JPH04173754A - Production of 2 position-substituted 6-isopropylnaphthalene - Google Patents
Production of 2 position-substituted 6-isopropylnaphthaleneInfo
- Publication number
- JPH04173754A JPH04173754A JP2301289A JP30128990A JPH04173754A JP H04173754 A JPH04173754 A JP H04173754A JP 2301289 A JP2301289 A JP 2301289A JP 30128990 A JP30128990 A JP 30128990A JP H04173754 A JPH04173754 A JP H04173754A
- Authority
- JP
- Japan
- Prior art keywords
- substituted
- isopropylnaphthalene
- raw material
- naphthalene
- isopropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- TVYVQNHYIHAJTD-UHFFFAOYSA-N 2-propan-2-ylnaphthalene Chemical class C1=CC=CC2=CC(C(C)C)=CC=C21 TVYVQNHYIHAJTD-UHFFFAOYSA-N 0.000 title description 7
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000011541 reaction mixture Substances 0.000 claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 5
- 239000003377 acid catalyst Substances 0.000 claims abstract description 4
- -1 2-substituted 6-isopropylnaphthalene Chemical class 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract 6
- 238000006243 chemical reaction Methods 0.000 description 18
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 16
- 229950011260 betanaphthol Drugs 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 7
- MDWFMRLBXKFHHI-UHFFFAOYSA-N 6-propan-2-ylnaphthalen-2-ol Chemical compound C1=C(O)C=CC2=CC(C(C)C)=CC=C21 MDWFMRLBXKFHHI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- AAKRTZRMVMTCPV-UHFFFAOYSA-N 2-methoxy-6-propan-2-ylnaphthalene Chemical compound C1=C(C(C)C)C=CC2=CC(OC)=CC=C21 AAKRTZRMVMTCPV-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- NNTAZSMBJGXUIE-UHFFFAOYSA-N 1,3-di(propan-2-yl)naphthalen-2-ol Chemical compound C1=CC=C2C(C(C)C)=C(O)C(C(C)C)=CC2=C1 NNTAZSMBJGXUIE-UHFFFAOYSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- CMIDJZRXBSHKDE-UHFFFAOYSA-N 1-propan-2-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C(C)C)=C(O)C=CC2=C1 CMIDJZRXBSHKDE-UHFFFAOYSA-N 0.000 description 3
- PTNFQHCXMZTQMC-UHFFFAOYSA-N 2-methoxy-1-propan-2-ylnaphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(OC)=CC=C21 PTNFQHCXMZTQMC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-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
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 229960002009 naproxen Drugs 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
童栗上少胴１１亘
本発明は、２位置換６−イソプロピルナフタレンの製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-substituted 6-isopropylnaphthalene.
従来夏技術
例えば、２−メトキシ−６−イソプロピルナフタレンや
６−イツブロビルー２−ナフトール等は、解熱鎮痛消炎
剤であるナプロキセンの重要な前駆体である。Conventional summer technology For example, 2-methoxy-6-isopropylnaphthalene and 6-itubrobyl-2-naphthol are important precursors of naproxen, which is an antipyretic, analgesic, and antiinflammatory agent.
しかし、従来、２位置換６−イソプロピルナフタレンの
工業的に有利な選択的製造法や精製法は知られていない
。However, no industrially advantageous selective production method or purification method for 2-substituted 6-isopropylnaphthalene has been known so far.
■が”しようとする課
本発明者らは、２位置換６−イソプロピルナフタレンの
工業的に有利な製造方法を得るべく鋭意研究した結果、
２位置換６−イソプロピルナフタレンが２位置換イソプ
ロピルナフタレン類のなかで、２５〜６０％もの高い平
衡濃度を有すると共に、特に結晶性がよく、また、イソ
プロピル基が異性化を起こしやすいことを見出し、かか
る知見に立脚して、本発明に至ったものである。As a result of intensive research to obtain an industrially advantageous production method for 2-substituted 6-isopropylnaphthalene,
We discovered that 2-position-substituted 6-isopropylnaphthalene has a high equilibrium concentration of 25 to 60% among 2-position-substituted isopropylnaphthalenes, has particularly good crystallinity, and that the isopropyl group is susceptible to isomerization. Based on this knowledge, the present invention has been achieved.
即ち、本発明は、２位置換６−イソプロピルナフタレン
の工業的に有利な製造方法を提供することを目的とする
。That is, an object of the present invention is to provide an industrially advantageous method for producing 2-substituted 6-isopropylnaphthalene.
量 ゛ るための
本発明による２位置換６−イソプロピルナフタレンの製
造方法は、２位が水酸基、メトキシ基又はエトキシ基で
置換された原料ナフタレン誘導体を酸触媒の存在下にプ
ロピレン及びイソプロパノールから選ばれるイソプロピ
ル化剤にてイソプロピル化し、イソプロピル基数／ナツ
タ１フＭ数の比が０．４〜２．２の範囲にある反応混合
物を得、この反応混合物を蒸留して、２位置換６−イソ
プロピルナフタレンが濃縮された留分を得、この留分を
脂肪族炭化水素から晶析させて、２位置換６−イソプロ
ピルナフタレンを回収すると共に、上記蒸留及び晶析に
よる回収物以外の一部又は全部を原料ナフタレン誘導体
と共にイソプロピル化することを特徴とする。The method for producing 6-isopropylnaphthalene substituted at the 2-position according to the present invention for producing a large amount of 6-isopropylnaphthalene is carried out by using a raw material naphthalene derivative substituted at the 2-position with a hydroxyl group, a methoxy group, or an ethoxy group in the presence of an acid catalyst selected from propylene and isopropanol. Isopropylation is carried out using an isopropylating agent to obtain a reaction mixture in which the ratio of isopropyl group number/Natsuta 1F M number is in the range of 0.4 to 2.2, and this reaction mixture is distilled to obtain 2-substituted 6-isopropylnaphthalene. is obtained, and this fraction is crystallized from aliphatic hydrocarbons to recover 2-substituted 6-isopropylnaphthalene, and at the same time, part or all of the residue other than those recovered by the above-mentioned distillation and crystallization is recovered. It is characterized by isopropylation together with the raw material naphthalene derivative.
本発明の方法においては、先ず、２位が水酸基、メトキ
シ基又はエトキシ基で置換されたナフタレン誘導体を原
料とし、これを酸触媒の存在下にプロピレン及びイソプ
ロパノールから選ばれるイソプロピル化剤にてイソプロ
ピル化し、イソプロピル基数／ナフタレン環数の比が０
．４〜２．２の範囲にある反応混合物を得る。In the method of the present invention, first, a naphthalene derivative in which the 2-position is substituted with a hydroxyl group, a methoxy group, or an ethoxy group is used as a raw material, and this is isopropylated using an isopropylating agent selected from propylene and isopropanol in the presence of an acid catalyst. , the ratio of the number of isopropyl groups/number of naphthalene rings is 0
．． A reaction mixture ranging from 4 to 2.2 is obtained.
上記原料ナフタレン誘導体のイソプロピル化の触媒とし
ては、例えば、シリカアルミナ、シリカチタニア、シリ
カマグネシア、シリカポレア等の複合酸化物や酸化ニオ
ブのほか、酸化ジルコニウム、酸化チタン、シリカ、ア
ルミナ、酸化スズ、酸化鉄等の酸化物に硫酸根を担持さ
せた固体超強酸、ＨＦ−ＢＦ、等の液体超強酸、Ｘ型ゼ
オライト、Ｙ型ゼオライト、安定化Ｙ型ゼオライＩ−（
ＵＳＹ）、Ａ型ゼオライト、Ｌ型ゼオライト、モルデナ
イト、ＺＳＭ−５等のゼオライト類のプロトン又は金属
イオン交換体、活性白土や酸性白土、モンモリロナイト
、ベントナイト、バーミキュライト、テトラシリシック
マイカ、ヘクトライト、サボナイト、テニオライト等の
層状化合物のプロトン、金属イオン若しくはアルミニウ
ム、ジルコニウム、鉄、クロム等の多核水酸化イオンの
１種又は２種による交換体、アルミナ、ジルコニア、チ
タニア等によるこれら交換体の架橋物、ＭＥＬＳ、スル
ホン化ポリフェニルシロキサンやこれらのフッ素若しく
はトリフルオロメチル基置換体、アンバーリスト１５、
ナフィオン等のイオン交換樹脂、塩化アルミニウム、臭
化アルミニウム、塩化ガリウム、塩化鉄、塩化チタン、
塩化スズやこれらを金属酸化物等の適当な担体に担持若
しくは固定させたもの、リンタングステン酸、リンモリ
ブデン酸、ケイモリブデン酸等のへテロポリ酸、リン酸
、塩化水素、硫酸、ｐ−１−ルエンスルホン酸、トリフ
ルオロメタンスルホン酸、フッ化スルホン酸、フン化水
素、三フッ化ホウ素、酢酸、クロロ酢酸、フルオロ酢酸
等を挙げることができる。Catalysts for the isopropylation of the raw material naphthalene derivatives include, for example, complex oxides such as silica alumina, silica titania, silica magnesia, and silica polea, and niobium oxide, as well as zirconium oxide, titanium oxide, silica, alumina, tin oxide, and iron oxide. solid superacids with sulfate groups supported on oxides such as, liquid superstrong acids such as HF-BF, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite
USY), proton or metal ion exchangers of zeolites such as A-type zeolite, L-type zeolite, mordenite, and ZSM-5, activated clay and acid clay, montmorillonite, bentonite, vermiculite, tetrasilicic mica, hectorite, sabonite, Exchangers with one or two types of protons of layered compounds such as taeniolite, metal ions or polynuclear hydroxide ions such as aluminum, zirconium, iron, chromium, etc., crosslinked products of these exchangers with alumina, zirconia, titania, etc., MELS, Sulfonated polyphenylsiloxanes and their fluorine or trifluoromethyl group substituted products, Amberlyst 15,
Ion exchange resins such as Nafion, aluminum chloride, aluminum bromide, gallium chloride, iron chloride, titanium chloride,
Tin chloride and those supported or immobilized on suitable carriers such as metal oxides, heteropolyacids such as phosphotungstic acid, phosphomolybdic acid, and silicomolybdic acid, phosphoric acid, hydrogen chloride, sulfuric acid, p-1- Examples include luenesulfonic acid, trifluoromethanesulfonic acid, fluorinated sulfonic acid, hydrogen fluoride, boron trifluoride, acetic acid, chloroacetic acid, and fluoroacetic acid.
原料ナフタレン誘導体のイソプロピル化反応は、液相又
は気相のいずれでもよく、常圧、加圧、減圧下のいずれ
でもよく、更に、−段でも多段でもよい。しかしながら
、本発明の方法においては、２位置換ナフタレン類のモ
ノ及びポリイソプロピル化と共に、そのモノ及びポリイ
ソプロピル化によって得られたモノ及びポリイソプロピ
ルナフタレン誘導体のイソプロピル基の異性化を起こさ
せて、２位置換６−イソプロピルナフタレンの平衡濃度
を高めることが必要である。従って、本発明においては
、反応温度は、液相反応では４０〜３００℃の範囲が好
ましく、気相反応では１００〜５００℃の範囲が好まし
い。但し、本発明の方法においては、反応混合物を必ず
しも平衡組成に達せしめる必要はない。The isopropylation reaction of the raw material naphthalene derivative may be carried out in either a liquid phase or a gas phase, and may be carried out under normal pressure, increased pressure, or reduced pressure, and may be carried out in one stage or in multiple stages. However, in the method of the present invention, in addition to the mono- and polyisopropylation of the 2-substituted naphthalenes, the isomerization of the isopropyl groups of the mono- and polyisopropyl naphthalene derivatives obtained by the mono- and polyisopropylation is caused. It is necessary to increase the equilibrium concentration of substituted 6-isopropylnaphthalene. Therefore, in the present invention, the reaction temperature is preferably in the range of 40 to 300°C in liquid phase reaction, and preferably in the range of 100 to 500°C in gas phase reaction. However, in the method of the present invention, it is not necessary to bring the reaction mixture to an equilibrium composition.
上記した反応において、必要に応じて、溶剤を用いても
よい。反応溶剤としては、例えば、ヘキサン、ヘプタン
、オクタン、デカン、デカリン等の炭化水！、クロロベ
ンゼン、ジクロロベンゼン、ブロモベンゼン、ジブロモ
ベンゼン等のハロゲン化炭化水素、ジクロロメタン、１
，２−ジクロロエタン等のハロゲン化脂肪族炭化水素、
ジエチルエーテル、テトラヒドロフラン等のエーテル類
、二硫化炭素、酢酸エチル、ニトロベンゼン、ニトロエ
タン等を挙げることができる。In the above reaction, a solvent may be used if necessary. Examples of reaction solvents include hydrocarbons such as hexane, heptane, octane, decane, and decalin! , halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, dibromobenzene, dichloromethane, 1
, halogenated aliphatic hydrocarbons such as 2-dichloroethane,
Examples include ethers such as diethyl ether and tetrahydrofuran, carbon disulfide, ethyl acetate, nitrobenzene, and nitroethane.
本発明の方法によれば、反応混合物を蒸留して、２位置
換６−イソプロピルナフタレンが濃縮された留分を得、
この留分を脂肪族炭化水素から晶析させて、２位置換６
−イソプロピルナフタレンを回収すると共に、上記蒸留
及び晶析による回収物以外の一部又は全部を戻し分とし
て、原料ナフタレン誘導体のイソプロピル化に再使用す
る。即ち、上記戻し分は、新たな原料ナフタレン誘導体
に加えられて、再び、原料ナフタレン誘導体のイソプロ
ピル化反応において、原料及び／又はイソプロピル化剤
として利用される。According to the method of the present invention, the reaction mixture is distilled to obtain a fraction enriched in 2-substituted 6-isopropylnaphthalene,
This fraction was crystallized from aliphatic hydrocarbons, and the 2-substituted 6
-Isopropylnaphthalene is recovered, and part or all of the recovered material from the above-mentioned distillation and crystallization is returned and reused for isopropylation of the raw material naphthalene derivative. That is, the returned amount is added to a new raw material naphthalene derivative and used again as a raw material and/or an isopropylation agent in the isopropylation reaction of the raw material naphthalene derivative.
ここに、前述したイソプロピル基数／ナフタレン環数の
比が０．４〜２．２の範囲にある反応混合物は、通常、
イソプロピル化剤として用いられるプロピレン又はイソ
プロパノールのモル数と原料ナフタレン誘導体に戻され
る戻し背中のイソプロピルナフタレン類のイソプロピル
基や反応中間体の有するイソプロポキシ基等のイソプロ
ピル基のモル数の合計量のナフタレン環に対するモル比
が０゜４１〜６．０の範囲となる条件で反応を行なうこ
とによって得ることができる。Here, the reaction mixture in which the ratio of the number of isopropyl groups/number of naphthalene rings is in the range of 0.4 to 2.2 is usually
The total amount of naphthalene rings, including the number of moles of propylene or isopropanol used as an isopropylating agent and the number of moles of isopropyl groups such as isopropyl groups in the isopropylnaphthalenes returned to the raw material naphthalene derivatives and isopropoxy groups in reaction intermediates. It can be obtained by carrying out the reaction under conditions such that the molar ratio to 0.41 to 6.0.
次いで、本発明によれば、イソプロピル基数／ナフタレ
ン環数の比が０．４〜２．２の範囲にある反応混合物を
蒸留して、２位置換６−イソプロピルナフタレンが濃縮
された留分を得る。この留分を得るための蒸留は、２位
置換６−イソプロピルナフタレンの濃度を高めることが
できれば、どのような方法によってもよい。例えば、２
位置換６−イソプロピルナフタレンよりも低沸点留分を
除去してもよく、或いは２位置換６−イソプロピルナフ
タレンよりも高沸点留分を除去してもよい。勿論、両方
の留分を除去してもよい。また、蒸留は、常圧、減圧又
は加圧下のいずれでも行なうことができるが、減圧下に
行なうのが好ましい。Then, according to the present invention, the reaction mixture in which the ratio of the number of isopropyl groups/the number of naphthalene rings is in the range of 0.4 to 2.2 is distilled to obtain a fraction enriched in 2-substituted 6-isopropylnaphthalene. . Distillation for obtaining this fraction may be performed by any method as long as it can increase the concentration of 2-substituted 6-isopropylnaphthalene. For example, 2
A fraction having a boiling point lower than that of 6-isopropylnaphthalene substituted at the position may be removed, or a fraction having a boiling point higher than that of 6-isopropylnaphthalene substituted at the second position may be removed. Of course, both fractions may be removed. Further, the distillation can be carried out under normal pressure, reduced pressure or increased pressure, but it is preferably carried out under reduced pressure.
このようにして、２位置換６−イソプロピルナフタレン
が濃縮された留分を得、次いで、この留分を脂肪族炭化
水素から晶析させて、２位置換６−イソプロピルナフタ
レンを回収する。晶析溶剤としての脂肪族炭化水素は、
炭素数５〜１０のものが好ましく、例えば、ペンタン、
ヘキサン、ヘプタン、オクタン又はこれらの２種以上の
混合物が好ましく用いられる。通常、ナフタレン類１１
当りに晶析溶剤は５〜０．０３ ｇ、好ましくは１〜０
、０７ ｇの範囲で用いられる。In this way, a fraction enriched in 2-substituted 6-isopropylnaphthalene is obtained, and this fraction is then crystallized from aliphatic hydrocarbons to recover 2-substituted 6-isopropylnaphthalene. Aliphatic hydrocarbons as crystallization solvents are
Those having 5 to 10 carbon atoms are preferred, such as pentane,
Hexane, heptane, octane or a mixture of two or more thereof is preferably used. Usually naphthalenes 11
5 to 0.03 g of crystallization solvent, preferably 1 to 0
, 07 g.
本発明の方法においては、上記蒸留及び晶析による回収
物以外の一部又は全部を戻し分として、新たな原料ナフ
タレン誘導体に加え、再度、イソプロピル化反応に用い
られる。In the method of the present invention, part or all of the recovered material from the above-mentioned distillation and crystallization is added to a new raw material naphthalene derivative as a return amount and used again in the isopropylation reaction.
即ち、上記戻し分は、未反応ナフタレン類、モノイソプ
ロピルナフタレン類及びポリイソプロピルナフタレン類
を含んでおり、これらは、イソプロピル化原料及び／又
はイソプロピル化剤として用いられる。ここに、戻し分
の組成に応じて、前述したように、原料系におけるイソ
プロピル基のモル数の合計量のナフタレン環に対するモ
ル比が０．４１〜６．０の範囲となるように、２位置換
ナフタレンの適量と共に、原料ナフタレン誘導体を調製
し、プロピレン又はイソプロパノール量を調整して、イ
ソプロピル化を行ない、がくして、ががる反応を繰り返
すことによって、目的とする２位置換−６−イソプロピ
ルナフタレンを工業的に有利に製造することができる。That is, the returned amount contains unreacted naphthalenes, monoisopropylnaphthalenes, and polyisopropylnaphthalenes, which are used as an isopropylation raw material and/or an isopropylation agent. Here, depending on the composition of the returned product, as described above, the 2-position The desired 2-substituted-6-isopropylnaphthalene can be obtained by preparing a raw material naphthalene derivative with an appropriate amount of substituted naphthalene, adjusting the amount of propylene or isopropanol, performing isopropylation, and repeating the peeling and peeling reactions. can be produced industrially advantageously.
光所■四来
以上のように、本発明の方法によれば、原料ナフタレン
誘導体をイソプロピル化して、目的とする２位置換−６
−イソプロピルナフタレンを回収すると共に、回収物以
外の一部又は全部を再度、原料ナフタレン誘導体と共に
イソプロピル化することによって、工業的に有利に２位
置換−６−イソプロピルナフタレンを製造することがで
きる。As described above, according to the method of the present invention, the raw material naphthalene derivative is isopropylated to form the desired 2-substituted -6
-6-isopropylnaphthalene substituted at the 2-position can be industrially advantageously produced by recovering -isopropylnaphthalene and isopropylating a part or all of the other than the recovered material again together with the raw material naphthalene derivative.
大施開
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
２−ナフトール３５ｇ、ナフィオン６ｇ及びｎ−オクタ
ン２００ｍ１からなる混合物を予め加熱還流させ、これ
にイソプロパノール３５ｍ１のオクタン１００ｍ１溶液
を滴下ろうとから３時間を要して滴下した。滴下終了後
、更に、１時間加熱還流した。反応によって生成する水
は、ディーン・スターク水捕集トラップを用いて反応系
外に除去した。Example 1 A mixture consisting of 35 g of 2-naphthol, 6 g of Nafion, and 200 ml of n-octane was heated to reflux in advance, and a solution of 35 ml of isopropanol in 100 ml of octane was added dropwise to the mixture over a period of 3 hours. After the dropwise addition was completed, the mixture was further heated under reflux for 1 hour. Water produced by the reaction was removed from the reaction system using a Dean Stark water trap.
反応成績は、２−ナフトール転化率８４％、モノイソプ
ロピル−２−ナフトール選択率７１％、ジイソプロピル
−２−ナフトール選択率２１％及びポリイソプロピル−
２−ナフトール選択率８％であった。The reaction results were as follows: 2-naphthol conversion rate 84%, monoisopropyl-2-naphthol selectivity 71%, diisopropyl-2-naphthol selectivity 21%, and polyisopropyl-2-naphthol selectivity 21%.
The 2-naphthol selectivity was 8%.
この反応混合物４６ｇを５段のオールダシヨーカラムを
用いて減圧２ＩＨｇ下に蒸留して、１４０〜１５０℃の
留分２３ｇを得た。この留分の組成は、２−ナフト−ル
１％、６−イソプロビル−２−ナフトール２８％、その
他のイソプロピル−２−ナフトール６５％及びジイソプ
ロピル−２−ナフトール６％であった。46 g of this reaction mixture was distilled under reduced pressure of 2 IHg using a 5-stage old column to obtain 23 g of a fraction at 140 to 150°C. The composition of this fraction was 1% 2-naphthol, 28% 6-isopropyl-2-naphthol, 65% other isopropyl-2-naphthol, and 6% diisopropyl-2-naphthol.
この留分をｎ−オクタン８５龍から晶析させたところ、
純度９５％の６−イソプロビル−２−ナフ１−−ル４．
７ｇを得た。When this fraction was crystallized from n-octane 85,
6-isopropyl-2-naph 1--ol with 95% purity4.
7g was obtained.
次に、上記晶析にて回収した６−イソプロピル−２−ナ
フトール以外の反応混合物４１ｇを戻し分とし、これに
２−ナフトール４ｇ、ナフィオン６ｇ及びｎ−オクタン
２００ｍ１を加え、この混合物を予め加熱還流させ、こ
れにイソプロパノール３ｍｌのｎ−オクタン１０ｍ１溶
液を滴下ろうかから１５分を要して滴下した。滴下終了
後、更に、１時間加熱還流して、反応混合物４６ｇを得
た。Next, 41 g of the reaction mixture other than 6-isopropyl-2-naphthol recovered in the above crystallization was returned, and 4 g of 2-naphthol, 6 g of Nafion, and 200 ml of n-octane were added thereto, and the mixture was heated to reflux in advance. Then, a solution of 3 ml of isopropanol in 10 ml of n-octane was added dropwise from a dropping funnel over a period of 15 minutes. After the dropwise addition was completed, the mixture was further heated under reflux for 1 hour to obtain 46 g of a reaction mixture.
この反応混合物の組成は、２−ナフトール１４％、イソ
プロピル−２−ナフトール５９％、ジイソプロピル−２
−ナフトール１８％、ポリイソプロピル−２−ナフトー
ル９％であった。The composition of this reaction mixture was 14% 2-naphthol, 59% isopropyl-2-naphthol, diisopropyl-2-naphthol,
-naphthol 18% and polyisopropyl-2-naphthol 9%.
この反応混合物を前記と同様に蒸留して、１４５〜ｂ
分をｎ−オクタン９０１１から晶析させさたところ、純
度９６％の６−イソプロビル−２−ナフトール５．２ｇ
を得た。This reaction mixture was distilled in the same manner as above, and the fraction 145-b was crystallized from n-octane 9011, resulting in 5.2 g of 6-isopropyl-2-naphthol with a purity of 96%.
I got it.
以下、上記と全く同様にして、晶析にて回収した６−イ
ソプロビル−２−ナフトール以外の反応混合物に２−ナ
フトール４ｇ、ナフィオン６ｇ及びｎ−オクタン２００
ｍ１を加え、これにイソプロパノール３ｆｆ１１のｎ−
オクタ７１０ｍｌ溶液を加え、加熱撹拌して、アルキル
化、異性化及びトランスアルキル化を行なった後、蒸留
し、続いて晶析して、６−イソプロビル−２−ナフトー
ルを回収する操作を３回繰返して、純度９５％の６−イ
ツブロビルー２−ナフトールを合わせて１３．９ ｇ得
た。Hereinafter, in exactly the same manner as above, 4 g of 2-naphthol, 6 g of Nafion, and 200 g of n-octane were added to the reaction mixture other than 6-isopropyl-2-naphthol recovered by crystallization.
m1 and to this isopropanol 3ff11 n-
Add 710 ml of Octa solution, heat and stir to perform alkylation, isomerization, and transalkylation, followed by distillation, followed by crystallization to recover 6-isopropyl-2-naphthol three times. The procedure was repeated to obtain a total of 13.9 g of 6-itubroby-2-naphthol with a purity of 95%.
このようにして、６−イソプロビル−２−ナフトール以
外の反応生成物を反応系に戻し、且つ、反応系でのイソ
プロピル基数／ナフトール環数の比を所定の範囲に保つ
ことによって、５１ｇの２−ナフトールから２４ｇの６
−イツブロピル〜２−ナフトールを得ることができた。In this way, by returning the reaction products other than 6-isopropyl-2-naphthol to the reaction system and maintaining the ratio of the number of isopropyl groups/number of naphthol rings in the reaction system within a predetermined range, 51 g of 2 -24g of 6 from naphthol
-Itubropil~2-naphthol could be obtained.
実施例２
２−メトキシナフタレン３０ｇ、プロ１−ン型のｕｓｙ
＜東ソー側製ＴＳＺ３３０）４ｇ及びｎ−デカン１６
０ｍ１からなる混合物を予め加熱還流させ、これに窒素
で１０％に希釈したプロピレンを１００ｍ１／分の速度
で２０時間導入した。プロピレンの導入を止めた後、更
に、１時間加熱還流した。Example 2 30 g of 2-methoxynaphthalene, pro-1-type usy
<TSZ330 manufactured by Tosoh) 4g and n-decane 16
A mixture of 0 ml was previously heated to reflux, and propylene diluted to 10% with nitrogen was introduced thereto at a rate of 100 ml/min for 20 hours. After stopping the introduction of propylene, the mixture was further heated under reflux for 1 hour.
反応成績は、２−メトキシナフタレン転化率８６％、モ
ノイソプロピル−２−メトキシナフタレン選択率７０％
、ジイソプロピル−２−メトキシナフタレン選択率２３
％及びポリイソプロピル−２−メトキシナフタレン選択
率７％であった。The reaction results were 2-methoxynaphthalene conversion rate of 86% and monoisopropyl-2-methoxynaphthalene selectivity of 70%.
, diisopropyl-2-methoxynaphthalene selectivity 23
% and polyisopropyl-2-methoxynaphthalene selectivity was 7%.
この反応混合物３９ｇを５段のオールダシヨーカラムを
用いて減圧２鶴Ｈｇ下に蒸留して、１４３〜１４９℃の
留分２１ｇを得た。この留分の組成は、２−メトキシナ
フタレン１％、６−イソプロビル−２−メトキシナフタ
レン３０％、その他のイソプロピル−２−メトキシナフ
タレン６２％及びジイソプロピル−２−メトキシナフタ
レン７％であった。39 g of this reaction mixture was distilled under reduced pressure of 2 Tsuru Hg using a 5-stage old column to obtain 21 g of a fraction having a temperature of 143 to 149°C. The composition of this fraction was 1% 2-methoxynaphthalene, 30% 6-isopropyl-2-methoxynaphthalene, 62% other isopropyl-2-methoxynaphthalene, and 7% diisopropyl-2-methoxynaphthalene.
次いで、この反応混合物をｎ−ヘキサン６０＋＋ｍから
晶析させたところ、純度９４％の６−イソプロビル−２
−メトキシナフタレン４．４ｇを得た。This reaction mixture was then crystallized from 60++ m of n-hexane, yielding 6-isopropyl-2 with a purity of 94%.
-4.4 g of methoxynaphthalene was obtained.
次に、上記晶析にて回収した６−イソプロビル−２−メ
トキシナフタレン以外の反応生成物３４ｇに２−メトキ
シナフタレン４ｇ、プロトン型のＵＳＹ４ ｇ及びｎ−
デカン１６０ｍ１を加え、この混合物を予め加熱還流さ
せ、これに窒素で１０％に希釈したプロピレンを４０ｍ
１／分の速度で３時間導入した。この後、更に、１時間
加熱を続けた。Next, 4 g of 2-methoxynaphthalene, 4 g of proton type USY, and n-
160 ml of decane was added, the mixture was previously heated to reflux, and 40 ml of propylene diluted to 10% with nitrogen was added.
The introduction was carried out at a rate of 1/min for 3 hours. After this, heating was further continued for 1 hour.
得られた反応生成物３９ｇの組成は、２−メトキシナフ
タレン１３％、モノイソプロピル−２一メトキシナフク
レン６１％、ジイソプロピル−２−メトキシナフタレン
１７％、ポリイソプロピル−２−メトキシナフタレン９
％であった。The composition of 39 g of the obtained reaction product was 13% of 2-methoxynaphthalene, 61% of monoisopropyl-2-methoxynaphthalene, 17% of diisopropyl-2-methoxynaphthalene, and 9% of polyisopropyl-2-methoxynaphthalene.
%Met.
この反応混合物を前記と同様に蒸留して、１４３〜ｂ
分をｎ−ヘキサン６０ｍ１から晶析させたところ、純度
９５％の６−イソプロビル−２−メトキシナフタレン４
．８ｇを得た。This reaction mixture was distilled in the same manner as above, and the fraction 143-b was crystallized from 60 ml of n-hexane.
．． 8g was obtained.
以下、上記と全く同様にして、晶析にて回収した６−イ
ツブロビルー２−メトキシナフタレン１＼外の反応生成
物に２−メトキシナフタレン４ｇ、プロトン型のＵＳＹ
４ｇ及びｎ−デカン１６０ｍ１を加え、この混合物を予
め加熱還流させ、これに窒素で１０％に希釈したプロピ
レンを４０ｍ１／分の速度で３時間導入して、加熱撹拌
して、アルキル化、異性化及びトランスアルキル化を行
なった後、蒸留し、続いて晶析して、６−イソプロパノ
−ルー２−メトキシナフタレンを回収する操作を３回繰
返して、純度９４％の６−イソプロビル−２−メトキシ
ナフタレンを合わせて１３．６ ｇ得た。Hereinafter, in exactly the same manner as above, 4 g of 2-methoxynaphthalene and proton type USY were added to the reaction product other than 6-itubrobyl-2-methoxynaphthalene 1\ recovered by crystallization.
4 g and 160 ml of n-decane were added, and the mixture was heated to reflux in advance. Propylene diluted to 10% with nitrogen was introduced into this at a rate of 40 ml/min for 3 hours, and the mixture was heated and stirred for alkylation and isomerization. After performing transalkylation and distillation, the operation of recovering 6-isopropanol-2-methoxynaphthalene by subsequent crystallization was repeated three times to obtain 6-isopropyl-2-methoxy with a purity of 94%. A total of 13.6 g of naphthalene was obtained.
このようにして、６−イソプロビル−２−メトキシナフ
タレン以外の反応生成物を反応系に戻し、且つ、反応系
でのイソプロピル基数／ナフトール環数の比を所定の範
囲に保つことによって、４６ｇの２−メトキシナフタレ
ンから２３ｇの６−イソプロビル−２−メトキシナフタ
レンを得ることができた。In this way, by returning the reaction products other than 6-isopropyl-2-methoxynaphthalene to the reaction system and maintaining the ratio of the number of isopropyl groups/number of naphthol rings in the reaction system within a predetermined range, 46 g of 23 g of 6-isopropyl-2-methoxynaphthalene could be obtained from 2-methoxynaphthalene.
Claims (3)
された原料ナフタレン誘導体を酸触媒の存在下にプロピ
レン及びイソプロパノールから選ばれるイソプロピル化
剤にてイソプロピル化し、イソプロピル基数／ナフタレ
ン環数の比が０．４〜２．２の範囲にある反応混合物を
得、この反応混合物を蒸留して、２位置換６−イソプロ
ピルナフタレンが濃縮された留分を得、この留分を脂肪
族炭化水素から晶析させて、２位置換６−イソプロピル
ナフタレンを回収すると共に、上記蒸留及び晶析による
回収物以外の一部又は全部を戻し分として原料ナフタレ
ン誘導体に加え、原料ナフタレン誘導体をイソプロピル
化することを特徴とする２位置換６−イソプロピルナフ
タレンの製造方法。(1) A raw material naphthalene derivative in which the 2-position is substituted with a hydroxyl group, a methoxy group, or an ethoxy group is isopropylated with an isopropylating agent selected from propylene and isopropanol in the presence of an acid catalyst, and the ratio of the number of isopropyl groups/the number of naphthalene rings is A reaction mixture ranging from 0.4 to 2.2 is obtained, and this reaction mixture is distilled to obtain a fraction enriched in 2-substituted 6-isopropylnaphthalene, which is then crystallized from aliphatic hydrocarbons. 2-substituted 6-isopropylnaphthalene is recovered, and a part or all of the material other than the recovered material from the above-mentioned distillation and crystallization is added to the raw material naphthalene derivative as a return amount, and the raw material naphthalene derivative is isopropylated. A method for producing 2-substituted 6-isopropylnaphthalene.
ロピル基／ナフタレン環のモル比を０．４１〜６．０の
範囲とすることを特徴とする請求項第１項記載の２位置
換６−イソプロピルナフタレンの製造方法。(2) The 2-substituted 6- substituted at the 2-position according to claim 1, characterized in that the returned amount is added to the raw material naphthalene derivative so that the molar ratio of isopropyl group/naphthalene ring is in the range of 0.41 to 6.0. Method for producing isopropylnaphthalene.
タン又はこれらの２種以上の混合物であることを特徴と
する請求項第１項記載の２位置換６−イソプロピルナフ
タレンの製造方法。(3) The method for producing 2-substituted 6-isopropylnaphthalene according to claim 1, wherein the crystallization solvent is pentane, hexane, heptane, octane, or a mixture of two or more thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2301289A JPH04173754A (en) | 1990-11-06 | 1990-11-06 | Production of 2 position-substituted 6-isopropylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2301289A JPH04173754A (en) | 1990-11-06 | 1990-11-06 | Production of 2 position-substituted 6-isopropylnaphthalene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04173754A true JPH04173754A (en) | 1992-06-22 |
Family
ID=17895044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2301289A Pending JPH04173754A (en) | 1990-11-06 | 1990-11-06 | Production of 2 position-substituted 6-isopropylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04173754A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005087368A1 (en) * | 2004-03-10 | 2005-09-22 | Japan Science And Technology Agency | Catalyst and method for producing methylnaphthalene |
-
1990
- 1990-11-06 JP JP2301289A patent/JPH04173754A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005087368A1 (en) * | 2004-03-10 | 2005-09-22 | Japan Science And Technology Agency | Catalyst and method for producing methylnaphthalene |
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