JP2021187752A - Method of producing 2,3,4,5,6-pentafluorostyrene - Google Patents
Method of producing 2,3,4,5,6-pentafluorostyrene Download PDFInfo
- Publication number
- JP2021187752A JP2021187752A JP2020091979A JP2020091979A JP2021187752A JP 2021187752 A JP2021187752 A JP 2021187752A JP 2020091979 A JP2020091979 A JP 2020091979A JP 2020091979 A JP2020091979 A JP 2020091979A JP 2021187752 A JP2021187752 A JP 2021187752A
- Authority
- JP
- Japan
- Prior art keywords
- pentafluorostyrene
- pentafluorophenyl
- zinc
- halide
- nickel
- 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
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 pentafluorophenyl-zinc halide Chemical class 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- XEKTVXADUPBFOA-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Br)C(F)=C1F XEKTVXADUPBFOA-UHFFFAOYSA-N 0.000 claims description 15
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- KGCDGLXSBHJAHZ-UHFFFAOYSA-N 1-chloro-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Cl)C(F)=C1F KGCDGLXSBHJAHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004791 alkyl magnesium halides Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- OPYHNLNYCRZOGY-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-iodobenzene Chemical compound FC1=C(F)C(F)=C(I)C(F)=C1F OPYHNLNYCRZOGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- JNLDBRDEDAKZEE-UHFFFAOYSA-N Fc1c(F)c(F)c([Zn])c(F)c1F Chemical compound Fc1c(F)c(F)c([Zn])c(F)c1F JNLDBRDEDAKZEE-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- YPXUXAAWLKJCIZ-UHFFFAOYSA-M [Cl-].FC1=C(C(=C(C(=C1[Zn+])F)F)F)F Chemical compound [Cl-].FC1=C(C(=C(C(=C1[Zn+])F)F)F)F YPXUXAAWLKJCIZ-UHFFFAOYSA-M 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- OGDMUXMDSAVJLP-UHFFFAOYSA-M [Br-].Fc1c(F)c(F)c([Zn+])c(F)c1F Chemical compound [Br-].Fc1c(F)c(F)c([Zn+])c(F)c1F OGDMUXMDSAVJLP-UHFFFAOYSA-M 0.000 description 6
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- TURVSLXVJYZFII-UHFFFAOYSA-N zinc;1,2,3,4,5-pentafluorobenzene-6-ide Chemical compound [Zn+2].FC1=[C-]C(F)=C(F)C(F)=C1F.FC1=[C-]C(F)=C(F)C(F)=C1F TURVSLXVJYZFII-UHFFFAOYSA-N 0.000 description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SHPQVJNNBXMZRW-UHFFFAOYSA-N 6-butyldec-5-en-5-yltin Chemical compound CCCCC([Sn])=C(CCCC)CCCC SHPQVJNNBXMZRW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 2
- VPLLTGLLUHLIHA-UHFFFAOYSA-N dicyclohexyl(phenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1CCCCC1 VPLLTGLLUHLIHA-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- YYKBFGMYHQMXIL-UHFFFAOYSA-N 1-phenyl-2,3,4-tri(propan-2-yl)benzene Chemical group CC(C)C1=C(C(C)C)C(C(C)C)=CC=C1C1=CC=CC=C1 YYKBFGMYHQMXIL-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- JFVHHXOSEDMKHN-UHFFFAOYSA-L 2-amino-5-methylbenzenesulfonate;nickel(2+) Chemical compound [Ni+2].CC1=CC=C(N)C(S([O-])(=O)=O)=C1.CC1=CC=C(N)C(S([O-])(=O)=O)=C1 JFVHHXOSEDMKHN-UHFFFAOYSA-L 0.000 description 1
- LRLQQERNMXHASR-UHFFFAOYSA-N 2-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 LRLQQERNMXHASR-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OIYDMFLWYJTIRX-UHFFFAOYSA-N C(C)(C)C1(C=CC=C1)[Ni]C1(C=CC=C1)C(C)C Chemical compound C(C)(C)C1(C=CC=C1)[Ni]C1(C=CC=C1)C(C)C OIYDMFLWYJTIRX-UHFFFAOYSA-N 0.000 description 1
- FLAKGKCBSLMHQU-UHFFFAOYSA-N CC[Mg] Chemical compound CC[Mg] FLAKGKCBSLMHQU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- NYIORHZHYZIHEK-UHFFFAOYSA-M FC(C(F)=C(C([Zn+])=C1F)F)=C1F.[F-] Chemical compound FC(C(F)=C(C([Zn+])=C1F)F)=C1F.[F-] NYIORHZHYZIHEK-UHFFFAOYSA-M 0.000 description 1
- FPPYBBOIFQGHHZ-UHFFFAOYSA-M Fc1c(F)c(F)c([Mg]Cl)c(F)c1F Chemical compound Fc1c(F)c(F)c([Mg]Cl)c(F)c1F FPPYBBOIFQGHHZ-UHFFFAOYSA-M 0.000 description 1
- 229910021588 Nickel(II) iodide Inorganic materials 0.000 description 1
- UXRZLDREKITWRO-UHFFFAOYSA-N P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 Chemical compound P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 UXRZLDREKITWRO-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- GUMQWPGMMSFQEQ-UHFFFAOYSA-M [I-].CC(C)(C)[Mg+] Chemical compound [I-].CC(C)(C)[Mg+] GUMQWPGMMSFQEQ-UHFFFAOYSA-M 0.000 description 1
- LQHZUFWVUJVYQR-UHFFFAOYSA-M [I-].CCCC[Mg+] Chemical compound [I-].CCCC[Mg+] LQHZUFWVUJVYQR-UHFFFAOYSA-M 0.000 description 1
- KWEWNAXCUWXEHQ-UHFFFAOYSA-M [I-].CCC[Mg+] Chemical compound [I-].CCC[Mg+] KWEWNAXCUWXEHQ-UHFFFAOYSA-M 0.000 description 1
- CDKFWIMBZAUBRS-UHFFFAOYSA-M [I-].CC[Mg+] Chemical compound [I-].CC[Mg+] CDKFWIMBZAUBRS-UHFFFAOYSA-M 0.000 description 1
- BCBYVHVPDUPMQN-UHFFFAOYSA-M [I-].FC1=C(C(=C(C(=C1[Zn+])F)F)F)F Chemical compound [I-].FC1=C(C(=C(C(=C1[Zn+])F)F)F)F BCBYVHVPDUPMQN-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- AMQDBUIQKQUCKY-UHFFFAOYSA-M magnesium;1,2,3,4,5-pentafluorobenzene-6-ide;bromide Chemical compound [Mg+2].[Br-].FC1=[C-]C(F)=C(F)C(F)=C1F AMQDBUIQKQUCKY-UHFFFAOYSA-M 0.000 description 1
- UKZCGMDMXDLAGZ-UHFFFAOYSA-M magnesium;2-methylpropane;bromide Chemical compound [Mg+2].[Br-].C[C-](C)C UKZCGMDMXDLAGZ-UHFFFAOYSA-M 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- XGITVAYMIKUXIN-UHFFFAOYSA-M magnesium;propane;iodide Chemical compound [Mg+2].[I-].C[CH-]C XGITVAYMIKUXIN-UHFFFAOYSA-M 0.000 description 1
- ZKUUVVYMPUDTGJ-UHFFFAOYSA-N methyl 5-hydroxy-4-methoxy-2-nitrobenzoate Chemical compound COC(=O)C1=CC(O)=C(OC)C=C1[N+]([O-])=O ZKUUVVYMPUDTGJ-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- CHPLEWYRKUFKQP-UHFFFAOYSA-N nickel(2+);1,2,3,5,5-pentamethylcyclopenta-1,3-diene Chemical compound [Ni+2].CC1=[C-]C(C)(C)C(C)=C1C.CC1=[C-]C(C)(C)C(C)=C1C CHPLEWYRKUFKQP-UHFFFAOYSA-N 0.000 description 1
- VBLNFWKVZVKXPH-UHFFFAOYSA-L nickel(2+);2,2,2-trifluoroacetate Chemical compound [Ni+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F VBLNFWKVZVKXPH-UHFFFAOYSA-L 0.000 description 1
- CTMZMYIKVZENEQ-UHFFFAOYSA-N nickel(2+);triphenylphosphane Chemical compound [Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CTMZMYIKVZENEQ-UHFFFAOYSA-N 0.000 description 1
- QEKXARSPUFVXIX-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dibromide Chemical compound [Ni+2].[Br-].[Br-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QEKXARSPUFVXIX-UHFFFAOYSA-L 0.000 description 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- JUJLDYVCLNLGTH-UHFFFAOYSA-N nickel;1,2,3,4-tetramethylcyclopentane Chemical compound [Ni].C[C]1[CH][C](C)[C](C)[C]1C.C[C]1[CH][C](C)[C](C)[C]1C JUJLDYVCLNLGTH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、２，３，４，５，６−ペンタフルオロスチレンの製造方法に関する。２，３，４，５，６−ペンタフルオロスチレンは、単独重合又は様々な炭素−炭素二重結合を有する化合物との共重合が可能で、光学材料や電子材料の製造中間体として有用な化合物である。 The present invention relates to a method for producing 2,3,4,5,6-pentafluorostyrene. 2,3,4,5,6-pentafluorostyrene is a compound that can be homopolymerized or copolymerized with compounds having various carbon-carbon double bonds and is useful as a production intermediate for optical materials and electronic materials. Is.
従来より、２，３，４，５，６−ペンタフルオロスチレンの製造方法としては、クロロペンタフルオロベンゼン又はブロモペンタフルオロベンゼンとマグネシウム金属を反応させペンタフルオロフェニルマグネシウムハライドを調製し、アセトアルデヒドを反応の後、脱水反応により調製する方法（例えば特許文献１参照）、ヘキサフルオロベンゼンとビニル−リチウムを反応させ調製する方法（例えば非特許文献１参照）、ペンタフルオロフェニル−イッテリビウムジブロミドと臭化ビニルを塩化コバルト触媒存在下反応させる方法（例えば非特許文献２参照）、ペンタブロモフェニルトリフラートとトリ（ｎ−ブチル）ビニルスズをテトラキス（トリフェニルホスフィン）パラジウム（０）触媒存在下、反応させる方法（例えば非特許文献３参照）等が知られている。 Conventionally, as a method for producing 2,3,4,5,6-pentafluorostyrene, pentafluorophenylmagnesium halide is prepared by reacting chloropentafluorobenzene or bromopentafluorobenzene with magnesium metal, and acetaldehyde is reacted. Later, a method for preparing by dehydration reaction (see, for example, Patent Document 1), a method for preparing by reacting hexafluorobenzene and vinyl-lithium (see, for example, Non-Patent Document 1), and bromide with pentafluorophenyl-itteribium dibromid. A method of reacting vinyl in the presence of a cobalt chloride catalyst (see, for example, Non-Patent Document 2), and a method of reacting pentabromophenyltriflate with tri (n-butyl) vinyl tin in the presence of a tetrakis (triphenylphosphine) palladium (0) catalyst (see Non-Patent Document 2). For example, see Non-Patent Document 3) and the like.
この内、特許文献１に記載の方法は、ブロモペンタフルオロベンゼンとマグネシウム金属を反応させペンタフルオロフェニルマグネシウムハライドを調製し、アセトアルデヒドを反応の後、アルミナ（Ａｌ２Ｏ３）の存在下、３４５℃〜３５０℃の温度で、窒素雰囲気下での脱水反応により調製する方法である。この方法は、脱水反応時に高温で実施する必要があるか、又は、工業的に使用が困難な五酸化リン等の強い脱水剤が必要という課題がある。 Among these, the method described in Patent Document 1 reacts bromopentafluorobenzene with a magnesium metal to prepare pentafluorophenylmagnesium halide, reacts with acetaldehyde, and then reacts with alumina (Al 2 O 3 ) at 345 ° C. It is a method of preparing by a dehydration reaction in a nitrogen atmosphere at a temperature of about 350 ° C. This method has a problem that it needs to be carried out at a high temperature during the dehydration reaction, or a strong dehydrating agent such as phosphorus pentoxide, which is difficult to use industrially, is required.
非特許文献１に記載の方法は、ヘキサフルオロベンゼンとビニル−リチウムを、室温下で反応させ調製する方法であり、１段の反応で２，３，４，５，６−ペンタフルオロスチレンを製造できるが、収率が２０％と低く、また高分子のヘキサフルオロベンゼンのビニル誘導体と思われる固形分がかなりの量(considerable quantity)生成してしまうという課題がある。 The method described in Non-Patent Document 1 is a method of preparing by reacting hexafluorobenzene and vinyl-lithium at room temperature, and producing 2,3,4,5,6-pentafluorostyrene by a one-step reaction. However, there is a problem that the yield is as low as 20% and a considerable amount of solid content (considerable quantity), which is considered to be a vinyl derivative of high-molecular-weight hexafluorobenzene, is produced.
非特許文献２に記載の方法は、収率８０％と高収率ではあるが、高価な臭化イッテリビウムが必要という課題がある。さらに非特許文献３に記載の方法は、毒性が高く、環境への負担が高いトリ（ｎ−ブチル）ビニルスズを用いるという課題がある。 The method described in Non-Patent Document 2 has a high yield of 80%, but has a problem that expensive itteribium bromide is required. Further, the method described in Non-Patent Document 3 has a problem of using tri (n-butyl) vinyl tin, which is highly toxic and has a high burden on the environment.
本発明の目的は、従来技術を鑑み、２，３，４，５，６−ペンタフルオロスチレンを経済的にかつ簡便に製造する方法を提供することにある。 An object of the present invention is to provide a method for economically and easily producing 2,3,4,5,6-pentafluorostyrene in view of the prior art.
本発明者は、２，３，４，５，６−ペンタフルオロスチレンを安価かつ簡便な製造方法について、鋭意検討した結果、クロロペンタフルオロベンゼン又はブロモペンタフルオロベンゼンから誘導されるペンタフルオロ−亜鉛ハライドとビニルハライドをニッケル触媒存在下反応させることにより容易に２，３，４，５，６−ペンタフルオロスチレンが得られることを見出し、本発明を完成させるに至った。 The present inventor has diligently studied an inexpensive and simple method for producing 2,3,4,5,6-pentafluorostyrene, and as a result, pentafluoro-zinc halide derived from chloropentafluorobenzene or bromopentafluorobenzene. We have found that 2,3,4,5,6-pentafluorostyrene can be easily obtained by reacting vinyl halide with vinyl halide in the presence of a nickel catalyst, and have completed the present invention.
すなわち本発明は、以下の発明を提供するものである。
［１］ 下記一般式（１）
で表される、ペンタフルオロフェニル−亜鉛ハライドと、ビニルハライドとを、有機溶媒中、ニッケル触媒及び配位子存在下、反応させることを特徴とする、下記式（２）
［２］ 上記のペンタフルオロフェニル−亜鉛ハライドが、有機溶媒中、ブロモペンタフルオロベンゼン又はクロロペンタフルオロベンゼンとマグネシウムを反応させて得られるペンタフルオロマグネシウムハライドと、亜鉛ハロゲン化物とを反応させて得られる上記一般式（１）で表されるペンタフルオロフェニル−亜鉛ハライドである、２，３，４，５，６−ペンタフルオロスチレンの製造方法に係る。
［３］ 上記のペンタフルオロフェニル−亜鉛ハライドが、有機溶媒中、ブロモペンタフルオロベンゼン又はペンタフルオロヨードベンゼンと亜鉛を反応させて得られる上記一般式（１）で表されるペンタフルオロフェニル−亜鉛ハライドである、２，３，４，５，６−ペンタフルオロスチレンの製造方法に係る。
［４］ ニッケル触媒が、０価のニッケル触媒であることを特徴とする、上記［１］〜［３］のいずれかに記載の２，３，４，５，６−ペンタフルオロスチレンの製造方法。
［５］ ２価のニッケル触媒と配位子の混合溶液にアルキルマグネシウムハライドを添加し調製した０価のニッケル触媒であることを特徴とする、上記［１］〜［４］のいずれかに記載の２，３，４，５，６−ペンタフルオロスチレンの製造方法。
［６］ 配位子が、１，３−ビス（ジフェニルホスフィノ）プロパンであることを特徴とする、上記［１］〜［５］のいずれかに記載の２，３，４，５，６−ペンタフルオロスチレンの製造方法。
That is, the present invention provides the following inventions.
[1] The following general formula (1)
The following formula (2) is characterized in that a pentafluorophenyl-zinc halide represented by the above is reacted with a vinyl halide in an organic solvent in the presence of a nickel catalyst and a ligand.
[2] The above pentafluorophenyl-zinc halide is obtained by reacting a pentafluoromagnesium halide obtained by reacting bromopentafluorobenzene or chloropentafluorobenzene with magnesium in an organic solvent and a zinc halide. The present invention relates to a method for producing 2,3,4,5,6-pentafluorostyrene, which is a pentafluorophenyl-zinc halide represented by the general formula (1).
[3] The above pentafluorophenyl-zinc halide is obtained by reacting bromopentafluorobenzene or pentafluoroiodobenzene with zinc in an organic solvent, and is represented by the above general formula (1). The present invention relates to a method for producing 2,3,4,5,6-pentafluorostyrene.
[4] The method for producing 2,3,4,5,6-pentafluorostyrene according to any one of the above [1] to [3], wherein the nickel catalyst is a zero-valent nickel catalyst. ..
[5] The description according to any one of [1] to [4] above, which is a 0-valent nickel catalyst prepared by adding an alkylmagnesium halide to a mixed solution of a divalent nickel catalyst and a ligand. 2,3,4,5,6-Pentafluorostyrene production method.
[6] The 2,3,4,5,6 according to any one of the above [1] to [5], wherein the ligand is 1,3-bis (diphenylphosphino) propane. -A method for producing pentafluorostyrene.
本発明により、２，３，４，５，６−ペンタフルオロスチレンの経済的かつ簡便な、より工業的な製造が可能となった。 INDUSTRIAL APPLICABILITY According to the present invention, economical, simple and more industrial production of 2,3,4,5,6-pentafluorostyrene has become possible.
以下、本発明を詳細に説明する。
本発明のペンタフルオロフェニル−亜鉛ハライドとしては、具体的には例えば、ペンタフルオロフェニル−亜鉛フルオリド、ペンタフルオロフェニル−亜鉛クロリド、ペンタフルオロフェニル−亜鉛ブロミド、ペンタフルオロフェニル−亜鉛ヨージド等が挙げられる。
これらを製造するには、通常、クロロペンタフルオロベンゼン又はブロモペンタフルオロベンゼンとマグネシウムの反応により得られるペンタフルオロフェニルマグネシウムハライドと、フッ化亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛等の亜鉛ハライドとを、テトラヒドフラン（以下ＴＨＦと略す）等のエーテル系溶媒中で、０℃〜２５℃の温度範囲で、１時間〜２４時間反応させることにより得ることができる。あるいは、、ブロモペンタフルオロベンゼンやペンタフルオロヨードベンゼンと、亜鉛粉末とを、ＴＨＦ等の有機溶媒中で、０℃〜６０℃の温度範囲で、１時間〜２４時間反応させることにより得ることができる。
Hereinafter, the present invention will be described in detail.
Specific examples of the pentafluorophenyl-zinc halide of the present invention include pentafluorophenyl-zinc fluoride, pentafluorophenyl-zinc chloride, pentafluorophenyl-zinc bromide, and pentafluorophenyl-zinc iodide.
In order to produce these, usually, pentafluorophenylmagnesium halide obtained by the reaction of chloropentafluorobenzene or bromopentafluorobenzene and magnesium, and zinc halides such as zinc fluoride, zinc chloride, zinc bromide and zinc iodide are used. Can be obtained by reacting in an ether-based solvent such as tetrahydrofuran (hereinafter abbreviated as THF) in a temperature range of 0 ° C to 25 ° C for 1 hour to 24 hours. Alternatively, it can be obtained by reacting bromopentafluorobenzene or pentafluoroiodobenzene with zinc powder in an organic solvent such as THF in a temperature range of 0 ° C to 60 ° C for 1 hour to 24 hours. ..
本発明に適用可能なビニルハライドとしては、具体的には例えば、塩化ビニル、臭化ビニル、ヨウ化ビニル等が挙げられ、反応に具するペンタフルオロフェニル−亜鉛ハライド１．０モルに対して、１．０モル〜１．５モル使用すると良い。 Specific examples of the vinyl halide applicable to the present invention include vinyl chloride, vinyl bromide, vinyl iodide and the like, with respect to 1.0 mol of pentafluorophenyl-zinc halide used in the reaction. It is recommended to use 1.0 mol to 1.5 mol.
本発明に適用可能なニッケル触媒としては、具体的には例えば、塩化ニッケル（ＩＩ）、臭化ニッケル（ＩＩ）、ヨウ化ニッケル（ＩＩ）、ビス（トリフルオロ酢酸）ニッケル（ＩＩ）、トリフルオロメタンスルホン酸ニッケル（ＩＩ）、２−アミノ−５−メチルベンゼンスルホン酸ニッケル（ＩＩ）、塩化メタリルニッケル（ＩＩ）ダイマー、ビス（１，５−シクロオクタジエン）ニッケル（０）、ビス（シクロペンタジエニル）ニッケル（ＩＩ）、ビス（テトラメチルシクロペンタジエニル）ニッケル（ＩＩ）、ビス（ペンタメチルシクロペンタジエニル）ニッケル（ＩＩ）、ビス（エチルシクロペンタジエニル）ニッケル（ＩＩ）、ビス（イソプロピルシクロペンタジエニル）ニッケル（ＩＩ）等が挙げられ、反応に具するペンタフルオロフェニル−亜鉛ハライド１．０モルに対して、０．００１モル〜０．３００モル量使用すると良い。 Specific examples of the nickel catalyst applicable to the present invention include nickel (II) chloride, nickel (II) bromide, nickel (II) iodide, nickel (II) bis (trifluoroacetic acid), and trifluoromethane. Nickel (II) sulfonate, nickel (II) 2-amino-5-methylbenzene sulfonate, nickel chloride (II) dimer, bis (1,5-cyclooctadiene) nickel (0), bis (cyclopenta) Dienyl) Nickel (II), Bis (Tetramethylcyclopentadienyl) Nickel (II), Bis (Pentamethylcyclopentadienyl) Nickel (II), Bis (Eethylcyclopentadienyl) Nickel (II), Bis (Isopropylcyclopentadienyl) Nickel (II) and the like can be mentioned, and 0.001 mol to 0.300 mol is preferable with respect to 1.0 mol of pentafluorophenyl-zinc halide used for the reaction.
本発明に適用可能な配位子としては、具体的には例えば、トリ−ｔｅｒｔ−ブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、４，５−ビス（ジフェニルホスフィノ）−９，９−ジメチルキサンテン、ビス［２−（ジフェニルホスフィノ）フェニル］エーテル、（±）−２，２´−ビス（ジフェニルホスフィノ）−１，１´−ビナフチル、（Ｒ）−（＋）−２，２´−ビス（ジフェニルホスフィノ）−１，１´−ビナフチル、（Ｓ）−（−）−２，２´−ビス（ジフェニルホスフィノ）−１，１´−ビナフチル、１，２−ビス（ジフェニルホスフィノ）エタン、１，３−ビス（ジフェニルホスフィノ）プロパン、１，４−ビス（ジフェニルホスフィノ）ブタン、１，２−ビス（ジシクロヘキシルホスフィノ）エタン、トリ（２−フリル）ホスフィン、２−（ジシクロヘキシルホスフィノ）−２´，４´，６´−トリイソプロピルビフェニル、ジシクロヘキシルフェニルホスフィン、トリシクロヘキシルホスフィン、トリ−ｏ−トリルホスフィン、トリシクロペンチルホスフィン、１，１´−ビス（ジフェニルホスフィノ）フェロセン、１，１０−フェナントロリン等が挙げられる。
これらの配位子を選択する際、反応させる基質、反応の種類等により好ましい配位子が変わることがあるため、目的に応じてスクリーニングするとよい。
また、用いられる配位子の使用量としては、使用するパラジウム触媒１モルに対して、配位子中に含有されるリン原子又は窒素原子の個数換算で、１．０モル〜３．０モル使用すると良い。
Specific examples of the ligand applicable to the present invention include tri-tert-butylphosphine, methyldiphenylphosphine, triphenylphosphine, and 4,5-bis (diphenylphosphine) -9,9-dimethylxanthene. , Bis [2- (diphenylphosphine) phenyl] ether, (±) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, (R)-(+) -2,2'- Bis (diphenylphosphino) -1,1'-binaphthyl, (S)-(-)-2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 1,2-bis (diphenylphosphino) ) Etan, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (dicyclohexylphosphino) ethane, tri (2-furyl) phosphine, 2- ( Dicyclohexylphosphine) -2', 4', 6'-triisopropylbiphenyl, dicyclohexylphenylphosphine, tricyclohexylphosphine, tri-o-trilphosphine, tricyclopentylphosphine, 1,1'-bis (diphenylphosphine) ferrocene, 1,10-phenanthroline and the like can be mentioned.
When selecting these ligands, the preferred ligand may change depending on the substrate to be reacted, the type of reaction, and the like, so screening may be performed according to the purpose.
The amount of the ligand used is 1.0 mol to 3.0 mol in terms of the number of phosphorus atoms or nitrogen atoms contained in the ligand with respect to 1 mol of the palladium catalyst used. Good to use.
また、これら配位子等とニッケルとをあらかじめ反応させたニッケル錯体やさらにそのニッケル錯体の誘導体として知られている、具体的には例えば、ビス（トリフェニルホスフィン）ニッケル（ＩＩ）ジクロリド、ビス（トリフェニルホスフィン）ニッケル（ＩＩ）ジブロミド、ビス（トリフェニルホスフィン）ニッケル（ＩＩ）ジヨージド、ビス（トリフェニルホスフィン）ニッケル（ＩＩ）ジカルボニル、ビス（ジシクロヘキシルフェニルホスフィン）ニッケル（ＩＩ）ジクロリド、ビス[ジシクロヘキシル（フェニル）ホスフィノ]（ｏ−トリル）ニッケル（ＩＩ）ジクロリド、ビス（トリシクロホスフィン）ニッケル（ＩＩ）ジクロリド、［１，１´−ビス（ジフェニルホスフィノ）フェロセン］ニッケル（ＩＩ）ジクロリド、［１，２−ビス（ジフェニルホスフィノ）エタン］ニッケル（ＩＩ）ジクロリド、［１，３−ビス（ジフェニルホスフィノ）プロパン］ニッケル（ＩＩ）ジクロリド、ブロモ［２，６−ピリジンジイル］ビス（３−メチル−１−イミダゾイル−２−イリデン］ニッケル（ＩＩ）ブロミド、［１，３−ビス（２，６−ジイソプロピルフェニル）イミダゾール−２−イリデン］トリフェニルホスフィンニッケル（ＩＩ）ジクロリド等を使用しても良く、これらニッケル錯体を使用する際は、反応に具するペンタフルオロフェニル−亜鉛ハライド１．０モルに対して、０．００１モル〜０．３００モル量使用すると良い。 Further, a nickel complex obtained by reacting these ligands and the like with nickel in advance and further known as a derivative of the nickel complex, specifically, for example, bis (triphenylphosphine) nickel (II) dichloride, bis ( Triphenylphosphine) nickel (II) dibromid, bis (triphenylphosphine) nickel (II) diyodide, bis (triphenylphosphine) nickel (II) dicarbonyl, bis (dicyclohexylphenylphosphine) nickel (II) dichloride, bis [dicyclohexyl) (Phenyl) phosphine] (o-tril) nickel (II) dichloride, bis (tricyclophosphine) nickel (II) dichloride, [1,1'-bis (diphenylphosphine) ferrocene] nickel (II) dichloride, [1 , 2-Bis (diphenylphosphine) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphine) propane] nickel (II) dichloride, bromo [2,6-pyridinediyl] bis (3-methyl) -1-imidazolyl-2-iriden] nickel (II) bromide, [1,3-bis (2,6-diisopropylphenyl) imidazol-2-iriden] triphenylphosphine nickel (II) dichloride or the like may be used. When these nickel complexes are used, it is preferable to use 0.001 mol to 0.300 mol with respect to 1.0 mol of pentafluorophenyl-zinc halide used in the reaction.
本発明の実施に当たって、２価のニッケル触媒を使用する場合は、あらかじめ、２価のニッケル触媒と配位子の混合溶液に、所定量のアルキルマグネシウムハライドを添加し、還元し、０価のニッケル触媒を発生させた後に使用する。
本発明の実施に当たって、２価のニッケル触媒を０価に還元する際に、適用可能なアルキルマグネシウムハライドとしては、具体的には例えば、メチルマグネシウムクロリド、メチルマグネシウムブロミド、メチルマグネシウムヨージド、エチルマグネシウムクロリド、エチルマグネシウムブロミド、エチルマグネシウムヨージド、ｎ−プロピルマグネシウムクロリド、ｎ−プロピルマグネシウムブロミド、ｎ−プロピルマグネシウムヨージド、ｉｓｏ−プロピルマグネシウムクロリド、ｉｓｏ−プロピルマグネシウムブロミド、ｉｓｏ−プロピルマグネシウムヨージド、ｎ−ブチルマグネシウムクロリド、ｎ−ブチルマグネシウムブロミド、ｎ−ブチルマグネシウムヨージド、ｔｅｒｔ−ブチルマグネシウムクロリド、ｔｅｒｔ−ブチルマグネシウムブロミド、ｔｅｒｔ−ブチルマグネシウムヨージド等が挙げられ、反応に具する２価のニッケル触媒１モルに対して、２．０モル〜２．５モル量使用すると良い。
When a divalent nickel catalyst is used in carrying out the present invention, a predetermined amount of alkylmagnesium halide is added to a mixed solution of the divalent nickel catalyst and the ligand in advance, and the mixture is reduced to obtain zero-valent nickel. Used after generating the catalyst.
In carrying out the present invention, specific examples of the alkylmagnesium halide that can be applied when reducing a divalent nickel catalyst to zero valence include methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, and ethylmagnesium. Chloride, Ethyl Magnesium Bromide, Ethyl Magnesium Iodide, n-propyl Magnesium Chloride, n-propyl Magnesium Bromide, n-propyl Magnesium Iodide, iso-propyl Magnesium Chloride, iso-propyl Magnesium Bromide, iso-propyl Magnesium Iodide, n -Butylmagnesium chloride, n-butylmagnesium bromide, n-butylmagnesium iodide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, tert-butylmagnesium iodide and the like can be mentioned as divalent nickel catalysts for the reaction. It is advisable to use 2.0 mol to 2.5 mol per 1 mol.
本発明の実施に当たって、必要に応じて反応を促進する目的で、塩化リチウム、Ｎ−メチルイミダゾール（以下、ＮＭＩと略す）、Ｎ，Ｎ，Ｎ，Ｎ−テトラメチルエチレンジアミン等の副資材を添加してもよく、反応に使用するニッケル触媒１．０モルに対して、０．１モル〜３．０モル使用すると良い。 In carrying out the present invention, auxiliary materials such as lithium chloride, N-methylimidazole (hereinafter abbreviated as NMI), N, N, N and N-tetramethylethylenediamine are added for the purpose of accelerating the reaction as necessary. It may be preferable to use 0.1 mol to 3.0 mol with respect to 1.0 mol of the nickel catalyst used for the reaction.
本発明に適用可能な溶剤としては、反応に不活性なものであれば特に規定はないが、好ましくは、ＴＨＦ、ＴＨＦとＮ-メチルピリリドン（以下、ＮＭＰと略す）の混合溶剤、ＴＨＦとジオキサンの混合溶剤等で、反応に具するペンタフルオロフェニル−亜鉛ハライドの重量に対して、４重量倍量〜１００重量倍量使用すると良い。混合溶剤を用いる場合のＴＨＦと他の溶剤の量比は特に規定はないが、ＴＨＦ／他溶剤の重量比が、１０／１〜１／１の範囲が好ましい。 The solvent applicable to the present invention is not particularly specified as long as it is inert to the reaction, but is preferably carried out with THF, a mixed solvent of THF and N-methylpyrryridone (hereinafter abbreviated as NMP), and THF. It is preferable to use a mixed solvent of dioxane in an amount of 4 to 100 times by weight with respect to the weight of pentafluorophenyl-zinc halide used in the reaction. The amount ratio of THF to other solvents when a mixed solvent is used is not particularly specified, but the weight ratio of THF / other solvents is preferably in the range of 10/1 to 1/1.
本発明の反応温度及び時間は、使用するビニルハライド、ニッケル触媒、配位子及び溶剤により異なるが、通常、３０℃〜９０℃の温度範囲で、５時間〜４８時間反応を行うことにより、反応は完結する。 The reaction temperature and time of the present invention vary depending on the vinyl halide, nickel catalyst, ligand and solvent used, but usually, the reaction is carried out by carrying out the reaction in a temperature range of 30 ° C. to 90 ° C. for 5 hours to 48 hours. Is complete.
本発明の製造後の後処理としては、周知の方法で実施可能で、水を添加しニッケル等を析出させ、ろ別した後、濃縮、蒸留することにより、目的物の２，３，４，５，６−ペンタフルオロスチレンを得ることが可能である。目的物の２，３，４，５，６−ペンタフルオロスチレンは自己重合性の化合物のため、反応後の後処理操作時及び保管時に、ジブチルヒドロキシトルエンや４−ｔｅｒｔ−ブチルカテコール等の重合禁止剤を０．０１重量％〜１．００重量％添加しても良い。 The post-production post-treatment of the present invention can be carried out by a well-known method. Water is added to precipitate nickel and the like, the mixture is filtered, and then concentrated and distilled to concentrate, 3, 4, and the target product. It is possible to obtain 5,6-pentafluorostyrene. Since the target product 2,3,4,5,6-pentafluorostyrene is a self-polymerizable compound, polymerization of dibutylhydroxytoluene, 4-tert-butylcatechol, etc. is prohibited during post-treatment operations and storage after the reaction. The agent may be added in an amount of 0.01% by weight to 1.00% by weight.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
なお、分析には下記機器を使用した。
１Ｈ−ＮＭＲ （４００ ＭＨｚ）， １９Ｆ−ＮＭＲ （３７６ ＭＨｚ）， １３Ｃ−ＮＭＲ （１００ ＭＨｚ）：ブルカー製アバンス４００（Ｂｕｒｕｋｅｒ Ａｖａｎｃｅ ４００）。
ＧＣＭＳ（ＥＩ）：島津製作所製ＧＣＭＳ−ＱＰ２０１０Ｐｌｕｓ。
The following equipment was used for the analysis.
1 1 H-NMR (400 MHz), 19 F-NMR (376 MHz), 13 C-NMR (100 MHz): Bruker Avance 400.
GCMS (EI): GCMS-QP2010Plus manufactured by Shimadzu Corporation.
参考例１ ペンタフルオロフェニル−亜鉛クロリドの調製（調製法１）
マグネット撹拌子を備えた５０ｍＬのナス型フラスコに、マグネシウム（０．２３６ｇ，９．７１８ｍｍｏｌ）、ヨウ素（０．００５ｇ，０．０２０ｍｍｏｌ）を入れ、窒素置換した後、ＴＨＦ（２０ｍＬ）を添加し、室温下、１時間撹拌した。
次いで、これを氷浴上、５℃に冷却し、ブロモペンタフルオロベンゼン（２．０００ｇ，８．０９８ｍｍｏｌ）を１．５時間かけて滴下した後、室温下、さらに１時間撹拌し、ペンタフルオロフェニル−マグネシウムブロミドを調製した。
マグネット撹拌子を備えた１００ｍＬのナス型フラスコを、窒素置換下後、塩化亜鉛（１．５４６ｇ，１１．３４ｍｍｏｌ）及びＴＨＦ（２０ｍＬ）を仕込み、氷浴上、５℃に冷却した後、これに先に調製したペンタフルオロフェニル−マグネシウムブロミドのＴＨＦ溶液を添加、さらに室温下、３時間撹拌し、目的物のペンタフルオロフェニル−亜鉛クロリドのＴＨＦ溶液を得た。
Reference Example 1 Preparation of pentafluorophenyl-zinc chloride (preparation method 1)
Magnesium (0.236 g, 9.718 mmol) and iodine (0.005 g, 0.020 mmol) were placed in a 50 mL eggplant-shaped flask equipped with a magnetic stir bar, and after nitrogen substitution, THF (20 mL) was added. The mixture was stirred at room temperature for 1 hour.
Then, this was cooled to 5 ° C. on an ice bath, bromopentafluorobenzene (2.000 g, 8.098 mmol) was added dropwise over 1.5 hours, and then the mixture was stirred at room temperature for another 1 hour to pentafluorophenyl. -Magnesium bromide was prepared.
A 100 mL eggplant-shaped flask equipped with a magnetic stirrer was charged with zinc chloride (1.546 g, 11.34 mmol) and THF (20 mL) after substituting with nitrogen, cooled to 5 ° C. on an ice bath, and then placed therein. The previously prepared THF solution of pentafluorophenyl-magnesium bromide was added, and the mixture was further stirred at room temperature for 3 hours to obtain a THF solution of the desired pentafluorophenyl-zinc chloride.
得られたペンタフルオロフェニル−亜鉛クロリドのＴＨＦ溶液を１９Ｆ−ＮＭＲで測定したところ、ペンタフルオロフェニル−亜鉛クロリド（ｍａｊｏｒ）と平衡関係で生成するビス（ペンタフルオロフェニル）−亜鉛（ｍｉｎｏｒ）のピークが観測され、（ｍａｊｏｒ）／（ｍｉｎｏｒ）比は、１．００／０．２３であった。
１９Ｆ−ＮＭＲ（ＣＤＣｌ３，３７６ＭＨｚ）δ（ｍａｊｏｒ）−１１７．６６−−１１７．７３（ｍ，２Ｆ），−１５７．１６−−１５７．５１（ｍ，１Ｆ），−１６２．４６−−１６２．５１（ｍ，２Ｆ），（ｍｉｎｏｒ）−１１８．３０−−１１８．３５（ｍ，２Ｆ），−１５７．１６（ｍ，１Ｆ），−１６２．４６−−１６２．５１（ｍ，２Ｆ）。
When the obtained THF solution of pentafluorophenyl-zinc chloride was measured by 19 F-NMR, the peak of bis (pentafluorophenyl) -zinc (minor) produced in equilibrium with pentafluorophenyl-zinc chloride (major). Was observed, and the (major) / (minor) ratio was 1.00 / 0.23.
19 F-NMR (CDCl 3 , 376 MHz) δ (major) -117.66--117.73 (m, 2F), 157.16-1577.51 (m, 1F), -162.46-- 162.51 (m, 2F), (minor) -118.30--118.35 (m, 2F), 157.16 (m, 1F), 162.46-162.51 (m, 2F) ).
参考例２ ペンタフルオロフェニル−亜鉛クロリドの調製（調製法２）
マグネット撹拌子を備えた５０ｍＬのナス型フラスコに、マグネシウム（０．２３６ｇ，９．７１８ｍｍｏｌ）、ヨウ素（０．００５ｇ，０．０２０ｍｍｏｌ）を入れ、窒素置換した後、ＴＨＦ（２０ｍＬ）を添加し、室温下、１時間撹拌した。
次いで、これを氷浴上、５℃に冷却し、クロロペンタフルオロベンゼン（１．６４０ｇ，８．０９８ｍｍｏｌ）を１．５時間かけて滴下した後、室温下、さらに１時間撹拌し、ペンタフルオロフェニル−マグネシウムクロリドを調製した。
マグネット撹拌子を備えた１００ｍＬのナス型フラスコを、窒素置換下後、塩化亜鉛（１．５４６ｇ，１１．３４ｍｍｏｌ）及びＴＨＦ（２０ｍＬ）を仕込み、氷浴上、５℃に冷却した後、これに先に調製したペンタフルオロフェニル−マグネシウムクロリドのＴＨＦ溶液を添加、さらに室温下、３時間撹拌し、目的物のペンタフルオロフェニル−亜鉛クロリドのＴＨＦ溶液を得た。
Reference Example 2 Preparation of pentafluorophenyl-zinc chloride (preparation method 2)
Magnesium (0.236 g, 9.718 mmol) and iodine (0.005 g, 0.020 mmol) were placed in a 50 mL eggplant-shaped flask equipped with a magnetic stir bar, and after nitrogen substitution, THF (20 mL) was added. The mixture was stirred at room temperature for 1 hour.
Next, this was cooled to 5 ° C. on an ice bath, chloropentafluorobenzene (1.640 g, 8.098 mmol) was added dropwise over 1.5 hours, and then the mixture was stirred at room temperature for another 1 hour to pentafluorophenyl. -Magnesium chloride was prepared.
A 100 mL eggplant-shaped flask equipped with a magnetic stirrer was charged with zinc chloride (1.546 g, 11.34 mmol) and THF (20 mL) after substituting with nitrogen, cooled to 5 ° C. on an ice bath, and then placed therein. The previously prepared THF solution of pentafluorophenyl-magnesium chloride was added, and the mixture was further stirred at room temperature for 3 hours to obtain a THF solution of the desired pentafluorophenyl-zinc chloride.
得られたペンタフルオロフェニル−亜鉛クロリドのＴＨＦ溶液を１９Ｆ−ＮＭＲで測定したところ、ペンタフルオロフェニル−亜鉛クロリド（ｍａｊｏｒ）と平衡関係で生成するビス（ペンタフルオロフェニル）−亜鉛（ｍｉｎｏｒ）のピークが観測され、（ｍａｊｏｒ）／（ｍｉｎｏｒ）比は、１．００／０．２５であった。
１９Ｆ−ＮＭＲ（ＣＤＣｌ３，３７６ＭＨｚ）δ（ｍａｊｏｒ）−１１７．６６−−１１７．７３（ｍ，２Ｆ），−１５７．１６−−１５７．５１（ｍ，１Ｆ），−１６２．４６−−１６２．５１（ｍ，２Ｆ），（ｍｉｎｏｒ）−１１８．３０−−１１８．３５（ｍ，２Ｆ），−１５７．１６（ｍ，１Ｆ），−１６２．４６−−１６２．５１（ｍ，２Ｆ）。
When the obtained THF solution of pentafluorophenyl-zinc chloride was measured by 19 F-NMR, the peak of bis (pentafluorophenyl) -zinc (minor) produced in equilibrium with pentafluorophenyl-zinc chloride (major). Was observed, and the (major) / (minor) ratio was 1.00 / 0.25.
19 F-NMR (CDCl 3 , 376 MHz) δ (major) -117.66--117.73 (m, 2F), 157.16-1577.51 (m, 1F), -162.46-- 162.51 (m, 2F), (minor) -118.30--118.35 (m, 2F), 157.16 (m, 1F), 162.46-162.51 (m, 2F) ).
参考例３ ペンタフルオロフェニル−亜鉛ブロミドの調製（調製法３）
マグネット撹拌子を備えた５０ｍＬのナス型フラスコを、窒素置換した後、亜鉛（０．５５６ｇ，８．５０４ｍｍｏｌ）、ＴＨＦ（２０ｍＬ）及びトリメチルシリルクロリド（１０μＬ）を添加し、室温下、３０分撹拌した。
次いで、ブロモペンタフルオロベンゼン（２．０００ｇ，８．０９８ｍｍｏｌ）を同温度で添加した後、４０℃で４時間反応を行い、目的物のペンタフルオロフェニル−亜鉛ブロミドのＴＨＦ溶液を得た。
Reference Example 3 Preparation of pentafluorophenyl-zinc bromide (preparation method 3)
A 50 mL eggplant-shaped flask equipped with a magnetic stirrer was replaced with nitrogen, zinc (0.556 g, 8.504 mmol), THF (20 mL) and trimethylsilyl chloride (10 μL) were added, and the mixture was stirred at room temperature for 30 minutes. ..
Then, bromopentafluorobenzene (2.000 g, 8.098 mmol) was added at the same temperature, and then the reaction was carried out at 40 ° C. for 4 hours to obtain a THF solution of the desired pentafluorophenyl-zinc bromide.
得られたペンタフルオロフェニル−亜鉛ブロミドのＴＨＦ溶液を１９Ｆ−ＮＭＲで測定したところ、ペンタフルオロフェニル−亜鉛ブロミド（ｍａｊｏｒ）と平衡関係で生成するビス（ペンタフルオロフェニル）−亜鉛（ｍｉｎｏｒ）のピークが観測され、（ｍａｊｏｒ）／（ｍｉｎｏｒ）比は、１．００／０．３５であった。
１９Ｆ−ＮＭＲ（ＣＤＣｌ３，３７６ＭＨｚ）δ（ｍａｊｏｒ）−１１７．８３−−１１７．９７（ｍ，２Ｆ），−１５６．５７（ｔ，１Ｆ，Ｊ＝１９．２Ｈｚ），−１６２．０６−−１６２．１９（ｍ，２Ｆ），（ｍｉｎｏｒ）−１１８．３１−−１１８．４２（ｍ，２Ｆ），−１５７．４４（ｔ，１Ｆ，１９．２Ｈｚ），−１６２．４３−−１６２．４８（ｍ，２Ｆ）。
When the obtained THF solution of pentafluorophenyl-zinc bromide was measured by 19 F-NMR, the peak of bis (pentafluorophenyl) -zinc (minor) produced in equilibrium with pentafluorophenyl-zinc bromide (major). Was observed, and the (major) / (minor) ratio was 1.00 / 0.35.
19 F-NMR (CDCl 3 , 376 MHz) δ (major) -117.83-117.97 (m, 2F), -156.57 (t, 1F, J = 19.2 Hz), -162.06- -162.19 (m, 2F), (minor) -118.31--118.42 (m, 2F), -157.44 (t, 1F, 19.2Hz), -162.43-162. 48 (m, 2F).
実施例１ ２，３，４，５，６−ペンタフルオロスチレンの調製
マグネット撹拌子を備えた１００ｍＬのナス型フラスコに、塩化ニッケル（ＩＩ）（０．１０５ｇ，０．８１０ｍｍｏｌ）、１，３−ビス（ジフェニルホスフィノ）プロパン（０．３３４ｇ，０．８１０ｍｍｏｌ）を仕込み、窒素置換した後、ＴＨＦ（３０ｍＬ）を添加し、室温下、３０分攪拌した。次いでこれに、エチルマグネシウムブロミド（１．０Ｍ−ＴＨＦ溶液，１．７８ｍＬ，１．７８ｍｍｏｌ）を添加、１０分撹拌し、０価のニッケル触媒溶液を調製した。
別のマグネット撹拌子を備えた１００ｍＬのナス型フラスコで、参考例１と同じ方法で、ブロモペンタフルオロベンゼン（２．０００ｇ，８．０９８ｍｍｏｌ）より調製した、ペンタフルオロフェニル亜鉛クロリドのＴＨＦ（４０ｍＬ）溶液に、室温下、塩化ビニル（０．６０７ｇ,９．７１８ｍｍｏｌ）を供給し、吸収させた。次いで、同混合物を６０℃に加熱した後、先に調製した０価のニッケル触媒溶液を３０分かけて添加し、同温度で２０時間反応を行った。
反応終了後、水（２ｍＬ）を添加し沈殿物を析出させ、有機層を分離の後、さらに沈殿物をイソプロピルエーテル（１０ｍＬ）で２回洗浄した。
Example 1 Preparation of 2,3,4,5,6-pentafluorostyrene Nickel (II) chloride (0.105 g, 0.810 mmol), 1,3- in a 100 mL eggplant-shaped flask equipped with a magnetic stir bar. Bis (diphenylphosphino) propane (0.334 g, 0.810 mmol) was charged, substituted with nitrogen, THF (30 mL) was added, and the mixture was stirred at room temperature for 30 minutes. Then, ethyl magnesium bromide (1.0 M-THF solution, 1.78 mL, 1.78 mmol) was added thereto, and the mixture was stirred for 10 minutes to prepare a zero-valent nickel-catalyzed solution.
THF (40 mL) of pentafluorophenyl zinc chloride prepared from bromopentafluorobenzene (2.000 g, 8.098 mmol) in the same manner as in Reference Example 1 in a 100 mL eggplant-shaped flask equipped with another magnet stir bar. Vinyl chloride (0.607 g, 9.718 mmol) was supplied to the solution at room temperature and absorbed. Then, after heating the mixture to 60 ° C., the previously prepared 0-valent nickel catalyst solution was added over 30 minutes, and the reaction was carried out at the same temperature for 20 hours.
After completion of the reaction, water (2 mL) was added to precipitate a precipitate, the organic layer was separated, and the precipitate was further washed twice with isopropyl ether (10 mL).
得られた有機層は合わせて、ベンゾトリフルオリドを内部標準物質として用いた１９Ｆ−ＮＭＲでの分析の結果、目的物の２，３，４，５−ペンタフルオロスチレン（１．１６３ｇ，５．９９２ｍｍｏｌ，収率７４％）が生成していた。
１Ｈ−ＮＭＲ（ＣＤＣｌ３，４００ＭＨｚ）δ６．６２（ｄｄ，１Ｈ，１８．０，１２．０Ｈｚ），６．０７（ｄ，１Ｈ，１８．０Ｈｚ），５．７１（ｄ，１Ｈ，１２．０Ｈｚ）ｐｐｍ。
１９Ｆ−ＮＭＲ（ＣＤＣｌ３，３７６ＭＨｚ）δ−１４３．９８（ｄｄ，２Ｆ，２１．１，７．９Ｈｚ），−１５６．７２（ｔ，１Ｆ，２０．７Ｈｚ），−１６３．６７−−１６３．８０（ｍ、２Ｆ）ｐｐｍ。
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）δ１４５．２０（ｄｍ，２４８．９Ｈｚ），１４０．４０（ｄｍ，２４４．５Ｈｚ），１３７．９３（ｄｍ，２５９．８Ｈｚ），１２３．６７（ｄｔ，５．４，２．３Ｈｚ），１２１．５８（ｄ，２．０Ｈｚ），１１２．４６（ｄｔ，９．６，４．２Ｈｚ）ｐｐｍ。
ＧＣＭＳ（ＥＩ，ｍ／ｚ）：１９４（Ｍ＋）。
The obtained organic layers were combined and analyzed by 19 F-NMR using benzotrifluoride as an internal standard. As a result, the target product was 2,3,4,5-pentafluorostyrene (1.163 g, 5. 992 mmol, yield 74%) was produced.
1 1 H-NMR (CDCl 3 , 400 MHz) δ6.62 (dd, 1H, 18.0, 12.0 Hz), 6.07 (d, 1H, 18.0 Hz), 5.71 (d, 1H, 12. 0 Hz) ppm.
19 F-NMR (CDCl 3 , 376 MHz) δ-143.98 (dd, 2F, 21.1, 7.9 Hz), -156.72 (t, 1F, 20.7 Hz), 163.67-163 .80 (m, 2F) ppm.
13 C-NMR (100 MHz, CDCl 3 ) δ145.20 (dm, 248.9 Hz), 140.40 (dm, 244.5 Hz), 137.93 (dm, 259.8 Hz), 123.67 (dt, 5). .4,2.3Hz), 121.58 (d, 2.0Hz), 112.46 (dt, 9.6, 4.2Hz) ppm.
GCMS (EI, m / z): 194 (M + ).
実施例２ ２，３，４，５，６−ペンタフルオロスチレンの調製
実施例１と同じ反応装置を用い、参考例３と同じ方法で、ブロモペンタフルオロベンゼン（２．０００ｇ，８．０９８ｍｍｏｌ）より調製した、ペンタフルオロフェニル亜鉛ブロミドのＴＨＦ（２０ｍＬ）溶液を用い、６０℃で３０時間反応を行った以外は実施例１と同じ操作を行い、目的物の２，３，４，５−ペンタフルオロスチレン（０．９７５ｇ，５．０２３ｍｍｏｌ，収率６２％）を得た。
Example 2 Preparation of 2,3,4,5,6-pentafluorostyrene Using the same reaction apparatus as in Example 1 and the same method as in Reference Example 3, from bromopentafluorobenzene (2.000 g, 8.098 mmol). Using the prepared solution of pentafluorophenylzinc bromide in THF (20 mL), the same operation as in Example 1 was carried out except that the reaction was carried out at 60 ° C. for 30 hours, and the target product was 2,3,4,5-pentafluoro. Styrene (0.975 g, 5.023 mmol, yield 62%) was obtained.
実施例３〜１０ ２，３，４，５，６−ペンタフルオロスチレンの調製
実施例１と同じ反応装置を用い、表１中に示した条件下、反応を行った。結果を表１中に示した。
なお、実施例３〜実施例８については、ニッケル触媒１モルに対して２．２モル量のエチルマグネシウムブロミド（１Ｍ−ＴＨＦ溶液）を用いて０価のニッケル触媒を発生させ、実施例９〜実施例１２については、ニッケル触媒１モルに対して２．１モル量のｉｓｏ−プロピルマグネシウムブロミド（１Ｍ−ＴＨＦ溶液）を用いて０価のニッケル触媒を発生させた。また、実施例１３〜実施例１５は、０価のニッケル触媒のため、そのまま用いた。
表１中の溶剤量には、アルキルマグネシウムハライド由来の量は考慮していない。
Preparation of Examples 3 to 10 2,3,4,5,6-pentafluorostyrene The reaction was carried out under the conditions shown in Table 1 using the same reaction apparatus as in Example 1. The results are shown in Table 1.
In Examples 3 to 8, a zero-valent nickel catalyst was generated using 2.2 mol of ethyl magnesium bromide (1 M-THF solution) with respect to 1 mol of the nickel catalyst, and Examples 9 to 9 were to be used. For Example 12, a zero-valent nickel catalyst was generated using 2.1 mol of iso-propylmagnesium bromide (1M-THF solution) with respect to 1 mol of the nickel catalyst. Moreover, since Examples 13 to 15 were 0-valent nickel catalysts, they were used as they were.
The amount of the solvent derived from alkylmagnesium halide is not taken into consideration in the amount of the solvent in Table 1.
１）パラジウム原子とリン原子のモル比を示す。
２）ブロモペンタフルオロベンゼン（１モル）に対する触媒のモル量を示す。
３）ブロモペンタフルオロベンゼン（１モル）に対するハロゲン化ビニルのモル量を示す。
４）１，２−ビス（ジフェニルホスフィノ）エタンの略号を示す。
５）トリフェニルホスフィンの略号を示す。
６）[１，３−ビス（ジフェニルホスフィノ）プロパン]ニッケル（ＩＩ）ジクロリドの略号を示す。
７）トリシクロヘキシルホスフィンの略号を示す。
８）１，２−ビス（ジシクロヘキシルホスフィノ）エタンの略号を示す。
９）トリシクロペンチルホスフィンの略号を示す。
１０）４，５−ビス（ジフェニルホスフィノ）−９，９−ジメチルキサンテンの略号を示す。
１１）２−（ジシクロヘキシルホスフィノ）−２´，４´，６´−トリイソプロピルビフェニルの略号を示す。
１２）[１，２−ビス（ジフェニルホスフィノ）エタン]ニッケル（ＩＩ）ジクロリドの略号を示す。
１３）１，３−ビス（ジフェニルホスフィノ）プロパンの略号を示す。
１４）ビス（１，５−シクロオクタジエン）ニッケル（０）の略号を示す。
1) The molar ratio of palladium atom and phosphorus atom is shown.
2) The molar amount of the catalyst with respect to bromopentafluorobenzene (1 mol) is shown.
3) The molar amount of vinyl halide with respect to bromopentafluorobenzene (1 mol) is shown.
4) The abbreviation for 1,2-bis (diphenylphosphino) ethane is shown.
5) The abbreviation for triphenylphosphine is shown.
6) [1,3-Bis (diphenylphosphino) propane] The abbreviation for nickel (II) dichloride is shown.
7) The abbreviation for tricyclohexylphosphine is shown.
8) The abbreviation for 1,2-bis (dicyclohexylphosphino) ethane is shown.
9) The abbreviation for tricyclopentylphosphine is shown.
10) The abbreviations for 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene are shown.
11) 2- (Dicyclohexylphosphino) -2', 4', 6'-The abbreviation for triisopropylbiphenyl is shown.
12) [1,2-Bis (diphenylphosphino) ethane] An abbreviation for nickel (II) dichloride.
13) The abbreviation for 1,3-bis (diphenylphosphino) propane is shown.
14) Bis (1,5-cyclooctadiene) Nickel (0) is an abbreviation.
本発明の方法で得られる２，３，４，５，６−ペンタフルオロスチレンは、光学材料、電子材料等の共重合用モノマーとして有用である。 The 2,3,4,5,6-pentafluorostyrene obtained by the method of the present invention is useful as a monomer for copolymerization of optical materials, electronic materials and the like.
Claims (6)
で表される、ペンタフルオロフェニル−亜鉛ハライドと、ビニルハライドとを、有機溶媒中、ニッケル触媒及び配位子存在下、反応させることを特徴とする、下記式（２）
The following formula (2) is characterized in that a pentafluorophenyl-zinc halide represented by the above is reacted with a vinyl halide in an organic solvent in the presence of a nickel catalyst and a ligand.
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