JP4423691B2 - Method for producing styrene derivative - Google Patents
Method for producing styrene derivative Download PDFInfo
- Publication number
- JP4423691B2 JP4423691B2 JP02178799A JP2178799A JP4423691B2 JP 4423691 B2 JP4423691 B2 JP 4423691B2 JP 02178799 A JP02178799 A JP 02178799A JP 2178799 A JP2178799 A JP 2178799A JP 4423691 B2 JP4423691 B2 JP 4423691B2
- Authority
- JP
- Japan
- Prior art keywords
- iron
- cobalt
- iii
- rhodium
- catalyst
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims 3
- 239000003054 catalyst Substances 0.000 claims description 70
- 239000007818 Grignard reagent Substances 0.000 claims description 43
- 150000004795 grignard reagents Chemical class 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 40
- -1 vinyl halide Chemical class 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 150000004677 hydrates Chemical class 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 claims description 2
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 2
- YNWSXIWHOSSPCO-UHFFFAOYSA-N rhodium(2+) Chemical compound [Rh+2] YNWSXIWHOSSPCO-UHFFFAOYSA-N 0.000 claims description 2
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 claims description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances 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 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 claims 1
- WEZJBAOYGIDDLB-UHFFFAOYSA-N cobalt(3+);borate Chemical compound [Co+3].[O-]B([O-])[O-] WEZJBAOYGIDDLB-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 80
- 239000000243 solution Substances 0.000 description 62
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 61
- 239000002904 solvent Substances 0.000 description 37
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 32
- 239000012299 nitrogen atmosphere Substances 0.000 description 31
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 30
- 238000010992 reflux Methods 0.000 description 27
- 239000000203 mixture Substances 0.000 description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 20
- 239000012044 organic layer Substances 0.000 description 19
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- 229910052749 magnesium Inorganic materials 0.000 description 18
- 239000011777 magnesium Substances 0.000 description 18
- 235000019270 ammonium chloride Nutrition 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 150000003440 styrenes Chemical class 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 15
- FIMHASWLGDDANN-UHFFFAOYSA-M methyl sulfate;tributyl(methyl)azanium Chemical compound COS([O-])(=O)=O.CCCC[N+](C)(CCCC)CCCC FIMHASWLGDDANN-UHFFFAOYSA-M 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 15
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 11
- 229910052740 iodine Inorganic materials 0.000 description 11
- 239000011630 iodine Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 9
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000011565 manganese chloride Substances 0.000 description 5
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VOKXPKSMYJLAIW-UHFFFAOYSA-N nickel;phosphane Chemical compound P.[Ni] VOKXPKSMYJLAIW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 231100000925 very toxic Toxicity 0.000 description 3
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CXWYTOFTBOZXGQ-UHFFFAOYSA-N (1,2-dichloro-2-diphenylphosphanylethyl)-diphenylphosphane;nickel Chemical compound [Ni].C=1C=CC=CC=1P(C=1C=CC=CC=1)C(Cl)C(Cl)P(C=1C=CC=CC=1)C1=CC=CC=C1 CXWYTOFTBOZXGQ-UHFFFAOYSA-N 0.000 description 1
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- GOSJVWAVTQTMGH-UHFFFAOYSA-N [Mn].[I] Chemical compound [Mn].[I] GOSJVWAVTQTMGH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZAENXHXQWSDUOG-UHFFFAOYSA-N benzene;iodine Chemical class [I].C1=CC=CC=C1 ZAENXHXQWSDUOG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N c1ccnc(-c2ccccn2)c1 Chemical compound c1ccnc(-c2ccccn2)c1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- FJNQKAYLLNDYTJ-UHFFFAOYSA-N cobalt(2+);diborate Chemical compound [Co+2].[Co+2].[Co+2].[O-]B([O-])[O-].[O-]B([O-])[O-] FJNQKAYLLNDYTJ-UHFFFAOYSA-N 0.000 description 1
- ZUKDFIXDKRLHRB-UHFFFAOYSA-K cobalt(3+);triacetate Chemical compound [Co+3].CC([O-])=O.CC([O-])=O.CC([O-])=O ZUKDFIXDKRLHRB-UHFFFAOYSA-K 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- ZQZQURFYFJBOCE-FDGPNNRMSA-L manganese(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Mn+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZQZQURFYFJBOCE-FDGPNNRMSA-L 0.000 description 1
- QMZIDZZDMPWRHM-UHFFFAOYSA-L manganese(2+);dibenzoate Chemical compound [Mn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QMZIDZZDMPWRHM-UHFFFAOYSA-L 0.000 description 1
- QOPRBRXXQMXHGV-UHFFFAOYSA-N manganese(2+);diborate Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] QOPRBRXXQMXHGV-UHFFFAOYSA-N 0.000 description 1
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、スチレン誘導体の製造方法に関する。更に詳しくは、芳香族ハロゲン化合物から調製したグリニャ−ル試薬を、触媒の存在下にビニルハライドと反応させて、スチレン誘導体を製造する方法に関するものである。
【０００２】
本発明の目的化合物であるスチレン誘導体は、機能性高分子、医農薬等の原料として非常に有用である。例えば、パラ−第三級−ブトキシスチレン（以下、ＰＴＢＳと略記する）は、超ＬＳＩ用途等に使用されるレジスト原料として極めて有効であることが知られている（特開昭５９−１９９７０５号公報、特開平３−２７７６０８号公報）。また、メタ−第三級−ブトキシスチレン（以下、ＭＴＢＳと略記する）は、機能性高分子、医農薬等の中間原料として有用であることが知られている（特開平２−１６０７３９号公報）。
【０００３】
【従来の技術】
ＰＴＢＳやＭＴＢＳのごときスチレン誘導体については、従来２通りの製造法が知られている。
【０００４】
即ち、米国特許第４，６０３，１０１号明細書及び特開昭５９−１９９７０５号公報においては、ハロスチレンから調製したグリニャ−ル試薬を過安息香酸−第三級−ブチルエステルと反応させる方法が開示されている。しかしながらこの方法は、反応収率が低いことに加えて、大量入手が困難で且つ爆発性を有する過安息香酸−第三級−ブチルエステルを必要とする問題があり、ＰＴＢＳやＭＴＢＳのごときスチレン誘導体を工業的に製造する方法としては満足できるものでない。
【０００５】
一方、特公平４−７１８９６号公報及び特開平２−１６０７３９号公報においては、第三級−ブトキシフェニルハライドから調製したグリニャ−ル試薬を、ニッケルホスフィン錯体触媒の存在下にビニルハライドと反応させる方法が開示されている。しかしながらこの方法では、反応収率は改善されるものの、高価で非常に毒性の強いニッケルホスフィン錯体触媒を必要とする問題がある。特公平４−７１８９６号公報及び特開平２−１６０７３９号公報には、この反応を収率良く進行させるためには、ジクロロ［１，２−ビス（ジフェニルホスフィノ）エタン］ニッケル、ジクロロ［１，３−ビス（ジフェニルホスフィノ）プロパン］ニッケル等の二座配位ホスフィン錯体が有効であると明記されているが、これらの触媒は高価で且つ非常に毒性の強い触媒である。したがって、本法を用いてもＰＴＢＳやＭＴＢＳのごときスチレン誘導体を経済性良く、安全に製造することは困難であり、本法もまたＰＴＢＳやＭＴＢＳのごときスチレン誘導体を工業的に製造する方法としては満足できるものではない。
【０００６】
【発明が解決しようとする課題】
本発明は上記の課題に鑑みてなされたものであり、その目的は、従来の方法では満足できなかったスチレン誘導体の工業的製造法を提供することにある。すなわち、ＰＴＢＳやＭＴＢＳのごときスチレン誘導体に関して、従来の問題点を解決し、経済性及び安全性に優れた工業的製造方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、従来の問題点を解決すべく鋭意検討した結果、第三級−ブトキシフェニルハライドから調製したグリニャ−ル試薬を、触媒の存在下にビニルハライドと反応させてＰＴＢＳやＭＴＢＳのごときスチレン誘導体を製造する方法において、特定の触媒を用いることにより、ＰＴＢＳやＭＴＢＳのごときスチレン誘導体を工業的規模で経済性良く、安全に製造することが可能となることを見出した。更に、本触媒法は、各種スチレン誘導体の製造にも有効なことを確認し、本発明を完成させるに至った。
【０００８】
即ち本発明は、芳香族ハロゲン化合物から調製したグリニャ−ル試薬を、触媒の存在下にビニルハライドと反応させて、スチレン誘導体を製造する方法において、触媒として、マンガン系触媒、鉄系触媒、コバルト系触媒及びロジウム系触媒からなる群より選ばれる一種又は二種以上の触媒を用いることを特徴とするスチレン誘導体の製造方法である。
【０００９】
以下、ＰＴＢＳの製造を例に、本発明を詳細に説明する。
【００１０】
本発明の方法において使用されるグリニャ−ル試薬は、芳香族ハロゲン化合物から調製したグリニャ−ル試薬であれば特に限定するものではなく、常法により容易に調製できる。即ち、溶媒中で金属マグネシウムとパラ−第三級−ブトキシフェニルハライドとを反応させる方法等を実施することにより、容易に調製できる。本調製反応では、活性化した金属マグネシウムを用いた場合、特に良好な結果が得られる。金属マグネシウムの活性化法としては、溶媒に懸濁させた金属マグネシウムを加熱攪拌する方法や、これに微量のヨウ素、ヨウ化メチルのようなヨウ化物、ジブロモエタンのような臭化物等を添加して攪拌する方法が有効である。
【００１１】
本発明の方法では、上記の方法で調製したグリニャ−ル試薬を、マンガン系触媒、鉄系触媒、コバルト系触媒及びロジウム系触媒からなる群より選ばれる一種又は二種以上の触媒の存在下にビニルハライドと反応させることにより、ＰＴＢＳを高収率で安価に安全に製造することが可能となる。
【００１２】
本発明の方法において使用されるビニルハライドは、フッ化ビニル、塩化ビニル、臭化ビニル、ヨウ化ビニルであり、これらを単独に又は混合物として使用することができる。通常は、経済性及び入手の容易さを考慮して塩化ビニルガス及び／又は臭化ビニルガスが選ばれる。
【００１３】
本発明の方法で使用される触媒は、マンガン系触媒、鉄系触媒、コバルト系触媒及びロジウム系触媒よりなる群から選ばれる一種又は二種以上の触媒である。
【００１４】
本発明の方法においてマンガン系触媒とは、マンガン元素を有効成分とする触媒をいい、特に限定するものではないが、例えば、マンガン粉末や、塩化マンガン（ＩＩ）、臭化マンガン（ＩＩ）、ヨウ化マンガン（ＩＩ）、フッ化マンガン（ＩＩ）、酢酸マンガン（ＩＩ）、酢酸マンガン（ＩＩＩ）、ギ酸マンガン（ＩＩ）、シュウ酸マンガン（ＩＩ）、安息香酸マンガン（ＩＩ）、ステアリン酸マンガン（ＩＩ）、ホウ酸マンガン（ＩＩ）、マンガン（ＩＩ）アセチルアセトナート、マンガン（ＩＩＩ）アセチルアセトナート、炭酸マンガン（ＩＩ）、硫酸マンガン（ＩＩ）、硝酸マンガン（ＩＩ）、リン酸マンガン（ＩＩ）等の化合物、それら化合物の水和物、又はそれら化合物から誘導される各種錯体触媒等が挙げられる。
【００１５】
本発明の方法において鉄系触媒とは、鉄元素を有効成分とする触媒のことをいい、特に限定するものではないが、例えば、ハロゲン化第一鉄、ハロゲン化第二鉄、ハロゲン化第一鉄から調製できる触媒、ハロゲン化第二鉄から調製できる触媒等が挙げられる。なお、本発明においてハロゲン化第一鉄から調製できる触媒とは、ハロゲン化第一鉄から誘導できる触媒又はハロゲン化第一鉄を有効成分とする触媒をいい、例えば、ハロゲン化第一鉄の水和物や各種錯体触媒が挙げられる。ハロゲン化第一鉄から調製できる触媒についても同様に定義され、例えば、ハロゲン化第二鉄の水和物や各種錯体触媒が挙げられる。
【００１６】
本発明の方法において鉄系触媒としては、具体的には、鉄粉や、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、臭化鉄（ＩＩ）、臭化鉄（ＩＩＩ）、ヨウ化鉄（ＩＩ）、フッ化鉄（ＩＩ）、フッ化鉄（ＩＩＩ）、酢酸鉄（ＩＩ）、シュウ酸鉄（ＩＩ）、シュウ酸鉄（ＩＩＩ）、クエン酸鉄（ＩＩＩ）、過塩素酸鉄（ＩＩＩ）、鉄（ＩＩＩ）アセチルアセトナート、硝酸鉄（ＩＩＩ）、リン酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸鉄（ＩＩ）等の化合物、それら化合物の水和物、又はそれら化合物から誘導される各種錯体触媒等が例示される。
【００１７】
本発明の方法においてコバルト系触媒とは、コバルト元素を有効成分とする触媒をいい、特に限定するものではないが、例えば、コバルト粉末や、塩化コバルト（ＩＩ）、臭化コバルト（ＩＩ）、ヨウ化コバルト（ＩＩ）、フッ化コバルト（ＩＩ）、酢酸コバルト（ＩＩ）、酢酸コバルト（ＩＩＩ）、ギ酸コバルト（ＩＩ）、シュウ酸コバルト（ＩＩ）、安息香酸コバルト（ＩＩ）、ステアリン酸コバルト（ＩＩ）、ホウ酸コバルト（ＩＩ）、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート、炭酸コバルト（ＩＩ）、硫酸コバルト（ＩＩ）、硝酸コバルト（ＩＩ）、リン酸コバルト（ＩＩ）等の化合物、それら化合物の水和物、又はそれら化合物から誘導される各種錯体触媒等が挙げられる。
【００１８】
本発明の方法においてロジウム系触媒とは、ロジウム元素を有効成分とする触媒をいい、特に限定するものではないが、例えば、ロジウム粉末やロジウム−カーボン、塩化ロジウム（ＩＩ）、臭化ロジウム（ＩＩ）、酢酸ロジウム（ＩＩ）、酢酸ロジウム（ＩＩＩ）、ロジウム（ＩＩ）アセチルアセトナート、ロジウム（ＩＩＩ）アセチルアセトナート等の化合物、それら化合物の水和物、又はそれら化合物から誘導される各種錯体触媒等が挙げられる。
【００１９】
本発明の方法においては、上記した触媒を単独に又は混合物として使用することができるが、ハロゲン化マンガン、酢酸マンガン、ハロゲン化鉄、酢酸鉄、ハロゲン化コバルト、酢酸コバルト、ハロゲン化ロジウム、及び酢酸ロジウムからなる群から選ばれる一種又は二種以上の触媒を用いた場合に、特に良好な結果（高収率）が得られる。なお、本発明の方法において使用される触媒の使用量については格別の限定はないが、通常、グリニヤ−ル試薬に対して１０-4〜１０-1倍モル程度の使用量が選ばれる。
【００２０】
前述した従来法（例えば、特公平４−７１８９６号公報記載の方法）は、高価で且つ非常に毒性の強いニッケルホスフィン錯体触媒を必要とする問題があり、ＰＴＢＳの工業的製造法としては満足できるものではなかった。本発明者らは、パラ−第三級−ブトキシフェニルハライドから調製したグリニャ−ル試薬とビニルハライドとの反応に対し、安価で安全な、マンガン系触媒、鉄系触媒、コバルト系触媒及びロジウム系触媒からなる群より選ばれる一種又は二種以上の触媒が有効であることを初めて見出した。これらのうち、ハロゲン化マンガン、酢酸マンガン、ハロゲン化鉄、酢酸鉄、ハロゲン化コバルト、酢酸コバルト、ハロゲン化ロジウム及び酢酸ロジウムからなる群より選ばれる一種又は二種以上の触媒は、非常に安価で安全な触媒であり、このような触媒を用いる本発明の方法は、ＰＴＢＳの工業的製造法として極めて有用である。
【００２１】
本発明の方法は、通常、窒素及び／又はアルゴン等の不活性ガス雰囲気下に、溶媒中で実施される。本発明の方法おいて使用される反応溶媒としては、エ−テル系溶媒、含酸素系溶媒、含窒素系溶媒、芳香族炭化水素系溶媒、脂肪族炭化水素系溶媒等が挙げられる。通常、これらの溶媒を単独に又は混合して使用することができるが、特にテトラヒドロフラン溶媒、又はテトラヒドロフランを含む混合溶媒を使用した場合に良好な結果（高収率）が得られる。また、本発明の方法は、通常０℃〜溶媒還流温度の条件下で実施される。
【００２２】
反応終了後は、常法に従い反応液に酸性水溶液を加えて処理した後、有機層を分離する。続いて、有機層を水洗処理した後、溶媒を留去して、これに第三級−ブチルカテコ−ル等の重合禁止剤を添加して蒸留することにより、目的とするＰＴＢＳを得る。
【００２３】
本発明の方法は、上述したＰＴＢＳ製造に留まらず、芳香族ハロゲン化合物からスチレン誘導体を製造する同種の反応に広く適用できるが、ＰＴＢＳやＭＴＢＳのごとき第三級−ブトキシスチレンの製造に適用した場合に、特に良好な結果（高収率）が得られる。尚、本発明の方法において言う芳香族ハロゲン化合物とは、芳香環の少なくとも一箇所がハロゲン置換された化合物の総称であり、例えば、フッ化ベンゼン誘導体、塩素化ベンゼン誘導体、臭素化ベンゼン誘導体、ヨウ素化ベンゼン誘導体等が挙げられる。
【００２４】
【発明の効果】
以上の説明から明らかなように本発明の方法によれば、従来の問題点を解決して、スチレン誘導体を工業的規模で経済性良く、安全に製造することが可能となる。
【００２５】
【実施例】
以下に、本発明の方法を実施例により具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。
【００２６】
参考例１
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラ−第三級−ブトキシブロモベンゼン１１．４６ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００２７】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化マンガン（ＩＩ）四水和物（ＭｎＣｌ2・４Ｈ2Ｏ）０．０５ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００２８】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析し、ＰＴＢＳ収率を求めた。反応結果を表１に示す。
【００２９】
【表１】
参考例２〜４、実施例５〜１４、参考例１５〜１７、実施例１８
参考例１で使用した塩化マンガン（ＩＩ）四水和物（０．２５ｍｍｏｌ）に代えて、表１に示した触媒（０．２５ｍｍｏｌ）を用いた以外は、実施例１の方法に準じて反応を行った。反応結果を表１にあわせて示す。
【００３１】
参考例１６
参考例１で使用した塩化マンガン（ＩＩ）四水和物（０．２５ｍｍｏｌ）に代えて、塩化マンガン（ＩＩ）四水和物０．０３ｇ（０．１３ｍｍｏｌ）及び塩化鉄（ＩＩＩ）０．０２ｇ（０．１３ｍｍｏｌ）の混合物を用いた以外は、参考例１の方法に準じて反応を行った。反応結果を表１にあわせて示す。
【００３２】
参考例１７
参考例１で使用した塩化マンガン（ＩＩ）四水和物（０．２５ｍｍｏｌ）に代えて、塩化マンガン（ＩＩ）四水和物０．０３ｇ（０．１３ｍｍｏｌ）及び塩化コバルト（ＩＩ）０．０２ｇ（０．１３ｍｍｏｌ）の混合物を用いた以外は、参考例１の方法に準じて反応を行った。反応結果を表１にあわせて示す。
【００３３】
実施例１８
参考例１で使用した塩化マンガン（ＩＩ）四水和物（０．２５ｍｍｏｌ）に代えて、塩化鉄（ＩＩＩ）０．０２ｇ（０．１３ｍｍｏｌ）及び塩化コバルト（ＩＩ）０．０２ｇ（０．１３ｍｍｏｌ）の混合物を用いた以外は、参考例１の方法に準じて反応を行った。反応結果を表１にあわせて示す。
【００３４】
比較例１〜比較例６
参考例１で使用した塩化マンガン（ＩＩ）四水和物（０．２５ｍｍｏｌ）に代えて、表１に示した触媒（０．２５ｍｍｏｌ）を用いた以外は、参考例１に準じて反応を行った。反応結果を表１にあわせて示す。
【００３５】
参考例１９
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、メタ−第三級−ブトキシブロモベンゼン１１．４６ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００３６】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に酢酸マンガン（ＩＩ）四水和物［Ｍｎ（ＣＨ3ＣＯ2）2・４Ｈ2Ｏ］０．０６ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００３７】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、ＭＴＢＳが８１．８％の収率で生成していた。
【００３８】
参考例２０
窒素雰囲気で置換した１００ｍｌフラスコに、ジエチルエーテル１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を２０〜３０℃に保ちながら、メタ−第三級−ブトキシブロモベンゼン１１．４６ｇ（５０ｍｍｏｌ）をジエチルエーテル２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００３９】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に酢酸マンガン（ＩＩ）四水和物［Ｍｎ（ＣＨ3ＣＯ2）2・４Ｈ2Ｏ］０．０６ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００４０】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、ＭＴＢＳが７１．３％の収率で生成していた。
【００４１】
参考例２１
窒素雰囲気で置換した１００ｍｌフラスコに、ジブチルエーテル１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、メタ−第三級−ブトキシブロモベンゼン１１．４６ｇ（５０ｍｍｏｌ）をジブチルエーテル２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００４２】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に酢酸マンガン（ＩＩ）四水和物［Ｍｎ（ＣＨ3ＣＯ2）2・４Ｈ2Ｏ］０．０６ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００４３】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、ＭＴＢＳが６８．９％の収率で生成していた。
【００４４】
実施例２２
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、メタ−第三級−ブトキシブロモベンゼン１１．４６ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャール試薬を得た。
【００４５】
上記の操作によって得られたグリニャール試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化コバルト（ＩＩ）（ＣｏＣｌ2）０．０３ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００４６】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィーで分析した結果、ＭＴＢＳが８０．４％の収率で生成していた。
【００４７】
実施例２３
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム２．６８ｇ（１１０ｍｍｏｌ）、臭化エチル０．６５ｇ（６ｍｍｏｌ）を仕込み、溶媒還流条件下で２０分間攪拌した。続いて、溶媒還流条件下で、メタ−第三級−ブトキシクロロベンゼン１８．４７ｇ（１００ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を、約２時間かけて滴下した。更に、溶媒還流条件下で３時間攪拌し、グリニャ−ル試薬を得た。
【００４８】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化鉄（ＩＩ）（ＦｅＣｌ2）０．１３ｇ（１ｍｍｏｌ）、テトラヒドロフラン２０ｍｌを加えた後、反応温度を４０〜５０℃に保ちながら塩化ビニルガス６．８８ｇ（１１０ｍｍｏｌ）を３時間かけて吹き込み、更に同温度で３０分間攪拌を行った。
【００４９】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、ＭＴＢＳが８３．３％の収率で生成していた。
【００５０】
実施例２４
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム２．６８ｇ（１１０ｍｍｏｌ）、臭化エチル０．６５ｇ（６ｍｍｏｌ）を仕込み、溶媒還流条件下で２０分間攪拌した。続いて、溶媒還流条件下で、メタ−第三級−ブトキシクロロベンゼン１８．４７ｇ（１００ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を、約２時間かけて滴下した。更に、溶媒還流条件下で３時間攪拌し、グリニャ−ル試薬を得た。
【００５１】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化鉄（ＩＩ）（ＦｅＣｌ2）０．１３ｇ（１ｍｍｏｌ）、トルエン２０ｍｌを加えた後、反応温度を４０〜５０℃に保ちながら塩化ビニルガス６．８８ｇ（１１０ｍｍｏｌ）を３時間かけて吹き込み、更に同温度で３０分間攪拌を行った。
【００５２】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、ＭＴＢＳが８１．９％の収率で生成していた。
【００５３】
参考例２５
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラブロモトルエン８．５５ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００５４】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化マンガン（ＩＩ）四水和物（ＭｎＣｌ2・４Ｈ2Ｏ）０．０５ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００５５】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、パラメチルスチレンが６４．１％の収率で生成していた。
【００５６】
実施例２６
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラブロモトルエン８．５５ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャール試薬を得た。
【００５７】
上記の操作によって得られたグリニャール試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化コバルト（ＩＩ）（ＣｏＣｌ2）０．０３ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００５８】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィーで分析した結果、パラメチルスチレンが６４．３％の収率で生成していた。
【００５９】
実施例２７
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム２．６８ｇ（１１０ｍｍｏｌ）、臭化エチル０．６５ｇ（６ｍｍｏｌ）を仕込み、溶媒環流条件下で２０分間攪拌した。続いて、溶媒環流条件下で、パラクロロトルエン１２．６６ｇ（１００ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を、約２時間をかけて滴下した。更に、溶媒還流条件下で３時間攪拌し、グリニャ−ル試薬を得た。
【００６０】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化鉄（ＩＩ）（ＦｅＣｌ2）０．１３ｇ（１ｍｍｏｌ）、テトラヒドロフラン２０ｍｌを加えた後、反応温度を４０〜５０℃に保ちながら塩化ビニルガス６．８８ｇ（１１０ｍｍｏｌ）を約３時間かけて吹き込み、更に同温度で３０分攪拌を行った。
【００６１】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、パラメチルスチレンが６４．３％の収率で生成していた。
【００６２】
参考例２８
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラブロモクロロベンゼン９．５７ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００６３】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に酢酸マンガン（ＩＩ）四水和物［Ｍｎ（ＣＨ3ＣＯ2）２・４Ｈ2Ｏ］０．０６ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００６４】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、パラクロロスチレンが６０．７％の収率で生成していた。
【００６５】
実施例２９
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラブロモクロロベンゼン９．５７ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００６６】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化コバルト（ＩＩ）（ＣｏＣｌ2）０．０３ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００６７】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、パラクロロスチレンが６７．１％の収率で生成していた。
【００６８】
実施例３０
窒素雰囲気で置換した１００ｍｌフラスコに、ジブチルエーテル１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラブロモクロロベンゼン９．５７ｇ（５０ｍｍｏｌ）をジブチルエーテル２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００６９】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化コバルト（ＩＩ）（ＣｏＣｌ2）０．０３ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００７０】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、パラクロロスチレンが５５．４％の収率で生成していた。
【００７１】
実施例３１
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム１．３４ｇ（５５ｍｍｏｌ）、ヨウ素１片を仕込み、室温条件下で攪拌した。ヨウ素の色が消えるのを確認した後、反応液を４０〜５０℃に保ちながら、パラブロモクロロベンゼン９．５７ｇ（５０ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約１時間かけて滴下した。更に、溶媒還流条件下で１時間攪拌し、グリニャ−ル試薬を得た。
【００７２】
上記の操作によって得られたグリニャ−ル試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化ロジウム（ＩＩＩ）三水和物（ＲｈＣｌ3・３Ｈ2Ｏ）０．０７ｇ（０．２５ｍｍｏｌ）を加えた後、反応温度を２０〜３０℃に保ちながら塩化ビニルガス３．４４ｇ（５５ｍｍｏｌ）を１０分間かけて吹き込み、更に同温度で１時間攪拌を行った。
【００７３】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィ−で分析したところ、パラクロロスチレンが６４．８％の収率で生成していた。
【００７４】
実施例３２
窒素雰囲気で置換した１００ｍｌフラスコに、テトラヒドロフラン１０ｍｌ、金属マグネシウム２．６８ｇ（１１０ｍｍｏｌ）、臭化エチル０．６５ｇ（６ｍｍｏｌ）を仕込み、溶媒還流条件下で２０分間攪拌した。続いて、溶媒還流条件下で、パラジクロロベンゼン１４．７５ｇ（１００ｍｍｏｌ）をテトラヒドロフラン２０ｍｌに溶かした溶液を約２時間をかけて滴下した。更に、溶媒還流条件下で３時間攪拌し、グリニャール試薬を得た。
【００７５】
上記の操作によって得られたグリニャール試薬の上澄液を、窒素雰囲気で置換した１００ｍｌフラスコに移した。続いて、この反応液に塩化第二鉄（ＦｅＣｌ3）０．０８ｇ（０．５ｍｍｏｌ）、トルエン３０ｍｌを加えた後、反応温度を４０〜５０℃に保ちながら塩化ビニルガス１０．４６ｇ（１６７ｍｍｏｌ）を約３時間かけて吹き込み、更に同温度で３０分間攪拌を行った。
【００７６】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解した。有機層を分取した後、これをガスクロマトグラフィーで分析した結果、パラクロロスチレンが６２．９％の収率で生成していた。
【００７７】
実施例３３
窒素雰囲気で置換した５０Ｌフラスコに、テトラヒドロフラン６Ｌ、金属マグネシウム０．７３ｋｇ（３０ｍｏｌ）、臭化エチル０．２２ｋｇ（２ｍｏｌ）を仕込み、溶媒環流条件下で１時間撹拌した。続いて、溶媒環流条件下で、パラ−第三級−ブトキシクロロベンゼン４．６２ｋｇ（２５ｍｏｌ）をテトラヒドロフラン５Ｌに溶かした溶液を、約２時間をかけて滴下した。更に、溶媒環流条件下で４時間撹拌し、グリニャール試薬を得た。
【００７８】
上記の操作によって得られたグリニャール試薬を４０℃まで冷却した後、この反応液に塩化鉄（ＩＩＩ）（ＦｅＣｌ3）０．０２ｋｇ（０．１２ｍｏｌ）、テトラヒドロフラン１２Ｌを加えた。続いて、反応温度を４０〜５０℃に保ちながら塩化ビニルガス１．８８ｋｇ（３０ｍｏｌ）を約７時間かけて吹き込み、更に同温度で１時間撹拌を行った。
【００７９】
反応終了後、反応液に塩化アンモニウム水溶液を加えて生成した塩を溶解し、有機層を分離した。得られた有機層を飽和食塩水で洗浄後、溶媒を留去し、これに重合禁止剤を加えて減圧蒸留を行い、沸点９２℃／５ｍｍＨｇのＰＴＢＳ留分（３．５８ｋｇ、収率８１．２％）を得た。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a styrene derivative. More specifically, the present invention relates to a method for producing a styrene derivative by reacting a Grignard reagent prepared from an aromatic halogen compound with a vinyl halide in the presence of a catalyst.
[0002]
The styrene derivative which is the target compound of the present invention is very useful as a raw material for functional polymers, medicines and agricultural chemicals. For example, para-tertiary-butoxystyrene (hereinafter abbreviated as PTBS) is known to be extremely effective as a resist material used for VLSI applications (Japanese Patent Laid-Open No. 59-199705). JP-A-3-277608). Further, it is known that meta-tertiary-butoxystyrene (hereinafter abbreviated as MTBS) is useful as an intermediate material for functional polymers, medical pesticides and the like (JP-A-2-160739). .
[0003]
[Prior art]
For styrene derivatives such as PTBS and MTBS, two conventional production methods are known.
[0004]
That is, US Pat. No. 4,603,101 and JP-A-59-199705 disclose a method of reacting a Grignard reagent prepared from halostyrene with perbenzoic acid-tertiary-butyl ester. Has been. However, this method has a problem that a peroxybenzoic acid-tertiary-butyl ester which is difficult to obtain in large quantities and has explosive properties is required in addition to low reaction yield, and styrene derivatives such as PTBS and MTBS. Is not satisfactory as a method for industrially producing
[0005]
On the other hand, in Japanese Patent Publication No. 4-71896 and Japanese Patent Laid-Open No. 2-160739, a Grignard reagent prepared from tertiary-butoxyphenyl halide is reacted with vinyl halide in the presence of a nickel phosphine complex catalyst. Is disclosed. However, although this method improves the reaction yield, there is a problem that an expensive and very toxic nickel phosphine complex catalyst is required. In Japanese Patent Publication No. 4-71896 and Japanese Patent Laid-Open No. 2-160739, dichloro [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1, Although bidentate phosphine complexes such as 3-bis (diphenylphosphino) propane] nickel are stated to be effective, these catalysts are expensive and very toxic catalysts. Therefore, it is difficult to produce styrene derivatives such as PTBS and MTBS economically and safely even if this method is used, and this method is also an industrial method for producing styrene derivatives such as PTBS and MTBS. It is not satisfactory.
[0006]
[Problems to be solved by the invention]
This invention is made | formed in view of said subject, The objective is to provide the industrial manufacturing method of the styrene derivative which was not satisfied with the conventional method. That is, an object of the present invention is to solve the conventional problems related to styrene derivatives such as PTBS and MTBS and to provide an industrial production method excellent in economic efficiency and safety.
[0007]
[Means for Solving the Problems]
As a result of diligent studies to solve the conventional problems, the present inventors reacted a Grignard reagent prepared from tertiary-butoxyphenyl halide with vinyl halide in the presence of a catalyst to produce PTBS and MTBS. In the method for producing styrene derivatives, it has been found that by using a specific catalyst, styrene derivatives such as PTBS and MTBS can be produced safely on an industrial scale with good economic efficiency. Furthermore, the present catalytic method was confirmed to be effective for the production of various styrene derivatives, and the present invention was completed.
[0008]
That is, the present invention relates to a method for producing a styrene derivative by reacting a Grignard reagent prepared from an aromatic halogen compound with a vinyl halide in the presence of a catalyst. A method for producing a styrene derivative, wherein one or two or more catalysts selected from the group consisting of a catalyst based on a catalyst and a rhodium catalyst are used.
[0009]
Hereinafter, the present invention will be described in detail by taking the production of PTBS as an example.
[0010]
The Grignard reagent used in the method of the present invention is not particularly limited as long as it is a Grignard reagent prepared from an aromatic halogen compound, and can be easily prepared by a conventional method. That is, it can be easily prepared by carrying out a method of reacting magnesium metal with para-tertiary-butoxyphenyl halide in a solvent. In this preparation reaction, particularly good results are obtained when activated magnesium metal is used. As a method for activating the metal magnesium, a method of heating and stirring the metal magnesium suspended in a solvent, adding a trace amount of iodine, an iodide such as methyl iodide, a bromide such as dibromoethane, etc. A method of stirring is effective.
[0011]
In the method of the present invention, the Grignard reagent prepared by the above method is added in the presence of one or more catalysts selected from the group consisting of manganese-based catalysts, iron-based catalysts, cobalt-based catalysts, and rhodium-based catalysts. By reacting with vinyl halide, PTBS can be produced safely at a high yield and at a low cost.
[0012]
The vinyl halide used in the method of the present invention is vinyl fluoride, vinyl chloride, vinyl bromide or vinyl iodide, and these can be used alone or as a mixture. Usually, vinyl chloride gas and / or vinyl bromide gas are selected in consideration of economy and availability.
[0013]
The catalyst used in the method of the present invention is one or two or more catalysts selected from the group consisting of manganese-based catalysts, iron-based catalysts, cobalt-based catalysts, and rhodium-based catalysts.
[0014]
In the method of the present invention, the manganese-based catalyst refers to a catalyst containing manganese element as an active ingredient, and is not particularly limited. For example, manganese powder, manganese chloride (II), manganese bromide (II), iodine Manganese (II), manganese fluoride (II), manganese acetate (II), manganese acetate (III), manganese formate (II), manganese oxalate (II), manganese benzoate (II), manganese stearate (II) ), Manganese (II) borate, manganese (II) acetylacetonate, manganese (III) acetylacetonate, manganese carbonate (II), manganese sulfate (II), manganese nitrate (II), manganese phosphate (II), etc. , Hydrates of these compounds, or various complex catalysts derived from these compounds.
[0015]
In the method of the present invention, the iron-based catalyst refers to a catalyst containing iron element as an active ingredient, and is not particularly limited. For example, ferrous halide, ferric halide, ferrous halide Examples include catalysts that can be prepared from iron, catalysts that can be prepared from ferric halide, and the like. In the present invention, the catalyst that can be prepared from ferrous halide refers to a catalyst that can be derived from ferrous halide or a catalyst containing ferrous halide as an active ingredient, such as water of ferrous halide. Examples include Japanese and various complex catalysts. Catalysts that can be prepared from ferrous halide are defined in the same manner, and examples thereof include ferric halide hydrates and various complex catalysts.
[0016]
Specific examples of the iron-based catalyst in the method of the present invention include iron powder, iron chloride (II), iron chloride (III), iron bromide (II), iron bromide (III), iron iodide ( II), iron fluoride (II), iron fluoride (III), iron acetate (II), iron oxalate (II), iron oxalate (III), iron citrate (III), iron perchlorate (III) ), Iron (III) acetylacetonate, iron nitrate (III), iron phosphate (III), iron sulfate (II), iron sulfate (II) and the like, hydrates of these compounds, or derived from these compounds Examples of the various complex catalysts are shown.
[0017]
In the method of the present invention, the cobalt-based catalyst means a catalyst containing cobalt element as an active ingredient, and is not particularly limited. For example, cobalt powder, cobalt chloride (II), cobalt bromide (II), iodine Cobalt (II) fluoride, cobalt (II) fluoride, cobalt (II) acetate, cobalt (III) acetate, cobalt (II) formate, cobalt (II) oxalate, cobalt (II) benzoate, cobalt stearate (II) ), Cobalt (II) borate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) carbonate, cobalt (II) sulfate, cobalt (II) nitrate, cobalt (II) phosphate, etc. , Hydrates of these compounds, or various complex catalysts derived from these compounds.
[0018]
In the method of the present invention, the rhodium-based catalyst means a catalyst containing a rhodium element as an active ingredient, and is not particularly limited. For example, rhodium powder, rhodium-carbon, rhodium chloride (II), rhodium bromide (II ), Rhodium acetate (II), rhodium acetate (III), rhodium (II) acetylacetonate, rhodium (III) acetylacetonate, hydrates of these compounds, or various complex catalysts derived from these compounds Etc.
[0019]
In the method of the present invention, the above-mentioned catalysts can be used alone or as a mixture, but manganese halide, manganese acetate, iron halide, iron acetate, cobalt halide, cobalt acetate, rhodium halide, and acetic acid can be used. Particularly good results (high yield) are obtained when one or more catalysts selected from the group consisting of rhodium are used. The amount of the catalyst used in the method of the present invention is not particularly limited, but is usually 10% with respect to the Grignard reagent.-Four-10-1The amount used is about double moles.
[0020]
The conventional methods described above (for example, the method described in Japanese Patent Publication No. 4-71896) have a problem of requiring an expensive and very toxic nickel phosphine complex catalyst, which is satisfactory as an industrial production method of PTBS. It was not a thing. The present inventors have provided an inexpensive and safe manganese-based catalyst, iron-based catalyst, cobalt-based catalyst, and rhodium-based reaction for the reaction of a Grignard reagent prepared from para-tertiary-butoxyphenyl halide and vinyl halide. It has been found for the first time that one or more catalysts selected from the group consisting of catalysts are effective. Among these, one or more catalysts selected from the group consisting of manganese halide, manganese acetate, iron halide, iron acetate, cobalt halide, cobalt acetate, rhodium halide and rhodium acetate are very inexpensive. It is a safe catalyst, and the method of the present invention using such a catalyst is extremely useful as an industrial production method of PTBS.
[0021]
The method of the present invention is usually carried out in a solvent under an inert gas atmosphere such as nitrogen and / or argon. Examples of the reaction solvent used in the method of the present invention include ether solvents, oxygen-containing solvents, nitrogen-containing solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents and the like. Usually, these solvents can be used singly or in combination, but good results (high yield) are obtained particularly when a tetrahydrofuran solvent or a mixed solvent containing tetrahydrofuran is used. In addition, the method of the present invention is usually performed under conditions of 0 ° C. to solvent reflux temperature.
[0022]
After completion of the reaction, the reaction solution is treated with an acidic aqueous solution according to a conventional method, and then the organic layer is separated. Subsequently, after the organic layer is washed with water, the solvent is distilled off, and a polymerization inhibitor such as tertiary-butylcatechol is added thereto and distilled to obtain the target PTBS.
[0023]
The method of the present invention is not limited to the above-mentioned PTBS production, but can be widely applied to the same kind of reaction for producing a styrene derivative from an aromatic halogen compound, but when applied to the production of tertiary-butoxystyrene such as PTBS and MTBS. Particularly good results (high yield) are obtained. The aromatic halogen compound referred to in the method of the present invention is a general term for compounds in which at least one part of the aromatic ring is substituted with halogen. For example, a fluorinated benzene derivative, a chlorinated benzene derivative, a brominated benzene derivative, iodine Benzene derivatives and the like.
[0024]
【The invention's effect】
As is clear from the above description, according to the method of the present invention, it is possible to solve the conventional problems and to safely produce a styrene derivative on an industrial scale with good economic efficiency.
[0025]
【Example】
EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0026]
Reference example 1
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 11.46 g (50 mmol) of para-tertiary-butoxybromobenzene in 20 ml of tetrahydrofuran was maintained for about 1 hour while keeping the reaction solution at 40 to 50 ° C. It was dripped. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0027]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, manganese chloride (II) tetrahydrate (MnCl2・ 4H2O) 0.05 g (0.25 mmol) was added, and then, while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. .
[0028]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. After separating the organic layer, this was analyzed by gas chromatography to determine the PTBS yield. The reaction results are shown in Table 1.
[0029]
[Table 1]
Reference Examples 2-4, Example 514Reference examples15-17, Example 18
The reaction was performed according to the method of Example 1 except that the catalyst (0.25 mmol) shown in Table 1 was used instead of the manganese (II) chloride tetrahydrate (0.25 mmol) used in Reference Example 1. Went. The reaction results are also shown in Table 1.
[0031]
Reference Example 16
Reference example 1In place of the manganese (II) chloride tetrahydrate (0.25 mmol) used in Example 1, 0.03 g (0.13 mmol) of manganese (II) chloride tetrahydrate and 0.02 g (0. 13 mmol)Reference example 1The reaction was carried out according to the method. The reaction results are also shown in Table 1.
[0032]
Reference Example 17
Reference example 1In place of the manganese (II) chloride tetrahydrate (0.25 mmol) used in Example 1, 0.03 g (0.13 mmol) of manganese (II) chloride tetrahydrate and 0.02 g (0. 13 mmol)Reference example 1The reaction was carried out according to the method. The reaction results are also shown in Table 1.
[0033]
Example 18
Reference example 1In place of manganese (II) chloride tetrahydrate (0.25 mmol) used in 1), 0.02 g (0.13 mmol) of iron (III) chloride and 0.02 g (0.13 mmol) of cobalt (II) chloride Except usingReference example 1The reaction was carried out according to the method. The reaction results are also shown in Table 1.
[0034]
Comparative Examples 1 to 6
Reference example 1Except that the catalyst (0.25 mmol) shown in Table 1 was used instead of the manganese (II) chloride tetrahydrate (0.25 mmol) used inReference example 1The reaction was carried out according to. The reaction results are also shown in Table 1.
[0035]
Reference Example 19
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 11.46 g (50 mmol) of meta-tertiary-butoxybromobenzene in 20 ml of tetrahydrofuran was maintained for about 1 hour while keeping the reaction solution at 40 to 50 ° C. It was dripped. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0036]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, manganese (II) acetate tetrahydrate [Mn (CHThreeCO2)2・ 4H2O] 0.06 g (0.25 mmol) was added, and while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. .
[0037]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. After the organic layer was separated, it was analyzed by gas chromatography. As a result, MTBS was produced in a yield of 81.8%.
[0038]
Reference Example 20
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of diethyl ether, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution obtained by dissolving 11.46 g (50 mmol) of meta-tertiary-butoxybromobenzene in 20 ml of diethyl ether was kept for about 1 hour while keeping the reaction solution at 20 to 30 ° C. And dripped. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0039]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, manganese (II) acetate tetrahydrate [Mn (CHThreeCO2)2・ 4H2O] 0.06 g (0.25 mmol) was added, and while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. .
[0040]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. After separating the organic layer, it was analyzed by gas chromatography. MTBS was produced in a yield of 71.3%.
[0041]
Reference Example 21
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of dibutyl ether, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 11.46 g (50 mmol) of meta-tertiary-butoxybromobenzene in 20 ml of dibutyl ether was kept for about 1 hour while keeping the reaction solution at 40 to 50 ° C. And dripped. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0042]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, manganese (II) acetate tetrahydrate [Mn (CHThreeCO2)2・ 4H2O] 0.06 g (0.25 mmol) was added, and while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. .
[0043]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. After separating the organic layer, it was analyzed by gas chromatography. As a result, MTBS was produced in a yield of 68.9%.
[0044]
Example 22
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 11.46 g (50 mmol) of meta-tertiary-butoxybromobenzene in 20 ml of tetrahydrofuran was maintained for about 1 hour while keeping the reaction solution at 40 to 50 ° C. It was dripped. Furthermore, the mixture was stirred for 1 hour under solvent reflux conditions to obtain a Grignard reagent.
[0045]
The supernatant of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, cobalt (II) chloride (CoCl2) After adding 0.03 g (0.25 mmol), while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in for 10 minutes, and further stirred at the same temperature for 1 hour.
[0046]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. After separating the organic layer, it was analyzed by gas chromatography. As a result, MTBS was produced in a yield of 80.4%.
[0047]
Example 23
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 2.68 g (110 mmol) of metallic magnesium and 0.65 g (6 mmol) of ethyl bromide, and stirred for 20 minutes under solvent reflux conditions. Subsequently, a solution prepared by dissolving 18.47 g (100 mmol) of meta-tertiary-butoxychlorobenzene in 20 ml of tetrahydrofuran was added dropwise over about 2 hours under solvent reflux conditions. Further, the mixture was stirred for 3 hours under a solvent reflux condition to obtain a Grignard reagent.
[0048]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, iron (II) chloride (FeCl2) After adding 0.13 g (1 mmol) and 20 ml of tetrahydrofuran, 6.88 g (110 mmol) of vinyl chloride gas was blown in over 3 hours while maintaining the reaction temperature at 40 to 50 ° C., and further stirred at the same temperature for 30 minutes. .
[0049]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. MTBS was produced in a yield of 83.3%.
[0050]
Example 24
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 2.68 g (110 mmol) of metallic magnesium and 0.65 g (6 mmol) of ethyl bromide, and stirred for 20 minutes under solvent reflux conditions. Subsequently, a solution prepared by dissolving 18.47 g (100 mmol) of meta-tertiary-butoxychlorobenzene in 20 ml of tetrahydrofuran was added dropwise over about 2 hours under solvent reflux conditions. Further, the mixture was stirred for 3 hours under a solvent reflux condition to obtain a Grignard reagent.
[0051]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, iron (II) chloride (FeCl2) After adding 0.13 g (1 mmol) and 20 ml of toluene, 6.88 g (110 mmol) of vinyl chloride gas was blown in over 3 hours while maintaining the reaction temperature at 40 to 50 ° C., and further stirred at the same temperature for 30 minutes. .
[0052]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. After separating the organic layer, it was analyzed by gas chromatography. As a result, MTBS was produced in a yield of 81.9%.
[0053]
Reference Example 25
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 8.55 g (50 mmol) of parabromotoluene in 20 ml of tetrahydrofuran was dropped over about 1 hour while keeping the reaction solution at 40 to 50 ° C. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0054]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, manganese chloride (II) tetrahydrate (MnCl2・ 4H2O) 0.05 g (0.25 mmol) was added, and then, while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. .
[0055]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, paramethylstyrene was produced in a yield of 64.1%.
[0056]
Example 26
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 8.55 g (50 mmol) of parabromotoluene in 20 ml of tetrahydrofuran was dropped over about 1 hour while keeping the reaction solution at 40 to 50 ° C. Furthermore, the mixture was stirred for 1 hour under solvent reflux conditions to obtain a Grignard reagent.
[0057]
The supernatant of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, cobalt (II) chloride (CoCl2) After adding 0.03 g (0.25 mmol), while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in for 10 minutes, and further stirred at the same temperature for 1 hour.
[0058]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, paramethylstyrene was produced in a yield of 64.3%.
[0059]
Example 27
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 2.68 g (110 mmol) of metallic magnesium and 0.65 g (6 mmol) of ethyl bromide, and stirred for 20 minutes under solvent reflux conditions. Subsequently, a solution prepared by dissolving 12.66 g (100 mmol) of parachlorotoluene in 20 ml of tetrahydrofuran was added dropwise over about 2 hours under solvent reflux conditions. Further, the mixture was stirred for 3 hours under a solvent reflux condition to obtain a Grignard reagent.
[0060]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, iron (II) chloride (FeCl2) After adding 0.13 g (1 mmol) and 20 ml of tetrahydrofuran, 6.88 g (110 mmol) of vinyl chloride gas was blown in over about 3 hours while maintaining the reaction temperature at 40 to 50 ° C., and further stirred at the same temperature for 30 minutes. It was.
[0061]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, paramethylstyrene was produced in a yield of 64.3%.
[0062]
Reference Example 28
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 9.57 g (50 mmol) of parabromochlorobenzene in 20 ml of tetrahydrofuran was dropped over about 1 hour while keeping the reaction solution at 40 to 50 ° C. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0063]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, manganese (II) acetate tetrahydrate [Mn (CHThreeCO2) 2.4H2O] 0.06 g (0.25 mmol) was added, and while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. .
[0064]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, parachlorostyrene was produced in a yield of 60.7%.
[0065]
Example 29
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 9.57 g (50 mmol) of parabromochlorobenzene in 20 ml of tetrahydrofuran was dropped over about 1 hour while keeping the reaction solution at 40 to 50 ° C. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0066]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, cobalt (II) chloride (CoCl2) After adding 0.03 g (0.25 mmol), while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in for 10 minutes, and further stirred at the same temperature for 1 hour.
[0067]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, parachlorostyrene was produced in a yield of 67.1%.
[0068]
Example 30
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of dibutyl ether, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 9.57 g (50 mmol) of parabromochlorobenzene in 20 ml of dibutyl ether was dropped over about 1 hour while keeping the reaction solution at 40 to 50 ° C. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0069]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, cobalt (II) chloride (CoCl2) After adding 0.03 g (0.25 mmol), while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in for 10 minutes, and further stirred at the same temperature for 1 hour.
[0070]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, parachlorostyrene was produced in a yield of 55.4%.
[0071]
Example 31
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 1.34 g (55 mmol) of metallic magnesium and one piece of iodine, and stirred at room temperature. After confirming that the color of iodine disappeared, a solution prepared by dissolving 9.57 g (50 mmol) of parabromochlorobenzene in 20 ml of tetrahydrofuran was dropped over about 1 hour while keeping the reaction solution at 40 to 50 ° C. Further, the mixture was stirred for 1 hour under a solvent reflux condition to obtain a Grignard reagent.
[0072]
The supernatant liquid of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, the reaction solution was mixed with rhodium (III) chloride trihydrate (RhCl).Three・ 3H2O) 0.07 g (0.25 mmol) was added, and while maintaining the reaction temperature at 20 to 30 ° C., 3.44 g (55 mmol) of vinyl chloride gas was blown in over 10 minutes, and stirring was further performed at the same temperature for 1 hour. .
[0073]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, parachlorostyrene was produced in a yield of 64.8%.
[0074]
Example 32
A 100 ml flask substituted with a nitrogen atmosphere was charged with 10 ml of tetrahydrofuran, 2.68 g (110 mmol) of metallic magnesium and 0.65 g (6 mmol) of ethyl bromide, and stirred for 20 minutes under solvent reflux conditions. Subsequently, a solution prepared by dissolving 14.75 g (100 mmol) of paradichlorobenzene in 20 ml of tetrahydrofuran was added dropwise over about 2 hours under solvent reflux conditions. Further, the mixture was stirred for 3 hours under a solvent reflux condition to obtain a Grignard reagent.
[0075]
The supernatant of the Grignard reagent obtained by the above operation was transferred to a 100 ml flask replaced with a nitrogen atmosphere. Subsequently, ferric chloride (FeClThree) After adding 0.08 g (0.5 mmol) and 30 ml of toluene, 10.46 g (167 mmol) of vinyl chloride gas was blown in over about 3 hours while maintaining the reaction temperature at 40 to 50 ° C., and further stirred at the same temperature for 30 minutes. Went.
[0076]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt. The organic layer was separated and analyzed by gas chromatography. As a result, parachlorostyrene was produced in a yield of 62.9%.
[0077]
Example 33
A 50 L flask substituted with a nitrogen atmosphere was charged with 6 L of tetrahydrofuran, 0.73 kg (30 mol) of metal magnesium and 0.22 kg (2 mol) of ethyl bromide, and stirred for 1 hour under solvent reflux conditions. Subsequently, a solution prepared by dissolving 4.62 kg (25 mol) of para-tertiary-butoxychlorobenzene in 5 L of tetrahydrofuran was added dropwise over about 2 hours under solvent reflux conditions. Further, the mixture was stirred for 4 hours under solvent reflux conditions to obtain a Grignard reagent.
[0078]
After cooling the Grignard reagent obtained by the above operation to 40 ° C., this reaction solution was mixed with iron (III) chloride (FeClThree) 0.02 kg (0.12 mol) and 12 L of tetrahydrofuran were added. Subsequently, while maintaining the reaction temperature at 40 to 50 ° C., 1.88 kg (30 mol) of vinyl chloride gas was blown in over about 7 hours, and further stirred at the same temperature for 1 hour.
[0079]
After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt, and the organic layer was separated. The obtained organic layer was washed with a saturated saline solution, the solvent was distilled off, a polymerization inhibitor was added thereto and distilled under reduced pressure, and a PTBS fraction having a boiling point of 92 ° C./5 mmHg (3.58 kg, yield 81.81). 2%).
Claims (2)
で表される第三級−ブトキシフェニルハライドから調製したグリニャ−ル試薬を、触媒の存在下にビニルハライドと反応させて、スチレン誘導体を製造する方法において、触媒として、鉄系触媒、コバルト系触媒及びロジウム系触媒からなる群より選ばれる一種又は二種以上の触媒を用いるスチレン誘導体の製造方法であって、
鉄系触媒が、鉄粉、塩化鉄（ＩＩ）、塩化鉄（ＩＩＩ）、臭化鉄（ＩＩ）、臭化鉄（ＩＩＩ）、ヨウ化鉄（ＩＩ）、フッ化鉄（ＩＩ）、フッ化鉄（ＩＩＩ）、酢酸鉄（ＩＩ）、シュウ酸鉄（ＩＩ）、シュウ酸鉄（ＩＩＩ）、クエン酸鉄（ＩＩＩ）、過塩素酸鉄（ＩＩＩ）、鉄（ＩＩＩ）アセチルアセトナート、硝酸鉄（ＩＩＩ）、リン酸鉄（ＩＩＩ）、硫酸鉄（ＩＩ）、硫酸鉄（ＩＩ）、それら化合物の水和物、及びそれら化合物と下記式（１）
コバルト系触媒が、コバルト粉末、塩化コバルト（ＩＩ）、臭化コバルト（ＩＩ）、ヨウ化コバルト（ＩＩ）、フッ化コバルト（ＩＩ）、酢酸コバルト（ＩＩ）、酢酸コバルト（ＩＩＩ）、ギ酸コバルト（ＩＩ）、シュウ酸コバルト（ＩＩ）、安息香酸コバルト（ＩＩ）、ステアリン酸コバルト（ＩＩ）、ホウ酸コバルト（ＩＩ）、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート、炭酸コバルト（ＩＩ）、硫酸コバルト（ＩＩ）、硝酸コバルト（ＩＩ）、リン酸コバルト（ＩＩ）、それら化合物の水和物、及びそれら化合物と上記式（１）で示されるｄｐｐｐ若しくは上記式（２）で示されるｄｐｙとの錯体触媒からなる群より選ばれ、かつ
ロジウム系触媒が、ロジウム粉末、ロジウム−カーボン、塩化ロジウム（ＩＩ）、臭化ロジウム（ＩＩ）、酢酸ロジウム（ＩＩ）、酢酸ロジウム（ＩＩＩ）、ロジウム（ＩＩ）アセチルアセトナート、ロジウム（ＩＩＩ）アセチルアセトナート、それら化合物の水和物、及びそれら化合物と上記式（１）で示されるｄｐｐｐ若しくは上記式（２）で示されるｄｐｙとの錯体触媒からなる群より選択されることを特徴とする製造方法。The following general formula (I)
In the method of producing a styrene derivative by reacting a Grignard reagent prepared from a tertiary-butoxyphenyl halide represented by the formula (I) with a vinyl halide in the presence of a catalyst, an iron-based catalyst and a cobalt-based catalyst are used. And a method for producing a styrene derivative using one or more catalysts selected from the group consisting of rhodium-based catalysts,
Iron catalyst is iron powder, iron chloride (II), iron chloride (III), iron bromide (II), iron bromide (III), iron iodide (II), iron fluoride (II), fluoride Iron (III), iron acetate (II), iron oxalate (II), iron oxalate (III), iron (III) citrate, iron (III) perchlorate, iron (III) acetylacetonate, iron nitrate (III), iron (III) phosphate, iron (II) sulfate, iron (II) sulfate, hydrates of these compounds , and these compounds and the following formula (1)
The cobalt catalyst is cobalt powder, cobalt chloride (II), cobalt bromide (II), cobalt iodide (II), cobalt fluoride (II), cobalt acetate (II), cobalt acetate (III), cobalt formate ( II), cobalt oxalate (II), cobalt benzoate (II), cobalt stearate (II), cobalt borate (II), cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt carbonate ( II), cobalt sulfate (II), cobalt nitrate (II), cobalt phosphate (II), hydrates of these compounds, and those compounds and dppp represented by the above formula (1) or represented by the above formula (2) It is selected from the group consisting of complex catalyst and dpy, and rhodium-based catalysts, rhodium powder, rhodium - carbon, chloride Indium (II), rhodium bromide (II), rhodium acetate (II), rhodium acetate (III), rhodium (II) acetylacetonate, rhodium (III) acetylacetonate, hydrates of these compounds, and their compounds And dppp represented by the above formula (1) or a dpy catalyst represented by the above formula (2) .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02178799A JP4423691B2 (en) | 1998-01-30 | 1999-01-29 | Method for producing styrene derivative |
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1868198 | 1998-01-30 | ||
| JP10-165389 | 1998-06-12 | ||
| JP16538998 | 1998-06-12 | ||
| JP20948898 | 1998-07-24 | ||
| JP10-209488 | 1998-07-24 | ||
| JP10-209489 | 1998-07-24 | ||
| JP20948998 | 1998-07-24 | ||
| JP10-18681 | 1998-12-16 | ||
| JP35743898 | 1998-12-16 | ||
| JP10-357438 | 1998-12-16 | ||
| JP02178799A JP4423691B2 (en) | 1998-01-30 | 1999-01-29 | Method for producing styrene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000239192A JP2000239192A (en) | 2000-09-05 |
| JP4423691B2 true JP4423691B2 (en) | 2010-03-03 |
Family
ID=27548806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02178799A Expired - Lifetime JP4423691B2 (en) | 1998-01-30 | 1999-01-29 | Method for producing styrene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4423691B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479709B1 (en) | 1998-01-30 | 2002-11-12 | Tosoh Corporation | Process for the production of styrene derivative |
| US6608212B1 (en) * | 2002-06-04 | 2003-08-19 | Pfizer, Inc. | Process for preparing vinylaromatic compounds |
| JP5540117B2 (en) * | 2010-02-09 | 2014-07-02 | サルティゴ・ゲーエムベーハー | Method for allylating and vinylating aryl halides, heteroaryl halides, alkyl halides, and halogenated alkenes using transition metal catalysis |
| JP5885213B2 (en) * | 2013-11-27 | 2016-03-15 | 東ソー有機化学株式会社 | Process for producing unsaturated alkyl halides |
| CN108884085B (en) | 2016-03-29 | 2022-11-15 | 诺华股份有限公司 | Reaction medium comprising a water-surfactant mixture |
-
1999
- 1999-01-29 JP JP02178799A patent/JP4423691B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000239192A (en) | 2000-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dilman et al. | Advances in the chemistry of organozinc reagents | |
| Endres et al. | Dirhodium (II) tetrakis (perfluoroalkylbenzoates) as partially recyclable catalysts for carbene transfer reactions with diazoacetates | |
| JP4423691B2 (en) | Method for producing styrene derivative | |
| JP5377309B2 (en) | Novel cyclopentadienyl, indenyl or fluorenyl substituted phosphine compounds and their use in catalytic reactions | |
| US6479709B1 (en) | Process for the production of styrene derivative | |
| US6472567B2 (en) | Process for the production of styrene compound, and styrene compound free from biphenyl | |
| JPS5865241A (en) | Carbonylation of secondary benzylhalide | |
| JP2002053515A (en) | Tertiary-butoxystyrene | |
| JPH01106835A (en) | Synthesis method of para-tertiary-butoxystyrene | |
| US5159082A (en) | Process for producing aromatic compound | |
| JP6245605B2 (en) | Process for producing .ALPHA.,. BETA.-unsaturated carbonyl compounds. | |
| Black et al. | Olefin insertion reactivity of a (phosphine-arenesulfonate) palladium (II) fluoride complex | |
| CA1243041A (en) | Process for the conversion of a terminal carbon- carbon double bond of an olefinic hydrocarbon to carbonyl groups | |
| JP4876476B2 (en) | Chloroalkoxystyrene and process for producing the same | |
| JP3353046B2 (en) | Method for producing organic compound using organic bismuth compound | |
| CN106431822B (en) | Industrial production method of 3,3 ', 4, 4' -tetrafluorobiphenyl | |
| JPH02160739A (en) | Production of m-tert-butoxystyrene | |
| JPH0134208B2 (en) | ||
| JP2001158779A (en) | Method for producing para-tetrahydropyranyloxystyrene | |
| JP2990850B2 (en) | Palladium compound and method for producing alkoxyalkadiene using the same | |
| JP3001122B2 (en) | Synthesis of substituted chlorobenzenes | |
| JPS6132295B2 (en) | ||
| JP3206452B2 (en) | Method for producing diaryl carbonate | |
| JP2003313194A (en) | Method for producing tertiary phosphine having a bulky hydrocarbon group | |
| JP3027872B2 (en) | Telomerization catalyst and method for producing alkoxyalkadiene using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090525 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090602 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090731 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090825 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091019 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20091117 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091130 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121218 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131218 Year of fee payment: 4 |
|
| EXPY | Cancellation because of completion of term |