CN107614473A - The manufacture method of hydroxyl substituted aromatic compound - Google Patents
The manufacture method of hydroxyl substituted aromatic compound Download PDFInfo
- Publication number
- CN107614473A CN107614473A CN201680030656.5A CN201680030656A CN107614473A CN 107614473 A CN107614473 A CN 107614473A CN 201680030656 A CN201680030656 A CN 201680030656A CN 107614473 A CN107614473 A CN 107614473A
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- CN
- China
- Prior art keywords
- substituted aromatic
- aromatic compound
- hydroxyl substituted
- formula
- integer
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 167
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 163
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 133
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000243 solution Substances 0.000 claims abstract description 64
- 239000003960 organic solvent Substances 0.000 claims abstract description 62
- 239000007864 aqueous solution Substances 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001301 oxygen Substances 0.000 claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 44
- 230000002378 acidificating effect Effects 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000004615 ingredient Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 96
- 150000001875 compounds Chemical class 0.000 claims description 78
- 229910052799 carbon Inorganic materials 0.000 claims description 72
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 16
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 16
- -1 hydroxyl Aromatic compound Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 150000002576 ketones Chemical class 0.000 claims description 11
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 235000005985 organic acids Nutrition 0.000 claims description 5
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229960005137 succinic acid Drugs 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 229960004106 citric acid Drugs 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229960002598 fumaric acid Drugs 0.000 claims description 3
- 229940098895 maleic acid Drugs 0.000 claims description 3
- 229960001367 tartaric acid Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- 238000000746 purification Methods 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 230000006837 decompression Effects 0.000 description 24
- 238000005342 ion exchange Methods 0.000 description 24
- 239000008346 aqueous phase Substances 0.000 description 21
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 16
- 230000008676 import Effects 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- BIJNHUAPTJVVNQ-UHFFFAOYSA-N 1-Hydroxypyrene Chemical class C1=C2C(O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 BIJNHUAPTJVVNQ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940075894 denatured ethanol Drugs 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical class C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 229940117955 isoamyl acetate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- MERJTCXDDLWWSK-UHFFFAOYSA-N 1-methylpyrrole pyrrolidin-2-one Chemical compound CN1C=CC=C1.N1C(CCC1)=O MERJTCXDDLWWSK-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical class CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YENIOYBTCIZCBJ-UHFFFAOYSA-N acetic acid;1-methoxypropan-2-ol Chemical compound CC(O)=O.COCC(C)O YENIOYBTCIZCBJ-UHFFFAOYSA-N 0.000 description 1
- LTOATULEBMBWSO-UHFFFAOYSA-N acetic acid;2-ethoxyethanol Chemical compound CC(O)=O.CCOCCO LTOATULEBMBWSO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
First manufacture method of the hydroxyl substituted aromatic compound of the present invention includes following process (Contact operation)：Hydroxyl substituted aromatic compound is set to be contacted in atmosphere of the oxygen concentration less than 20 volume % with organic solvent and/or water.In addition, the second manufacture method of the hydroxyl substituted aromatic compound of the present invention includes following process：Make to contact comprising the organic solvent not mixed arbitrarily with water and the solution (α) of hydroxyl substituted aromatic compound, with acidic aqueous solution, the metal ingredient in hydroxyl substituted aromatic compound is extracted.
Description
Technical field
The present invention relates to the manufacture method of hydroxyl substituted aromatic compound (such as dihydroxy naphthlene).
Background technology
Hydroxyl substituted aromatic compound, such as dihydroxy naphthlene are as the encapsulant of semiconductor, smears, anti-
It is useful (referring for example to patent document 1 to lose agent with the raw material of material, the compound of semiconductor lower floor film formation material or resin
~2).In addition, as hydroxyl substituted aromatic compound, the purification process of such as dihydroxy naphthlene, it is known to specific method (example
As with reference to patent document 3).
Prior art literature
Patent document
Patent document 1：International Publication No. 2013/024778
Patent document 2：International Publication No. 2013/024779
Patent document 3：Chinese patent application discloses No. 103467249
The content of the invention
Problems to be solved by the invention
For conventional disclosed hydroxyl substituted aromatic compound, the purification process of such as dihydroxy naphthlene, purity be present
There is limit or have the problem of fluctuation of purity and yield in raising, seek hydroxyl substituted aromatic compound, such as dihydroxy naphthlene
Purification process improvement.
In addition, in such use described in background technology, particularly tenor turns into the weight for make it that yield rate improves
The performance evaluation project wanted.That is, using hydroxyl substituted aromatic compound, such as dihydroxy naphthlene as compound obtained from raw material or
In the case of including a large amount of metals in resin, metal residual makes the electrical characteristics of semiconductor reduce in semiconductor, it is therefore desirable to
Reduce the content of the metal as impurity.
As it is for the purpose of reducing tenor, obtained by hydroxyl substituted aromatic compound, such as dihydroxy naphthlene
The purification process of compound or resin, it is contemplated that make to include the compound or the mixture and ion exchange of resin and organic solvent
The method of resin contact, the method filtered with filter etc..However, use the high hydroxyl substituted aromatic of tenor
When compound, such as dihydroxy naphthlene are used as raw material, using the above method, have that, cost big to the load of metal removal uprise asks
Topic.
Therefore, it is desirable to establish hydroxyl substituted aromatic compound, such as dihydroxy for the high-purity that tenor reduces
The industrial favourable purification process of naphthalene.
In addition, in the case that the purity of hydroxyl substituted aromatic compound, such as dihydroxy naphthlene is low, exists and substituted by hydroxyl
The problem of compound or the yield of resin that aromatic compound, such as dihydroxy naphthlene obtain decline or yield fluctuates.
And then for conventional disclosed hydroxyl substituted aromatic compound, the purification process of such as dihydroxy naphthlene, do not close
In the record for reducing tenor, in addition, it is insufficient that tenor, which reduces,.
It is an object of the present invention to provide：Hydroxyl substituted aromatic compound, such as dihydroxy naphthlene it is industrial favourable
Manufacture method.
The solution used to solve the problem
The present inventor etc. have made intensive studies, as a result found to solve above-mentioned problem：By by hydroxyl substituted aroma
Compounds of group (such as dihydroxy naphthlene) is purified under given conditions, so as to high-purity high-yield and stably
Ground manufacture hydroxyl substituted aromatic compound (such as dihydroxy naphthlene), completes the present invention.
In addition, the present inventor etc. have made intensive studies, as a result found to solve above-mentioned problem：By making to include hydroxyl
The solution of base substituted aromatic compound (such as dihydroxy naphthlene) and specific organic solvent, contact and carry out with acidic aqueous solution
Extraction process, it is complete so as to reduce the content of the various metals in hydroxyl substituted aromatic compound (such as dihydroxy naphthlene)
Into the present invention.
That is, the present invention is as described below.
[1]
A kind of manufacture method of hydroxyl substituted aromatic compound, it includes following process (Contact operation)：Take hydroxyl
Contacted for aromatic compound in atmosphere of the oxygen concentration less than 20 volume % with organic solvent and/or water.
[2]
The manufacture method of hydroxyl substituted aromatic compound according to [1], wherein, foregoing hydroxy substituted aromatic
Compound is following formula (A0) and/or (B0) shown in hydroxyl substituted aromatic compound.
(above-mentioned formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0It is each independent for 0~9 integer, Ra
Ground is the alkyl of hydrogen atom, hydroxyl, halogen group, the straight-chain of carbon number 1~40, branched or ring-type, optionally has substitution
The group that the aryl of the carbon number 6~40 of base or the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkene
Base optionally includes ehter bond, ketonic bond or ester bond.
Above-mentioned formula (B0) in, n1For 0~9 integer, p1For 0~9 integer, RbBe each independently hydrogen atom, hydroxyl,
The virtue of halogen group, the straight-chain of carbon number 1~40, branched or the alkyl of ring-type, the optionally carbon number 6~40 with substituent
The group that the alkenyl and combinations thereof of base or carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl are optionally comprising ehter bond, ketone
Key or ester bond.)
[3]
According to the manufacture method described in [2], wherein, previously described formula (A0) shown in hydroxyl substituted aromatic compound to be following
Compound shown in formula (A), previously described formula (B0) shown in hydroxyl substituted aromatic compound be the chemical combination shown in following formula (B)
Thing.
(in above-mentioned formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, R0Independently of one another
For the alkyl of the straight-chain of carbon number 1~30, branched or ring-type, the aryl or carbon of the optional carbon number 6~15 with substituent
The alkenyl of number 2~15,
In above-mentioned formula (B), n1For 0~9 integer, p1For 0~9 integer, R1It is each independently the straight of carbon number 1~30
Chain, the alkyl of branched or ring-type, the aryl of carbon number 6~15 or the alkenyl of carbon number 2~15 optionally with substituent.)
[4]
According to the manufacture method described in [3], wherein, hydroxyl substituted aromatic compound shown in previously described formula (A) be selected from
As the compound shown in following formula (A-1), the compound shown in following formula (A-2), the compound shown in following formula (A-3) and
Compound group shown in following formula (A-4) into group in more than a kind,
Hydroxyl substituted aromatic compound shown in previously described formula (B) is the compound shown in following formula (B-1).
(in above-mentioned formula (A-1)~(A-4), n0For 0~9 integer, in above-mentioned formula (B-1), n1For 0~9 integer.)
[5]
According to the manufacture method described in [3], wherein, the hydroxyl substituted aromatic compound shown in previously described formula (A) is following
Compound shown in formula (1).
[6]
According to the manufacture method any one of [1]~[5], it includes following process：Make foregoing hydroxy substituted aroma
Compounds of group is dissolved in organic solvent.
[7]
According to the manufacture method described in [6], wherein, foregoing hydroxy substituted aromatic compound is dissolved in organic solvent
Afterwards, including the process that contacts the solution of the hydroxyl substituted aromatic compound and activated carbon.
[8]
According to the manufacture method described in [6] or [7], wherein, it is dissolved in foregoing hydroxy substituted aromatic compound organic
After solvent, including make the process of the hydroxyl substituted aromatic compound crystallization.
[9]
According to the manufacture method any one of [1]~[8], wherein, aforementioned organic solvents are selected from by methanol, second
Alcohol, isopropanol, acetone, 1-METHYLPYRROLIDONE, propylene glycol monomethyl ether, toluene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl tert-butyl
More than a kind in the group of base ketone, propylene glycol methyl ether acetate and ethyl acetate composition.
[10]
A kind of manufacture method of hydroxyl substituted aromatic compound, it includes following process：Make comprising arbitrarily mixed not with water
The organic solvent of sum and the solution (α) of hydroxyl substituted aromatic compound, contact with acidic aqueous solution, to hydroxyl substituted aromatic
Metal ingredient in compound is extracted.
[11]
According to the manufacture method described in [10], wherein, foregoing hydroxy substituted aromatic compound is following formula (A0) and/or
(B0) shown in hydroxyl substituted aromatic compound.
(above-mentioned formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0It is each independent for 0~9 integer, Ra
Ground is the alkyl of hydrogen atom, hydroxyl, halogen group, the straight-chain of carbon number 1~40, branched or ring-type, optionally has substitution
The group that the aryl of the carbon number 6~40 of base or the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkene
Base optionally includes ehter bond, ketonic bond or ester bond.
Above-mentioned formula (B0) in, n1For 0~9 integer, p1For 0~9 integer, RbBe each independently hydrogen atom, hydroxyl,
The virtue of halogen group, the straight-chain of carbon number 1~40, branched or the alkyl of ring-type, the optionally carbon number 6~40 with substituent
The group that the alkenyl and combinations thereof of base or carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl are optionally comprising ehter bond, ketone
Key or ester bond.)
[12]
According to the manufacture method described in [11], wherein, previously described formula (A0) shown in hydroxyl substituted aromatic compound be under
State the compound shown in formula (A), previously described formula (B0) shown in hydroxyl substituted aromatic compound be the chemical combination shown in following formula (B)
Thing.
(in above-mentioned formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, R0Independently of one another
For the alkyl of the straight-chain of carbon number 1~30, branched or ring-type, the aryl or carbon of the optional carbon number 6~15 with substituent
The alkenyl of number 2~15,
In above-mentioned formula (B), n1For 0~9 integer, p1For 0~9 integer, R1It is each independently the straight of carbon number 1~30
Chain, the alkyl of branched or ring-type, the aryl of carbon number 6~15 or the alkenyl of carbon number 2~15 optionally with substituent.)
[13]
According to the manufacture method described in [12], wherein, hydroxyl substituted aromatic compound shown in previously described formula (A) be selected from
As the compound shown in following formula (A-1), the compound shown in following formula (A-2), the compound shown in following formula (A-3) and
Compound group shown in following formula (A-4) into group in more than a kind,
Hydroxyl substituted aromatic compound shown in previously described formula (B) is the compound shown in following formula (B-1).
(in above-mentioned formula (A-1)~(A-4), n0For 0~9 integer, in above-mentioned formula (B-1), n1For 0~9 integer.)
[14]
According to the manufacture method described in [12], wherein, the hydroxyl substituted aromatic compound shown in previously described formula (A) is following
Compound shown in formula (1).
[15]
According to the manufacture method any one of [10]~[14], wherein, it is less than 20 volume % atmosphere in oxygen concentration
Lower progress.
[16]
According to the manufacture method any one of [10]~[15], wherein, after the process of foregoing extraction, in addition to it is as follows
Process：The extraction process of the metal ingredient in hydroxyl substituted aromatic compound is carried out using water.
[17]
According to the manufacture method any one of [10]~[16], wherein, the organic solvent not mixed arbitrarily with water is
Selected from being made up of toluene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl iso-butyl ketone (MIBK), propylene glycol methyl ether acetate and ethyl acetate
Group in more than a kind.
[18]
According to the manufacture method any one of [10]~[17], wherein, the aforementioned acid aqueous solution be selected from by hydrochloric acid,
Sulfuric acid, nitric acid and phosphoric acid composition group in more than a kind of inorganic acid aqueous solution or be selected from by acetic acid, propionic acid, oxalic acid, third
Diacid, butanedioic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid and trifluoroacetic acid
More than a kind of aqueous solutions of organic acids in the group of composition.
[19]
According to the manufacture method any one of [10]~[18], wherein, foregoing hydroxy substituted aromatic compound is
More than a kind in the group being made up of 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene.
The effect of invention
According to the present invention it is possible to industrially advantageously provide the system of hydroxyl substituted aromatic compound (such as dihydroxy naphthlene)
Make method, can with high yield stably manufacture high-purity hydroxyl substituted aromatic compound (such as dihydroxy naphthlene).
In addition, according to the present invention it is possible to the content of various metals, hydroxyl substitution can be reduced by industrially advantageously providing
The manufacture method of aromatic compound (such as dihydroxy naphthlene).
Embodiment
Hereinafter, embodiments of the present invention (being also denoted as below " present embodiment ") are described in detail.Need to illustrate
, following embodiment is the example for illustrating the present invention, and the present invention is not limited to the embodiment.
The manufacture method ＞ of ＜ hydroxyl substituted aromatic compounds
First manufacture method of the hydroxyl substituted aromatic compound of present embodiment includes following process (Contact operation)：
The hydroxyl substituted aromatic compound is set to be contacted in atmosphere of the oxygen concentration less than 20 volume % with organic solvent and/or water.
In first manufacture method of present embodiment, as long as foregoing hydroxy substituted aromatic compound is with least one
The aromatic compound of phenolic hydroxyl group is just not particularly limited, such as preferred following formula (A0) and/or (B0) shown in hydroxyl substitution
Aromatic compound.
(above-mentioned formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0It is each independent for 0~9 integer, Ra
Ground is the alkyl of hydrogen atom, hydroxyl, halogen group, the straight-chain of carbon number 1~40, branched or ring-type, optionally has substitution
The group that the aryl of the carbon number 6~40 of base or the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkene
Base optionally includes ehter bond, ketonic bond or ester bond.
Above-mentioned formula (B0) in, n1For 0~9 integer, p1For 0~9 integer, RbBe each independently hydrogen atom, hydroxyl,
The virtue of halogen group, the straight-chain of carbon number 1~40, branched or the alkyl of ring-type, the optionally carbon number 6~40 with substituent
The group that the alkenyl and combinations thereof of base or carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl are optionally comprising ehter bond, ketone
Key or ester bond.)
In first manufacture method of present embodiment, previously described formula (A0) shown in hydroxyl substituted aromatic compound be preferably
Compound shown in following formula (A).
In addition, in the first manufacture method of present embodiment, previously described formula (B0) shown in hydroxyl substituted aromatic compound
Compound preferably shown in following formula (B).
(in above-mentioned formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, R0Independently of one another
For the alkyl of the straight-chain of carbon number 1~30, branched or ring-type, the aryl or carbon of the optional carbon number 6~15 with substituent
The alkenyl of number 2~15,
In above-mentioned formula (B), n1For 0~9 integer, p1For 0~9 integer, R1It is each independently the straight of carbon number 1~30
Chain, the alkyl of branched or ring-type, the aryl of carbon number 6~15 or the alkenyl of carbon number 2~15 optionally with substituent.)
In first manufacture method of present embodiment, the hydroxyl substituted aromatic compound shown in previously described formula (A) is preferably
Selected from as the compound shown in following formula (A-1), the compound shown in following formula (A-2), the chemical combination shown in following formula (A-3)
Thing and the compound group shown in following formula (A-4) into group in more than a kind.
In addition, in the first manufacture method of present embodiment, the hydroxyl substituted aromatic compound shown in previously described formula (B) is excellent
Elect the compound shown in following formula (B-1) as.
(in above-mentioned formula (A-1)~(A-4), n0For 0~9 integer, in above-mentioned formula (B-1), n1For 0~9 integer.)
According to the first manufacture method of present embodiment, by making hydroxyl substituted aromatic compound be less than 20 in oxygen concentration
Contacted in volume % atmosphere with organic solvent and/or water, for example, being dissolved in the impurity in hydroxyl substituted aromatic compound
Organic solvent and/or water simultaneously separate, so as to in high yield stably by hydroxyl substituted aromatic compound high purity.
In addition, the problem of being particularly easy to generate dimer be present in hydroxyl substituted aromatic compound, such as dihydroxy naphthlene, but
By carrying out above-mentioned Contact operation in atmosphere of the oxygen concentration less than 20 volume %, so as to suppress hydroxyl substituted aromatic
The generation of compound, the accessory substance such as the dimer caused by the oxidation of dihydroxy naphthlene, stably it can be received so that high-purity is high
Rate manufacture hydroxyl substituted aromatic compound, such as dihydroxy naphthlene.
In first manufacture method of present embodiment, the oxygen concentration of Contact operation is preferably shorter than 10 volume %, more preferably low
In 5 volume %, even more preferably below 1 volume %.The oxygen concentration of Contact operation is lower, hydroxyl substituted aromatic compound, example
Rotten inhibition such as dihydroxy naphthlene is bigger.The lower limit of the oxygen concentration of drying process is not particularly limited, for example, 0.01 body
Product %.
The method that alloing oxygen concentration reduces applies known method, is not particularly limited, such as can enumerate such as lower section
Method：Nitrogen is imported after nitrogen is flowed or is depressurized in the kettle purified, so as to carry out gas displacement.Or can be with
Enumerate the method for being depressurized and being carried out under vacuo.The method that nitrogen is imported after the kettle purified decompression is easy and true
It is real, it is preferred.
The confirmation of oxygen concentration can be implemented in a known manner, be not particularly limited, such as can enumerate following method：Make
Nitrogen flows in the kettle purified, the oxygen concentration using oxymeter measure from the gas of exhaust outlet discharge, so as to carry out.
The method that oxymeter is set in the kettle purified can also be enumerated.
In above-mentioned Contact operation, as long as Contact Temperature can suppress hydroxyl substituted aromatic compound, such as dihydroxy naphthlene
It is rotten be just not particularly limited, preferably 0~150 DEG C of scope, more preferably 5~100 DEG C of scope, further preferred 5~60
DEG C scope.When Contact Temperature is in aforementioned range, purity and yield become good, also have temperature adjustment to become readily tendency.
In above-mentioned Contact operation, as long as time of contact can suppress hydroxyl substituted aromatic compound, such as dihydroxy naphthlene
It is rotten be just not particularly limited, the scope of preferably 1 minute~120 minutes, the scope of more preferably 1 minute~60 minutes, enter one
The step scope of preferably 1 minute~30 minutes.When time of contact is in aforementioned range, purity and yield become good, also there is productivity ratio
The tendency of raising.
In addition, the pressure in above-mentioned Contact operation can apply decompression, normal pressure and pressurization.
Hydroxyl substituted aromatic compound shown in the previously described formula (A) used in first manufacture method of present embodiment is special
Compound that You Xuanwei be shown in following formula (1).
Herein, the compound shown in above-mentioned formula (1) is not particularly limited, from the viewpoint of the supply of raw material, preferably
Selected from by 1,2- dihydroxy naphthlenes, 1,3- dihydroxy naphthlenes, 1,4- dihydroxy naphthlenes, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 1,7- bis-
Hydroxyl naphthalene, 1,8- dihydroxy naphthlenes, 2,3- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene composition group in a kind with
On.
In addition, the compound shown in above-mentioned formula (1) is not particularly limited, from the compound obtained using the compound as raw material
Or from the viewpoint of the heat resistance of resin, it is more preferably selected from by 1 in the group of 2,6- dihydroxy naphthlenes and 2,7- dihydroxy naphthlene composition
More than kind.
Compound shown in above-mentioned formula (1) is not particularly limited, from the compound or tree obtained using the compound as raw material
From the viewpoint of the further heat resistance of fat, further preferred 2,6- dihydroxy naphthlenes.
Compound shown in above-mentioned formula (1) can utilize means known to manufacturer and reagent manufacturer etc. and easily obtain
.Furthermore it is possible to method known to applying and suitably synthesize, its synthetic method is not particularly limited.
The hydroxyl substituted aromatic compound used in first manufacture method of present embodiment, which can be used alone, also may be used
To mix two or more use.In addition, hydroxyl substituted aromatic compound can contain various surfactants, various crosslinking agents,
Various acid agents, various stabilizers etc..
The organic solvent and/or water used in first manufacture method of present embodiment is not particularly limited, for example, it is preferable to
The organic solvent and/or water of semiconductor fabrication process can be can be safely used for.The organic solvent that uses and/or the amount of water relative to
Hydroxyl substituted aromatic compound generally preferable 0.1~1000 mass times used or so, it is more excellent from the viewpoint of economy
Select 0.5~500 mass times, further preferred 1~100 mass times.
As the concrete example of the organic solvent used in the first manufacture method of present embodiment, following, example is not limited to
Alcohols, acetone, MEK, the methyl such as tetrahydrofuran, 1,3- dioxolanes ethers, methanol, ethanol, isopropanol can such as be enumerated
The ketones such as isobutyl ketone, ethyl isobutylo ketone, cyclohexanone, cyclopentanone, 2-HEPTANONE, 2 pentanone, 1-METHYLPYRROLIDONE, ethylene glycol
Glycol ethers, diethyl ether, the diisopropyl ethers such as single ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), dihydroxypropane single-ether
Deng the esters such as ethers, ethyl acetate, n-butyl acetate, isoamyl acetate, ethylene glycol monoethylether acetate, ethylene glycol monobutyl ether second
Glycol ethers acetate esters, n-hexane, the positive heptan such as acid esters, propylene glycol methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate
Halogenated hydrocarbons such as the aliphatic hydrocarbons such as alkane, toluene, dimethylbenzene etc. are aromatic hydrocarbon, dichloromethane, chloroform etc..
Wherein, it is preferably selected from by methanol, ethanol, isopropanol, acetone, 1-METHYLPYRROLIDONE, propylene glycol monomethyl ether, first
In the group that benzene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl iso-butyl ketone (MIBK), propylene glycol methyl ether acetate and ethyl acetate form
More than a kind, it is more preferably selected from by methanol, ethanol, isopropanol, acetone, 1-METHYLPYRROLIDONE, propylene glycol monomethyl ether, cyclohexanone
With more than a kind in the group of propylene glycol methyl ether acetate composition.
As the concrete example of the water used in the first manufacture method of present embodiment, be not limited to it is following, such as can be with
Enumerate running water, industrial water, ion exchange water, ultra-pure water etc..Alternatively, it is also possible to being acidic aqueous solution.As acid water-soluble
Liquid, it is not particularly limited, can be suitably selected in the aqueous solution dissolved with commonly known organic and inorganic based compound from water
Select.Such as it can enumerate：The aqueous solution dissolved with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid in water；Or, second is dissolved with water
Acid, propionic acid, oxalic acid, malonic acid, butanedioic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, to toluene
The aqueous solution of the organic acids such as sulfonic acid, trifluoroacetic acid.The pH of acidic aqueous solution is not particularly limited, and considers to hydroxyl substituted aromatic
The harmful effect of compound, preferably adjust the acid degree of the aqueous solution.Generally, the pH scopes preferably 0~5 or so of acidic aqueous solution,
More preferably pH0~4 or so, further preferred pH0~3 or so.
Wherein, in order to suppress the pollution of metal and chlorine component, preferred ion exchanged water, ultra-pure water etc..
These organic solvents, water individually can use or mix two or more and use.
Additionally, it is preferred that reduce dissolved oxygen in advance from these organic solvents and/or water.The method of dissolved oxygen is reduced without spy
Do not limit, known method can be applied, the nonactive gas such as nitrogen of being ventilated under normal or reduced pressure into organic solvent and/or water
Body or the method for applying ultrasonic wave are effective.
First manufacture method of present embodiment preferably includes following process：It is dissolved in hydroxyl substituted aromatic compound
Organic solvent.
In first manufacture method of present embodiment, in order to decolourize, demetalization and removing impurities matter etc., it is preferred that make hydroxyl
After substituted aromatic compound is dissolved in organic solvent, including connect the solution of the hydroxyl substituted aromatic compound and activated carbon
Tactile process.In addition, the Contact operation of the activated carbon is more preferably carried out in atmosphere of the oxygen concentration less than 20 volume %.Reduce and live
Property charcoal in the method for oxygen that remains be not particularly limited, known method can be applied, following method can be enumerated：In purification kettle
Middle addition activated carbon, nitrogen is imported after nitrogen is flowed or is depressurized, so as to carry out.
On the other hand, when the Contact operation of activated carbon is carried out in atmosphere of the oxygen concentration less than 20 volume %, there is suppression hydroxyl
The purity for deteriorating, further improving hydroxyl substituted aromatic compound of base substituted aromatic compound, such as dihydroxy naphthlene
Tendency, or suppress the fluctuation of purity and yield, turn into industrial more favourable technique.
First manufacture method of present embodiment is preferably, and hydroxyl substituted aromatic compound is dissolved in organic solvent
Afterwards, including the process of the hydroxyl substituted aromatic compound crystallization is made.
The method that hydroxyl substituted aromatic compound is separated can apply decompression remove, using reprecipitation separation and
Method known to combinations thereof etc..As needed, concentration operation, filter operation can be carried out, operation is centrifuged, dries behaviour
Processing known to work etc..
When carrying out these operations, in order to improve purity or suppress the fluctuation of purity and yield, it is also preferred that being less than in oxygen concentration
Implement in 20 volume % atmosphere.
Second manufacture method of the hydroxyl substituted aromatic compound of present embodiment includes following process：Make comprising not with
Organic solvent and the solution (α) of hydroxyl substituted aromatic compound that water arbitrarily mixes, contact with acidic aqueous solution, hydroxyl is taken
Extracted for the metal ingredient in aromatic compound.
In second manufacture method of present embodiment, as long as foregoing hydroxy substituted aromatic compound is with least one
The aromatic compound of phenolic hydroxyl group is just not particularly limited, such as preferred following formula (A0) and/or (B0) shown in hydroxyl substitution
Aromatic compound.
(above-mentioned formula (A0) in, n0For 0~9 integer, m0For 0~2 integer, p0It is each independent for 0~9 integer, Ra
Ground is the alkyl of hydrogen atom, hydroxyl, halogen group, the straight-chain of carbon number 1~40, branched or ring-type, optionally has substitution
The group that the aryl of the carbon number 6~40 of base or the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkene
Base optionally includes ehter bond, ketonic bond or ester bond.
Above-mentioned formula (B0) in, n1For 0~9 integer, p1For 0~9 integer, RbBe each independently hydrogen atom, hydroxyl,
The virtue of halogen group, the straight-chain of carbon number 1~40, branched or the alkyl of ring-type, the optionally carbon number 6~40 with substituent
The group that the alkenyl and combinations thereof of base or carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl are optionally comprising ehter bond, ketone
Key or ester bond.)
In second manufacture method of present embodiment, previously described formula (A0) shown in hydroxyl substituted aromatic compound be preferably
Compound shown in following formula (A).
In addition, in the second manufacture method of present embodiment, previously described formula (B0) shown in hydroxyl substituted aromatic compound
Compound preferably shown in following formula (B).
(in above-mentioned formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, R0Independently of one another
For the alkyl of the straight-chain of carbon number 1~30, branched or ring-type, the aryl or carbon of the optional carbon number 6~15 with substituent
The alkenyl of number 2~15,
In above-mentioned formula (B), n1For 0~9 integer, p1For 0~9 integer, R1It is each independently the straight of carbon number 1~30
Chain, the alkyl of branched or ring-type, the aryl of carbon number 6~15 or the alkenyl of carbon number 2~15 optionally with substituent.)
In second manufacture method of present embodiment, the hydroxyl substituted aromatic compound shown in previously described formula (A) is preferably
Selected from as the compound shown in following formula (A-1), the compound shown in following formula (A-2), the chemical combination shown in following formula (A-3)
Thing and the compound group shown in following formula (A-4) into group in more than a kind.
In addition, in the second manufacture method of present embodiment, the hydroxyl substituted aromatic compound shown in previously described formula (B) is excellent
Elect the compound shown in following formula (B-1) as.
(in above-mentioned formula (A-1)~(A-4), n0For 0~9 integer, in above-mentioned formula (B-1), n1For 0~9 integer.)
According to the second manufacture method of present embodiment, do not appointed by being dissolved in hydroxyl substituted aromatic compound with water
The organic solvent for mixing of anticipating, makes its solution be contacted with acidic aqueous solution and carries out extraction process, so that including hydroxyl substitutes virtue
After contained metal ingredient migrates to aqueous phase in the solution (α) of fragrant compounds of group and organic solvent, organic phase and aqueous phase are separated into,
The hydroxyl substituted aromatic compound that tenor reduces can be obtained.
Hydroxyl substituted aromatic compound shown in the previously described formula (A) used in second manufacture method of present embodiment is special
Compound that You Xuanwei be shown in following formula (1).
Herein, the compound shown in above-mentioned formula (1) is not particularly limited, from the viewpoint of the supply of raw material, preferably
Selected from by 1,2- dihydroxy naphthlenes, 1,3- dihydroxy naphthlenes, 1,4- dihydroxy naphthlenes, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 1,7- bis-
Hydroxyl naphthalene, 1,8- dihydroxy naphthlenes, 2,3- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene composition group in a kind with
On.
In addition, from the viewpoint of gained compound or the heat resistance of resin, the compound shown in above-mentioned formula (1) is more preferably
More than a kind in the group being made up of 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene.
From the viewpoint of gained compound or the further heat resistance of resin, the compound shown in above-mentioned formula (1) is entered
The preferred 2,6- dihydroxy naphthlenes of one step.
Compound shown in above-mentioned formula (1) can utilize means known to manufacturer and reagent manufacturer etc. and easily obtain
.Furthermore it is possible to method known to applying and suitably synthesize, its synthetic method is not particularly limited.
The hydroxyl substituted aromatic compound used in second manufacture method of present embodiment, which can be used alone, also may be used
To mix two or more use.In addition, hydroxyl substituted aromatic compound can contain various surfactants, various crosslinking agents,
Various acid agents, various stabilizers etc..
As organic solvent being used in the second manufacture method of present embodiment, not mixed arbitrarily with water, without spy
Do not limit, can preferably can be safely used for the organic solvent of semiconductor fabrication process.
It should be noted that the organic solvent not mixed arbitrarily with water refers to, the solubility of water at room temperature is less than
30%th, it is more preferably less than 20%, especially preferably less than 10% organic solvent.
As the concrete example of the organic solvent used in the second manufacture method of present embodiment, following, example is not limited to
Can such as enumerate the esters such as diethyl ether, diisopropyl ether ethers, ethyl acetate, n-butyl acetate, isoamyl acetate, MEK,
The ketones such as methyl iso-butyl ketone (MIBK), ethyl isobutylo ketone, cyclohexanone, cyclopentanone, 2-HEPTANONE, 2 pentanone, ethylene glycol monoethyl ether acetic acid
The glycol ethers second such as ester, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate
The halos such as the aliphatic hydrocarbons such as esters of gallic acid, n-hexane, normal heptane, toluene, dimethylbenzene etc. are aromatic hydrocarbon, dichloromethane, chloroform
Hydro carbons etc..Wherein, it is preferably selected from by toluene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether acetic acid
More than a kind in the group of ester and ethyl acetate composition, it is more preferably selected from by cyclohexanone, propylene glycol methyl ether acetate and acetic acid second
More than a kind in the group of ester composition.
These organic solvents individually can use or mix two or more and use.
Relative to the hydroxyl substituted aromatic compound used, the amount generally preferable 0.1~1000 of the organic solvent used
Quality times or so, from the viewpoint of economy, more preferably 0.5~500 mass times, further preferred 1~100 mass times.
In second manufacture method of present embodiment, solution (α) has also comprising the excellent of the organic solvent arbitrarily mixed with water
Selection condition.By comprising the organic solvent arbitrarily mixed with water, so as to increase the input of hydroxyl substituted aromatic compound
Amount, in addition, liquid separation improves, it can be manufactured with high kettle efficiency.The method for adding the organic solvent arbitrarily mixed with water
It is not particularly limited.Such as can be following any means：It is previously added to the method for the solution comprising organic solvent；Add in advance
Enter the method to water or acidic aqueous solution；The side for making the solution comprising organic solvent be added after being contacted with water or acidic aqueous solution
Method, the management easiness aspect of workability, input amount from operation, is preferably previously added to comprising the molten of organic solvent
The method of liquid.
As organic solvent being used in the second manufacture method of present embodiment, arbitrarily being mixed with water, without special
Limit, can preferably can be safely used for the organic solvent of semiconductor fabrication process.It should be noted that have with what water arbitrarily mixed
Solvent refers to, the solubility to the water at room temperature is more than 70%, more preferably more than 80%, particularly preferably 90% with
On organic solvent.
As the concrete example of the organic solvent arbitrarily mixed with water, be not limited to it is following, such as can enumerate tetrahydrofuran,
The ketones such as the alcohols such as the ethers such as 1,3- dioxolanes, methanol, ethanol, isopropanol, acetone, 1-METHYLPYRROLIDONE, ethylene glycol list
The glycol ethers such as ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), dihydroxypropane single-ether.Wherein, preferred N- methyl pyrrole
Pyrrolidone, propylene glycol monomethyl ether etc., further preferably in the group being made up of 1-METHYLPYRROLIDONE and propylene glycol monomethyl ether
More than a kind.
Above-mentioned organic solvent individually can use or mix two or more and use.
In addition, as long as the amount of the organic solvent arbitrarily mixed with water is that the scope of solution and aqueous phase separation is just no special
Do not limit, relative to the hydroxyl substituted aromatic compound used, it is usually preferred to 0.1~1000 mass times or so, from economy
From the viewpoint of, more preferably 0.5~500 mass times, further preferred 1~100 mass times.
As the acidic aqueous solution used in the second manufacture method of present embodiment, be not limited to it is following, can be from water
In dissolved with commonly known organic and inorganic based compound the aqueous solution in suitably select.Such as it can enumerate：It is dissolved with water
The aqueous solution of the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid；Or, dissolved with acetic acid, propionic acid, oxalic acid, malonic acid, amber in water
The organic acids such as acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid, trifluoroacetic acid
The aqueous solution.These acidic aqueous solutions individually can use or combine two or more and use.
In these acidic aqueous solutions, be preferably selected from the group that is made up of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid more than a kind
Inorganic acid aqueous solution or for selected from by acetic acid, propionic acid, oxalic acid, malonic acid, butanedioic acid, fumaric acid, maleic acid, tartaric acid, lemon
More than a kind of aqueous solutions of organic acids in the group that lemon acid, methanesulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid and trifluoroacetic acid form, more
The aqueous solution of the carboxylic acid such as preferably sulfuric acid, nitric acid and acetic acid, oxalic acid, tartaric acid, citric acid, further preferred sulfuric acid, oxalic acid, wine
Stone acid, the aqueous solution of citric acid, the aqueous solution of particularly preferred oxalic acid.The polybasic carboxylic acids such as oxalic acid, tartaric acid, citric acid are coordinated in gold
Belong to ion, produce complexing effect, result, it is believed that in the presence of the tendency for more effectively removing metal.In addition, water used herein according to
The purpose of present embodiment and it is preferred that the few water of tenor, such as ion exchange water.
The pH of the acidic aqueous solution used in present embodiment is not particularly limited, and considers to hydroxyl substituted aromatic chemical combination
The harmful effect of thing, preferably adjust the acid degree of the aqueous solution.Generally, pH scopes preferably 0~5 or so of acidic aqueous solution, more excellent
Select pH0~4 or so, further preferred 0~3 or so.
The dosage of the acidic aqueous solution used in second manufacture method of present embodiment is not particularly limited, and is used from reducing
From the viewpoint of removing the viewpoint of extraction time of metal and considering overall liquid measure to ensure operability, the use is preferably adjusted
Amount.From such a viewpoint, the dosage of acidic aqueous solution be commonly angled relative to comprising the organic solvent that is not mixed arbitrarily with water and
The solution (α) of hydroxyl substituted aromatic compound, preferably 0.01~200 mass %, more preferably 0.05~20 mass %, further
It is preferred that 0.1~10 mass %.
In second manufacture method of present embodiment, by making above-mentioned acidic aqueous solution and comprising hydroxyl substituted aromatic
The solution of compound and the organic solvent not mixed arbitrarily with water (α) contacts, so as to hydroxyl substituted aromatic compound
In metal ingredient extracted.
In second manufacture method of present embodiment, temperature when carrying out extraction process is generally preferable 0~90 DEG C, more preferably
10~85 DEG C of scope, further preferred 20~80 DEG C of scope.Extraction operation is not particularly limited, such as is filled by stirring etc.
Stood after dividing mixing, so as to carry out.Thus, it is contained in the solution comprising hydroxyl substituted aromatic compound and organic solvent
Metal ingredient to aqueous phase migrate.In addition, by this operation, the acid degree of solution reduces, and can suppress hydroxyl substituted aromatic
Compound goes bad.
By aforesaid operations, solution and aqueous phase comprising hydroxyl substituted aromatic compound and organic solvent are separated into,
Therefore, by decantation etc., the solution comprising hydroxyl substituted aromatic compound and organic solvent is reclaimed.The time of standing does not have
It is particularly limited to, from the viewpoint of the separation for the solution and aqueous phase for making to include organic solvent is better, preferably adjusts the standing
Time.It is preferably more than 1 minute, more preferably more than the 10 minutes time generally stood, further preferred more than 30 minutes.
In addition, extraction process can be only 1 time, the operation for repeating repeatedly mixing, standing, separation etc is also effective
's.
In second manufacture method of present embodiment, carried using the process for making solution (α) be contacted with acidic aqueous solution
After taking processing, the work of the extraction process of the metal ingredient in hydroxyl substituted aromatic compound is preferably also carried out using water
Sequence.Namely it is preferred that after carrying out extraction process using acidic aqueous solution, by the hydroxyl substituted aromatic compound comprising recovery
The extraction process using water is further supplied to the solution of organic solvent.It is not particularly limited using the extraction process of water, such as
Stood after being sufficiently mixed by stirring etc., so as to carry out.The solution obtained after the standing is separated into substitutes virtue comprising hydroxyl
The solution and aqueous phase of fragrant compounds of group and organic solvent, therefore, by decantation etc., it can will include hydroxyl substituted aromatic
The solution of compound and organic solvent reclaims.
In addition, water used herein is according to the purpose of present embodiment and it is preferred that the few water of tenor, such as ion are handed over
Change water, ultra-pure water etc..It can be only 1 time using the extraction process of water, repeat the behaviour of repeatedly mixing, standing, separation etc
Make and effective.It is in addition, not special using conditions such as both use ratios in the extraction process of water, temperature, times
Limit, can the contact with above-mentioned acidic aqueous solution handle situation it is same.
For possible mixed water in the so obtained solution comprising hydroxyl substituted aromatic compound and organic solvent
Point, it can be readily removable by implementing the operation such as vacuum distillation.
In addition, organic solvent can be added as needed, the concentration of hydroxyl substituted aromatic compound is adjusted to any
Concentration.
The solution for including hydroxyl substituted aromatic compound and organic solvent from gained separates hydroxyl substituted aromatic chemical combination
The method of thing is not particularly limited, such as can be removed, using known to the separation of reprecipitation and combinations thereof etc. with decompression
Method is carried out.In addition, as needed, concentration operation, filter operation can be carried out, centrifuge the public affairs such as operation, drying process
The processing known.
In addition, the second manufacture method of present embodiment is preferably carried out in atmosphere of the oxygen concentration less than 20 volume %.It is logical
Crossing makes oxygen concentration be less than 20 volume %, can suppress the rotten of hydroxyl substituted aromatic compound, can obtain the hydroxyl of high-purity
Base substituted aromatic compound.
In second manufacture method of present embodiment, oxygen concentration is more preferably less than 10 volume %, even more preferably below 5 bodies
Product %, especially preferably less than 1 volume %.Oxygen concentration is lower, can more suppress present embodiment the second manufacture method it is rotten.
The lower limit of oxygen concentration in second manufacture method of present embodiment is not particularly limited, for example, 0.01 volume %.
The method that alloing oxygen concentration reduces applies known method, is not particularly limited, such as can enumerate such as lower section
Method：Nitrogen is imported after nitrogen is flowed or is depressurized in the kettle purified, so as to carry out gas displacement.Or can be with
Enumerate the method for being depressurized and being carried out under vacuo.The method that nitrogen is imported after the kettle purified decompression is easy and true
It is real, it is preferred.
The confirmation of oxygen concentration can apply known method, be not particularly limited, such as can enumerate following method：Make nitrogen
Gas flows in the kettle purified, the oxygen concentration using oxymeter measure from the gas of exhaust outlet discharge, so as to carry out.Separately
Outside, the method that oxymeter is set in the kettle purified can also be enumerated.
Embodiment
Hereinafter, embodiment is enumerated, present embodiment is further specifically described.But present embodiment does not limit
In these embodiments.
(embodiment 1)
In the glass lining purification kettle of 3000L capacity, 2, the 6- dihydroxy naphthlenes of purity 90% (are also denoted as below
" 2,6-DHN ") runic 100kg put into acetone 220kg and ion exchange water 280g, then the air decompression inside kettle is gone
Remove and import nitrogen, be heated to 50 DEG C while stirring and dissolve to obtain solution.In the process, the oxygen concentration in purification kettle is less than 1
Volume %.
Then, added into resulting solution and carried out the activated carbon 10kg of deoxidation treatment in advance, be cooled to that to be stirred at room temperature 1 small
Shi Hou, filter out activated carbon.Then, filtrate is rinsed with acetone/ion exchange water (1/1) 100kg.
Afterwards, remove acetone and to centrifuge filtering from filtrate decompression, afterwards, be dried in vacuo, with 90kg (yields
90%) 2,6-DHN of purity 99% is obtained.
Think that this technique industrially can be purified advantageously.
(embodiment 2)
In the glass lining purification kettle of 5000mL capacity, by 2, the 6- dihydroxy naphthlenes (2,6-DHN) of purity 90%
Runic 500g is put into isopropanol denatured ethanol 1000g, is then removed the air decompression inside kettle and is imported nitrogen, side stirring
While it is heated to 60 DEG C and dissolves to obtain solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, ion exchange water 1250g is put into foregoing purification kettle, separates out crystal, and then puts into ion exchange water
1250g, less than 10 DEG C are cooled to, stirred 2 hours.
Afterwards, after to centrifuge filtering, rinsed, be dried in vacuo, with 450g (yields with ion exchange water 500g
90%) 2,6-DHN of purity 99% is obtained.
(embodiment 3)
In the glass lining purification kettle of 3000L capacity, by the 4 of purity 98%, the runic 100kg of 4 '-xenol is thrown
Enter to acetone 150kg and ion exchange water 200kg, then the air decompression inside kettle is removed and imports nitrogen, while stirring
It is heated to 50 DEG C and dissolves to obtain solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, added into resulting solution and carried out the activated carbon 10kg of deoxidation treatment in advance, be cooled to that to be stirred at room temperature 1 small
Shi Hou, filter out activated carbon.Then, filtrate is rinsed with acetone/ion exchange water (1/1) 100kg.
Afterwards, after removing acetone from filtrate decompression and being filtered with centrifugation, it is dried in vacuo, with 95kg (yields
95%) 4,4 '-xenol of purity 99% is obtained.
(embodiment 4)
In the glass lining purification kettle of 5000mL capacity, by the 4 of purity 98%, 4 '-xenol runic 300g inputs
To isopropanol denatured ethanol 1000g, then the air decompression inside kettle is removed and imports nitrogen, is heated to 60 DEG C while stirring
And dissolve and obtain solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, ion exchange water 1200g is put into foregoing purification kettle, separates out crystal, and then puts into ion exchange water
1200g, less than 10 DEG C are cooled to, stirred 2 hours.
Afterwards, after to centrifuge filtering, rinsed, be dried in vacuo, with 280g (yields with ion exchange water 500g
95%) 4,4 '-xenol of purity 99% is obtained.
(embodiment 5)
In the glass lining purification kettle of 3000L capacity, by the resorcinol (1,3- dihydroxy benzenes) of purity 90%
Runic 100kg is put into acetone 150kg and ion exchange water 200kg, is then removed the air decompression inside kettle and is imported nitrogen
Gas, it is heated to 50 DEG C while stirring and dissolves to obtain solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, added into resulting solution and carried out the activated carbon 10kg of deoxidation treatment in advance, be cooled to that to be stirred at room temperature 1 small
Shi Hou, filter out activated carbon.Then, filtrate is rinsed with acetone/ion exchange water (1/1) 100kg.
Afterwards, remove acetone and to centrifuge filtering from filtrate decompression, afterwards, be dried in vacuo, with 90kg (yields
90%) resorcinol of purity 98% is obtained.
(embodiment 6)
In the glass lining purification kettle of 5000mL capacity, by the runic 300g of the resorcinol of purity 90% put into
Isopropanol denatured ethanol 1000g, then the air decompression inside kettle is removed and imports nitrogen, is heated to 60 DEG C while stirring simultaneously
Dissolving obtains solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, ion exchange water 1000g is put into foregoing purification kettle, separates out crystal, and then puts into ion exchange water
1500g, less than 10 DEG C are cooled to, stirred 2 hours.
Afterwards, after to centrifuge filtering, rinsed, be dried in vacuo, with 270g (yields with ion exchange water 500g
90%) resorcinol of purity 98% is obtained.
(embodiment 7)
In the glass lining purification kettle of 5000mL capacity, by the runic 300g of 9, the 10- dihydroxy-anthracenes of purity 98%
Air decompression inside kettle is then removed and imports nitrogen to MEK 1000g by input, is heated to 60 DEG C and molten while stirring
Solution obtains solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, ion exchange water 1000g is put into foregoing purification kettle, separates out crystal, and then puts into ion exchange water
1500g, less than 10 DEG C are cooled to, stirred 2 hours.
Afterwards, after to centrifuge filtering, rinsed, be dried in vacuo, with 255g (yields with ion exchange water 500g
85%) the 9,10- dihydroxy-anthracenes of purity 99% are obtained.
(embodiment 8)
In the glass lining purification kettle of 5000mL capacity, by the runic 300g of the 1- hydroxyl pyrenes of purity 98% put into
Isopropanol denatured ethanol 1000g, then the air decompression inside kettle is removed and imports nitrogen, is heated to 80 DEG C while stirring simultaneously
Dissolving obtains solution.In the process, the oxygen concentration in purification kettle is less than 1 volume %.
Then, ion exchange water 1000g is put into foregoing purification kettle, separates out crystal, and then puts into ion exchange water
1500g, less than 10 DEG C are cooled to, stirred 2 hours.
Afterwards, after to centrifuge filtering, rinsed, be dried in vacuo, with 280g (yields with ion exchange water 500g
95%) the 1- hydroxyl pyrenes of purity 99% are obtained.
Think that this technique industrially can be manufactured advantageously.
(comparative example 1)
Air decompression inside kettle is removed and does not import nitrogen, in addition, is carried out similarly to Example 1.The process
In, the oxygen concentration in purification kettle is 20.8 volume %.As a result, the 2,6-DHN of purity 95% are obtained with 90kg (yield 90%).
2,6-DHN purity is insufficient, therefore, for further high purity, is again carried out same with this comparative example
Operation, as a result obtains the 2,6-DHN of purity 98% with 80kg (yield 89%).80kg purifying product are obtained from 100kg runic,
Total recovery as little as 80%.
Think that this technique is not advantageous to manufacture industrially.
(comparative example 2)
Air decompression inside kettle is removed and does not import nitrogen, in addition, is carried out similarly to Example 2.The process
In, the oxygen concentration in purification kettle is 20.8 volume %.As a result, the 2,6-DHN of purity 95% are obtained with 450g (yield 90%).
2,6-DHN purity is insufficient, therefore, for further high purity, is again carried out same with this comparative example
Operation, as a result obtains the 2,6-DHN of purity 98% with 400g (yield 89%).400g purifying product are obtained from 500g runic,
Total recovery as little as 80%.
Think that this technique is not advantageous to manufacture industrially.
The manufacture of the ethyl acetate solution of compound shown in the formula (1) that (embodiment 1-1) tenor reduces
In the four-hole boiling flask (no die bed) of 1000mL capacity, put into ethyl acetate in dissolved with 2,6- dihydroxy naphthlenes (with
Under be also denoted as " 2,6-DHN ") solution (2.5 mass %) 150g, then the decompression of the air of flask interior is removed and imports nitrogen
Gas, 25 DEG C are heated to while stirring and obtains solution.In the process, the oxygen concentration in flask is less than 1 volume %.Then, in institute
Obtain and oxalic acid aqueous solution (pH1.3) 37.5g is added in solution, after stirring 5 minutes, stand 30 minutes.Thus, oil phase and water are separated into
Phase, therefore, aqueous phase is removed.After repeating the operation 1 time, ultra-pure water 37.5g is put into gained oil phase, it is quiet after stirring 5 minutes
Put 30 minutes, aqueous phase is removed.The operation 3 times is repeated, the ethyl acetate for thus obtaining 2, the 6-DHN that tenor reduces is molten
Liquid.
(embodiment 2-1)
The step of air decompression inside kettle is removed and imports nitrogen is omitted, in addition, in the same manner as embodiment 1-1
Processing, obtains 2,6-DHN ethyl acetate solution.In the process, the oxygen concentration in flask is 20.8 volume %.
(embodiment 3-1)
In the four-hole boiling flask (no die bed) of 1000mL capacity, put into ethyl acetate in be dissolved with 4,4 '-xenol it is thick
Solution (5.0 mass %) 300g of body,
Then the air decompression of flask interior is removed and imports nitrogen, be heated to 40 DEG C while stirring and obtain solution.
In the process, the oxygen concentration in flask is less than 1 volume %.Then, oxalic acid aqueous solution (pH1.3) 75g is added in resulting solution,
After stirring 5 minutes, 30 minutes are stood.Thus, oil phase and aqueous phase are separated into, therefore, aqueous phase is removed.After repeating the operation 1 time,
Ultra-pure water 75g is put into gained oil phase, after stirring 5 minutes, 30 minutes is stood and removes aqueous phase.The operation 3 times is repeated, thus
Obtain the ethyl acetate solution for 4,4 '-xenol that tenor reduces.
(embodiment 5-1)
In the four-hole boiling flask (no die bed) of 1000mL capacity, the runic dissolved with resorcinol in ethyl acetate is put into
Solution (5.0 mass %) 300g, then the air decompression of flask interior is removed and imports nitrogen, is heated to 40 DEG C while stirring
And obtain solution.In the process, the oxygen concentration in flask is less than 1 volume %.Then, oxalic acid aqueous solution is added in resulting solution
(pH1.3) 75g, after stirring 5 minutes, 30 minutes are stood.Thus, oil phase and aqueous phase are separated into, therefore, aqueous phase is removed.Repeat
After the operation 1 time, ultra-pure water 75g is put into gained oil phase, after stirring 5 minutes, 30 minutes is stood and removes aqueous phase.Repeating should
Operation 3 times, thus obtain the ethyl acetate solution for the resorcinol that tenor reduces.
(embodiment 7-1)
In the four-hole boiling flask (no die bed) of 1000mL capacity, put into and 9,10- dihydroxy-anthracenes are dissolved with ethyl acetate
Solution (2.5 mass %) 300g of runic, then the air decompression of flask interior is removed and imports nitrogen, is heated while stirring
Solution is obtained to 40 DEG C.In the process, the oxygen concentration in flask is less than 1 volume %.Then, oxalic acid is added in resulting solution
The aqueous solution (pH1.3) 75g, after stirring 5 minutes, stand 30 minutes.Thus, oil phase and aqueous phase are separated into, therefore, aqueous phase is gone
Remove.After repeating the operation 1 time, ultra-pure water 75g is put into gained oil phase, after stirring 5 minutes, stand 30 minutes and go aqueous phase
Remove.The operation 3 times is repeated, thus obtains the ethyl acetate solution for 9, the 10- dihydroxy-anthracenes that tenor reduces.
(embodiment 8-1)
In the four-hole boiling flask (no die bed) of 1000mL capacity, the runic dissolved with 1- hydroxyl pyrenes in ethyl acetate is put into
Solution (2.0 mass %) 300g, then the air decompression of flask interior is removed and imports nitrogen, is heated to 40 DEG C while stirring
And obtain solution.In the process, the oxygen concentration in flask is less than 1 volume %.Then, oxalic acid aqueous solution is added in resulting solution
(pH1.3) 75g, after stirring 5 minutes, 30 minutes are stood.Thus, oil phase and aqueous phase are separated into, therefore, aqueous phase is removed.Repeat
After the operation 1 time, ultra-pure water 75g is put into gained oil phase, after stirring 5 minutes, 30 minutes is stood and removes aqueous phase.Repeating should
Operation 3 times, thus obtain the ethyl acetate solution for the 1- hydroxyl pyrenes that tenor reduces.
For each solution before and after the processing obtained in embodiment 1~8 and embodiment 1-1~8-1, determined by ICP-MS
Various tenors.Measurement result is shown in table 1.
[table 1]
Table 1
Then, before processing, for 2, the 6-DHN obtained in embodiment 1-1 and embodiment 2-1 each solution, liquid phase is utilized
Chromatography (LC) determines 2,6-DHN purity.As a result, before treatment, being 99% purity, but in embodiment 1-1, maintain
99% purity.It is 91% purity in embodiment 2-1.For embodiment 2-1, omit and the air inside kettle is depressurized into removal
And the step of importing nitrogen, it is in addition, same with embodiment 1-1, embody the effect implemented in nitrogen atmosphere.
Industrial applicability
According to the present invention it is possible to the change shown in industrial advantageously manufacture hydroxyl substituted aromatic compound, such as formula (1)
Compound.
In addition, the according to the present invention it is possible to hydroxyl substituted aromatic that industrial advantageously manufacture tenor reduces
Compound shown in compound, such as formula (1).
Claims (19)
1. a kind of manufacture method of hydroxyl substituted aromatic compound, it includes following process i.e. Contact operation：Substitute hydroxyl
Aromatic compound contacts in atmosphere of the oxygen concentration less than 20 volume % with organic solvent and/or water.
2. the manufacture method of hydroxyl substituted aromatic compound according to claim 1, wherein, the hydroxyl substituted aroma
Compounds of group is following formula (A0) and/or (B0) shown in hydroxyl substituted aromatic compound,
Formula (the A0) in, n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, Ra is each independently hydrogen
Atom, hydroxyl, halogen group, the straight-chain of carbon number 1~40, branched or the alkyl of ring-type, the optionally carbon with substituent
The group that the aryl of number 6~40 or the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl are optional
Comprising ehter bond, ketonic bond or ester bond,
Formula (the B0) in, n1For 0~9 integer, p1For 0~9 integer, RbIt is each independently hydrogen atom, hydroxyl, halogen radical
Group, the straight-chain of carbon number 1~40, branched or ring-type alkyl, optionally with substituent carbon number 6~40 aryl or
The group that the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl optionally comprising ehter bond, ketonic bond or
Person's ester bond.
3. manufacture method according to claim 2, wherein, the formula (A0) shown in hydroxyl substituted aromatic compound be
Compound shown in following formula (A), the formula (B0) shown in hydroxyl substituted aromatic compound be the change shown in following formula (B)
Compound,
In the formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, R0It is each independently carbon number
1~30 straight-chain, the alkyl of branched or ring-type, the aryl of the optional carbon number 6~15 with substituent or carbon number 2~
15 alkenyl,
In the formula (B), n1For 0~9 integer, p1For 0~9 integer, R1Be each independently carbon number 1~30 straight-chain,
The alkyl of branched or ring-type, the aryl of carbon number 6~15 or the alkenyl of carbon number 2~15 optionally with substituent.
4. manufacture method according to claim 3, wherein, the hydroxyl substituted aromatic compound shown in the formula (A) is
Selected from as the compound shown in following formula (A-1), the compound shown in following formula (A-2), the chemical combination shown in following formula (A-3)
Thing and the compound group shown in following formula (A-4) into group in more than a kind,
Hydroxyl substituted aromatic compound shown in the formula (B) is the compound shown in following formula (B-1),
In formula (A-1)~(A-4), n0For 0~9 integer, in the formula (B-1), n1For 0~9 integer.
5. manufacture method according to claim 3, wherein, the hydroxyl substituted aromatic compound shown in the formula (A) is
Compound shown in following formula (1),
6. according to manufacture method according to any one of claims 1 to 5, it includes following process：Make the hydroxyl substitution virtue
Fragrant compounds of group is dissolved in organic solvent.
7. manufacture method according to claim 6, wherein, it is dissolved in the hydroxyl substituted aromatic compound organic molten
After agent, including the process for contacting the solution of the hydroxyl substituted aromatic compound and activated carbon.
8. the manufacture method according to claim 6 or 7, wherein, it has been dissolved in the hydroxyl substituted aromatic compound
After solvent, including make the process of the hydroxyl substituted aromatic compound crystallization.
9. according to manufacture method according to any one of claims 1 to 8, wherein, the organic solvent is selected from by methanol, second
Alcohol, isopropanol, acetone, 1-METHYLPYRROLIDONE, propylene glycol monomethyl ether, toluene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl tert-butyl
More than a kind in the group of base ketone, propylene glycol methyl ether acetate and ethyl acetate composition.
10. a kind of manufacture method of hydroxyl substituted aromatic compound, it includes following process：Make to include and do not mixed arbitrarily with water
Organic solvent and hydroxyl substituted aromatic compound solution (α), contact with acidic aqueous solution, to hydroxyl substituted aromatic
Metal ingredient in compound is extracted.
11. manufacture method according to claim 10, wherein, the hydroxyl substituted aromatic compound is following formula (A0)
And/or (B0) shown in hydroxyl substituted aromatic compound,
Formula (the A0) in, n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, Ra is each independently hydrogen
Atom, hydroxyl, halogen group, the straight-chain of carbon number 1~40, branched or the alkyl of ring-type, the optionally carbon with substituent
The group that the aryl of number 6~40 or the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl are optional
Comprising ehter bond, ketonic bond or ester bond,
Formula (the B0) in, n1For 0~9 integer, p1For 0~9 integer, RbIt is each independently hydrogen atom, hydroxyl, halogen radical
Group, the straight-chain of carbon number 1~40, branched or ring-type alkyl, optionally with substituent carbon number 6~40 aryl or
The group that the alkenyl and combinations thereof of carbon number 2~40 are formed, the alkyl, the aryl or the alkenyl optionally comprising ehter bond, ketonic bond or
Person's ester bond.
12. manufacture method according to claim 11, wherein, the formula (A0) shown in hydroxyl substituted aromatic compound
For the compound shown in following formula (A), the formula (B0) shown in hydroxyl substituted aromatic compound for shown in following formula (B)
Compound,
In the formula (A), n0For 0~9 integer, m0For 0~2 integer, p0For 0~9 integer, R0It is each independently carbon number
1~30 straight-chain, the alkyl of branched or ring-type, the aryl of the optional carbon number 6~15 with substituent or carbon number 2~
15 alkenyl,
In the formula (B), n1For 0~9 integer, p1For 0~9 integer, R1Be each independently carbon number 1~30 straight-chain,
The alkyl of branched or ring-type, the aryl of carbon number 6~15 or the alkenyl of carbon number 2~15 optionally with substituent.
13. manufacture method according to claim 12, wherein, the hydroxyl substituted aromatic compound shown in the formula (A)
For selected from as the compound shown in following formula (A-1), the compound shown in following formula (A-2), the chemical combination shown in following formula (A-3)
Thing and the compound group shown in following formula (A-4) into group in more than a kind,
Hydroxyl substituted aromatic compound shown in the formula (B) is the compound shown in following formula (B-1),
In formula (A-1)~(A-4), n0For 0~9 integer, in the formula (B-1), n1For 0~9 integer.
14. manufacture method according to claim 12, wherein, the hydroxyl substituted aromatic compound shown in the formula (A)
For the compound shown in following formula (1),
15. the manufacture method according to any one of claim 10~14, wherein, it is less than 20 volume % gas in oxygen concentration
Carried out under atmosphere.
16. the manufacture method according to any one of claim 10~15, wherein, after the process of the extraction, in addition to
Following process：The extraction process of the metal ingredient in hydroxyl substituted aromatic compound is carried out using water.
17. the manufacture method according to any one of claim 10~16, wherein, the organic solvent not mixed arbitrarily with water
For selected from by toluene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl iso-butyl ketone (MIBK), propylene glycol methyl ether acetate and ethyl acetate group
Into group in more than a kind.
18. the manufacture method according to any one of claim 10~17, wherein, the acidic aqueous solution is selected from by salt
Acid, sulfuric acid, nitric acid and phosphoric acid composition group in more than a kind of inorganic acid aqueous solution or be selected from by acetic acid, propionic acid, oxalic acid,
Malonic acid, butanedioic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid and trifluoro second
More than a kind of aqueous solutions of organic acids in the group of acid composition.
19. the manufacture method according to any one of claim 10~18, wherein, the hydroxyl substituted aromatic compound
For more than a kind in the group being made up of 2,6- dihydroxy naphthlenes and 2,7 dihydroxy naphthalene.
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| JP2015-107411 | 2015-05-27 | ||
| JP2015107411 | 2015-05-27 | ||
| JP2015107410 | 2015-05-27 | ||
| JP2015-107410 | 2015-05-27 | ||
| PCT/JP2016/063204 WO2016190044A1 (en) | 2015-05-27 | 2016-04-27 | Method for producing hydroxy-substituted aromatic compound |
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| CN107614473A true CN107614473A (en) | 2018-01-19 |
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| CN201680030656.5A Pending CN107614473A (en) | 2015-05-27 | 2016-04-27 | The manufacture method of hydroxyl substituted aromatic compound |
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| JP (2) | JP7233164B2 (en) |
| CN (1) | CN107614473A (en) |
| TW (1) | TW201708169A (en) |
| WO (1) | WO2016190044A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956853A (en) * | 2017-12-26 | 2019-07-02 | 信越化学工业株式会社 | The method of purification of dihydroxy naphthlene |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6136236A (en) * | 1984-07-30 | 1986-02-20 | Kawasaki Kasei Chem Ltd | Production of naphthohydroquinone |
| JPS6270334A (en) * | 1985-09-20 | 1987-03-31 | Mitsui Petrochem Ind Ltd | Production of 2,6-dihydroxynaphthalene |
| JPS6339831A (en) * | 1986-08-02 | 1988-02-20 | Mitsui Petrochem Ind Ltd | Method for purifying dihydroxynaphthalene |
| JP2011042583A (en) * | 2009-08-19 | 2011-03-03 | Kawasaki Kasei Chem Ltd | Method for producing aqueous solution of naphthohydroquinone compound and radical-trapping agent aqueous solution |
| CN102971281A (en) * | 2010-05-26 | 2013-03-13 | 三菱瓦斯化学株式会社 | Cyclic compound purification method |
| CN103467250A (en) * | 2013-09-25 | 2013-12-25 | 南通柏盛化工有限公司 | Preparation method of 1,7-dihydroxy naphthlene |
| CN103467249A (en) * | 2013-09-09 | 2013-12-25 | 南通柏盛化工有限公司 | Purification method of 2,6-dihydroxy naphthlene |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5534778B2 (en) * | 1972-07-05 | 1980-09-09 | ||
| JPS53144558A (en) * | 1977-05-23 | 1978-12-15 | Mitsui Toatsu Chem Inc | Color protection of beta-naphthol |
| JPS6055491B2 (en) * | 1977-05-23 | 1985-12-05 | 三井東圧化学株式会社 | Purification method of β-naphthol |
| JPS55164638A (en) * | 1979-06-11 | 1980-12-22 | Mitsui Petrochem Ind Ltd | Purification of phenol |
| JPS5643228A (en) * | 1979-09-19 | 1981-04-21 | Mitsui Toatsu Chem Inc | Prevention of color development of aromatic compound having hydroxyl group |
| JPS6270333A (en) * | 1985-09-20 | 1987-03-31 | Mitsui Petrochem Ind Ltd | Production of 2,6-dihydroxynaphthalene |
| JP2001011001A (en) * | 1999-06-25 | 2001-01-16 | Jsr Corp | Metal removal from phenolic compound |
| JP2001114717A (en) * | 1999-10-19 | 2001-04-24 | Sumitomo Chem Co Ltd | Production of phenolic compound reduced with metal content |
| DE102006019257B4 (en) | 2006-04-26 | 2010-08-05 | A. Raymond Et Cie | Fluid line coupling |
| JP5026739B2 (en) | 2006-06-03 | 2012-09-19 | イハラケミカル工業株式会社 | Process for producing β-naphthols |
| JP2009280566A (en) | 2008-04-25 | 2009-12-03 | Sanyo Chem Ind Ltd | 2,2-bis(4-hydroxycyclohexyl)propanedi(meth)allyl ether compound |
| CN102668257B (en) | 2009-12-25 | 2016-06-01 | 日本发条株式会社 | Connect terminal |
| KR101986346B1 (en) * | 2011-08-12 | 2019-06-05 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Resist composition, resist pattern formation method, polyphenol compound used therein, and alcohol compound capable of being derived therefrom |
| US9316913B2 (en) * | 2011-08-12 | 2016-04-19 | Mitsubishi Gas Chemical Company, Inc. | Underlayer film-forming material for lithography, underlayer film for lithography, and pattern formation method |
| JP6074902B2 (en) | 2012-03-28 | 2017-02-08 | 三菱化学株式会社 | Method for producing purified phenolic compound |
| US9738580B2 (en) | 2012-09-28 | 2017-08-22 | Dic Corporation | Epoxy compound, method for producing the same, epoxy resin composition, and cured product thereof |
| KR20140054589A (en) | 2012-10-29 | 2014-05-09 | 한국전자통신연구원 | Apparatus for providing robot control and method therefor |
| JP6136236B2 (en) | 2012-12-19 | 2017-05-31 | 東ソー株式会社 | Purification method of recombinant protein |
| WO2015137486A1 (en) * | 2014-03-13 | 2015-09-17 | 三菱瓦斯化学株式会社 | Compound, resin, base layer film-forming material for lithography, base layer film for lithography, pattern-forming method, and method for refining compound or resin |
| JP6339831B2 (en) | 2014-03-19 | 2018-06-06 | 矢崎総業株式会社 | Connector terminal holding structure |
-
2016
- 2016-04-27 CN CN201680030656.5A patent/CN107614473A/en active Pending
- 2016-04-27 JP JP2017520582A patent/JP7233164B2/en active Active
- 2016-04-27 WO PCT/JP2016/063204 patent/WO2016190044A1/en active Application Filing
- 2016-05-12 TW TW105114740A patent/TW201708169A/en unknown
-
2020
- 2020-09-28 JP JP2020161917A patent/JP7138853B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6136236A (en) * | 1984-07-30 | 1986-02-20 | Kawasaki Kasei Chem Ltd | Production of naphthohydroquinone |
| JPS6270334A (en) * | 1985-09-20 | 1987-03-31 | Mitsui Petrochem Ind Ltd | Production of 2,6-dihydroxynaphthalene |
| JPS6339831A (en) * | 1986-08-02 | 1988-02-20 | Mitsui Petrochem Ind Ltd | Method for purifying dihydroxynaphthalene |
| JP2011042583A (en) * | 2009-08-19 | 2011-03-03 | Kawasaki Kasei Chem Ltd | Method for producing aqueous solution of naphthohydroquinone compound and radical-trapping agent aqueous solution |
| CN102971281A (en) * | 2010-05-26 | 2013-03-13 | 三菱瓦斯化学株式会社 | Cyclic compound purification method |
| CN103467249A (en) * | 2013-09-09 | 2013-12-25 | 南通柏盛化工有限公司 | Purification method of 2,6-dihydroxy naphthlene |
| CN103467250A (en) * | 2013-09-25 | 2013-12-25 | 南通柏盛化工有限公司 | Preparation method of 1,7-dihydroxy naphthlene |
Non-Patent Citations (3)
| Title |
|---|
| CUI,JIA-HUA等: "A Convenient and Efficient Synthesis of 2,6-Dihydroxynaphthalene", 《JOURNAL OF CHEMICAL RESEARCH》 * |
| JIA-HUA等: "A convenient and efficient synthesis of 2,6-dihydroxynaphthalene", 《JOURNAL OF CHEMICAL RESEARCH》 * |
| 李加娥等: "《学生课外经典读物》", 31 December 2009 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956853A (en) * | 2017-12-26 | 2019-07-02 | 信越化学工业株式会社 | The method of purification of dihydroxy naphthlene |
| CN109956853B (en) * | 2017-12-26 | 2024-02-20 | 信越化学工业株式会社 | Method for purifying dihydroxynaphthalene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7233164B2 (en) | 2023-03-06 |
| JP2021001219A (en) | 2021-01-07 |
| WO2016190044A1 (en) | 2016-12-01 |
| TW201708169A (en) | 2017-03-01 |
| JP7138853B2 (en) | 2022-09-20 |
| JPWO2016190044A1 (en) | 2018-03-15 |
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