CA2857333A1 - Malonic acid di-salts and a method for preparing malonyl dihalides - Google Patents
Malonic acid di-salts and a method for preparing malonyl dihalides Download PDFInfo
- Publication number
- CA2857333A1 CA2857333A1 CA 2857333 CA2857333A CA2857333A1 CA 2857333 A1 CA2857333 A1 CA 2857333A1 CA 2857333 CA2857333 CA 2857333 CA 2857333 A CA2857333 A CA 2857333A CA 2857333 A1 CA2857333 A1 CA 2857333A1
- Authority
- CA
- Canada
- Prior art keywords
- compound
- phenyl
- formula
- alkyl
- optionally substituted
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 185
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title description 28
- 125000000346 malonyl group Chemical group C(CC(=O)*)(=O)* 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 259
- 230000002140 halogenating effect Effects 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- STGDIBRQQYGTQO-UHFFFAOYSA-N ethyl 2-(3,5-dichlorophenyl)ethanimidate Chemical compound CCOC(=N)CC1=CC(Cl)=CC(Cl)=C1 STGDIBRQQYGTQO-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 C1-alkoxy Chemical group 0.000 claims description 124
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 123
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 108
- 125000001424 substituent group Chemical group 0.000 claims description 101
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 97
- 229910052736 halogen Inorganic materials 0.000 claims description 87
- 150000002367 halogens Chemical group 0.000 claims description 87
- 125000000217 alkyl group Chemical group 0.000 claims description 76
- 125000004076 pyridyl group Chemical group 0.000 claims description 66
- 125000001188 haloalkyl group Chemical group 0.000 claims description 64
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 56
- HCMJWOGOISXSDL-UHFFFAOYSA-N (2-isothiocyanato-1-phenylethyl)benzene Chemical group C=1C=CC=CC=1C(CN=C=S)C1=CC=CC=C1 HCMJWOGOISXSDL-UHFFFAOYSA-N 0.000 claims description 50
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 46
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 42
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 40
- 125000003545 alkoxy group Chemical group 0.000 claims description 39
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052700 potassium Inorganic materials 0.000 claims description 36
- 229910052708 sodium Inorganic materials 0.000 claims description 34
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical group ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 125000004414 alkyl thio group Chemical group 0.000 claims description 20
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 13
- 125000000335 thiazolyl group Chemical group 0.000 claims description 13
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003944 tolyl group Chemical group 0.000 claims description 7
- OCXGTPDKNBIOTF-UHFFFAOYSA-N dibromo(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Br)(C=1C=CC=CC=1)(Br)C1=CC=CC=C1 OCXGTPDKNBIOTF-UHFFFAOYSA-N 0.000 claims description 4
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims description 4
- ASICOBSHKKJZSO-UHFFFAOYSA-N methyl 2-(3,5-dichlorophenyl)ethanimidate Chemical group COC(=N)CC1=CC(Cl)=CC(Cl)=C1 ASICOBSHKKJZSO-UHFFFAOYSA-N 0.000 claims description 4
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 4
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 23
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims 20
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims 15
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 9
- 230000008569 process Effects 0.000 abstract description 5
- SOVPDBUSUFGNCH-UHFFFAOYSA-N ClC=1C=C(C=C(C1)Cl)CC(OC)=N.ClC=1C=C(C=C(C1)Cl)CC(OC)=N Chemical group ClC=1C=C(C=C(C1)Cl)CC(OC)=N.ClC=1C=C(C=C(C1)Cl)CC(OC)=N SOVPDBUSUFGNCH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 179
- 239000000203 mixture Substances 0.000 description 88
- 229910052702 rhenium Inorganic materials 0.000 description 77
- 238000006243 chemical reaction Methods 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 54
- 239000011541 reaction mixture Substances 0.000 description 52
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 37
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 36
- 229910006121 SOBr2 Inorganic materials 0.000 description 35
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 35
- 238000002360 preparation method Methods 0.000 description 34
- 239000011734 sodium Substances 0.000 description 33
- 239000002904 solvent Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000003153 chemical reaction reagent Substances 0.000 description 29
- 229910019567 Re Re Inorganic materials 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- 238000004821 distillation Methods 0.000 description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- 238000009835 boiling Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229910003202 NH4 Inorganic materials 0.000 description 14
- 239000000010 aprotic solvent Substances 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000005457 ice water Substances 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical class [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 11
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 10
- 125000001721 carboxyacetyl group Chemical group 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- NEURYOYRKPFLKH-UHFFFAOYSA-N 2-chloro-1-isocyanato-4-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=C(N=C=O)C(Cl)=C1 NEURYOYRKPFLKH-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 150000004820 halides Chemical class 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 101150041968 CDC13 gene Proteins 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 238000005658 halogenation reaction Methods 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 7
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- MYJACJGIRSMGIO-UHFFFAOYSA-N dimethyl 2-(3,5-dichlorophenyl)propanedioate Chemical compound COC(=O)C(C(=O)OC)C1=CC(Cl)=CC(Cl)=C1 MYJACJGIRSMGIO-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 230000026030 halogenation Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 150000002691 malonic acids Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000007530 organic bases Chemical class 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000007942 carboxylates Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- PEISNPFOKRAAEV-UHFFFAOYSA-L disodium;2-[3-(trifluoromethyl)phenyl]propanedioate Chemical compound [Na+].[Na+].[O-]C(=O)C(C([O-])=O)C1=CC=CC(C(F)(F)F)=C1 PEISNPFOKRAAEV-UHFFFAOYSA-L 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 239000012258 stirred mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- YWUIQYVBRLYLBI-UHFFFAOYSA-N 2-(3,5-dichlorophenyl)propanedioyl dichloride Chemical compound ClC(=O)C(C(Cl)=O)C1=CC(Cl)=CC(Cl)=C1 YWUIQYVBRLYLBI-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012320 chlorinating reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- BDROYLJCVXAINE-UHFFFAOYSA-L dipotassium;2-(3,5-dichlorophenyl)propanedioate Chemical compound [K+].[K+].[O-]C(=O)C(C([O-])=O)C1=CC(Cl)=CC(Cl)=C1 BDROYLJCVXAINE-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- FQMYXUZNOBYEBJ-UHFFFAOYSA-N methyl 2-(3,5-dichlorophenyl)ethanimidate;hydrochloride Chemical group Cl.COC(=N)CC1=CC(Cl)=CC(Cl)=C1 FQMYXUZNOBYEBJ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DLAKEJZPXICNSC-UHFFFAOYSA-N 2-(3,5-dichlorophenyl)acetonitrile Chemical compound ClC1=CC(Cl)=CC(CC#N)=C1 DLAKEJZPXICNSC-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- BLFSSABBFANDKK-UHFFFAOYSA-N 3-(1,3-thiazol-2-yl)benzoic acid Chemical group OC(=O)C1=CC=CC(C=2SC=CN=2)=C1 BLFSSABBFANDKK-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- RWKMXHMCQLVSRQ-UHFFFAOYSA-L disodium;2-(3,5-dichlorophenyl)propanedioate Chemical compound [Na+].[Na+].[O-]C(=O)C(C([O-])=O)C1=CC(Cl)=CC(Cl)=C1 RWKMXHMCQLVSRQ-UHFFFAOYSA-L 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002463 imidates Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- ZKVZUSKNUTWXHC-UHFFFAOYSA-N methyl 2-(3,5-dichlorophenyl)acetate Chemical compound COC(=O)CC1=CC(Cl)=CC(Cl)=C1 ZKVZUSKNUTWXHC-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 229960003424 phenylacetic acid Drugs 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- AATPRMRVLQZEHB-UHFFFAOYSA-N 1,3-dichloro-5-iodobenzene Chemical compound ClC1=CC(Cl)=CC(I)=C1 AATPRMRVLQZEHB-UHFFFAOYSA-N 0.000 description 1
- PGGZAZHZNVKDLG-UHFFFAOYSA-N 1,4-dioxane;hexane Chemical class CCCCCC.C1COCCO1 PGGZAZHZNVKDLG-UHFFFAOYSA-N 0.000 description 1
- IGISPMBUGPHLBY-UHFFFAOYSA-N 1-iodo-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(I)=C1 IGISPMBUGPHLBY-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- HKVYINROOPCUIP-UHFFFAOYSA-N 2-chloro-4-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CSC(Cl)=N1 HKVYINROOPCUIP-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- WTAZAHLROWIQRC-UHFFFAOYSA-N 3-ethylpyridin-2-amine Chemical compound CCC1=CC=CN=C1N WTAZAHLROWIQRC-UHFFFAOYSA-N 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YMIRDEAWRBLXHF-UHFFFAOYSA-N C1(=CC=CC=C1)C.ClC=1C=C(C=C(C1)Cl)C(C(=O)Cl)C(=O)Cl Chemical compound C1(=CC=CC=C1)C.ClC=1C=C(C=C(C1)Cl)C(C(=O)Cl)C(=O)Cl YMIRDEAWRBLXHF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 108010033104 M-81 Proteins 0.000 description 1
- 238000003482 Pinner synthesis reaction Methods 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000005263 ab initio calculation Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 244000000054 animal parasite Species 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZAASRHQPRFFWCS-UHFFFAOYSA-P diazanium;oxygen(2-);uranium Chemical compound [NH4+].[NH4+].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[U].[U] ZAASRHQPRFFWCS-UHFFFAOYSA-P 0.000 description 1
- QVLNMVACLDLDQC-UHFFFAOYSA-N dimethyl 2-[3-(trifluoromethyl)phenyl]propanedioate 1,4-dioxane Chemical compound O1CCOCC1.FC(C=1C=C(C=CC1)C(C(=O)OC)C(=O)OC)(F)F QVLNMVACLDLDQC-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 108010023700 galanin-(1-13)-bradykinin-(2-9)-amide Proteins 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- KKOWOVGNELOLEJ-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;n,n-diethylethanamine;pyridine Chemical group C1=CC=NC=C1.CCN(CC)CC.CCCCN(CCCC)CCCC KKOWOVGNELOLEJ-UHFFFAOYSA-N 0.000 description 1
- KFPSYLVTBZCBEB-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;n-ethyl-n-propan-2-ylpropan-2-amine Chemical compound CCN(C(C)C)C(C)C.CCCCN(CCCC)CCCC KFPSYLVTBZCBEB-UHFFFAOYSA-N 0.000 description 1
- VVSSRZAVOQVJHG-UHFFFAOYSA-N n-(3-methylpyridin-2-yl)formamide Chemical compound CC1=CC=CN=C1NC=O VVSSRZAVOQVJHG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XLVVEEAVMUODOZ-UHFFFAOYSA-N n-pyridin-2-yl-1-pyrimidin-5-ylmethanimine Chemical compound C=1N=CN=CC=1C=NC1=CC=CC=N1 XLVVEEAVMUODOZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical class C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- FREJAOSUHFGDBW-UHFFFAOYSA-N pyrimidine-5-carbaldehyde Chemical compound O=CC1=CN=CN=C1 FREJAOSUHFGDBW-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000004235 valence bond calculation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/36—Acyl halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C57/34—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings containing more than one carboxyl group
- C07C57/36—Phenymalonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C57/34—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings containing more than one carboxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/64—Acyl halides
- C07C57/72—Acyl halides containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161570962P | 2011-12-15 | 2011-12-15 | |
| US61/570,962 | 2011-12-15 | ||
| PCT/US2012/069468 WO2013090547A1 (en) | 2011-12-15 | 2012-12-13 | Malonic acid di-salts and a method for preparing malonyl dihalides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2857333A1 true CA2857333A1 (en) | 2013-06-20 |
Family
ID=47459174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2857333 Abandoned CA2857333A1 (en) | 2011-12-15 | 2012-12-13 | Malonic acid di-salts and a method for preparing malonyl dihalides |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US9108965B2 (enExample) |
| EP (1) | EP2791107B1 (enExample) |
| JP (2) | JP2015501841A (enExample) |
| KR (1) | KR102066682B1 (enExample) |
| CN (1) | CN104066713B (enExample) |
| AR (1) | AR089221A1 (enExample) |
| AU (1) | AU2012352256B2 (enExample) |
| BR (1) | BR112014014232B1 (enExample) |
| CA (1) | CA2857333A1 (enExample) |
| CO (1) | CO7121339A2 (enExample) |
| HU (1) | HUE044394T2 (enExample) |
| IL (1) | IL232632A (enExample) |
| MX (1) | MX352470B (enExample) |
| RU (1) | RU2636942C2 (enExample) |
| TW (1) | TWI572587B (enExample) |
| WO (1) | WO2013090547A1 (enExample) |
| ZA (1) | ZA201403383B (enExample) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI528899B (zh) * | 2010-12-29 | 2016-04-11 | 杜邦股份有限公司 | 中離子性殺蟲劑 |
| MY168088A (en) | 2012-06-21 | 2018-10-11 | Du Pont | Solid forms of apyrido-pyrimidinium inner salt |
| CN105254515A (zh) * | 2015-11-13 | 2016-01-20 | 浙江汇能生物股份有限公司 | 一种氯化琥珀胆碱的制备方法 |
| TW201738229A (zh) | 2016-04-26 | 2017-11-01 | 杜邦股份有限公司 | 製備ｎ－［（５－嘧啶基）甲基］－２－吡啶胺之方法 |
| CN109982997A (zh) * | 2016-12-06 | 2019-07-05 | 日本化药株式会社 | 3-(吡啶基-2-氨基)丙腈及其类似物的制造方法 |
| JP6916161B2 (ja) * | 2018-02-20 | 2021-08-11 | インディアン オイル コーポレーション リミテッド | ポリオレフィンポリマー用添加剤および熱可塑性組成物 |
| US12356988B2 (en) | 2018-03-05 | 2025-07-15 | Corteva Agriscience Llc | Process and intermediates for the preparation of certain mesoionic pesticides |
| CN108373468B (zh) * | 2018-05-18 | 2019-12-17 | 武汉工程大学 | 一种n-2-吡啶-5-嘧啶甲胺的制备方法 |
| CN109020952A (zh) * | 2018-11-01 | 2018-12-18 | 雅本化学股份有限公司 | 一种n-2-吡啶基-5-嘧啶甲胺的制备方法 |
| JP2024541320A (ja) | 2021-11-10 | 2024-11-08 | コルテバ アグリサイエンス エルエルシー | 特定のメソイオン性殺虫剤の調製プロセス |
| JP2025526908A (ja) | 2022-08-18 | 2025-08-15 | コルテバ アグリサイエンス エルエルシー | ある特定のメソイオン性殺有害生物剤の中間体の調製及び単離プロセス |
| CN116003253A (zh) * | 2022-12-31 | 2023-04-25 | 上海试四化学品有限公司 | 一种三氟苯嘧啶中间体2-[3-(三氟甲基)苯基]丙二酸二甲酯的制备方法 |
| CN118359606A (zh) * | 2023-01-19 | 2024-07-19 | 华东理工大学 | 三氟苯嘧啶多晶型及其制备方法 |
| CN116715573B (zh) * | 2023-06-29 | 2025-08-19 | 河北华旭化工有限公司 | 一种2,2-二甲基丁酰氯的合成方法 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2290412A1 (fr) * | 1974-11-09 | 1976-06-04 | Gema Sa | Procede pour la preparation de chlorures d'acide a partir d'esters silyliques |
| US5358924A (en) | 1991-03-21 | 1994-10-25 | Bayer Aktiengesellschaft | 3-hydroxy-4-aryl-5-oxo-pyrozoline derivatives, compositions and use |
| DE19649665A1 (de) * | 1996-04-02 | 1997-10-09 | Bayer Ag | Neue substituierte Phenylketoenole |
| US6140358A (en) * | 1996-04-02 | 2000-10-31 | Bayer Aktiengesellschaft | Substituted phenyl keto enols as pesticides and herbicides |
| US6297400B1 (en) * | 1999-07-02 | 2001-10-02 | The Clorox Company | Synthesis of a tetraamido macrocycle ligand from a novel diamidodiol |
| JP3824483B2 (ja) * | 2000-10-31 | 2006-09-20 | 住友ベークライト株式会社 | 芳香族カルボン酸とその酸塩化物、および合成法 |
| JP4644957B2 (ja) * | 2001-03-09 | 2011-03-09 | 住友ベークライト株式会社 | 芳香族カルボン酸及びその酸塩化物誘導体、並びにそれらの合成法 |
| US6806380B2 (en) * | 2001-10-02 | 2004-10-19 | Lexicon Pharmaceuticals, Inc. | Modified safe and efficient process for the environmentally friendly synthesis of imidoesters |
| US7060818B2 (en) * | 2003-02-21 | 2006-06-13 | Carnegie Mellon University | Synthesis of macrocyclic tetraamido compounds and new metal insertion process |
| JP2004292393A (ja) * | 2003-03-27 | 2004-10-21 | Sumitomo Bakelite Co Ltd | 芳香族カルボン酸及びその酸塩化物誘導体の合成法 |
| JP2005187368A (ja) * | 2003-12-25 | 2005-07-14 | Sumitomo Chemical Co Ltd | カルボン酸クロリドの製造方法 |
| CN100402520C (zh) * | 2006-07-28 | 2008-07-16 | 马启明 | 2-取代丙二酸钙盐的制备方法及钙盐的用途 |
| RU2373182C2 (ru) * | 2007-12-19 | 2009-11-20 | Государственное образовательное учреждение высшего профессионального образования "Курский государственный технический университет" (КурскГТУ) | Способ получения малоната и сукцината марганца (ii) |
| TWI401023B (zh) | 2008-02-06 | 2013-07-11 | Du Pont | 中離子農藥 |
| BR112012002524A2 (pt) | 2009-08-05 | 2019-09-24 | Du Pont | "composto de fórmula, composição, composição para proteger um animal de uma praga parasítica de invertebrados, métodos para controlar uma praga invertebrada e semente tratada" |
| UA107804C2 (en) | 2009-08-05 | 2015-02-25 | Du Pont | Mixtures of pesticides mezoionnyh |
| UA110924C2 (uk) | 2009-08-05 | 2016-03-10 | Е. І. Дю Пон Де Немур Енд Компані | Мезоіонні пестициди |
| EP2461684A2 (en) * | 2009-08-05 | 2012-06-13 | E. I. du Pont de Nemours and Company | Mesoionic pesticides |
| WO2011091532A1 (en) * | 2010-01-28 | 2011-08-04 | Boehringer Ingelheim International Gmbh | Hepatitis c inhibitor compounds |
| TWI528899B (zh) | 2010-12-29 | 2016-04-11 | 杜邦股份有限公司 | 中離子性殺蟲劑 |
| WO2012106495A1 (en) * | 2011-02-03 | 2012-08-09 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
-
2012
- 2012-12-03 TW TW101145232A patent/TWI572587B/zh active
- 2012-12-13 CN CN201280061781.4A patent/CN104066713B/zh active Active
- 2012-12-13 MX MX2014006992A patent/MX352470B/es active IP Right Grant
- 2012-12-13 KR KR1020147019199A patent/KR102066682B1/ko active Active
- 2012-12-13 RU RU2014128826A patent/RU2636942C2/ru active
- 2012-12-13 JP JP2014547413A patent/JP2015501841A/ja active Pending
- 2012-12-13 AU AU2012352256A patent/AU2012352256B2/en active Active
- 2012-12-13 CA CA 2857333 patent/CA2857333A1/en not_active Abandoned
- 2012-12-13 HU HUE12808629 patent/HUE044394T2/hu unknown
- 2012-12-13 WO PCT/US2012/069468 patent/WO2013090547A1/en not_active Ceased
- 2012-12-13 BR BR112014014232A patent/BR112014014232B1/pt active IP Right Grant
- 2012-12-13 AR ARP120104695 patent/AR089221A1/es active IP Right Grant
- 2012-12-13 US US14/364,340 patent/US9108965B2/en active Active
- 2012-12-13 EP EP12808629.5A patent/EP2791107B1/en active Active
-
2014
- 2014-05-12 ZA ZA2014/03383A patent/ZA201403383B/en unknown
- 2014-05-14 IL IL232632A patent/IL232632A/en active IP Right Grant
- 2014-07-09 CO CO14147928A patent/CO7121339A2/es unknown
-
2017
- 2017-10-20 JP JP2017203098A patent/JP6579399B2/ja active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015501841A (ja) | 2015-01-19 |
| AU2012352256A1 (en) | 2014-05-29 |
| US20140343284A1 (en) | 2014-11-20 |
| CN104066713A (zh) | 2014-09-24 |
| TW201329037A (zh) | 2013-07-16 |
| TWI572587B (zh) | 2017-03-01 |
| IL232632A0 (en) | 2014-06-30 |
| RU2014128826A (ru) | 2016-02-10 |
| AU2012352256B2 (en) | 2017-05-25 |
| ZA201403383B (en) | 2015-12-23 |
| US9108965B2 (en) | 2015-08-18 |
| KR20140107420A (ko) | 2014-09-04 |
| CN104066713B (zh) | 2016-08-24 |
| EP2791107A1 (en) | 2014-10-22 |
| BR112014014232B1 (pt) | 2020-01-28 |
| IL232632A (en) | 2017-04-30 |
| EP2791107B1 (en) | 2019-03-13 |
| HUE044394T2 (hu) | 2019-10-28 |
| CO7121339A2 (es) | 2014-11-20 |
| MX2014006992A (es) | 2014-08-01 |
| AR089221A1 (es) | 2014-08-06 |
| JP2018058840A (ja) | 2018-04-12 |
| WO2013090547A1 (en) | 2013-06-20 |
| KR102066682B1 (ko) | 2020-01-16 |
| BR112014014232A2 (pt) | 2018-05-22 |
| MX352470B (es) | 2017-11-27 |
| JP6579399B2 (ja) | 2019-09-25 |
| RU2636942C2 (ru) | 2017-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2012352256B2 (en) | Malonic acid di-salts and a method for preparing malonyl dihalides | |
| KR100953251B1 (ko) | 치환된 디히드로 3-할로-1ｈ-피라졸-5-카르복실레이트, 그의 제조 방법 및 용도 | |
| KR101597839B1 (ko) | 5-할로알킬-4,5-다이하이드로아이속사졸 유도체의 제조 방법 | |
| KR101662852B1 (ko) | 3-트라이플루오로메틸 칼콘의 제조 방법 | |
| EA016615B1 (ru) | Способ получения n-замещенных (3-дигалометил-1-метилпиразол-4-ил)карбоксамидов | |
| CA2729697A1 (en) | Improved process for the preparation of 2-trifluoromethyl-5-(1-substituted)alkylpyridines | |
| CA2593345A1 (en) | Processes for preparing pyrazolo[3,4-d]pyrimidine ethers | |
| Génisson et al. | New chiral imidazolinic derivatives | |
| EA007164B1 (ru) | Фунгицидные триазолопиримидины, способ их получения и их применение для борьбы с фитопатогенными грибами, а также содержащие их средства | |
| IL268864A (en) | Production of arylpyrrole compounds in the presence of a diisopropylethylamine base | |
| JP6429016B2 (ja) | トリフルオロメタンスルホンアニリド化合物の製造方法 | |
| SU474981A3 (ru) | Способ получени 9(1-замещенный-4пиперидилиден)-тиоксантенов или их солей | |
| Kudelko et al. | The reaction of optically active α-aminocarboxylic acid hydrazides with triethyl orthoesters | |
| EP0323881B1 (en) | Cyano-dienes, halopyridines, intermediates and a process for their preparation | |
| JP5944597B2 (ja) | トリケトン化合物の製造方法 | |
| CN119032081A (zh) | 用于制备各种取代的氰基环丙基-杂芳烃或芳烃的方法 | |
| JP4619543B2 (ja) | カルバメート化合物からの６−（ペルフルオロアルキル）ウラシル化合物の製造方法 | |
| JPH08259539A (ja) | クロロメチルピリジン類の製造方法 | |
| US20230095589A1 (en) | One step process for the preparation of phenyl ethyl amine derivatives | |
| WO2010116121A1 (en) | Processes for making isoxazoline derivatives | |
| IL215023A (en) | Process for making anaminocarbonyl compounds | |
| JP2008513371A (ja) | ８−ハロ−１，７−ナフタピリジン誘導体と有機ボロン酸誘導体の反応による６，８−置換−１，７−ナフタピリジン誘導体の製造方法および該方法の中間体 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |
Effective date: 20171213 |