), a water-dispersible granules (WG) or flowable concentrate for seed treatment (FS).
In an embodiment of the eighth aspect of the invention, the crystalline modification I of cyflufenamid 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 from about 0.1 to about 75% by weight of the total mixture.
These formulations are prepared in a known manner by mixing the crystalline modification I of cyflufenamid with customary additives, for example, liquid diluents, solid diluents, wetting agents, dispersing agents, thickening agent, anti-freezing agents, biocide and any necessary adjuvants and other formulation ingredients.
Liquid diluents include, but are not limited to, water, N,N-dimethylmamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffines, alkylbenzenes, alkyl naphthalenes, glycerine, triacetine, oils of olive, castor, linseed, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, ketones such as 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as hexyl acetate, heptyl acetate and octyl acetate, water and alcohols such cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol.
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.
Wetting agents include, but are not limited to, alkyl sulfosuccinates, laureates, alkyl sulfates, phosphate esters, acetylenic diols, ethoxyfluornated 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
Dispersing agents 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 anti-freezing 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.
Other formulation ingredients can also be used in the present invention, such as dyes, anti-foaming agents, drying agents, and the like. These ingredients are known to one skilled in the art.
In an embodiment of the eighth aspect of the invention, the crystalline modification I of cyflufenamid 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, fertilizers and semiochemicals) or with agents for improving plant properties.
In an embodiment of the eighth aspect of the invention, when used as fungicides, the crystalline modification I of cyflufenamid according to the invention can furthermore be present in formulations and its use forms, prepared from these formulations, and as a mixture with inhibitors which reduce degradation of the active compounds after their use in the environment of the plant, on the surface of plant parts or in plant tissues.
Cyflufenamid, which is an active ingredient of the fungicidal composition of the invention, is known to be effective against diseases caused by fungal pathogens for example, but not limited to:
Powdery mildew (Erysiphe spp., Sphaerotheca spp., Podosphaera spp.; specifically Erysiphe cichoracearum, Sphaerotheca fuliginea, Erysiphe cichoracearum, Podosphaera xanthii, Podosphaera leucotricha, Podosphaera aphanis).
The benefits of the present invention are seen most when the fungicidal composition is applied to treat fungicidal infestation in growing crops of useful plants: such as cereals (for examples, wheat, triticale, rye), fruit (for examples, apples, grapes, pears, strawberries); cucurbitaceae (for examples, marrows, cucumbers, melons, water melons, courgettes, and pumpkins).
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.
Treatment according to the invention 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.
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 20°C.
As used herein, the term “about” or "around" when used in connection with a numerical amount or range, means somewhat more or somewhat less than the stated numerical amount or range, and for example 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.
All percentages are given in weight % unless otherwise indicated.
Brief Description of the Drawings
The invention can be more clearly understood by reference to the drawings, which are described below, and are intended to exemplify and illustrate, but not to limit, the scope of the invention, wherein: FIG. 1 is an infrared (IR) spectrograph of crystalline modification I of cyflufenamid; FIG. 2 is an X-ray powder diffractogram of crystalline modification I of cyflufenamid; and FIG. 3 is a Differential Scanning Calorimetry (DSC) of crystalline modification I of cyflufenamid.
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 powder diffractograms were determined using powder diffractometer in reflection geometry at 25° C, using the following acquisition parameters: X’Pert Pro MPD from PANalytical B.V.
Theta compensating slit and graphite monochromator Copper (K-alpha) radiation, 40 kV, 40 mA Step size: 0.03 degree 2-theta Count time: 1.0 second
Maximum peak intensity: 1705 counts per second Scan range: 3-60 degrees 2-theta
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 cyflufenamid can be identified by its characteristic functional group vibration peaks at wavenumbers (cm'1, ±0.2%) of 3244, 3022, 2929, 2880, 2161, 1674, 1620, 1599, 1505, 1457, 1430, 1399, 1317, 1282, 1199, 1153, 1029, 956, 697 and 581 cm'1 as shown in Figure 2.
All IR spectra were obtained using the following acquisition parameters: FT-IR spectrometer Nicolet™ iS 5
Diamond ATR unit Thermo Scientific™ iD5 ATR
Wavelength range 550 - 4000 cm”1
Resolution 4 cm”1
Number of scans 16
Example 1: Preparation of crystalline modification I of Cyflufenamid from xylene
Cyflufenamid sample (10 g) was taken in a 3-neck round-bottom flask along with xylene (30 ml_) and the resulting slurry was heated to 70 °C to get a homogeneous solution. The homogeneous solution was stirred at 70 °C for 2 hours and the insoluble particles, if any, were filtered. The resultant solution was slowly cooled to room temperature. Upon cooling, fine crystals were formed and the resulting mixture was stirred between 10 °C to 20 °C for 2 hours. Then, the slurry was filtered and washed with cold xylene (6 ml_). The filtered crystals were dried under vacuum at room temperature to remove the xylene traces from the crystalline product. The crystalline product obtained was having a purity of about 98% and the recovered product as crystal was found to be about 85% yield.
The obtained crystal was analyzed by IR and X-ray powder analyses and found to be crystalline modification I of cyflufenamid as shown in Figures 1 and 2 respectively.
The IR spectrum of the crystalline modification I of cyflufenamid exhibits the functional group characteristic vibrations at wavenumbers of one or more of 3244, 3022, 2929, 2880, 2161, 1674, 1620, 1599, 1505, 1457, 1430, 1399, 1317, 1282, 1199, 1153, 1029, 956, 697 and 581 cm'1 as shown in Figure 1.
The X-ray powder diffractogram of the crystalline modification I of cyflufenamid showed the reflexes as shown in Figure 2 and the values are summarized in Table 1.
The melting point of the crystalline modification I of cyflufenamid was 64 °C.
Table 1.
Crystalline Modification 2 Θ (°) d"(A) 11.19 ± 0.20 9.17 ± 0.05 12.98 ± 0.20 7.92 ± 0.05 15.85 ± 0.20 6.49 ± 0.05 18.63 ± 0.20 5.53 ± 0.05 " 19.76 ± 0.20 5.21 ± 0.05 ~ 21.09 ± 0.20 4.89 ± 0.05 22.26 ± 0.20 4.63 ± 0.05 23.32 ± 0.20 4.43 ± 0.05 24.23 ±0.20 4.26 ± 0.05 25.41 ± 0.20 4.07 ± 0.05 28.07 ± 0.20 3.69 ± 0.05 29.02 ± 0.20 3.57 ± 0.05 29.92 ± 0.20 3.47 ± 0.05 30.35 ± 0.20 3.42 ± 0.05 31.83 ± 0.20 3.26 ± 0.05 32.33 ± 0.20 3.21 ± 0.05 33.47 ± 0.20 3.11 ± 0.05 34.04 ± 0.20 3.06 ± 0.05 37.07 ± 0.20 2.81 ± 0.05 38.66 ± 0.20 2.70 ± 0.05 40.17 ± 0.20 2.61 ± 0.05 41.86 ± 0.20 2.50 ± 0.05 42.28 ± 0.20 2.48 ± 0.05 46.51 ± 0.20 2.27 ± 0.05 46.93 ± 0.20 2.25 ± 0.05 50.14 ± 0.20 2.11 ± 0.05 55.83 ± 0.20 1.91 ± 0.05
Example 2 - Preparation of crystalline modification I of cyflufenamid from methanol
Cyflufenamid (10 g) sample was taken in a 3-neck round-bottom flask along with methanol (30 ml_) 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 2 hours and filtered to remove the insoluble (if any) and the solution was slowly cooled to ambient temperature. The desired crystalline product was precipitated out as fine crystal during cooling and the mixture was stirred between 10 to 20 °C for 2 hours. Then, the slurry was filtered, washed with cold methanol (6 ml_) and dried under vacuum at room temperature to remove the methanol traces from the crystal. The crystal thus obtained was having a purity of about 98% and the recovered yield was found to be about 85%.
Example 3 - Preparation of crystalline modification I of Cyflufenamid from hexane (EP085148B1) 10.4g of N'-cyclopropylmethyloxy-2-fluoro-6-trifluoromethylbenzamidine was dissolved in 80ml_ of benzene. 8.9g of 4-methoxyphenylacetylchloride was added to the solution. The solution was heated under refluxing for 3 hours. After cooling, ethyl acetate was added to the solution, followed by washing with water and drying over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure and the residue obtained in crystal was washed with a mixed solvent hexane and ether to thereby obtain of crude crystal. The crystal was then recrystallized in hexane. The melting point of the crystal from example 3 was 61 °C.
Example 4: Preparation of suspension concentrate (SC) from crystals of Example 1
All 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) from crystals of Example 2
All 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: Preparation of suspension concentrate (SC) from crystals of Example 3
All the components listed in Table 4 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 4.
Example 7: Comparison of the storage stability
Samples prepared in Examples 4, 5 and 6 were stored at 54 °C for 1 month, 3 months and 6 months. The procedures are followed according to CIPAC MT 46.3. The concentration of cyflufenamid was tested at the end of each storage time by high pressure liquid chromatography (HPLC). The aggregation was measured by observation. The original concentration of cyflufenamid in each formulation was 10%. The results are listed in Table 5.
Table 5.
Remark: “+” means smal amount of aggregation. “+++++” means a lot of aggregation. means no aggregation.
Claims (5)
- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:1. A fungicidal composition comprising a crystalline modification I of (Z)-N-[a-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoromethyl)benzyl]-2-phenylacetamide (Cyflufenamid), exhibiting at least 3 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 : 2Θ = 11.19 ± 0.20 (1) 20= 12.98 ±0.20 (2) 20= 15.85 ±0.20 (3) 20= 18.63 ±0.20 (4) 20= 19.76 ±0.20 (5) 20 = 21.09 ±0.20 (6) 20 = 22.26 ±0.20 (7) 20 = 23.32 ±0.20 (8) 20 = 24.23 ±0.20 (9) 20 = 25.41 ±0.20 (10) 20 = 28.07 ±0.20 (11) 20 = 29.02 ±0.20 (12) 20 = 30.35 ±0.20 (13) 20 = 31.83 ±0.20 (14) 20 = 32.33 ±0.20 (15) 20 = 34.04 ± 0.20 (16) 20 = 37.07 ±0.20 (17) 20 = 38.66 ±0.20 (18) 20 = 50.14 ±0.20 (19); in combination with at least one auxiliary.
- 2. The composition of claim 1, wherein the crystalline modification I exhibits at least 3 of the following reflexes, as 2Θ±0.20 degree in an X-ray powder diffractogram recorded using Cu—Ka radiation at 25 °C: 20 = 11.19 ± 0.20 (1) 20= 12.98 ±0.20 (2) 20= 15.85 ±0.20 (3) 20= 19.76 ±0.20 (5) 20 = 21.09 ±0.20 (6) 20 = 22.26 ± 0.20 (7) 20 = 23.32 ± 0.20 (8) 20 = 24.23 ± 0.20 (9) 20 = 25.41 ±0.20 (10) 20 = 28.07 ± 0.20 (11) 20 = 29.02± 0.20 (12) 20 = 31.83 ±0.20 (14) 20 = 32.33 ± 0.20 (15) 20 = 34.04 ± 0.20 (16).
- 3. The composition of claim 1 or 2, wherein the crystalline modification I exhibits a Differential Scanning calorimeter (DSC) thermogram having the melting point of about 64 °C.
- 4. A method of controlling fungal infestation, comprising applying the composition of any one of claims 1 to 3 to growing crop plants.
- 5. The method of claim 4, wherein the plants are selected from cereals, fruits and cucurbitaceaes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2017101360A AU2017101360A4 (en) | 2017-09-22 | 2017-10-10 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2017232185A AU2017232185B2 (en) | 2017-09-22 | 2017-09-22 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
| AU2017232185 | 2017-09-22 | ||
| AU2017101360A AU2017101360A4 (en) | 2017-09-22 | 2017-10-10 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2017232185A Division AU2017232185B2 (en) | 2017-09-22 | 2017-09-22 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2017101360A4 true AU2017101360A4 (en) | 2017-11-09 |
Family
ID=60244791
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2017232185A Ceased AU2017232185B2 (en) | 2017-09-22 | 2017-09-22 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
| AU2017101360A Ceased AU2017101360A4 (en) | 2017-09-22 | 2017-10-10 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2017232185A Ceased AU2017232185B2 (en) | 2017-09-22 | 2017-09-22 | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109535034B (en) |
| AU (2) | AU2017232185B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL184687B1 (en) * | 1994-12-19 | 2002-11-29 | Nippon Soda Co | Derivatives of benzamide oxime, method of obtaining them and fungicide for agricultural and horticultural use |
| LT3154351T (en) * | 2014-06-11 | 2018-11-26 | Bayer Cropscience Aktiengesellschaft | Active compound combinations comprising cyflufenamid and spiroxamine |
-
2017
- 2017-09-22 AU AU2017232185A patent/AU2017232185B2/en not_active Ceased
- 2017-10-10 AU AU2017101360A patent/AU2017101360A4/en not_active Ceased
-
2018
- 2018-08-21 CN CN201810957512.5A patent/CN109535034B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN109535034A (en) | 2019-03-29 |
| AU2017232185B2 (en) | 2018-11-29 |
| AU2017232185A1 (en) | 2018-03-08 |
| CN109535034B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2021427503B2 (en) | Novel crystalline form of pyroxasulfone, methods for its preparation and use of the same | |
| WO2017197909A1 (en) | Novel form of sulfentrazone, process for its preparation and use thereof | |
| US10005754B2 (en) | Form of spirodiclofen, a process for its preparation and use the same | |
| AU2017202401B2 (en) | A novel crystalline form of spirotetramat, a process for its preparation and use of the same | |
| WO2018137387A1 (en) | Crystalline form of indoxacarb, process for its preparation and use thereof | |
| WO2018090787A1 (en) | Novel crystalline form of chlorfenapyr, process for its preparation and use | |
| AU2017101360A4 (en) | A novel crystalline form of cyflufenamid, a process for its preparation and use of the same | |
| US11602148B2 (en) | Crystalline form of oxamyl process for its preparation and use of the same | |
| US9617247B1 (en) | Form of halosulfuron-methyl, a process for its preparation and use of the same | |
| WO2018082456A1 (en) | A novel form of penoxsulam, a process for its preparation and use of the same | |
| WO2020164287A1 (en) | A novel form of metconazole, a process for its preparation and use of the same | |
| WO2021175029A1 (en) | A novel form of metrafenone, a process for its preparation and use of the same | |
| US10077248B2 (en) | Form of imazapyr, a process for its preparation and use the same | |
| WO2023040759A1 (en) | Crystalline form of methoxyfenozide, process for its preparation and use of the same | |
| WO2023031810A1 (en) | Crystalline form of florasulam, preparation and use of the same | |
| WO2020042052A1 (en) | A novel form of sulfometuron methyl, a process for its preparation and use the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGI | Letters patent sealed or granted (innovation patent) | ||
| MK22 | Patent ceased section 143a(d), or expired - non payment of renewal fee or expiry |