JP2016210700A - 4−ヒドロキシ安息香酸長鎖エステルの精製方法 - Google Patents
4−ヒドロキシ安息香酸長鎖エステルの精製方法 Download PDFInfo
- Publication number
- JP2016210700A JP2016210700A JP2015093393A JP2015093393A JP2016210700A JP 2016210700 A JP2016210700 A JP 2016210700A JP 2015093393 A JP2015093393 A JP 2015093393A JP 2015093393 A JP2015093393 A JP 2015093393A JP 2016210700 A JP2016210700 A JP 2016210700A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- chain ester
- formula
- organic layer
- hydroxybenzoic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 title claims abstract description 55
- 150000002148 esters Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000012044 organic layer Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 5
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 20
- 239000013078 crystal Substances 0.000 description 15
- -1 4-hydroxybenzoic acid ester Chemical class 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- XSFDAOSPLREHPH-UHFFFAOYSA-N 1-tetracosoxytetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCCCCCCCC XSFDAOSPLREHPH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- SJNCMISSTSMUFF-UHFFFAOYSA-N hexadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 SJNCMISSTSMUFF-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 2
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CMHMMKSPYOOVGI-UHFFFAOYSA-N Isopropylparaben Chemical compound CC(C)OC(=O)C1=CC=C(O)C=C1 CMHMMKSPYOOVGI-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GMMXJVUYXPXLPY-UHFFFAOYSA-N decyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 GMMXJVUYXPXLPY-UHFFFAOYSA-N 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- RXHIZFMFPLHZDT-UHFFFAOYSA-N hexadecyl 4-methylbenzenesulfonate Chemical compound CCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=C(C)C=C1 RXHIZFMFPLHZDT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 2
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 2
- 229960003415 propylparaben Drugs 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- MXAXVJBDSGPAIZ-UHFFFAOYSA-N tetracosyl 4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OCCCCCCCCCCCCCCCCCCCCCCCC)C=C1 MXAXVJBDSGPAIZ-UHFFFAOYSA-N 0.000 description 2
- FPLNRAYTBIFSFW-UHFFFAOYSA-N tricosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCO FPLNRAYTBIFSFW-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RTSZQXSYCGBHMO-UHFFFAOYSA-N 1,2,4-trichloro-3-prop-1-ynoxybenzene Chemical compound CC#COC1=C(Cl)C=CC(Cl)=C1Cl RTSZQXSYCGBHMO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VTIMKVIDORQQFA-UHFFFAOYSA-N 2-Ethylhexyl-4-hydroxybenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(O)C=C1 VTIMKVIDORQQFA-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- HZYCFUNVUSGJBL-UHFFFAOYSA-J C(C)(=[O+][O-])[O-].[Zr+4].C(C)(=[O+][O-])[O-].C(C)(=[O+][O-])[O-].C(C)(=[O+][O-])[O-] Chemical compound C(C)(=[O+][O-])[O-].[Zr+4].C(C)(=[O+][O-])[O-].C(C)(=[O+][O-])[O-].C(C)(=[O+][O-])[O-] HZYCFUNVUSGJBL-UHFFFAOYSA-J 0.000 description 1
- GNKIKWFLQLKHHD-UHFFFAOYSA-N CCCCC(CC)CO[Ti] Chemical compound CCCCC(CC)CO[Ti] GNKIKWFLQLKHHD-UHFFFAOYSA-N 0.000 description 1
- MDWILZWJWSHISN-UHFFFAOYSA-N CCCCC(CC)CO[Zr] Chemical compound CCCCC(CC)CO[Zr] MDWILZWJWSHISN-UHFFFAOYSA-N 0.000 description 1
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XPJVKCRENWUEJH-UHFFFAOYSA-N Isobutylparaben Chemical compound CC(C)COC(=O)C1=CC=C(O)C=C1 XPJVKCRENWUEJH-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NNOOSZUXECFEDH-UHFFFAOYSA-N OC1=CC=C(C(=O)OCCCCCCCCCCCCCCCCCCCCCCC)C=C1 Chemical compound OC1=CC=C(C(=O)OCCCCCCCCCCCCCCCCCCCCCCC)C=C1 NNOOSZUXECFEDH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CQOXUSHAXLMSEN-UHFFFAOYSA-N antimony(3+);propan-1-olate Chemical compound CCCO[Sb](OCCC)OCCC CQOXUSHAXLMSEN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- RGJOGVBIFBEFMC-UHFFFAOYSA-N docosyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 RGJOGVBIFBEFMC-UHFFFAOYSA-N 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- SNYRYVGRFMTVGK-UHFFFAOYSA-N heptadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 SNYRYVGRFMTVGK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- JVWIKEKXXPEYCW-UHFFFAOYSA-N icosyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 JVWIKEKXXPEYCW-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N n-nonadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 1
- RKYSGLYYPJTRCZ-UHFFFAOYSA-N nonadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 RKYSGLYYPJTRCZ-UHFFFAOYSA-N 0.000 description 1
- ITYCRFXTOMEQFF-UHFFFAOYSA-N octadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 ITYCRFXTOMEQFF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JGOJQVLHSPGMOC-UHFFFAOYSA-N triethyl stiborite Chemical compound [Sb+3].CC[O-].CC[O-].CC[O-] JGOJQVLHSPGMOC-UHFFFAOYSA-N 0.000 description 1
- KEUYHGXCOWNTEJ-UHFFFAOYSA-N trimethyl stiborite Chemical compound [Sb+3].[O-]C.[O-]C.[O-]C KEUYHGXCOWNTEJ-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- VNHZHSYTJBADIV-UHFFFAOYSA-N undecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 VNHZHSYTJBADIV-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明に使用される金属触媒の量は、4−ヒドロキシ安息香酸短鎖エステル100重量部に対し、0.1〜10重量部、好ましくは0.5〜7重量部、より好ましくは1〜5重量部であるのが良い。
脂肪族アルコールの仕込量に対する各成分の生成量のモル比を転化率とした。また、各出発物質の仕込量に対する残存量のモル比を残存率とした。
各成分の生成量および各出発物質の残存量は、以下の条件にて高速液体クロマトグラフィー(HLPC)およびガスクロマトグラフィー(GC)による定量分析により求めた。
装置: Waters アライアンス 2487/2996
カラム型番: L−Column
流量: 1.0mL/分
溶媒比: H2O(pH2.3)/CH3OH=58/42(30分)→5分→10/90(55分)、グラジエント分析
波長: 229nm/254nm
カラム温度: 40℃
装置: 株式会社島津製作所製GC−2014/GC−14A
カラム型番: G−100
注入量: 1.0μL
オーブン温度: 310℃
キャリアガス: ヘリウム
検出器: FID
撹拌機、温度センサーおよびディーンスターク装置を備えた1Lの4つ口フラスコに、ヘキサデカノール(CeOH)179gを加え、窒素気流下、70℃まで昇温し溶融させた。次いで、4−ヒドロキシ安息香酸メチル(MOB)125g、および触媒としてテトライソプロポキシチタン(TIPT)3.76gを加え、1時間かけて160℃まで昇温し、同温度で6時間反応させて粗組成物1を得た。
撹拌機、温度センサーおよびディーンスターク装置を備えた1Lの4つ口フラスコに、テトラコサノール(TcOH)263gを加え、窒素気流下、70℃まで昇温し溶融させた。次いで、4−ヒドロキシ安息香酸メチル(MOB)125g、および触媒としてテトライソプロポキシチタン(TIPT)3.76gを加え、1時間かけて160℃まで昇温し、同温度で6時間反応させた。
撹拌機、温度センサーおよび冷却管を備え、底部にコック付きの排出口を設けた1Lの底抜き4つ口フラスコに、水372g、メタノール875gおよび85重量%リン酸15gの混合溶液を仕込んだ。次いで、273gの粗組成物1を110℃まで冷却した後、混合溶液に加えた。溶液を60℃まで昇温して溶融させた後、同温度で1時間撹拌し、撹拌を停止して同温度で1時間静置することにより有機層と水層に分離し、下層の有機層を底部の排出口から回収した。
撹拌機、温度センサーおよび冷却管を備え、底部にコック付きの排出口を設けた2Lの底抜き4つ口フラスコに、水450g、メタノール1050gおよび48重量%水酸化ナトリウム4.5gの混合溶液を仕込んだ。次いで、386gの粗組成物1を110℃まで冷却した後、混合溶液に加えた。溶液を60℃まで昇温して溶解させた後、同温度で1時間撹拌し、撹拌を停止して同温度で1時間静置することにより有機層と水層に分離した。
抽出に用いた水とメタノールの重量比を、表1に示す比率としたこと以外は、実施例1と同様の操作を行った。分液性を確認し、分液処理出来たものについてはCEPBを得た。結果を表1に示す。
CeOH:へキサデカノール
CEPB:4−ヒドロキシ安息香酸ヘキサデシル
CE(PB)2:4−ヒドロキシ安息香酸4−(ヘキサデシルオキシカルボニル)フェニルエステル
Ce2O:ジセチルエーテル
POB:4−ヒドロキシ安息香酸
Ti:チタン
抽出に用いた酸を、表2に示す酸に変更したこと以外は、実施例1と同様の操作を行った。結果を表2に示す。
抽出に用いたリン酸を表3に示す量で用いたこと以外は、実施例1と同様の操作を行った。結果を表3に示す。
撹拌機、温度センサーおよび冷却管を備え、底部にコック付きの排出口を設けた1Lの底抜き4つ口フラスコに、水372g、メタノール875gおよび85重量%リン酸15gの混合溶液を仕込んだ。次いで、395gの粗組成物2を110℃まで冷却した後、混合溶液に加えた。溶液を60℃まで昇温して溶融させた後、同温度で1時間撹拌し、撹拌を停止して同温度で1時間静置することにより有機層と水層に分離し、下層の有機層を底部の排出口から回収した。
撹拌機、温度センサーおよび冷却管を備え、底部にコック付きの排出口を設けた2Lの底抜き4つ口フラスコに、水450g、メタノール1050gおよび48重量%水酸化ナトリウム4.5gの混合溶液を仕込んだ。次いで、474gの粗組成物2を110℃まで冷却した後、混合溶液に加えた。溶液を60℃まで昇温して溶融させた後、同温度で1時間撹拌し、撹拌を停止して同温度で1時間静置することにより有機層と水層に分離した。
Claims (9)
- 抽出工程において酸水溶液に含まれる溶媒が、水と低級アルコールとの混合物である、請求項1または2に記載の方法。
- 低級アルコールが、メタノール、エタノール、1−プロパノールおよび2−プロパノールからなる群から選択される1種以上である、請求項3に記載の方法。
- 水と低級アルコールの重量比が、5/5〜2/8である、請求項3または4に記載の方法。
- 抽出工程において酸水溶液に含まれる酸が、塩酸、硫酸、硝酸、リン酸、カルボン酸およびスルホン酸からなる群から選択される1種以上である、請求項1〜5のいずれかに記載の方法。
- 酸水溶液における酸の含有量が、0.1〜10重量%である、請求項1〜6のいずれかに記載の方法。
- 抽出した有機層に有機溶媒を添加して晶析する工程を更に含む、請求項1〜7のいずれかに記載の方法。
- 有機溶媒がメタノールである、請求項8に記載の方法。
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US15/130,180 US9790165B2 (en) | 2015-04-30 | 2016-04-15 | Production process and purification process of 4-hydroxy-benzoic acid long chain ester |
ES16166386.9T ES2643744T3 (es) | 2015-04-30 | 2016-04-21 | Procedimiento de producción y procedimiento de purificación de éster de cadena larga de ácido 4-hidroxibenzoico |
EP16166386.9A EP3088379B1 (en) | 2015-04-30 | 2016-04-21 | Production process and purification process of 4-hydroxy-benzoic acid long chain ester |
TW105112803A TWI703125B (zh) | 2015-04-30 | 2016-04-25 | 4-羥基-苯甲酸長鏈酯的製造方法及純化方法 |
CN201610273034.7A CN106083593B (zh) | 2015-04-30 | 2016-04-28 | 4-羟基苯甲酸长链酯的制备方法和纯化方法 |
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