EP3997076A1 - Procédé de fabrication de 2-(phénylimino)-1,3-thiazolidine-4-ones - Google Patents
Procédé de fabrication de 2-(phénylimino)-1,3-thiazolidine-4-onesInfo
- Publication number
- EP3997076A1 EP3997076A1 EP20737442.2A EP20737442A EP3997076A1 EP 3997076 A1 EP3997076 A1 EP 3997076A1 EP 20737442 A EP20737442 A EP 20737442A EP 3997076 A1 EP3997076 A1 EP 3997076A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl
- chlorine
- carbonate
- hydrogen
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 42
- IYGBTPGRKGQPLW-UHFFFAOYSA-N 2-anilino-1,3-thiazol-4-one Chemical class O=C1CSC(NC=2C=CC=CC=2)=N1 IYGBTPGRKGQPLW-UHFFFAOYSA-N 0.000 title abstract description 3
- -1 phenylimino Chemical group 0.000 claims description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 38
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 24
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 235000011181 potassium carbonates Nutrition 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 4
- HDGQICNBXPAKLR-UHFFFAOYSA-N 2,4-dimethylhexane Chemical compound CCC(C)CC(C)C HDGQICNBXPAKLR-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000003585 thioureas Chemical class 0.000 description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 3
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 3
- SAMVRRMUPIZILL-UHFFFAOYSA-N 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)aniline Chemical compound CC1=CC(F)=C(N)C=C1SCC(F)(F)F SAMVRRMUPIZILL-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002540 isothiocyanates Chemical class 0.000 description 2
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical compound COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 125000001607 1,2,3-triazol-1-yl group Chemical group [*]N1N=NC([H])=C1[H] 0.000 description 1
- 125000001766 1,2,4-oxadiazol-3-yl group Chemical group [H]C1=NC(*)=NO1 0.000 description 1
- 125000004515 1,2,4-thiadiazol-3-yl group Chemical group S1N=C(N=C1)* 0.000 description 1
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 0.000 description 1
- 125000004509 1,3,4-oxadiazol-2-yl group Chemical group O1C(=NN=C1)* 0.000 description 1
- 125000004521 1,3,4-thiadiazol-2-yl group Chemical group S1C(=NN=C1)* 0.000 description 1
- 125000004317 1,3,5-triazin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=N1 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- KIPSRYDSZQRPEA-UHFFFAOYSA-N 2,2,2-trifluoroethanamine Chemical compound NCC(F)(F)F KIPSRYDSZQRPEA-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical group [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- CQGFKTRTUGDSGZ-UHFFFAOYSA-N CC(C(SCC(F)(F)F)=C1)=CC(F)=C1N=C=S Chemical compound CC(C(SCC(F)(F)F)=C1)=CC(F)=C1N=C=S CQGFKTRTUGDSGZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 239000012217 radiopharmaceutical Substances 0.000 description 1
- 229940121896 radiopharmaceutical Drugs 0.000 description 1
- 230000002799 radiopharmaceutical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/38—Nitrogen atoms
Definitions
- the present invention relates to a process for the preparation of 2- (phenylimino) -l, 3-thiazolidin-4-ones of the general formula (I).
- 2- (Phenylimino) -l, 3-thiazolidin-4-ones and corresponding derivatives are of great importance in the pharmaceutical and agrochemical industry as intermediates for the production of, for example, chiral sulfoxides.
- Such sulfoxides are used, for example, in crop protection as acaricidal agents (see, for example, WO2013 / 092350 or WO2015 / 150348).
- a process that has become known for the preparation of 2- (phenylimino) -l, 3-thiazolidin-4-ones of the general formula (I) is accordingly characterized in that an aniline of the general formula (IV) is mixed with an isothiocyanate in a first step of the general formula (V) or an aryl isothiocyanate of the general formula (VI) is reacted with an amine of the general formula (VII) and then the thiourea of the general formula (II) thus formed is isolated, for example by filtration.
- the thiourea of the general formula (II) is then combined with an acetic acid derivative of the general formula (III) in the presence of a base to give 2- (phenylimino) -l, 3-thiazolidin-4-one of the general formula ( I) implemented.
- 2- (phenylimino) -l, 3-thiazolidin-4-ones of the general formula (I) can be prepared by preparing an aryl isothiocyanate of the general formula (VI) in the presence of an acetic acid derivative of the general formula (III) and a base is reacted with an amine of the general formula (VII), the thiourea of the general formula (II) formed as an intermediate reacting directly and preferably in situ to give the 2- (phenylimino) -l, 3-thiazolidin-4-one.
- the present invention relates to a process for the preparation of 2- (phenylimino) -l, 3- thiazolidin-4-ones of the general formula (I)
- Y 1 and Y 2 independently represent fluorine, chlorine or hydrogen
- R 1 and R 2 are independently hydrogen, (Ci-Ci2) alkyl, (Ci-Ci2) haloalkyl, cyano, halogen or nitro
- R 3 is optionally substituted (Ce-Cio) aryl, (Ci-Ci2) alkyl or (Ci-Ci2) haloalkyl, the substituents being selected from halogen, (Ci-C 6 ) alkyl, (C3-Cio) cycloalkyl, cyano, nitro, hydroxy, (Ci-C 6 ) alkoxy, (Ci-C 6 ) haloalkyl and (Ci-C 6 ) haloalkoxy, in particular from fluorine, chlorine, (Ci-C3) alkyl, (C3-C6) cycloalkyl, cyclopropyl, cyano, (Ci-C3) alkoxy, (Ci-C3) haloalkyl and (Ci -C3)
- X stands for bromine, chlorine, OSCFMe, OSO2PI1, 0S0 2 (4-Me-Ph) or OSO 2 CF 3 and
- W is OH or a radical 0 (Ci -Ce-alkyl), and in the presence of a base with an amine of the formula (VII)
- R 3 has the meaning given above, initially to the thiourea of the formula (II)
- the acetic acid derivative of the formula (III) is therefore already present when the aryl isothiocyanate of the formula (VI) reacts with the amine of the formula (VII) to form the thiourea of the formula (II). It does not have a negative effect on this reaction and rather has the effect that the thiourea of the formula (II) does not accumulate in the reaction mixture, but is directly further converted to the compound of the formula (I).
- the compounds of the formula (I) can exist as E or Z isomers or as a mixture of these isomers. This is illustrated by the crossed double bond in formula (I).
- the E isomer is present in each case.
- the Z isomer is present in each case.
- the Z isomer or a mixture of E and Z isomer is present in which the proportion of the Z isomer is greater than 50% and increasingly preferably greater than 60%, 65%, 70% , 75%, 80%, 85%, 90%, 95% based on the total amount of E and Z isomers in the mixture.
- Y 1 and Y 2 independently of one another represent fluorine, chlorine or hydrogen
- R 1 and R 2 independently of one another represent fluorine, chlorine (Ci-C3) alkyl or hydrogen, and
- R 3 for optionally substituted phenyl, (Ci-C 6 ) alkyl or (Ci-C 6 ) flalogenalkyl, the substituents being selected from flalogen, (Ci-C 6 ) alkyl, (C3-Cio) cycloalkyl, cyano, nitro, Flydroxy, (Ci-C 6 ) alkoxy, (Ci-C 6 ) flalogenalkyl and (Ci-C 6 ) flalogenalkoxy, in particular from fluorine, chlorine, (Ci- C3) alkyl, (C3-C6) cycloalkyl, cyclopropyl, cyano, (Ci-C3) alkoxy, (Ci-C3) flalogenalkyl and (Ci- C3) flalogenalkoxy.
- Y 1 and Y 2 independently of one another represent fluorine or hydrogen
- R 1 and R 2 independently of one another represent fluorine, chlorine, hydrogen or methyl
- R 3 represents (Ci-C 6 ) alkyl or (Ci-C 6 ) flalogenalkyl very particularly preferably X represent bromine or chlorine
- R 1 and R 2 are independently fluorine, hydrogen or methyl, and R 3 is (Ci-C 6 ) FlalogenalkyL Highlighted
- R 2 for fluorine
- R 3 for CH2CF3.
- the 2- (phenylimino) -l, 3-thiazolidin-4-ones of the formula (I) can be prepared with good yields and in high purity using the process according to the invention.
- the acetic acid derivative of the formula (III) does not or hardly negatively affects the reaction of the compounds of the formulas (VI) and (VII) to the thiourea of the formula (II) and, since it is already present when the thiourea of the formula (II) is formed, has the effect that this is further converted directly to the compound of the formula (I). Consequently, the formation of a sticky, mushy reaction mixture, which is difficult to handle, is avoided.
- Scheme (2) illustrates the pure implementation.
- the compound of the formula (III) is present in the reaction mixture before at least one of the compounds of the formulas (VI) and (VII) is added to the reaction mixture.
- halogens includes elements selected from the group consisting of fluorine, chlorine, bromine and iodine, fluorine, chlorine and bromine being preferred and fluorine and chlorine being particularly preferred are preferred.
- Optionally substituted groups can be monosubstituted or polysubstituted, and in the case of polysubstitutions the substituents can be identical or different.
- the substituents are selected from halogen, (CVO,) alkyl, (C3- Cio) cycloalkyl, cyano, nitro, hydroxy, (CVOjAlkoxy, (C 1 -O,) halogenalkyl and (Ci - OjHalogenalkoxy, in particular from fluorine, chlorine, (Ci-C3) alkyl, (C3-C6) cycloalkyl, cyclopropyl, cyano, (Ci-C3) alkoxy, (Ci-C3) haloalkyl and (Ci-C3) haloalkoxy.
- Alkyl groups substituted by one or more halogen atoms are selected, for example, from trifluoromethyl (CF 3 ), difluoromethyl (CHF 2 ), CF 3 CH 2 , CICH 2 , CF 3 CCI 2 .
- alkyl groups are linear, branched or ring-shaped saturated hydrocarbon groups.
- Ci-Ci2-alkyl comprises the largest range defined herein for an alkyl group.
- this definition includes, for example, the meanings methyl, ethyl, n-, iso-propyl, n-, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3- Dimethylbutyl, n-heptyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.
- aryl groups are aromatic hydrocarbon groups which can have one, two or more heteroatoms (selected from O, N, P and S).
- this definition includes, for example, the meanings cyclopentadienyl, phenyl, cycloheptatrienyl, cyclooctatetraenyl, naphthyl and anthracenyl; 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5- isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol- 3-yl, l, 2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl
- the reaction of the aryl isothiocyanate of the formula (VI) to give the compound of the formula (I) is preferably carried out in the presence of a diluent.
- a suitable diluent of the Process according to the invention should be mentioned in particular: tetrahydrofuran (THF), dioxane, diethyl ether, methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), 2-methyl-THF, acetonitrile (ACN), acetone, butyronitrile, ethyl acetate, isopropyl acetate, butyl acetate , Pentyl acetate, methyl isobutyl ketone, ethylene carbonate, propylene carbonate, N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N-methylpyrrolidone, dimethyl sulfoxide (DMSO),
- Preferred diluents for the process according to the invention are methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, acetone, ethyl acetate, methyl tert-butyl ether (MTBE), tetrahydrofuran (THF), 2-methyl-THF, N, N-dimethylacetamide (DMAc), N, N -Dimethylformamide (DMF), toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, mesitylene, chlorobenzene, 1,2-dichlorobenzene, anisole, n-heptane, n-octane, 1,2,4-trimethylpentane ( Isooctane), petroleum ether 40/55, special petrol 80/110, methylcyclohexane or mixtures of these diluents.
- Particularly preferred diluents are acetonitrile, ethyl acetate, tetrahydrofuran (THF), toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, mesitylene, chlorobenzene, 1,2-dichlorobenzene, anisole, n-heptane, 1,2,4 -Trimethylpentane (isooctane), petroleum ether 40/55, special petrol 80/110, methylcyclohexane or mixtures of these diluents. Toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene or chlorobenzene or mixtures of these diluents are very particularly preferred.
- the amine of the formula (VII) is preferably used in a molar quantitative ratio of 0.95: 1 to 2: 1, based on the aryl isothiocyanate of the formula (VI). More preferred are quantitative ratios of 1.01: 1 to 1.5: 1, again based in each case on the aryl isothiocyanate of the formula (VI).
- Organic and inorganic bases can be used as the base in the process according to the invention.
- organic bases that may be mentioned are trimethylamine, triethylamine, tributylamine and ethyldiisopropylamine.
- inorganic bases are potassium acetate, sodium acetate, lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium carbonate, sodium carbonate, cesium carbonate, calcium carbonate and magnesium carbonate. Potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate are preferred. Potassium carbonate is particularly preferred.
- the base is preferably used in a molar quantitative ratio of 0.8: 1 to 3: 1, based on the aryl isothiocyanate of the formula (VI). More preferred are quantitative ratios of 1: 1 to 2: 1, again based on the aryl isothiocyanate of the formula (VI).
- the acetic acid derivative of the formula (III) is preferably used in a molar quantitative ratio of 0.9 to 2, based on the aryl isothiocyanate of the formula (VI). Quantities of 1.0 to 1.5 are further preferred, again based in each case on the aryl isothiocyanate of the formula (VI).
- the process according to the invention is generally carried out at a temperature between -20 ° C. and 150 ° C., preferably between 0 ° C. and 120 ° C., very particularly preferably between 5 ° C. and 80 ° C.
- the reaction is typically carried out under normal pressure, but can also be carried out under increased or reduced pressure.
- the desired compounds of the formula (I) can be isolated, for example, by subsequent filtration or extraction. Such methods are known to the person skilled in the art.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP19185391 | 2019-07-10 | ||
PCT/EP2020/069172 WO2021005082A1 (fr) | 2019-07-10 | 2020-07-08 | Procédé de fabrication de 2-(phénylimino)-1,3-thiazolidine-4-ones |
Publications (1)
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EP3997076A1 true EP3997076A1 (fr) | 2022-05-18 |
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ID=67226093
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EP20737442.2A Pending EP3997076A1 (fr) | 2019-07-10 | 2020-07-08 | Procédé de fabrication de 2-(phénylimino)-1,3-thiazolidine-4-ones |
Country Status (10)
Country | Link |
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US (1) | US20220251053A1 (fr) |
EP (1) | EP3997076A1 (fr) |
JP (1) | JP2022540115A (fr) |
KR (1) | KR20220034151A (fr) |
CN (1) | CN114072391A (fr) |
BR (1) | BR112022000188A2 (fr) |
IL (1) | IL289664A (fr) |
MX (1) | MX2022000427A (fr) |
TW (1) | TW202116742A (fr) |
WO (1) | WO2021005082A1 (fr) |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4877880A (en) * | 1987-11-17 | 1989-10-31 | Ici Americas Inc. | Process for preparation of iminothiazolidines |
DE69305828T2 (de) * | 1992-12-04 | 1997-06-12 | Sumitomo Chemical Co | Verfahren zur Herstellung von 2-Iminothiazolin-Derivaten und Verfahren zur Herstellung ihrer Zwischenprodukte |
EP0985670A1 (fr) | 1998-08-13 | 2000-03-15 | American Cyanamid Company | Composés de 1-(3-hétérocyclylphényl)isothiourée, -isourée, -guanidine et -amidine comme herbicides |
AU2708700A (en) * | 1999-01-14 | 2000-08-01 | Bayer Corporation | Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents |
FR2796643B1 (fr) * | 1999-07-22 | 2005-04-29 | Sod Conseils Rech Applic | Derives de 2-arylimino-2, 3-dihydrothiazoles, leurs procedes de preparation et leur utilisation therapeutique |
TWI460166B (zh) * | 2006-11-23 | 2014-11-11 | Actelion Pharmaceuticals Ltd | 製備2-亞胺基-四氫噻唑-4-酮衍生物之新穎方法 |
JP5280972B2 (ja) | 2009-08-20 | 2013-09-04 | 日本曹達株式会社 | 殺ダニ剤および新規ウレア化合物 |
EP2606726A1 (fr) | 2011-12-21 | 2013-06-26 | Bayer CropScience AG | Dérivés de trifluoroéthylsulfure substitués par du N-arylamidine en tant qu'acaricides et insecticides |
TWI652012B (zh) | 2013-05-20 | 2019-03-01 | 杜邦股份有限公司 | 殺真菌吡唑的固態形式 |
BR112015031291A2 (pt) | 2013-06-20 | 2017-07-25 | Bayer Cropscience Ag | derivados de sulfureto de arila e derivados de arilalquil sulfóxido como acaricidas e inseticidas |
TR201904336T4 (tr) | 2014-04-04 | 2019-05-21 | Bayer Cropscience Ag | Dökme, damlatma uygulaması, daldırma uygulaması veya toprak enjeksiyonu vasıtasıyla kırmızı örümcekler ile mücadeleye yönelik N-arilamidin ile sübstitüe edilen trifloroetilsülfoksit türevlerinin kullanımı. |
CN107089978A (zh) * | 2016-02-17 | 2017-08-25 | 复旦大学 | 噻唑烷酮衍生物及其制备方法和用途 |
CN106892877A (zh) * | 2017-02-27 | 2017-06-27 | 北京师范大学 | 一种2‑取代亚氨基噻唑烷化合物及其合成方法 |
CN107935961B (zh) * | 2017-12-01 | 2019-10-29 | 赣南师范大学 | 一种2-亚氨基噻唑烷-4-酮类化合物的制备方法 |
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- 2020-07-08 BR BR112022000188A patent/BR112022000188A2/pt unknown
- 2020-07-08 EP EP20737442.2A patent/EP3997076A1/fr active Pending
- 2020-07-08 KR KR1020227003830A patent/KR20220034151A/ko not_active Application Discontinuation
- 2020-07-08 MX MX2022000427A patent/MX2022000427A/es unknown
- 2020-07-08 WO PCT/EP2020/069172 patent/WO2021005082A1/fr unknown
- 2020-07-08 CN CN202080048504.4A patent/CN114072391A/zh active Pending
- 2020-07-08 JP JP2022500695A patent/JP2022540115A/ja not_active Withdrawn
- 2020-07-08 TW TW109122957A patent/TW202116742A/zh unknown
- 2020-07-08 US US17/625,273 patent/US20220251053A1/en active Pending
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IL289664A (en) | 2022-03-01 |
KR20220034151A (ko) | 2022-03-17 |
JP2022540115A (ja) | 2022-09-14 |
MX2022000427A (es) | 2022-02-10 |
WO2021005082A1 (fr) | 2021-01-14 |
US20220251053A1 (en) | 2022-08-11 |
BR112022000188A2 (pt) | 2022-02-22 |
CN114072391A (zh) | 2022-02-18 |
TW202116742A (zh) | 2021-05-01 |
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