CN102459157A - 制备氟代烷基腈的方法 - Google Patents
制备氟代烷基腈的方法 Download PDFInfo
- Publication number
- CN102459157A CN102459157A CN201080025238XA CN201080025238A CN102459157A CN 102459157 A CN102459157 A CN 102459157A CN 201080025238X A CN201080025238X A CN 201080025238XA CN 201080025238 A CN201080025238 A CN 201080025238A CN 102459157 A CN102459157 A CN 102459157A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- chlorine
- fluorine
- aryl
- haloalkyl
- 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.)
- Granted
Links
- -1 fluoroalkyl nitriles Chemical class 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims description 30
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- 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 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 239000011737 fluorine Substances 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- 150000001266 acyl halides Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 6
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 3
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- PMWGIVRHUIAIII-UHFFFAOYSA-N 2,2-difluoropropanoic acid Chemical compound CC(F)(F)C(O)=O PMWGIVRHUIAIII-UHFFFAOYSA-N 0.000 claims description 2
- LDJUYMIFFNTKOI-UHFFFAOYSA-N 2,2-dimethylbutanoyl chloride Chemical compound CCC(C)(C)C(Cl)=O LDJUYMIFFNTKOI-UHFFFAOYSA-N 0.000 claims description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims description 2
- GPKYZQLMEPJAGJ-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropanoic acid Chemical compound OC(=O)C(F)C(F)(F)F GPKYZQLMEPJAGJ-UHFFFAOYSA-N 0.000 claims description 2
- OAWAZQITIZDJRB-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetic acid Chemical compound OC(=O)C(F)(F)Cl OAWAZQITIZDJRB-UHFFFAOYSA-N 0.000 claims description 2
- CBMCZKMIOZYAHS-NSCUHMNNSA-N [(e)-prop-1-enyl]boronic acid Chemical compound C\C=C\B(O)O CBMCZKMIOZYAHS-NSCUHMNNSA-N 0.000 claims description 2
- PZSXCNWLLFEOPM-UHFFFAOYSA-N [F].C(CC)(=O)O Chemical compound [F].C(CC)(=O)O PZSXCNWLLFEOPM-UHFFFAOYSA-N 0.000 claims description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- KCDNYRPDKSGQCM-UHFFFAOYSA-N 4-[4-(3-chlorophenyl)-4-(pyrrolidine-1-carbonyl)piperidin-1-yl]-1-(4-fluorophenyl)butan-1-one Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(C=2C=C(Cl)C=CC=2)(C(=O)N2CCCC2)CC1 KCDNYRPDKSGQCM-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- SFFUEHODRAXXIA-UHFFFAOYSA-N 2,2,2-trifluoroacetonitrile Chemical compound FC(F)(F)C#N SFFUEHODRAXXIA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- FVTWJXMFYOXOKK-UHFFFAOYSA-N 2-fluoroacetamide Chemical class NC(=O)CF FVTWJXMFYOXOKK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 0 *C(*)(C(N)=O)F Chemical compound *C(*)(C(N)=O)F 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- RQUBQBFVDOLUKC-UHFFFAOYSA-N 1-ethoxy-2-methylpropane Chemical compound CCOCC(C)C RQUBQBFVDOLUKC-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GNWLESJJKKIBJD-UHFFFAOYSA-N C(CC)#N.[F] Chemical compound C(CC)#N.[F] GNWLESJJKKIBJD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DRUIESSIVFYOMK-UHFFFAOYSA-N Trichloroacetonitrile Chemical compound ClC(Cl)(Cl)C#N DRUIESSIVFYOMK-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HIJIXCXMVYTMCY-UHFFFAOYSA-N diethyl 2-heptylpropanedioate Chemical compound CCCCCCCC(C(=O)OCC)C(=O)OCC HIJIXCXMVYTMCY-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/10—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and halogen atoms, or nitro or nitroso groups, bound to the same acyclic carbon skeleton
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Abstract
本发明涉及一种制备氟代烷基腈的方法，通过将氟化羧酸酰胺与酰基卤和氟化羧酸反应而进行。本发明的方法可以基于以下方案(I)定义，其中X1、X2、R1、Hal具有说明书所给出的含义。
Description
本发明涉及一种由氟代烷基羧酰胺制备氟代烷基腈的方法。
氟代烷基腈是制备活性农用化学成分的重要中间体。
US 2939878公开了可以由一氯二氟甲烷和氯化氰在500至750℃的温度反应获得氟代腈。这种无选择性的反应生成了三氟乙腈、氯二氟乙腈、2-氯四氟丙腈和其他氟化低沸物的混合物。
另一个专利申请(JP 59118751A)记载了式RFCCl3的氯氟烷烃与氨在800℃的温度下反应。Hellberg和Massonne描述了同样的方法(Chemiker-Ztg./Chem.Apparatur/Verfahrenstechnik，第93卷(1969)6，209-211)。R 113a与氨在500-800℃反应。这里同样获得了产物的混合物(CF3CN、CF3Cl、CF3H、CF3CCl3、C2F4Cl2、C2F2Cl4、C2F3Cl、CF2Cl2)。
Grunewald等(J.Med.Chem.2006，49，2939-2952)和Swarts(Bulletin Societes Chemiques Belges，1922，Vol 31，364-365)记载了由二氟乙酰胺与五氧化二磷制备二氟乙腈的方法。此方法包括将这两种固体加热，然后在-78℃冷凝挥发的腈。然而，残存在反应容器中的固体反应残留物难以去除。
另一个方法描述了乙腈的电化学氟化作用(Masatake Haruta andNobuatsu Watanabe，J.Fluorine Chemistry，7(1976)159-177)。该反应无选择性地进行，也得到了反应产物的混合物。
Foulletier(EP 55651B1)描述了三氯乙腈在400℃时进行气相氟化反应。这也同样获得了混合物。
Parker在Synthetic Communications(第34卷，2004，第903-907页)中记载了由三氟乙酰胺与三氟乙酸酐在吡啶中反应制备三氟乙腈。该方法的一个缺点是使用了昂贵的三氟乙酸酐，其必须以化学计量使用。
所有的上述方法都具有以下特点：其均需要专门的设备、非常高的温度、昂贵和危险的试剂，并且只有通过复杂的分离才能把所需的产物从产物混合物中分离出来。
由现有技术出发，本发明的一个目的是提供一种制备氟代烷基腈的方法，其可以优选地以简单和廉价的方式进行。由所述期望方法所获得的氟代烷基腈应优选以高产率和高纯度获得。更特别地，所述期望方法应当使得无需复杂的提纯方法就可以获得所需的目标化合物。
所述目的根据本发明通过一种制备通式(I)的氟代烷基腈的方法而实现，
其中
X1和X2各自独立地为氟、氯、溴、氢、C1-12烷基、C1-12卤代烷基、C5-18芳基、C7-19烷基芳基或者C7-19芳基烷基，
其特征在于
将式(II)的氟化羧酰胺
其中X1和X2各自定义如上，
在一种碱和催化量的式(III)的氟化羧酸的存在下
其中
Y1和Y2各自独立地为氟、氯、溴、氢、C1-12烷基、C1-12卤代烷基、C5-18芳基、C7-19烷基芳基或者C7-19芳基烷基，
与式(IV)的酰基卤反应
其中R1为C1-12烷基、C3-8环烷基、C1-12卤代烷基、C5-18芳基、C7-19芳基烷基或者C7-19烷基芳基，并且Hal为卤素。
上述通式(I)中示出的X1和X2基团的优选、特别优选和极特别优选的定义说明如下。
X1和X2优选各自独立地为氟、氯、氢、C1-12烷基、C1-12卤代烷基或者C5-18芳基，
X1和X2更优选各自独立地为氟、氯、氢或者C1-12卤代烷基，
X1和X2最优选各自独立地为氟、氢或者C1-12卤代烷基。
出乎意料地，在本发明的条件下，式(I)的氟代烷基腈可以以高产量和高纯度制备，因为本发明的方法不具有与现有技术有关的所述缺陷。
本发明的方法可以用以下方案(I)示例说明：
其中X1、X2、R1、Hal各自定义如上。
方案(I)
通用定义
就本发明而言，除非另有定义，术语“卤素”(Hal)包括那些选自氟、氯、溴和碘的元素，优选使用氟、氯和溴，特别优选使用氟和氯。
任选被取代的基团可以为单取代或多取代，其中在多取代的情况下取代基可以相同或不同。
被一个或多个卤素原子(-Hal)取代的烷基选自，例如，三氟甲基(CF3)、二氟甲基(CHF2)、CF3CH2、ClCH2、CF3CCl2。
就本发明而言，除非有不同定义，烷基是直链、支链或环状的饱和烃基团。
定义“C1-C12烷基”包括本文对于烷基所定义的最大范围。具体而言，该定义包括例如下述含义：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基、正戊基、正己基、1，3-二甲基丁基、3，3-二甲基丁基、正庚基、正壬基、正癸基、正十一烷基、正十二烷基。
就本发明而言，除非有不同定义，芳基为芳香族烃基，其可以具有一个、两个或更多个选自O、N、P和S的杂原子。
定义“C5-18芳基”包括本文对于具有5至18个框架碳原子的芳基所定义的最大范围，其中所述碳原子可以替换为杂原子。具体而言，该定义包括例如下述含义：环戊二烯基、苯基、环庚三烯基、环辛四烯基、萘基和蒽基；2-呋喃基、3-呋喃基、2-噻吩基、3-噻吩基、2-吡咯基、3-吡咯基、3-异噁唑基、4-异噁唑基、5-异噁唑基、3-异噻唑基、4-异噻唑基、5-异噻唑基、3-吡唑基、4-吡唑基、5-吡唑基、2-噁唑基、4-噁唑基、5-噁唑基、2-噻唑基、4-噻唑基、5-噻唑基、2-咪唑基、4-咪唑基、1，2，4-噁二唑-3-基、1，2，4-噁二唑-5-基、1，2，4-噻二唑-3-基、1，2，4-噻二唑-5-基、1，2，4-三唑-3-基、1，3，4-噁二唑-2-基、1，3，4-噻二唑-2-基和1，3，4-三唑-2-基；1-吡咯基、1-吡唑基、1，2，4-三唑-1-基、1-咪唑基、1，2，3-三唑-1-基、1，3，4-三唑-1-基；3-哒嗪基、4-哒嗪基、2-嘧啶基、4-嘧啶基、5-嘧啶基、2-吡嗪基、1，3，5-三嗪-2-基和1，2，4-三嗪-3-基。
就本发明而言，除非有不同定义，芳基烷基(芳烷基)为被芳基取代的烷基，并且可以具有C1-8-亚烷基链，并且在芳基的骨架中可以具有一个或多个选自O、N、P和S的杂原子。
定义“C7-19芳烷基”包括本文对于在框架和亚烷基链中具有总共7至19个原子的芳烷基所定义的最大范围。具体而言，该定义包括例如下述含义：苄基和苯乙基。
就本发明而言，除非另有定义，烷基芳基(烷芳基)为被烷基取代的芳基，并且具有C1-8-亚烷基链，并且在芳基的骨架中可以具有一个或多个选自O、N、P和S的杂原子。
定义“C7-19烷芳基”包括本文对于在框架和亚烷基链中具有总共7至19个原子的烷芳基所定义的最大范围。具体而言，该定义包括例如下述含义：甲苯基、2，3-、2，4-、2，5-、2，6-、3，4-或3，5-二甲基苯基。
氟化羧酸(III)
本发明使用的氟化羧酸为通式(III)的化合物：
其中
Y1和Y2各自独立地为氟、氯、溴、氢、C1-12烷基、C1-12卤代烷基、C5-18芳基、C7-19烷基芳基或者C7-19芳基烷基，优选氢、氟、氯、C2-8烷基或者C2-8卤代烷基，更优选氟、氯、氢、C3-6烷基、CF3或者CF2H。
本发明适合的氟化羧酸的实例为三氟乙酸、二氟乙酸、二氟氯乙酸、氯氟乙酸、2，3，3，3-四氟丙酸、，2，2，3，3-四氟丙酸、2，2-二氟丙酸、五氟丙酸、2，3，3，4，4，4-六氟丁烷甲酸。
所使用的式(III)的氟化羧酸与式(II)的氟化烷基酰胺的摩尔比可为例如0.05至1，优选0.11至0.8，更优选0.2至0.7。使用更大量(摩尔比大于1)的氟化羧酸也没有关系，但不经济。
酰基卤(IV)
加入式(IV)的酰基卤来转化上文所述的式(II)的氟化烷基酰胺。
在式(IV)中，R1选自C1-12烷基、C3-8环烷基、C1-12卤代烷基、C5-18芳基、C7-19芳基烷基或者C7-19烷基芳基，优选选自C5-18芳基或C2-8烷基，更优选选自C3-6烷基或C6芳基，
并且Hal为氟、氯、溴或碘，优选氯或溴，更优选氯。
本发明适合的酰基卤的实例为乙酰氯、新戊酰氯、2，2-二甲基丁酰氯、异戊酰氯和苯甲酰氯。
使用的式(IV)的酰基卤与式(II)的氟化烷基酰胺的摩尔比可为，例如0.5至5，优选1至3，更优选2至2.5。
碱
本发明的方法在一种碱的存在下进行。合适的碱为，例如，取代或未取代的吡啶类化合物，以及取代或未取代的喹啉类化合物。优选使用取代或未取代的吡啶类化合物和取代或未取代的喹啉类化合物。
碱的优选实例为吡啶、3-甲基吡啶、4-甲基吡啶、喹啉、喹哪啶、卤代吡啶类化合物。特别优选使用吡啶、4-甲基吡啶、2-氯吡啶。
所使用的碱与式(III)的氟化羧酸的摩尔比可以为，例如，0.5至10，优选1至8，更优选1.5至6。
使用更大量的碱也没有关系，但不经济。
制备通式(I)的化合物的反应通常可在减压、标准压力或加压下进行。使用的温度也可以根据所用的底物改变，并且可以由本领域技术人员通过常规试验容易地确定。例如，制备通式(I)的化合物的反应可以在-50至250℃的温度进行，优选0至170℃。特别优选在10至140℃的温度进行反应。
根据本发明使用的式(II)的氟化烷基酰胺是市售的，或者可以用文献方法简单地制备(WO 03/080563)。
溶剂
式(II)的氟化烷基酰胺生成式(I)化合物的反应可以在溶剂的存在下进行。优选在反应中不另行使用溶剂。合适的溶剂包括：卤代烃和芳香族烃，尤其是氯代烃，例如四氯乙烯、四氯乙烷、二氯丙烷、二氯甲烷、二氯丁烷、氯仿、四氯化碳、三氯乙烷、三氯乙烯、五氯乙烷、二氟苯、1，2-二氯乙烷、氯苯、溴苯、二氯苯、氯甲苯、三氯苯；醚类，例如乙基丙基醚、正丁醚、苯甲醚、苯乙醚、甲基环己基醚、甲醚、乙醚、二甲基乙二醇、苯基醚、丙醚、异丙醚、正丁醚、异丁醚、异戊醚、乙二醇二甲醚、乙基异丙基醚、甲基叔丁基醚、四氢呋喃、甲基四氢呋喃、二噁烷、二氯二乙基醚，以及环氧乙烷和/或环氧丙烷的聚醚；硝基烃，例如硝基甲烷、硝基乙烷、硝基丙烷、硝基苯、氯代硝基苯、邻硝基甲苯；脂肪族烃、环状脂肪族烃或芳香族烃，例如戊烷、正己烷、正庚烷、正辛烷、壬烷，例如组分的沸点在例如40℃到250℃范围内的石油溶剂、甲基异丙基苯、沸程为70℃至190℃的石油馏分、环己烷、甲基环己烷、石油醚、挥发油(ligroin)、辛烷、苯、甲苯、二甲苯；酯类，例如乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、以及碳酸二甲酯、碳酸二丁酯、碳酸亚乙酯。优选的溶剂为甲苯或氯苯。
所需的通式(I)化合物可以例如通过蒸馏分离。在这种情况下，产物(I)可以在计量加入式(IV)的酰基卤的过程中同时蒸馏出去。另一个分离的变化方案是仅在反应结束后将式(I)的产物蒸馏或过滤移出。
通过下述实施例详细说明本发明，但这些实施例不应以限制本发明的方式解释。
制备实施例
实施例1
将4.6g的三氟乙酸在48.9g的吡啶中的初始进料与13.4g三氟乙酰胺混合。之后将30.4g的2，2-二甲基丙酰氯在室温经5小时滴加至该溶液中。在滴加的过程中立刻产生气态的三氟乙腈。它可以在较低的温度(例如在-100℃)冷凝或者直接引入下一步反应。产率为92％。
实施例2
将2g的二氟乙酸在34.8g的吡啶中的初始进料与5g三氟乙酰胺混合。之后将10.9g的2，2-二甲基丙酰氯在室温经2小时滴加至该溶液中。在滴加的过程中立刻产生气态的三氟乙腈。产率为90％。
实施例3
将2.4g的三氟乙酸在34.8g的吡啶中的初始进料与5g三氟乙酰胺混合。之后将12.4g的2，2-二甲基丁酰氯在室温经2小时滴加至该溶液中。在滴加的过程中立刻产生气态的三氟乙腈。产率为84％。
实施例4
将4.6g的三氟乙酸在48.9g的吡啶中的初始进料与13.4g三氟乙酰胺混合。之后将35.5g的苯甲酰氯在室温经5小时滴加至该溶液中。在滴加的过程中立刻产生气态的三氟乙腈。产率为86％。
实施例5
将11.6g的三氟乙酸在146.7g的吡啶中的初始进料与19.2g二氟乙酰胺混合。之后将51.2g的2，2-二甲基丙酰氯在60℃经3小时滴加至该溶液中。随后，将反应混合物加热到100℃，蒸馏出二氟乙腈。得到二氟乙腈，产率为88％。
实施例6
将5.5g的三氟乙酸在78g的吡啶中的初始进料与16.1g五氟丙酰胺混合。之后将24.4g的2，2-二甲基丙酰氯在30℃经4小时滴加至该溶液中。在滴加的过程中立刻产生气态的五氟丙腈。它可以在较低的温度(例如在-80℃)冷凝或者直接引入下一步反应。产率为82％。
Claims (9)
1.制备通式(I)的氟代烷基腈的方法
其中
X1和X2各自独立地为氟、氯、溴、氢、C1-12烷基、C1-12卤代烷基、C5-18芳基、C7-19烷基芳基或者C7-19芳基烷基，
其特征在于
将式(II)的氟化羧酰胺
其中X1和X2各自定义如上，
在一种碱和催化量的式(III)的氟化羧酸的存在下
其中
Y1和Y2各自独立地为为氟、氯、溴、氢、C1-12烷基、C1-12卤代烷基、C5-18芳基、C7-19烷基芳基或者C7-19芳基烷基，
与式(IV)的酰基卤反应
其中R1为C1-12烷基、C3-8环烷基、C1-12卤代烷基、C5-18芳基、C7-19芳基烷基或者C7-19烷基芳基，并且Hal为卤素。
2.权利要求1的方法，其中
X1和X2各自独立地为氟、氯、氢、C1-12烷基、C1-12卤代烷基或C5-18芳基，
Y1和Y2各自独立地为氢、氟、氯、C2-8烷基或者C2-8卤代烷基，
Hal为氯或溴；
R1为C2-8烷基或者C5-18芳基。
3.权利要求1或2的方法，其中
X1和X2各自独立地为氟、氯、氢或者C1-12卤代烷基，
Y1和Y2各自独立地为氟、氯、氢、C3-6烷基、CF3或者CF2H，
R1为C3-6烷基或者C6芳基，
并且Hal为氯。
4.权利要求1至3之一的方法，其中所述氟化羧酸选自三氟乙酸、二氟乙酸、二氟氯乙酸、氯氟乙酸、2，3，3，3-四氟丙酸、2，2，3，3-四氟丙酸、2，2-二氟丙酸、五氟丙酸、2，3，3，4，4，4-六氟丁烷甲酸。
5.权利要求1至4之一的方法，其中所述酰基卤选自乙酰氯、新戊酰氯、2，2-二甲基丁酰氯、异戊酰氯和苯甲酰氯。
6.权利要求1至5之一的方法，其中所述通式(III)的氟化羧酸与通式(II)的氟化烷基酰胺的摩尔比为0.05至1。
7.权利要求1至6之一的方法，其中所述通式(IV)的酰基卤与通式(II)的氟化烷基酰胺的摩尔比为0.5至5。
8.权利要求1至7之一的方法，其中所述碱选自吡啶、3-甲基吡啶、4-甲基吡啶、喹啉、喹哪啶、卤代吡啶。
9.权利要求1至8中任一项的方法，其中所用的碱与通式(III)氟化羧酸的摩尔比为0.5至10。
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| EP09162172 | 2009-06-08 | ||
| EP09162172.2 | 2009-06-08 | ||
| PCT/EP2010/003209 WO2010142377A1 (de) | 2009-06-08 | 2010-05-26 | Verfahren zur herstellung von fluoralkylnitrilen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103804231A (zh) * | 2014-02-27 | 2014-05-21 | 江苏省激素研究所股份有限公司 | 一种农药中间体三氟乙腈的合成方法 |
| CN109563027A (zh) * | 2016-07-28 | 2019-04-02 | 拜耳作物科学股份公司 | 氟代烷基腈和相应的氟代烷基四唑的制备方法 |
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| FR2972452B1 (fr) * | 2011-03-09 | 2013-03-15 | Rhodia Operations | Procede de preparation du difluoroacetonitrile et de ses derives |
| FR2975990B1 (fr) * | 2011-06-01 | 2013-05-24 | Rhodia Operations | Procede de preparation d'un compose organique fluore |
| DK3589612T3 (da) * | 2017-02-28 | 2021-06-21 | Bayer Cropscience Ag | Fremgangsmåde til fremstilling af fluoralkylnitriler og de tilsvarende fluoralkyltetrazoler |
| IL280732B2 (en) | 2018-09-03 | 2024-04-01 | Pi Industries Ltd | A method for the preparation of fluoroalkyl nitrates and their use for the preparation of fluoroalkaline tetrazoles |
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| US5366989A (en) * | 1991-12-09 | 1994-11-22 | Toyama Chemical Co., Ltd. | Triazole derivatives and salts thereof and antifungal agent containing the same |
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| US2730543A (en) * | 1950-05-20 | 1956-01-10 | Minnesota Mining & Mfg | Fluorinated nitriles |
| US2939878A (en) | 1958-10-22 | 1960-06-07 | Dow Chemical Co | Preparation of fluoronitriles |
| US3928274A (en) * | 1973-08-29 | 1975-12-23 | Lilly Industries Ltd | Process for preparing nitriles |
| FR2501063A1 (fr) | 1980-12-29 | 1982-09-10 | Ugine Kuhlmann | Catalyseurs de fluoruration en phase gazeuse des derives chlores aliphatiques, a base de charbon actif impregne de sulfate de chrome, et procedes de fluoruration utilisant ces catalyseurs |
| JPS59118751A (ja) | 1982-12-24 | 1984-07-09 | Daikin Ind Ltd | フルオロアルキルニトリルの製法 |
| JPS63290843A (ja) * | 1987-05-25 | 1988-11-28 | Ihara Nikkei Kagaku Kogyo Kk | 芳香族ニトリルと芳香族カルボン酸とを製造する方法 |
| US5637748A (en) * | 1995-03-01 | 1997-06-10 | E. I. Du Pont De Nemours And Company | Process for synthesizing fluorinated nitrile compounds |
| DE10212526A1 (de) | 2002-03-21 | 2003-10-02 | Solvay Fluor & Derivate | Herstellung von verfestigten organischen Verbindungen, insbesondere von Carbonsäureamiden |
| DE102004003953A1 (de) * | 2004-01-26 | 2005-08-11 | Clariant Gmbh | Verfahren zur Herstellung von Nitrilen und Isonitrilen durch Dehydratisierungsreaktionen mit Propanphosphonsäureanhydriden |
| US20070293515A1 (en) * | 2004-08-03 | 2007-12-20 | Layton Mark E | 1,3-Disubstituted Heteroaryl Nmda/Nr2b Antagonists |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103804231A (zh) * | 2014-02-27 | 2014-05-21 | 江苏省激素研究所股份有限公司 | 一种农药中间体三氟乙腈的合成方法 |
| CN109563027A (zh) * | 2016-07-28 | 2019-04-02 | 拜耳作物科学股份公司 | 氟代烷基腈和相应的氟代烷基四唑的制备方法 |
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| WO2010142377A1 (de) | 2010-12-16 |
| CN102459157B (zh) | 2014-09-10 |
| US20100312002A1 (en) | 2010-12-09 |
| BRPI1010841A2 (pt) | 2016-04-05 |
| EP2440518A1 (de) | 2012-04-18 |
| KR101705287B1 (ko) | 2017-02-09 |
| IL216694A0 (en) | 2012-02-29 |
| MX2011013146A (es) | 2012-01-20 |
| TWI471294B (zh) | 2015-02-01 |
| US8203015B2 (en) | 2012-06-19 |
| TW201119982A (en) | 2011-06-16 |
| EP2440518B1 (de) | 2014-08-20 |
| IL216694A (en) | 2015-02-26 |
| ES2518465T3 (es) | 2014-11-05 |
| KR20120032518A (ko) | 2012-04-05 |
| JP5571779B2 (ja) | 2014-08-13 |
| JP2012529446A (ja) | 2012-11-22 |
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