TW201726640A - 賜派芬之新穎形式，其製備方法及其用途 - Google Patents
賜派芬之新穎形式，其製備方法及其用途 Download PDFInfo
- Publication number
- TW201726640A TW201726640A TW105140988A TW105140988A TW201726640A TW 201726640 A TW201726640 A TW 201726640A TW 105140988 A TW105140988 A TW 105140988A TW 105140988 A TW105140988 A TW 105140988A TW 201726640 A TW201726640 A TW 201726640A
- Authority
- TW
- Taiwan
- Prior art keywords
- variant
- genus
- crystalline
- group
- solvent
- Prior art date
Links
- 239000005664 Spirodiclofen Substances 0.000 title claims abstract description 4
- DTDSAWVUFPGDMX-UHFFFAOYSA-N spirodiclofen Chemical compound CCC(C)(C)C(=O)OC1=C(C=2C(=CC(Cl)=CC=2)Cl)C(=O)OC11CCCCC1 DTDSAWVUFPGDMX-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000008569 process Effects 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 241000607479 Yersinia pestis Species 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004562 water dispersible granule Substances 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000012053 oil suspension Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000001757 thermogravimetry curve Methods 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000007798 antifreeze agent Substances 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims 2
- 239000004531 microgranule Substances 0.000 claims 2
- 229930012538 Paclitaxel Natural products 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- PJMPHNIQZUBGLI-UHFFFAOYSA-N fentanyl Chemical compound C=1C=CC=CC=1N(C(=O)CC)C(CC1)CCN1CCC1=CC=CC=C1 PJMPHNIQZUBGLI-UHFFFAOYSA-N 0.000 claims 1
- 229960002428 fentanyl Drugs 0.000 claims 1
- 229960001592 paclitaxel Drugs 0.000 claims 1
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 claims 1
- 239000004549 water soluble granule Substances 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 15
- 239000003905 agrochemical Substances 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- -1 alkyl taurate Chemical compound 0.000 description 10
- 235000013399 edible fruits Nutrition 0.000 description 9
- 239000011877 solvent mixture Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 241001124076 Aphididae Species 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000642 acaricide Substances 0.000 description 4
- 244000038559 crop plants Species 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 241000219094 Vitaceae Species 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000020971 citrus fruits Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000021021 grapes Nutrition 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000014571 nuts Nutrition 0.000 description 3
- 230000000361 pesticidal effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 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
- 239000000969 carrier Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-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
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- IZEKFCXSFNUWAM-UHFFFAOYSA-N dipyridamole Chemical compound C=12N=C(N(CCO)CCO)N=C(N3CCCCC3)C2=NC(N(CCO)CCO)=NC=1N1CCCCC1 IZEKFCXSFNUWAM-UHFFFAOYSA-N 0.000 description 2
- 229960002768 dipyridamole Drugs 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 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
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 2
- 229960004134 propofol Drugs 0.000 description 2
- 230000001850 reproductive effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 239000004548 suspo-emulsion Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-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
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- LDJUYMIFFNTKOI-UHFFFAOYSA-N 2,2-dimethylbutanoyl chloride Chemical compound CCC(C)(C)C(Cl)=O LDJUYMIFFNTKOI-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- AMOYMEBHYUTMKJ-UHFFFAOYSA-N 2-(2-phenylethoxy)ethylbenzene Chemical compound C=1C=CC=CC=1CCOCCC1=CC=CC=C1 AMOYMEBHYUTMKJ-UHFFFAOYSA-N 0.000 description 1
- XSJVWZAETSBXKU-UHFFFAOYSA-N 2-ethoxypropane Chemical compound CCOC(C)C XSJVWZAETSBXKU-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 240000004507 Abelmoschus esculentus Species 0.000 description 1
- 241001506414 Aculus Species 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
- 239000005995 Aluminium silicate Substances 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
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 241001643374 Brevipalpus Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGJOEKWQDUBAIZ-IBOSZNHHSA-N CoASH Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCS)O[C@H]1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-IBOSZNHHSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 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
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 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
- 239000005909 Kieselgur Substances 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
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- 235000006679 Mentha X verticillata Nutrition 0.000 description 1
- 235000014749 Mentha crispa Nutrition 0.000 description 1
- 244000078639 Mentha spicata Species 0.000 description 1
- 235000002899 Mentha suaveolens Nutrition 0.000 description 1
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002725 Olea europaea Nutrition 0.000 description 1
- 241000238814 Orthoptera Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000488585 Panonychus Species 0.000 description 1
- 241000497193 Phyllocoptruta Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 244000299790 Rheum rhabarbarum Species 0.000 description 1
- 235000009411 Rheum rhabarbarum Nutrition 0.000 description 1
- 244000100205 Robinia Species 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 244000235659 Rubus idaeus Species 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000040738 Sesamum orientale Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 240000003829 Sorghum propinquum Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 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
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 240000000851 Vaccinium corymbosum Species 0.000 description 1
- 240000001717 Vaccinium macrocarpon Species 0.000 description 1
- 235000012545 Vaccinium macrocarpon Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 235000002118 Vaccinium oxycoccus Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000003082 abrasive agent 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012872 agrochemical composition Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000021015 bananas Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 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
- 229940092714 benzenesulfonic acid Drugs 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
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 238000010352 biotechnological method Methods 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229960002836 biphenylol Drugs 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- BRDOFYPYQFDHOQ-UHFFFAOYSA-N butyl acetate;hexanoic acid Chemical compound CCCCCC(O)=O.CCCCOC(C)=O BRDOFYPYQFDHOQ-UHFFFAOYSA-N 0.000 description 1
- DVNHAYKBQRMXPE-UHFFFAOYSA-N butyl prop-2-enoate;carbonic acid Chemical compound OC(O)=O.CCCCOC(=O)C=C DVNHAYKBQRMXPE-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates 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
- 229940105329 carboxymethylcellulose Drugs 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
- 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
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- RGJOEKWQDUBAIZ-UHFFFAOYSA-N coenzime A Natural products OC1C(OP(O)(O)=O)C(COP(O)(=O)OP(O)(=O)OCC(C)(C)C(O)C(=O)NCCC(=O)NCCS)OC1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-UHFFFAOYSA-N 0.000 description 1
- 239000005516 coenzyme A Substances 0.000 description 1
- 229940093530 coenzyme a Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 235000004634 cranberry Nutrition 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
- 238000010908 decantation Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction 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
- KDTSHFARGAKYJN-UHFFFAOYSA-N dephosphocoenzyme A Natural products OC1C(O)C(COP(O)(=O)OP(O)(=O)OCC(C)(C)C(O)C(=O)NCCC(=O)NCCS)OC1N1C2=NC=NC(N)=C2N=C1 KDTSHFARGAKYJN-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LVGBBZRMRVLEFH-UHFFFAOYSA-N ethyl 1-hydroxycyclohexane-1-carboxylate Chemical compound CCOC(=O)C1(O)CCCCC1 LVGBBZRMRVLEFH-UHFFFAOYSA-N 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-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
- 150000008376 fluorenones Chemical class 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 229940087559 grape seed Drugs 0.000 description 1
- 239000008169 grapeseed oil 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
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 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
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229940071676 hydroxypropylcellulose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000006838 isophorone group Chemical class 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229960002900 methylcellulose Drugs 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011859 microparticle 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- UMLARORAEPLXTC-UHFFFAOYSA-N n-ethyl-1-[3-(trifluoromethyl)phenyl]propan-2-amine;2-methyl-1-phenylpropan-2-amine Chemical compound CC(C)(N)CC1=CC=CC=C1.CCNC(C)CC1=CC=CC(C(F)(F)F)=C1 UMLARORAEPLXTC-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
- 229920005615 natural polymer Polymers 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
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 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
- 150000002989 phenols Polymers 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000003672 processing method 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
- 239000008262 pumice Substances 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 229960002078 sevoflurane Drugs 0.000 description 1
- DFEYYRMXOJXZRJ-UHFFFAOYSA-N sevoflurane Chemical compound FCOC(C(F)(F)F)C(F)(F)F DFEYYRMXOJXZRJ-UHFFFAOYSA-N 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
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229940104261 taurate Drugs 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical class [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 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
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- 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)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
具有式(I)之賜派芬的新結晶形式、晶體製備方法、藉由各種分析方法分析該晶體和利用該晶體製備穩定的農用化學配製物。本發明還描述各種溶劑對結晶形式製備條件之用途。
Description
本揭露關於3-(2,4-二氯苯基)-2-氧代-1-氧雜螺[4.5]癸-3-烯-4-基-2,2-二甲基丁酸酯(賜派芬(spirodiclofen))之結晶形式，其製備方法及其在農用化學品製劑中之用途。
相關技術的說明
通用名為賜派芬的3-(2,4-二氯苯基)-2-氧代-1-氧雜螺[4.5]癸-3-烯-4-基-2,2-二甲基丁酸酯係酮烯醇或特窗酸(tetronic acid)類化學品的成員。它係酮烯醇群組的具有獨特中毒症狀學和新穎生化作用模式的第一成員。它被用作廣範圍非系統性葉面殺昆蟲劑和殺蟎劑。它的殺有害生物作用模式係藉由經由乙醯輔酶A羧化酶的抑制來抑制脂質合成，所述酶為脂肪酸生物合成中的關鍵酶。它藉由干擾蟎蟲發育來控制有害生物，有害生物諸如全爪蟎屬(Panonychus spp.)、皺葉刺節蜱屬(Phyllocoptruta spp.)、短須蟎屬(Brevipalpus spp.)、刺癭蟎屬(Aculus spp.)和葉蟎屬(Tetranychus spp.)。它控制柑橘類水果、葡萄、仁果類水果、核果類水果和樹堅果作物中的蟎蟲和梨圓蚧(San Joe scale)。
賜派芬具有C21H24Cl2O4之分子式，其化學結構為
可商購獲得的賜派芬(通常藉由美國專利案號5,262,383A中所述方法來生產，其係出於所有目的藉由引用方式而併入本文)以非晶態存在，具有85℃至87℃的熔點。已發現非晶態賜派芬不適合製備成組成物或配製物，因其在長期儲存後的高聚集趨勢。因此，需要開發表現出改進的儲存穩定性的新穎賜派芬形式。
因此，本發明之實施方式提供賜派芬的新穎結晶形式，稱為“結晶變體I”，和其製備方法，以及含有其的農用化學組成物，和在農用化學應用中使用其的方法，諸如將其施用到植物、周圍環境和植物部分之方法。已經發現新穎結晶變體I有利地具有改進的儲存穩定性，在長期儲存之後的聚集顯著減少。
因此，本發明的具體實例還提供用於控制不期望有害生物如蟎蟲有害生物之組成物，該等組成物包含賜派芬之結晶變體I自身，與助劑和載體作為混合物，以及與其他活性化合物作為混合物。本發明之具體實例還提供賜派芬之結晶變體I在控制不期望有害生物中的用途及其使用方法。
可藉由參考附圖更清楚地理解本文揭露的本發明具體實例之各種特徵和方面，該等附圖意在例證和說明而非限制本發明之範圍，且其中：
圖1為賜派芬之結晶變體I的具體實例之紅外線(IR)光譜；圖2為賜派芬之結晶變體I的具體實例之X射線粉末繞射圖；圖3為賜派芬之結晶變體I的具體實例之示差掃描量熱(DSC)熱譜圖；且圖4為非晶態賜派芬之X射線粉末繞射圖。
可藉由參考以下特定具體實例的詳細說明更清楚地理解本發明，以下特定具體實例的詳細說明意在說明而非限制所附申請專利範圍的範疇。
已發現本發明賜派芬之結晶變體I在其穩定性方面具有顯著改進，在長期儲存後未形成聚集。此外，發現與根據美國專利案號5,262,383的揭露所製備的非晶態賜派芬相比，賜派芬之結晶變體I更易於過濾、粉碎和/或研磨。這允許製備商業配製物，諸如水懸劑(SC)、水分散性油懸劑(OD)、水分散性粒劑(WG)和水溶性粒劑(SG)。藉由其高儲存穩定性，賜派芬之結晶變體I賦予其配製物期望的長儲存期。因此，可以製備呈結晶變體I的賜派芬之任何配製物，其於下文中揭露。
根據本發明的具體實例，提供了賜派芬之結晶變體I，其在利用Cu-Kα輻射在25℃下記錄的X射線粉末繞射圖中呈現以下反射中的至少3個(以任何組合)，記為2θ值：
2θ=11.322±0.2 (1)
2θ=14.858±0.2 (2)
2θ=15.382±0.2 (3)
2θ=17.184±0.2 (4)
2θ=19.617±0.2 (5)
2θ=21.739±0.2 (6)
2θ=22.784±0.2 (7)
2θ=23.840±0.2 (8)
2θ=25.725±0.2 (9)
2θ=28.195±0.2 (10)
2θ=30.974±0.2 (11)
本發明具體實例的賜派芬之結晶變體I藉由具有上述反射中的至少三個(以其任何組合)的X射線粉末繞射圖來定特徵。較佳的是，結晶變體I係為具有上述反射中的至少四個、更佳的是所述反射中的至少五個、六個或七個、或八個(亦以其任何組合)的結晶變體。圖2中示出賜派芬之結晶變體I的X射線粉末繞射圖，其將在下文中詳細說明。
根據較佳的具體實例，結晶變體I呈現來自以下反射中的至少3個、4個、或5個或全部(以任何組合)：
2θ=11.322±0.2 (1)
2θ=14.858±0.2 (2)
2θ=15.382±0.2 (3)
2θ=17.184±0.2 (4)
2θ=19.617±0.2 (5)
2θ=22.784±0.2 (7)
2θ=23.840±0.2 (8)
2θ=25.725±0.2 (9)
X射線繞射圖係如下測定：在25℃下利用粉末繞射儀，反
射幾何結構在3°-60°的範圍內，增量為0.03°，利用Cu-Ka輻射。
在尤其較佳的具體實例中，賜派芬之結晶變體I呈現基本上與如圖2中所示相同的X射線粉末繞射圖案。
除X射線粉末繞射分析以外，賜派芬之結晶變體I還可藉由IR光譜學來定特徵。以4cm-1的解析度和16的掃描次數測量純化樣品的IR光譜。可藉由波數(cm-1，±0.2%)為約2971、2928、2854、1780、1749、1096、1061、862和819cm-1中的一個或多個的特徵官能基振動峰來鑑別賜派芬之結晶變體I，如圖1中所示。
所有IR光譜都是利用以下採集參數獲得：
根據本發明具體實例的賜派芬之結晶變體I可藉由差示掃描量熱法(DSC)進一步定特徵(圖3)。圖3中示出在約98.6℃下的吸熱峰。如本文所使用的，術語“約98.6℃”係指96℃至100℃的範圍。
本領域中已知製備非晶態賜派芬之方法。非晶態賜派芬係被生產並且可以商業規模使用。尤其適合用於製備非晶態賜派芬的方法描述在美國專利案號5,262,383中。
根據本發明的具體實例，賜派芬之結晶變體I可藉由下面的方法獲得：將非晶態的賜派芬溶解，並且然後從溶劑中結晶。
在一個方面，本發明的具體實例提供用於製備賜派芬之結晶變體I之方法，該方法包括以下步驟：i)將非晶態賜派芬溶解在溶劑中；
ii)使溶解的化合物沉澱成具有式I之賜派芬之結晶變體I；並且iii)分離沉澱的結晶變體I。
適合製備賜派芬結晶變體I的溶劑包括：鹵代烴(例如，氯苯、溴苯、二氯苯、氯甲苯、三氟甲苯和三氯苯)、醚類(例如，二乙醚、乙基丙基醚、正丁醚、苯甲醚、苯乙醚、環己基甲醚、二甲醚、二甲基乙二醇、二苯醚、二丙醚、二異丙醚、二正丁醚、二異丁醚、二異戊醚、乙二醇二甲醚、異丙基乙基醚、甲基三級丁醚、四氫呋喃、甲基四氫呋喃、二噁烷、二氯二乙醚、甲基-四氫呋喃、環氧乙烷和/或環氧丙烷的聚醚)、硝化烴(例如，乙腈、硝基甲烷、硝基乙烷、硝基丙烷、硝基苯、氯硝基苯、乙苯和鄰硝基甲苯)、芳烴(異丙基甲苯、沸程從70℃至190℃的石油餾分、石油醚、輕石油、均三甲苯、苯、甲苯和二甲苯)、酯類(例如，丙二酸酯、乙酸正丁酯(acetic acid n-butyl ester，n-butyl acetate)、乙酸甲酯、乙酸乙酯、乙酸異丁酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯和碳酸乙烯酯)和酮(例如，甲乙酮、丙酮)及其混合物。
較佳的溶劑包括甲苯、二甲苯、苯、氯苯、二氯苯、乙苯、三氟甲苯、均三甲苯、硝基苯、醚、甲乙酮、丙酮和乙腈。本發明的具體實例還設想超過2或3或4種組分的溶劑混合物。
在本發明的具體實例中，較佳的是，溶劑為視情況被一個或多個相同或不同、選自下列組成的群組之取代基取代的芳烴：烷基基團(例如低級烷基基團，例如C1至C4烷基基團，該等基團視情況被一個或多個鹵素進一步取代，該等鹵素可以相同或不同)、硝基和鹵素；和酮。
在本發明的具體實例中，較佳的是，溶劑為甲苯和丙酮。
因此，根據較佳的具體實例，在步驟(i)中，將非晶態賜派芬溶解在包含甲苯或丙酮的溶劑中。在較佳的實施方式中，溶劑基本上
由甲苯和/或丙酮組成。
根據步驟(i)的具體實例，在溶劑或溶劑混合物中，藉由從室溫或環境溫度加熱至該溶劑或該溶劑混合物的回流溫度或低於該回流溫度將非晶態賜派芬溶解成濃縮溶液。較佳的是，濃縮溶液可在溶劑的回流溫度下製備。溶液的濃度取決於賜派芬在相應溶劑或溶劑混合物中的溶解度。
然後將由此如步驟(i)中製備的濃縮均勻溶液冷卻至室溫或冷卻至約0℃至20℃的溫度，以使期望的結晶從該溶劑中結晶。賜派芬之結晶變體I也可藉由以下方式結晶出：藉由借助或不借助施加真空將溶劑或溶劑混合物移除到一定體積，並且冷卻至該溶劑或該溶劑混合物的回流溫度以下來濃縮均勻溶液。
在另一個具體實例，賜派芬之結晶變體I也可以藉由在結晶期間將具有期望結晶形式的晶種加入步驟(i)中製備的溶液得到，此舉可促進或加速結晶。
添加至濃縮溶液中的晶種量基於用於製備步驟(i)中的濃縮溶液的賜派芬的重量係典型地在按重量計0.001%至5%、通常在按重量計0.005%至0.5%的範圍內。較佳的是，在低於相應溶劑或溶劑混合物的沸點的溫度下將晶種添加至濃縮溶液中。
因此，熟習該項技術者可使賜派芬的結晶形式I有效地從濃縮溶液沉澱。
藉由常用的固體組分分離技術(諸如過濾、離心或傾析)從溶液中分離從步驟(ii)獲得的經沉澱的賜派芬之結晶變體I。然後，用溶劑洗滌分離的固體沉澱物一次或多次。較佳的是，用於洗滌階段的溶劑由用於製備步驟(i)中的濃縮溶液之溶劑或溶劑混合物的一種或多種組分組
成，如前文所述。洗滌通常利用相應溶劑或溶劑混合物在室溫與0℃之間進行(取決於晶體的溶解度)，以盡可能地最小化或避免結晶材料在相應洗滌溶劑中的損失。
在一具體實例中，本發明還關於包含賜派芬之結晶變體I之組成物。賜派芬之結晶變體I的量按組成物的重量計小於75%，較佳的是按組成物的重量計小於50%，更佳的是按組成物的重量計小於30%，仍更佳的是按組成物的重量計約25%。
非晶態賜派芬作為殺昆蟲劑和/或殺蟎劑的用途在本領域中係已知的，且以商業規模使用。賜派芬之結晶變體I在控制不期望有害生物，諸如蟎蟲，亦具有活性，例如如前文所述文獻中所揭露的。本發明的呈結晶變體I的賜派芬可以類似於針對非晶態賜派芬所述的那些方式配製和施用。
因此，在又一個方面，本發明的具體實例提供包含如前文所定義的呈結晶變體I的賜派芬之殺蟲組成物。
因此，本發明的具體實例另外提供利用賜派芬之結晶變體I製備用於控制不期望有害生物如蟎蟲的組成物之方法。
因此，本發明還提供控制植物、植物部分和/或其周圍環境中不期望有害生物之方法，該方法包括向植物的葉子或果實、植物部分和/或植物的周圍環境施用殺蟲有效量的賜派芬之結晶變體I。
可利用適合的助劑、載劑和溶劑，以類似於已知用於非晶態賜派芬的方式將賜派芬之結晶變體I摻入常規配製物中，諸如水懸劑(SC)、水分散性油懸劑(OD)、水溶性粒劑(SG)、水分散性乳劑(DC)、乳劑(EC)、乳液拌種劑、懸浮液拌種劑、粒劑(GR)、微粒劑(MG)、濃懸乳劑(SE)和水分散性粒劑(WG)。
在此背景下，賜派芬之結晶變體I可以按總混合物的重量計從約0.1%至約75%的濃度，即呈足以達到所需劑量的量。例如藉由在賜派芬之結晶變體I中摻入水、溶劑和載劑，如果合適的話，使用乳化劑和/或分散劑和/或其他助劑來製備配製物。
該等配製物係藉由混合賜派芬之結晶變體I與至少一種殺蟲上可接受的助劑，例如表面活性劑、液體稀釋劑、固體稀釋劑、潤濕劑、分散劑、增稠劑、消泡劑、防凍劑、防腐劑、抗氧化劑、固體附著劑、惰性填料和其他配製成分來製備。
表面活性劑可為離子型或非離子型的乳化劑、分散劑或潤濕劑。可使用的實例包括但不限於聚丙烯酸的鹽、木質素磺酸的鹽、苯磺酸或萘磺酸的鹽、環氧乙烷與脂肪醇或與脂肪酸或與脂肪胺的縮聚物、經取代的苯酚(尤其是烷基酚)、磺基琥珀酸酯鹽、牛磺酸衍生物(尤其是牛磺酸烷基酯)或聚乙氧基化酚或醇的磷酸酯。
液體稀釋劑包括但不限於水，N,N-二甲基甲醯胺，二甲亞碸，N-烷基吡咯啶酮，乙二醇，聚丙二醇，碳酸丙烯酯，二元酯，石蠟，烷基苯，烷基萘，甘油，三醋精，橄欖、蓖麻、亞麻籽、芝麻、玉米、花生、棉籽、大豆、葡萄籽和椰子的油，酮類(諸如環己酮、2-庚酮、異佛爾酮和4-羥基-4-甲基-2-戊酮)，乙酸酯(諸如乙酸己酯、乙酸庚酯和乙酸辛酯)和醇(諸如甲醇、環己醇、癸醇、苄醇和四氫糠醇、及其混合物。
固體稀釋劑可為水溶性或水不溶性的。水溶性固體稀釋劑包括但不限於鹽類，諸如鹼金屬磷酸鹽(例如，磷酸二氫鈉)，鹼土金屬磷酸鹽，鈉、鉀、鎂和鋅的硫酸鹽，氯化鈉和氯化鉀，乙酸鈉，碳酸鈉和苯甲酸鈉；以及糖和糖衍生物，諸如山梨醇、乳糖、蔗糖和甘露醇。水不溶性固體稀釋劑的實例包括但不限於黏土、合成和矽藻二氧化矽、矽酸鈣
和矽酸鎂、二氧化鈦、氧化鋁、氧化鈣和氧化鋅及其混合物。
潤濕劑包括但不限於磺基琥珀酸烷基酯、月桂酸酯、硫酸烷基酯、磷酸酯、炔屬二醇、乙氧基氟化醇、乙氧基化矽酮、烷基酚乙氧基化物、苯磺酸酯、經烷基取代的苯磺酸酯、α-烯烴磺酸烷基酯、萘磺酸酯、經烷基取代的萘磺酸酯、萘磺酸酯和經烷基取代的萘磺酸酯與甲醛的縮合物、和醇乙氧基化物及其混合物。萘磺酸鈉烷基酯尤其有用於本發明之組成物。
分散劑包括但不限於木質素磺酸的鈉鹽、鈣鹽和銨鹽(視情況被聚乙氧基化)；馬來酸酐共聚物的鈉鹽和銨鹽；縮合苯酚磺酸的鈉鹽；和萘磺酸酯-甲醛縮合物。木質素磺酸鹽如木質素磺酸鈉尤其有用於本發明的組成物。萘磺酸酯-甲醛縮合物如萘磺酸與甲醛和鈉鹽的聚合物尤其有用於本發明之組成物。
增稠劑包括但不限於瓜爾膠、果膠、酪蛋白、角叉菜膠、黃原膠、藻酸鹽、甲基纖維素、羥乙基纖維素、羥丙基纖維素和羧甲基纖維素及其混合物。合成增稠劑包括前面類別的衍生物，且還包括聚乙烯醇、聚丙烯醯胺、聚乙烯吡咯啶酮、各種聚醚、它們的共聚物以及聚丙烯酸和它們的鹽及其混合物。烷基聚乙烯吡咯啶酮尤其有用於本發明之組成物。
消泡劑包括正常地可以在農用化學組成物中用於此目的之所有物質。合適的消泡劑在本領域中係已知的，且為商業上可得。特別較佳的消泡劑係聚二甲基矽氧烷和全氟烷基膦酸的混合物，如可從GE或康普頓(Compton)獲得的矽酮消泡劑。
防腐劑包括正常地可以在這種類型的農用化學組成物中用於此目的之所有物質，並且也是本領域中熟知的。可提及的合適實例包括PREVENTOL®(來自拜耳公司(Bayer AG))以及PROXEL®(來自拜耳
公司)。
抗氧化劑包括正常地可以在農用化學組成物中用於此目的之所有物質，如在本領域中已知的。較佳的是二丁基羥基甲苯。
固體附著劑包括有機黏合劑，該等有機黏合劑包括增黏劑，如纖維素或經取代的纖維素，呈粉末、顆粒或晶格形式的天然及合成聚合物，以及無機黏合劑，如石膏、矽石或水泥。
惰性填料包括但不限於天然的地面礦物，如高嶺土、氧化鋁、滑石、白堊、石英、綠坡縷石、蒙脫石、和矽藻土；或合成地面礦物，如高度分散的矽酸、氧化鋁、矽酸鹽、以及磷酸鈣和磷酸氫鈣。用於顆粒的合適惰性填料包括例如，粉碎及分級的天然礦物(如方解石、大理石、浮石、海泡石、和白雲石)、或無機和有機研磨材料的合成顆粒，以及有機材料的顆粒(如鋸屑、椰子殼、玉米芯、和菸草莖)。
其他配製成分也可以用在本發明中，諸如染料、乾燥劑等。該等成分係熟習該項技術者所已知的。
根據本發明具體實例的賜派芬之結晶變體I可以配製物和以從該等配製物製備的其他形式存在，以及作為與其他活性化合物(諸如引誘劑、滅菌劑、殺細菌劑、殺蟎劑、殺線蟲劑、殺真菌劑、生長調節物質、除草劑、安全劑、肥料、訊息化合物和其他殺昆蟲劑)或與用於改進植物性狀的試劑之混合物存在。
當用作殺昆蟲劑或殺蟎劑時，根據本發明具體實例的賜派芬之結晶變體I可另外以配製物和以從該等配製物製備的其他形式存在，以及作為與減少活性化合物在用於植物環境中、用在植物部分表面上或用在植物組織中後的降解的抑制劑之混合物存在。
所有植物、植物部分和其等周圍環境都可用根據本發明具體實例的賜派芬之結晶變體I處理。在當前背景下，植物應理解為意指所有植物和植物種群，諸如期望和不期望的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以為可藉由常規育種和優化方法、藉由生物技術和基因工程方法、或藉由該等方法的組合獲得的植物，包括可以或不可以被植物育種者權利所保護的轉基因植物和植物栽培品種。植物部分應理解為意指植物的所有地上和地下部分和器官，如芽、葉子、針葉、桿、莖、花、子實體、果實、種子、根、塊莖以及根莖。還包括所收穫的材料、以及營養性和生殖性繁殖材料，例如插條、塊莖、分生組織、根莖、短匐莖、種子、單個及多個植物細胞及任何其他植物組織。
如本文所用的，術語“約”在與數值量或範圍連用時意指稍微大於或稍微小於所述數值量或範圍，偏差為所述數值量或範圍端值的±10%。
如本文所用的，術語“室溫”係指從約20℃-26℃的溫度範圍。
如本文所用的，“周圍環境”係指植物生長的地方、植物的該等植物繁殖材料進行播種的地方或者植物的該等植物繁殖材料將會播種的地方。
用本發明的組成物或配製物對植物和植物部分進行之根據本發明的處理係直接進行或藉由常規處理方法使得該等組成物或配製物作用於它們的周圍環境、棲息地或儲存空間來進行。該等常規處理方法的實例包括浸漬、噴霧、汽化、霧化、撒播、塗刷(在繁殖材料的情況下)和施加一個或多個塗層(尤其在種子的情況下)。
當施用殺蟲組成物來殺死種植有用植物作物時的有害生物
如蟎蟲時，本發明的益處最大，該等有用植物作物係：諸如玉米(maize，corn)(包括飼料玉米、爆粒玉米和甜玉米)、棉花、穀類、大麥、小麥、水稻、燕麥、馬鈴薯、甜菜、栽培作物(諸如香蕉、果樹、橡膠樹、樹木苗圃)、樹堅果作物、葡萄、柑橘類水果、仁果類水果、核果類水果、橄欖樹、風景林、蘆筍、灌木漿果(諸如藍莓)、懸鉤子、蔓越橘、亞麻、高粱、秋葵、薄荷、大黃、綠薄荷、草坪草和甘蔗。在本發明中，處理柑橘類水果、葡萄、仁果類水果、核果類水果和樹堅果作物係尤其有益的。
除非另外指明，否則所有百分比都以重量%給出。
現將藉由以下實例說明本發明的具體實例，該等實例只係出於說明的目的而被提供，並不旨在限制本揭露的範圍。
實例
實例1：根據經修改的美國專利案號5,262,38的揭露製備非晶態賜派芬。
1.製備己酯：經修改的實例1A(第125欄)
將0.1mol乙基-1-羥基環己烷羧酸酯引入200ml純二氯甲烷中，添加0.12mol三乙胺(Et3N)，並在0℃-10℃下逐滴添加0.1mol 2-(2,4-二氯苯基)乙醯氯在50ml純二氯甲烷中的溶液。
在室溫下攪拌該溶液16小時後，將它用檸檬酸水溶液和碳酸氫鈉水溶液洗滌，並在硫酸鈉上乾燥有機相，並藉由旋轉蒸發進行蒸發。
2.製備3-(2,4-二氯苯基)-4-羥基-5-環己烷-3-二氫呋喃-2-酮：經修改的
實例1a-2(第90欄)
將90mmol氫化鈉(80%)引入50ml純甲苯中。這個過程在氬氣氣氛下進行。將混合物加熱至回流溫度。然後在回流條件下逐滴添加溶解在70ml純甲苯中的60mmol己酯，並使混合物回流3小時。
在旋轉蒸發器上蒸發溶液，並將殘餘物溶解在水中，並使溶液酸化。將這個過程中分離出的沉澱物溶解在二氯甲烷中，並重複萃取含水母液。隨後在硫酸鈉上使萃取物乾燥，並在旋轉蒸發器上濃縮。
將產物懸浮在20ml熱氯仿中，在回流條件下緩慢添加60ml正己烷，允許混合物緩慢冷卻，並且借助抽吸濾出固體並乾燥。
3.製備賜派芬：經修改的實例1b-1(第95欄)
將5mmol 3-(2,4-二氯苯基)-4-羥基-5-環己烷-3-二氫呋喃-2-酮引入20ml純二氯甲烷中。向這個混合物中添加6mmol三乙胺(Et3N)，在0℃-10℃下添加6mmol 2,2-二甲基丁醯氯在5ml純二氯甲烷中的溶液，並在室溫下繼續攪拌1小時。
用檸檬酸水溶液和碳酸氫鈉水溶液洗滌溶液，在硫酸鈉上乾燥，並藉由旋轉蒸發進行蒸發。
方案1.合成賜派芬
製備賜派芬之結晶變體I
實例2-從甲苯中結晶
將如實例1中製備的非晶態賜派芬樣品(10g)連同甲苯(70mL)溶解在3頸圓底燒瓶中。將所得漿液加熱至90℃，以得到均勻溶液。過濾均勻溶液來去除不溶性顆粒(如果有的話)，並且使經過濾的溶液緩慢冷卻至室溫(rt)。在冷卻時形成細晶，並在室溫下攪拌所得不均勻混合物2小時。然後，過濾漿液，並用甲苯(3mL)洗滌。將經過濾的晶體在60℃下在真空下乾燥，以從結晶產物中去除甲苯痕跡。由此獲得的結晶產物具有98%的純度。發現作為晶體回收的產物的收率為85%。
藉由IR、粉末X射線和DSC分析所獲得的晶體並且發現為賜派芬之結晶變體I，分別如圖1、2和3中所示。
示差掃描量熱(DSC)熱譜圖(圖3)顯示在約98.6℃下的吸熱熔融峰。
賜派芬的IR光譜顯示在圖1中的波數(cm-1，±0.2%)為約2971、2928、2854、1780、1749、1096、1061、862和819cm-1中的一個或多個下之官能基特徵振動峰。
晶體的X射線粉末繞射圖在圖2中顯示出反射，並將值匯總在表1中。
實例3-從丙酮中結晶
將實例1中製備的賜派芬(5g)樣品連同丙酮(35mL)溶解在3頸圓底燒瓶中，並將所得漿液加熱至回流，以得到均勻溶液。過濾所得熱溶液來去除不溶物(如果有的話)，並使所得經過濾的溶液緩慢冷卻至室溫。產物在冷卻期間作為細晶沉澱出，並在室溫下攪拌混合物2小時。然後，過濾漿液，用丙酮(3mL)洗滌，並在40℃下在真空下乾燥，以從晶體中去除丙酮痕跡。由此所獲得的晶體具有98%的純度，且產物的回收收率為85%。
利用IR光譜法、X射線衍射和DSC將晶體定特徵為賜派芬結晶變體I，如實例2中所述。
實例4-製備非晶態賜派芬SC
均勻混合下表2中列出的所有組分，並用戴諾磨(Dyno-Mill)(由威利A.巴赫芬公司(Willy A.Bachofen AG)生產)研磨所得混合物，以獲得水懸劑。
實例5-製備賜派芬之結晶變體I SC
均勻混合下表3中列出的所有組分，並用戴諾磨(由威利A.巴赫芬公司生產)研磨所得混合物，以獲得水懸劑。
實例6：比較儲存穩定性
將實例4和5中製備的樣品儲存在54℃下1個月、3個月和6個月。過程遵循CIPAC MT 46.3。在每個儲存時間結束時藉由HPLC測量賜派芬的濃度。藉由觀察測量聚集。每種配製物中的賜派芬的原始濃度為25%。結果列在表4中。
備註：“+”意指少量聚集。“+++++”意指大量聚集。“-”意指無聚集。
Claims (16)
- 一種賜派芬(spirodiclofen)(3-(2,4-二氯苯基)-2-氧代-1-氧雜螺[4.5]癸-3-烯-4-基-2,2-二甲基丁酸酯)的結晶變體I，其在利用Cu-Kα輻射在25℃下記錄的X射線粉末繞射圖中呈現以下反射中以任何組合的至少3個，記為2θ值：2θ=11.322±0.2 (1) 2θ=14.858±0.2 (2) 2θ=15.382±0.2 (3) 2θ=17.184±0.2 (4) 2θ=19.617±0.2 (5) 2θ=21.739±0.2 (6) 2θ=22.784±0.2 (7) 2θ=23.840±0.2 (8) 2θ=25.725±0.2 (9) 2θ=28.195±0.2 (10) 2θ=30.974±0.2 (11)。
- 如申請專利範圍第1項所述之賜派芬之結晶變體I，其在利用Cu-Kα輻射在25℃下記錄的X射線粉末繞射圖中呈現以下反射中以任何組合的至少3個：2θ=11.322±0.2 (1) 2θ=14.858±0.2 (2) 2θ=15.382±0.2 (3) 2θ=17.184±0.2 (4) 2θ=19.617±0.2 (5) 2θ=22.784±0.2 (7) 2θ=23.840±0.2 (8) 2θ=25.725±0.2 (9)。
- 如申請專利範圍第1項所述之賜派芬之結晶變體I，其呈現特徵官能團振動峰在約2971、2928、2854、1780、1749、1096、1061、862和819cm-1中的一個或多個波數(cm-1，±0.2%)下的IR光譜。
- 如申請專利範圍第1項所述之賜派芬之結晶變體I，其呈現吸收熔融峰出現在約98.6℃下的示差掃描量熱(DSC)熱譜圖。
- 一種製備如申請專利範圍第1項所述之賜派芬之結晶變體I之方法，其包括：iii)將非晶態賜派芬溶解在溶劑中；iv)使該溶解的化合物沉澱成式I之賜派芬之結晶變體I；並且iii)分離該沉澱的結晶變體I。
- 如申請專利範圍第5項所述之方法，其中該溶劑選自由下列組成之群組：鹵代烴、醚、硝化烴、芳烴、酯和酮及其混合物，較佳的是芳烴和酮。
- 如申請專利範圍第5項所述之方法，其中該溶劑選自可視情況被一個或多個取代基取代的芳烴，該等取代基可為相同或不同且選自由下列組成之群組：烷基基團，其可視情況被一個或多個可為相同或不同的鹵素進一步取代，硝基基團和鹵素；和酮。
- 如申請專利範圍第6項所述之方法，其中該溶劑選自由下列組成之群組：甲苯、二甲苯、苯、氯苯、二氯苯、乙苯、三氟甲苯、均三甲苯、硝基苯、醚、甲乙酮、丙酮及其混合物。
- 如申請專利範圍第5項所述之方法，其中步驟i)包括濃縮該溶液，或冷 卻至室溫，或冷卻至約0℃至20℃，或添加該賜派芬之結晶變體I之晶種。
- 一種結晶材料，其包含如申請專利範圍第5項所述之方法獲得的賜派芬之結晶變體I，且具有按重量計至少98%的賜派芬之結晶變體I含量的含量。
- 一種組成物，其包含如申請專利範圍第1項所述之賜派芬之結晶變體I和至少一種助劑。
- 如申請專利範圍第11項所述之組成物，其中該助劑選自由下列組成之群組：表面活性劑、稀釋劑、潤濕劑、分散劑、增稠劑、消泡劑、防凍劑、防腐劑、抗氧化劑、固體附著劑、惰性填料及其混合物。
- 如申請專利範圍第11項所述之組成物，該組成物呈以下形式：水懸劑(SC)、水分散性油懸劑(OD)、水溶性粒劑(SG)、水分散性乳劑(DC)、乳劑(EC)、乳液拌種劑、懸浮液拌種劑、粒劑(GR)、微粒劑(MG)、濃懸乳劑(SE)或水分散性粒劑(WG)。
- 如申請專利範圍第13項所述之組成物，其係呈水懸劑(SC)形式。
- 一種控制不期望有害生物之方法，該方法包括向植物、植物部分或該植物的周圍環境施用殺蟲有效量的如申請專利範圍第1項所述之賜派芬之結晶變體I。
- 一種如申請專利範圍第1-4項中任一項所述之賜派芬之結晶變體I或如申請專利範圍第11-14項中任一項所述之組成物用於控制有害生物之用途。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/967,950 | 2015-12-14 | ||
| US14/967,950 US10005754B2 (en) | 2015-12-14 | 2015-12-14 | Form of spirodiclofen, a process for its preparation and use the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201726640A true TW201726640A (zh) | 2017-08-01 |
| TWI742024B TWI742024B (zh) | 2021-10-11 |
Family
ID=59018915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW105140988A TWI742024B (zh) | 2015-12-14 | 2016-12-12 | 賜派芬之新穎形式，其製備方法及其用途 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US10005754B2 (zh) |
| CN (1) | CN107922368A (zh) |
| BR (1) | BR112017023291A2 (zh) |
| MX (1) | MX2018005803A (zh) |
| TW (1) | TWI742024B (zh) |
| WO (1) | WO2017101515A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019197637A1 (de) * | 2018-04-13 | 2019-10-17 | Bayer Aktiengesellschaft | Hochbeladene formulierungen mit insektiziden aus der ketoenol-klasse zur verwendung bei drip- und drench- applikationen |
| CN108658913A (zh) * | 2018-06-13 | 2018-10-16 | 石家庄市绿丰化工有限公司 | 一种合成农药螺螨酯关键中间体的方法 |
| CN109053410A (zh) * | 2018-08-06 | 2018-12-21 | 兰博尔开封科技有限公司 | 一种合成1-羟基环己基甲酸的新工艺及应用 |
| CN108840846A (zh) * | 2018-08-20 | 2018-11-20 | 山东康乔生物科技有限公司 | 一种螺螨酯及其中间体的制备方法 |
| CN109369587A (zh) * | 2018-12-13 | 2019-02-22 | 新沂市永诚化工有限公司 | 一种高纯度高收率螺螨酯的生产工艺 |
| CN119462478A (zh) * | 2023-08-09 | 2025-02-18 | 天津大学 | 螺虫乙酯晶型ⅱ及其制备方法和农药组合物及其应用 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4216814A1 (de) | 1991-07-16 | 1993-01-21 | Bayer Ag | 3-aryl-4-hydroxy-(delta)(pfeil hoch)3(pfeil hoch)-dihydrofuranon- und 3-aryl-4-hydroxy-(delta)(pfeil hoch)3(pfeil hoch)-dihydrothiophenon-derivate |
| DE10012825B4 (de) * | 2000-03-16 | 2004-04-15 | Bayer Corp. | Verfahren zur Herstellung von spirocyclischen Tetronsäurederivaten |
| CN101235023B (zh) * | 2008-03-04 | 2010-06-02 | 浙江大学 | 一种螺螨酯的合成方法 |
| CN102372687A (zh) * | 2010-08-12 | 2012-03-14 | 南通德益化工有限公司 | 一种螺螨酯的生产方法 |
| CN104292197B (zh) * | 2014-09-19 | 2016-07-06 | 江苏安邦电化有限公司 | 一种螺螨酯的合成方法 |
-
2015
- 2015-12-14 US US14/967,950 patent/US10005754B2/en active Active
-
2016
- 2016-08-31 WO PCT/CN2016/097608 patent/WO2017101515A1/en not_active Ceased
- 2016-08-31 BR BR112017023291A patent/BR112017023291A2/pt not_active IP Right Cessation
- 2016-08-31 CN CN201680047625.0A patent/CN107922368A/zh active Pending
- 2016-08-31 MX MX2018005803A patent/MX2018005803A/es unknown
- 2016-12-12 TW TW105140988A patent/TWI742024B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BR112017023291A2 (pt) | 2018-08-14 |
| CN107922368A (zh) | 2018-04-17 |
| US10005754B2 (en) | 2018-06-26 |
| MX2018005803A (es) | 2018-09-17 |
| TWI742024B (zh) | 2021-10-11 |
| WO2017101515A1 (en) | 2017-06-22 |
| US20170166546A1 (en) | 2017-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI742024B (zh) | 賜派芬之新穎形式，其製備方法及其用途 | |
| TWI735574B (zh) | 甲磺草胺（ｓｕｌｆｅｎｔｒａｚｏｎｅ）之新穎形式、其製備方法及用途 | |
| TWI726884B (zh) | 純化甲胺基阿維菌素-苯甲酸鹽的方法以及含有所述甲胺基阿維菌素-苯甲酸鹽的組合物 | |
| TW202231637A (zh) | 新穎的碸吡草唑之結晶形式、其製備方法及其用途 | |
| CN109790115B (zh) | 螺虫乙酯的晶型、其制备方法及其用途 | |
| TWI760427B (zh) | 因得克的新穎晶型，其製備方法及其用途 | |
| TWI720975B (zh) | 碸嘧磺隆（ｒｉｍｓｕｌｆｕｒｏｎ）之新穎形式，其製備方法及其用途 | |
| AU2016102018A4 (en) | A novel crystalline form of chlorfenapyr, a process for its preparation and use of the same | |
| TWI735502B (zh) | 雙氯磺草胺之新穎結晶形式、其製備方法及用途 | |
| US9617247B1 (en) | Form of halosulfuron-methyl, a process for its preparation and use of the same | |
| WO2023031810A1 (en) | Crystalline form of florasulam, preparation and use of the same | |
| US9693558B2 (en) | Process for preparing a novel crystalline form of mesosulfuron-methyl and use of the same | |
| CN109790110B (zh) | 杀线威的新晶型、其制备方法及其用途 | |
| CN109503471B (zh) | 一种吡丙醚的晶型及其制备方法和用途 | |
| CN111132966B (zh) | 甲嘧磺隆的新形式、其制备方法及其用途 | |
| CN109803970B (zh) | 五氟磺草胺的新形式、其制备方法及其用途 | |
| CN109535034B (zh) | 环氟菌胺的新晶型、其制备方法及其用途 | |
| US10077248B2 (en) | Form of imazapyr, a process for its preparation and use the same | |
| WO2017071410A1 (en) | Process for preparing novel crystalline form of iodosulfuron-methyl-sodium and use | |
| CN117586328A (zh) | 多杀菌素晶型，其制备方法和用途 | |
| CN115244027A (zh) | 苯菌酮的新形式、其制备方法及其用途 | |
| TW202316965A (zh) | 吡氟醯草胺之結晶形式、其製備方法及其用途 | |
| BR102019017785A2 (pt) | Forma de sulfometuron-metílico, processo para sua preparação e uso da mesma |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |