JPH03275642A - Production of 2-substituted 1,4-naphthoquinone - Google Patents
Production of 2-substituted 1,4-naphthoquinoneInfo
- Publication number
- JPH03275642A JPH03275642A JP31304090A JP31304090A JPH03275642A JP H03275642 A JPH03275642 A JP H03275642A JP 31304090 A JP31304090 A JP 31304090A JP 31304090 A JP31304090 A JP 31304090A JP H03275642 A JPH03275642 A JP H03275642A
- Authority
- JP
- Japan
- Prior art keywords
- naphthoquinone
- substituted
- reaction
- methyl
- adduct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 2-substituted 1,4-naphthoquinone Chemical class 0.000 title claims abstract description 175
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims abstract 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims description 93
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000012071 phase Substances 0.000 claims description 63
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 claims description 42
- 239000008346 aqueous phase Substances 0.000 claims description 41
- OPKFWRVRCVCMJH-UHFFFAOYSA-N 6-methylnaphthalene-1,4-dione Chemical compound O=C1C=CC(=O)C2=CC(C)=CC=C21 OPKFWRVRCVCMJH-UHFFFAOYSA-N 0.000 claims description 39
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 26
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 239000011541 reaction mixture Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 229930192627 Naphthoquinone Natural products 0.000 claims description 8
- 150000002791 naphthoquinones Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 150000000191 1,4-naphthoquinones Chemical class 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- IPMNJIJPNCAGIK-UHFFFAOYSA-N naphthalene-1,4-dione;sulfurous acid Chemical compound OS(O)=O.C1=CC=C2C(=O)C=CC(=O)C2=C1 IPMNJIJPNCAGIK-UHFFFAOYSA-N 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- 150000002790 naphthalenes Chemical class 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229940075566 naphthalene Drugs 0.000 abstract 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 238000003756 stirring Methods 0.000 description 35
- 239000008096 xylene Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 24
- 238000001953 recrystallisation Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- LQBNXPOXIBHSBO-UHFFFAOYSA-N 2-methylnaphthalene-1,4-dione;sulfurous acid Chemical compound OS(O)=O.C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 LQBNXPOXIBHSBO-UHFFFAOYSA-N 0.000 description 10
- 150000004056 anthraquinones Chemical class 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 7
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 5
- 238000010411 cooking Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 4
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical class C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940078552 o-xylene Drugs 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000219495 Betulaceae Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- XDPFHGWVCTXHDX-UHFFFAOYSA-M menadione sodium sulfonate Chemical compound [Na+].C1=CC=C2C(=O)C(C)(S([O-])(=O)=O)CC(=O)C2=C1 XDPFHGWVCTXHDX-UHFFFAOYSA-M 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UZSCBEJDBQICON-UHFFFAOYSA-N 1,4-naphthoquinone-2-carboxylic acid Chemical compound C1=CC=C2C(=O)C(C(=O)O)=CC(=O)C2=C1 UZSCBEJDBQICON-UHFFFAOYSA-N 0.000 description 2
- CCTJHVLTAJTPBV-UHFFFAOYSA-N 2-chloro-1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C(Cl)=CC(=O)C2=C1 CCTJHVLTAJTPBV-UHFFFAOYSA-N 0.000 description 2
- CGYGETOMCSJHJU-UHFFFAOYSA-N 2-chloronaphthalene Chemical compound C1=CC=CC2=CC(Cl)=CC=C21 CGYGETOMCSJHJU-UHFFFAOYSA-N 0.000 description 2
- QBHSRQVIJSKBPX-UHFFFAOYSA-N 2-ethylnaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(CC)=CC(=O)C2=C1 QBHSRQVIJSKBPX-UHFFFAOYSA-N 0.000 description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 2
- OCLZSFJBDFHWHX-UHFFFAOYSA-N 2-nitronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C([N+](=O)[O-])=CC(=O)C2=C1 OCLZSFJBDFHWHX-UHFFFAOYSA-N 0.000 description 2
- RVWULRYSVVDSEW-UHFFFAOYSA-N 5,8-dioxonaphthalene-2-carboxylic acid Chemical compound O=C1C=CC(=O)C2=CC(C(=O)O)=CC=C21 RVWULRYSVVDSEW-UHFFFAOYSA-N 0.000 description 2
- UVHMQBSPOCXMKB-UHFFFAOYSA-N 6-ethylnaphthalene-1,4-dione Chemical compound O=C1C=CC(=O)C2=CC(CC)=CC=C21 UVHMQBSPOCXMKB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003674 animal food additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 description 1
- FDHDUXOBMHHFFJ-UHFFFAOYSA-N 1-pentylnaphthalene Chemical compound C1=CC=C2C(CCCCC)=CC=CC2=C1 FDHDUXOBMHHFFJ-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- KUWXWSOGHBXOGK-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)naphthalene Chemical compound C1=CC=CC2=CC(C(C)(C)CC)=CC=C21 KUWXWSOGHBXOGK-UHFFFAOYSA-N 0.000 description 1
- KJROTUIFOSDERR-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)naphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(C(C)(C)CC)=CC(=O)C2=C1 KJROTUIFOSDERR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- ZSPDYGICHBLYSD-UHFFFAOYSA-N 2-methylnaphthalene-1-carboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C)=CC=C21 ZSPDYGICHBLYSD-UHFFFAOYSA-N 0.000 description 1
- ZJYJZEAJZXVAMF-UHFFFAOYSA-N 2-nitronaphthalene Chemical compound C1=CC=CC2=CC([N+](=O)[O-])=CC=C21 ZJYJZEAJZXVAMF-UHFFFAOYSA-N 0.000 description 1
- ZQCIMPBZCZUDJM-UHFFFAOYSA-N 2-octoxyethanol Chemical compound CCCCCCCCOCCO ZQCIMPBZCZUDJM-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- NWOFOLCIBJMXNH-UHFFFAOYSA-N 6-(2-methylbutan-2-yl)naphthalene-1,4-dione Chemical compound O=C1C=CC(=O)C2=CC(C(C)(C)CC)=CC=C21 NWOFOLCIBJMXNH-UHFFFAOYSA-N 0.000 description 1
- AAJHGPQAUGRPPP-UHFFFAOYSA-N 6-methyl-1,4,4a,9a-tetrahydroanthracene-9,10-dione 6-methylnaphthalene-1,4-dione Chemical compound O=C1C=CC(=O)C2=CC(C)=CC=C21.C1C=CCC2C(=O)C3=CC(C)=CC=C3C(=O)C21 AAJHGPQAUGRPPP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229940030225 antihemorrhagics Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- RWACICCRNCPMDT-UHFFFAOYSA-N cerium sulfuric acid Chemical compound [Ce].S(O)(O)(=O)=O RWACICCRNCPMDT-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000002874 hemostatic agent Substances 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- ZFXHWMLOCWAPNG-UHFFFAOYSA-M sodium;hydrogen sulfite;2-methylnaphthalene-1,4-dione Chemical compound [Na+].OS([O-])=O.C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 ZFXHWMLOCWAPNG-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000012711 vitamin K3 Nutrition 0.000 description 1
- 239000011652 vitamin K3 Substances 0.000 description 1
- 229940041603 vitamin k 3 Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は２−置換−ナフタリンを酸化して、２−置換−
１，４−ナフトキノンを工業的に製造する方法に関する
ものである。詳しくは、本発明は２−置換−ナフタリン
の酸化によって得られる２−置換−１，４−ナフトキノ
ンと６−置換−１゜４−ナフトキノンからなる混合物よ
り、６−置換−１，４−ナフトキノンを分離除去し、高
純度の２−置換−１，４−ナフトキノンを製造する方法
に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention oxidizes 2-substituted naphthalene to form a 2-substituted naphthalene.
This invention relates to a method for industrially producing 1,4-naphthoquinone. Specifically, the present invention provides 6-substituted-1,4-naphthoquinone from a mixture of 2-substituted-1,4-naphthoquinone and 6-substituted-1.4-naphthoquinone obtained by oxidation of 2-substituted-naphthalene. The present invention relates to a method for separating and removing high purity 2-substituted-1,4-naphthoquinone.
２−置換−１，４−ナフトキノンのなかでも２−メチル
−１，４−ナフトキノンはメナジオンまたはビタミンに
、とも呼ばれ、血液凝固作用を持つビタミンの１種であ
って人体用医薬品、家畜飼料添加剤として有用な薬剤で
ある。また、その亜硫酸水素塩は水溶性があり、医薬品
やその原料及び飼料の添加物として有用である。Among the 2-substituted-1,4-naphthoquinones, 2-methyl-1,4-naphthoquinone is also called menadione or vitamin, and is a type of vitamin that has a blood coagulation effect and is used in human medicines and livestock feed additives. It is a useful drug as a drug. In addition, the bisulfite salt is water-soluble and is useful as an additive for pharmaceuticals, raw materials thereof, and feed.
更には、本発明は２−置換−ナフタリンの酸化によって
副生した６−置換−１，４−ナフトキノンからバルブ蒸
解助剤やアントラキノン誘導体の原料として有用な５．
８−ジヒドロ−２−置換−アントラキノン及び／又は２
−置換−アントラキノン（以下、両者を総称して２−置
換−アントラキノン類という）を得る方法に関するもの
である。Furthermore, the present invention provides 5. useful as a raw material for valve cooking aids and anthraquinone derivatives from 6-substituted-1,4-naphthoquinone produced by oxidation of 2-substituted naphthalene.
8-dihydro-2-substituted-anthraquinone and/or 2
The present invention relates to a method for obtaining -substituted anthraquinones (hereinafter both are collectively referred to as 2-substituted anthraquinones).
【従来の技術］
２−置換−１，４−ナフトキノンの製法としては、従来
、クロム酸や過酸化水素等の酸化剤により２−置換−ナ
フタレンを酸化する方法が行われている。しかし、この
ような方法では生成した２−置換−１，４−ナフトキノ
ンには副生６−置換−１，４−ナフトキノンが不純物と
して多量に含まれ、これを分離、除去する必要がある。[Prior Art] Conventionally, 2-substituted-1,4-naphthoquinone has been produced by oxidizing 2-substituted naphthalene with an oxidizing agent such as chromic acid or hydrogen peroxide. However, in such a method, the 2-substituted-1,4-naphthoquinone produced contains a large amount of by-product 6-substituted-1,4-naphthoquinone as an impurity, which needs to be separated and removed.
また、副生した６−置換−１，４−ナフトキノンはその
ままでは用途はなく、通常は廃棄されるが、その処理の
ための手間やコストも無視できず、大きな問題である。In addition, the 6-substituted-1,4-naphthoquinone produced as a by-product has no use as it is and is normally discarded, but the effort and cost for its treatment cannot be ignored, which is a big problem.
また、第二セリウム塩の酸性水溶液により２−置換−ナ
フタレンを酸化させた後、生成した第一セリウム塩を電
解酸化して第二セリウム塩の酸性水溶液として再生し再
使用する間接電解酸化反応も行なわれている。この方法
は、有害なりロムを使用せず、２−置換−１，４−ナフ
トキノンの選択性が改善されるという利点を有するもの
の、６−置！−１，４−ナフトキノンが副生ずるという
欠点を有することにかわりはない。There is also an indirect electrolytic oxidation reaction in which 2-substituted naphthalene is oxidized with an acidic aqueous solution of a ceric salt, and then the generated cerous salt is electrolytically oxidized to be regenerated and reused as an acidic aqueous solution of a ceric salt. It is being done. Although this method has the advantage of not using harmful ROMs and improved selectivity for 2-substituted-1,4-naphthoquinones, the 6-substituted! There is still the drawback that -1,4-naphthoquinone is produced as a by-product.
２−置換−ナフタレンを酸化して２−置換−１゜４−ナ
フトキノンを得る際に副生した６−置換−１．４−ナフ
トキノンは２−置換−１，４−ナフトキノンと互いに異
性体の関係にあり、両者は物性的にも非常に酷似してい
て分離が困難なものである。例えば、２−メチル−ナフ
タリンの酸化によって得られた２−メチル−１，４−ナ
フトキノン及び６−メチル−１，４−ナフトキノンを含
む反応混合物から高純度の２−メチル−１，４−ナフト
キノンを得る方法として、反応混合物を亜硫酸水素水溶
液で処理する方法（特開昭６０−２５２４４５号）が提
案されているが、この方法は工程が多く、各工程を経る
毎に収率が低下するため全体を通しての収率が不十分で
ある。6-substituted-1,4-naphthoquinone, which is produced as a by-product when oxidizing 2-substituted-naphthalene to obtain 2-substituted-1゜4-naphthoquinone, has an isomeric relationship with 2-substituted-1,4-naphthoquinone. The two are physically very similar and difficult to separate. For example, highly purified 2-methyl-1,4-naphthoquinone can be obtained from a reaction mixture containing 2-methyl-1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone obtained by oxidation of 2-methyl-naphthalene. A method of treating the reaction mixture with an aqueous hydrogen sulfite solution (Japanese Patent Application Laid-Open No. 60-252445) has been proposed as a method for obtaining this, but this method involves many steps and the yield decreases with each step, so the overall Yield is insufficient.
なお、出発原料の２−置換−ナフタリンには充分に精製
したものでない限り１−置換ナフタリンやナフタリンな
ど他のナフタリン類が含まれやすい。これらのナフタリ
ン類も酸化反応によって５−置換−１，４−ナフトキノ
ン、１，４−ナフトキノンなどの対応する１、４−ナフ
トキノン類に転化されるが、これらは６−メチル−１，
４−ナフトキノンと同様に２−置換−１，４−ナフトキ
ノンと物性的に酷似していて分離が困難なものである。Note that unless the 2-substituted naphthalene as a starting material is sufficiently purified, it tends to contain other naphthalenes such as 1-substituted naphthalene and naphthalene. These naphthalenes are also converted into corresponding 1,4-naphthoquinones such as 5-substituted-1,4-naphthoquinone and 1,4-naphthoquinone, but these are converted into 6-methyl-1,
Like 4-naphthoquinone, it has physical properties very similar to 2-substituted-1,4-naphthoquinone and is difficult to separate.
［発明が解決しようとする課題］
本発明の目的は、２−置換−ナフタリンの酸化による２
−置換−１，４−ナフトキノンの製造において、副生し
た６−置換−１，４−ナフトキノンを効率よく分離して
除去することにより高純度の２−置換−１，４−ナフト
キノンを得る方法を提供することにある。[Problems to be Solved by the Invention] The object of the present invention is to solve the problem of 2-substituted naphthalene by oxidation.
- A method for obtaining highly purified 2-substituted-1,4-naphthoquinone by efficiently separating and removing by-produced 6-substituted-1,4-naphthoquinone in the production of substituted-1,4-naphthoquinone. It is about providing.
本発明の他の目的は、２−置換−ナフタリンの酸化によ
って副生した６−置換−１，４−ナフトキノンを２−置
換−アントラキノン類にすることによって有効に利用し
、その結果２−置換−１゜４−ナフトキノンを安価に製
造することにある。Another object of the present invention is to effectively utilize 6-substituted-1,4-naphthoquinone by-produced by oxidation of 2-substituted-naphthalene by converting it into 2-substituted-anthraquinones. 1. To produce 4-naphthoquinone at low cost.
［課題を解決する為の手段］
本発明者らは上記目的を解決する方法について鋭意検討
した結果、２−置換−ナフタリン酸化反応生成物にジエ
ン化合物を加えて加熱した場合、立体障害及び電子密度
の違いから２−置換−１゜４−ナフトキノンは殆どジエ
ン化合物と反応しないが６−ｆｉｌｍ−１，４−ナフト
キノンはジエン化合物と容易に反応して対応するディー
ルズ・アルダー反応付加物を生成することを見い出した
。[Means for Solving the Problems] As a result of intensive studies on methods for solving the above objects, the present inventors found that when a diene compound is added to a 2-substituted naphthalene oxidation reaction product and heated, steric hindrance and electron density Because of the difference in 2-substituted-1゜4-naphthoquinone hardly reacts with diene compounds, 6-film-1,4-naphthoquinone easily reacts with diene compounds to produce the corresponding Diels-Alder reaction adduct. I found out.
かくして、本発明によれば、２−置換−ナフタリン［下
記の反応式において一般式（Ａ）で表される］を酸化反
応して２−Ｍ換−１，４−ナフトキノンＥ下記の反応式
において一般式（Ｂ）で表されるコ及び６−置換−１，
４−ナフトキノン［下記の反応式において一般式（Ｃ）
で表される］を含む反応生成物を得、該反応生成物にジ
エン化合物［例えば、下記の反応式においては一般式（
Ｄ）で表される１、３−ブタジェン］を加えて加熱する
ことにより該ジエン化合物と該反応生成物中の６−置換
−１，４−ナフトキノンとのディールズ・アルダー反応
付加物［下記の反応式においては一般式（Ｅ）で表され
る］を形成し、２−置換−１，４−ナフトキノンを該付
加物から分離することを要旨とする２−置換−１，４−
ナフトキノンの製造法が提供される。Thus, according to the present invention, 2-substituted-naphthalene [represented by general formula (A) in the following reaction formula] is oxidized to produce 2-M-converted-1,4-naphthoquinone E in the following reaction formula. co- and 6-substituted-1 represented by general formula (B),
4-naphthoquinone [General formula (C) in the following reaction formula]
A reaction product containing a diene compound [for example, in the reaction formula below, a reaction product containing a diene compound [represented by the general formula (
1,3-butadiene represented by D) and heating to form a Diels-Alder reaction adduct of the diene compound and the 6-substituted-1,4-naphthoquinone in the reaction product 2-substituted-1,4-naphthoquinone is separated from the adduct by forming a 2-substituted-1,4-naphthoquinone represented by the general formula (E)
A method of making naphthoquinone is provided.
（ここでＲ１，Ｒ２，Ｒ３は置換基を表す。）更に、本
発明によれば６−置換−１，４−ナフトキノンとジエン
化合物とのディールズ・アルダー反応付加物を酸化して
２−置換−アントラキノン類［下記の反応式において、
一般式（Ｆ）で表される５、８−ジヒドロ−２−置換−
アントラキノンあるいは一般式（Ｇ）で表される２−置
換−アントラキノン］を一貫的に製造する方法をも提り
（Ｇ）
（ここでＲ１，Ｒ２，Ｒ３は前記と同じである。）供す
るものである。(Here, R1, R2, and R3 represent substituents.) Furthermore, according to the present invention, the Diels-Alder reaction adduct of 6-substituted-1,4-naphthoquinone and a diene compound is oxidized to Anthraquinones [In the reaction formula below,
5,8-dihydro-2-substituted- represented by general formula (F)
We also provide a method for consistently producing anthraquinone or 2-substituted anthraquinone represented by the general formula (G) (G) (where R1, R2, and R3 are the same as above). be.
なお、出発原料の２−置換−ナフタリンに１−置換ナフ
タリンやナフタリンなど他のナフタリン類が含まれてい
る場合、前述したように、これらのナフタリン類も前述
の酸化反応によって５−置換−１，４−ナフトキノン、
ＩＩ ４−ナフトキノンなどの対応する１、４−ナフト
キノン類に転化される。これらの１．４−ナフトキノン
類もディールス・アルダ−反応によって容易にジエン化
合物との付加物となり、２−置換−１，４−ナフトキノ
ンとは各種の物性が大きく異なるので容易に２−置換−
１，４−ナフトキノンを分離・精製することができる。Note that if the 2-substituted naphthalene used as the starting material contains other naphthalenes such as 1-substituted naphthalene or naphthalene, these naphthalenes can also be converted to 5-substituted-1, 4-naphthoquinone,
II is converted to the corresponding 1,4-naphthoquinones such as 4-naphthoquinone. These 1,4-naphthoquinones also easily form adducts with diene compounds through the Diels-Alder reaction, and since their various physical properties are significantly different from 2-substituted-1,4-naphthoquinones, they are easily converted into 2-substituted-1,4-naphthoquinones.
1,4-naphthoquinone can be separated and purified.
更に、これらの１，４−ナフトキノン類とジエン化合物
との付加物もまた一般式（Ｅ）で表される付加物と同様
に、分離し、酸化することによってバルブ蒸解助剤など
に有用なアントラキノン類とすることができる。以下の
記載では、１−置換ナフタリンやナフタリンなどに起因
する上記の反応等については詳しい説明はしないが、６
−置換−１，４−ナフトキノンについて述べると同様で
ある。１−置換ナフタリンの場合についてこれら一連の
反応式を示す。Furthermore, similar to the adduct represented by the general formula (E), adducts of these 1,4-naphthoquinones and diene compounds can also be separated and oxidized to produce anthraquinones useful as valve cooking aids, etc. It can be made into a class. In the following description, the above reactions caused by 1-substituted naphthalene, naphthalene, etc. will not be explained in detail, but 6
The same applies to the -substituted-1,4-naphthoquinone. A series of these reaction formulas is shown for the case of 1-substituted naphthalene.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において用いられる２−置換−ナフタリンは、ナ
フタリンの２位の位置に置換基が導入されているもので
あり、置換基［上記一般式（Ａ）におけるＲ’］として
は例えば炭素数１〜５のアルキル基 ニトロ五 カルボ
キシル龜 ハロゲン原子などが挙げられる。The 2-substituted naphthalene used in the present invention has a substituent introduced at the 2-position of naphthalene, and the substituent [R' in the above general formula (A)] has, for example, a carbon number of 1 to Examples of the alkyl group of 5 include nitro, carboxyl, halogen, and the like.
２−置換−ナフタリンの酸化反応は上述したような従来
から知られている一般的な方法で行なえる。なかでも、
２−Ｎ換−ナフタリンを第二セリウム塩の酸性水溶液に
より酸化反応させる間接電解酸化反応は、有害なりロム
を使用せず、比較的選択性よく２−置換−１，４−ナフ
トキノンが生成するので好ましい方法である。第二セリ
ウム塩の酸性水溶液を構成する第二セリウム塩としては
硫酸第二セリウム、硝酸第二七リウムなどの第二セリウ
ム塩が挙げられ、酸としては硫酸、硝酸などの無機酸や
メタンスルホン酸、酢酸などの有機酸が挙げられる。一
般に酸化反応によって２−置換−ナフタリンは２−置換
−１，４−ナフトキノンに転化されるが６−置換−１，
４−ナフトキノンの副生も避けられない。The oxidation reaction of 2-substituted naphthalene can be carried out by conventionally known general methods as described above. Among them,
The indirect electrolytic oxidation reaction in which 2-N-substituted naphthalene is oxidized with an acidic aqueous solution of ceric salt does not use harmful ROM and produces 2-substituted-1,4-naphthoquinone with relatively high selectivity. This is the preferred method. Examples of ceric salts constituting an acidic aqueous solution of ceric salts include ceric salts such as ceric sulfate and 77ium nitrate, and examples of acids include inorganic acids such as sulfuric acid and nitric acid, and methanesulfonic acid. , and organic acids such as acetic acid. Generally, 2-substituted-naphthalene is converted to 2-substituted-1,4-naphthoquinone by oxidation reaction, but 6-substituted-1,
The by-product of 4-naphthoquinone is also unavoidable.
次いで、酸化反応生成物中の６−置換−１，４−ナフト
キノンを溶媒の存在下にジエン化合物と反応させてディ
ールス・アルダ−反応付加物を形成させる。The 6-substituted-1,4-naphthoquinone in the oxidation reaction product is then reacted with a diene compound in the presence of a solvent to form a Diels-Alder reaction adduct.
ディールス・アルダ−反応に用いられるジエン化合物と
しては、ブタジェン、メチルブタジェン。Diene compounds used in the Diels-Alder reaction include butadiene and methylbutadiene.
ジメチルブタジェン、シクロペンタジェン、シクロへキ
サジエン等の１．３−ブタジェン類が好適に用いられる
が他のジエン化合物でもよい。ジエン化合物として一般
式（Ｄ）
（ここでＲ２，Ｒ１は各々独立して水素原子、メチル基
またはエチル基のいずれかである）で示される１、３−
ブタジェンを用いた場合には、形成された６−置換−１
，４−ナフトキノンと１゜３−ブタジェンとのディール
ス・アルダ−反応付加物を分離して、酸化することによ
って、バルブ蒸解助剤やアントラキノン誘導体合成の原
料として有用な２−置換−アントラキノン類が得られる
。1,3-butadienes such as dimethylbutadiene, cyclopentadiene, and cyclohexadiene are preferably used, but other diene compounds may also be used. As a diene compound, a 1,3- represented by the general formula (D) (where R2 and R1 are each independently a hydrogen atom, a methyl group or an ethyl group)
When using butadiene, the 6-substituted-1 formed
By separating and oxidizing the Diels-Alder reaction adduct of ,4-naphthoquinone and 1゜3-butadiene, 2-substituted anthraquinones, which are useful as valve cooking aids and raw materials for the synthesis of anthraquinone derivatives, can be obtained. It will be done.
即ちこの場合には好ましいことには、従来副生物として
廃棄されていた６−置換−１，４−ナフトキノンが有効
に利用でき、その結果２−置換−１゜４−ナフトキノン
も安価に製造できることとなる。That is, in this case, it is preferable that 6-substituted-1,4-naphthoquinone, which was conventionally discarded as a by-product, can be effectively utilized, and as a result, 2-substituted-1.4-naphthoquinone can also be produced at low cost. Become.
ジエン化合物の使用量は、少なすぎると反応速度が遅く
、また一方、多すぎるとジエン化合物の重合等を起こす
ので、６−置換−１，４−ナフトキノンに対して１．０
〜２．０倍モル、好ましくは１．１〜１．５倍モルであ
る。If the amount of the diene compound used is too small, the reaction rate will be slow, while if it is too large, polymerization of the diene compound will occur, so the amount should be 1.0 to 6-substituted-1,4-naphthoquinone
~2.0 times the mole, preferably 1.1 to 1.5 times the mole.
ディールス・アルダ−反応に使用される溶媒としては、
６−置換−１，４−ナフトキノン及びジエン化合物に対
する溶解度が大きいものであれば良く、ベンゼン、トル
エン、キシレン等の芳香族炭化水素； エチレングリコ
ールモノオクチルエーテル、ジエチレングリコールモノ
エチルエーテル。The solvent used in the Diels-Alder reaction is
Aromatic hydrocarbons such as benzene, toluene, xylene, etc.; ethylene glycol monooctyl ether, diethylene glycol monoethyl ether;
トリエチレングリコールモノメチル等のモノ、ジあるい
はトリエチレングリコールモノアルキルエーテル；クロ
ロホルム、四塩化炭素等の有機塩素化合物などが好まし
い溶媒として例示される。Preferred solvents include mono-, di-, or triethylene glycol monoalkyl ethers such as triethylene glycol monomethyl; organic chlorine compounds such as chloroform and carbon tetrachloride.
ディールス・アルダ−反応に供する６−置換−１，４−
ナフトキノンの濃度は、低過ぎると反応速度が遅く、ま
た一方、濃度が高すぎると重合等の副反応を起こす。従
って、ディールス・アルダ−反応に使用される溶媒の使
用量は６−置換−１゜４−ナフトキノンの濃度が好まし
くは０．５〜１５重量％、より好ましくは１〜１０重量
％となるようにする。また、ディールス・アルダ−反応
温度は高すぎると６−置換−１，４−ナフトキノンのみ
ならず２−置換−１，４−ナフトキノンもジエン化合物
と反応して収率の低下を来たすし、また一方、低すぎる
と反応時間が長くなり、コスト面で不利となる。従って
、好ましくは５０〜２００℃、より好ましくは８０〜１
５０℃とする。反応時間はコスト面及び副反応の観点か
ら２〜２０時間、好ましくは３〜１０時間が適切である
。6-substituted-1,4-substituted for Diels-Alder reaction
If the concentration of naphthoquinone is too low, the reaction rate will be slow, while if the concentration is too high, side reactions such as polymerization will occur. Therefore, the amount of solvent used in the Diels-Alder reaction is such that the concentration of 6-substituted-1°4-naphthoquinone is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight. do. Furthermore, if the Diels-Alder reaction temperature is too high, not only 6-substituted-1,4-naphthoquinone but also 2-substituted-1,4-naphthoquinone will react with the diene compound, resulting in a decrease in yield; If it is too low, the reaction time will be long, which will be disadvantageous in terms of cost. Therefore, preferably 50 to 200°C, more preferably 80 to 1
The temperature shall be 50°C. The appropriate reaction time is 2 to 20 hours, preferably 3 to 10 hours, from the viewpoint of cost and side reactions.
また、ディールス・アルダ−反応においては重合禁止剤
を用いるのが好ましい。Further, it is preferable to use a polymerization inhibitor in the Diels-Alder reaction.
立体障害及び電子密度の違いから２−置換−１゜４−ナ
フトキノンは殆どジエン化合物と反応しないにも拘らず
、６−置換−１，４−ナフトキノンはジエン化合物と容
易に反応して対応するディールス・アルダ−反応付加物
を生成する。該付加物は２−置換−１，４−ナフトキノ
ンとは各種の特性が大きく異なり、従って２−置換−１
，４−ナフトキノンの分離・精製が非常に容易になり、
例えば再結晶や抽出などの簡単な操作で容易に高純度の
２−置換−１，４−ナフトキノンが得られる。Although 2-substituted-1゜4-naphthoquinone hardly reacts with diene compounds due to differences in steric hindrance and electron density, 6-substituted-1,4-naphthoquinone easily reacts with diene compounds and reacts with the corresponding Diels.・Produces an Alder reaction adduct. The adducts have various properties that are significantly different from 2-substituted-1,4-naphthoquinones, and therefore 2-substituted-1,4-naphthoquinones
, 4-naphthoquinone becomes very easy to separate and purify.
For example, highly pure 2-substituted-1,4-naphthoquinone can be easily obtained by simple operations such as recrystallization and extraction.
２−置換−１，４−ナフトキノンの分離・精製を再結晶
によって行なう場合には、ディールス・アルダ−反応に
よって得られた反応混合物から溶媒を留去した後、再結
晶溶媒を用いて２−置換−１，４−ナフトキノンを再結
晶させ、濾別し乾燥して高純度の２−置換−１，４−ナ
フトキノンが得られる。再結晶溶媒としては２−置換−
１，４−ナフトキノンと付加物との溶解度に差があるも
のが良く、メタノール、エタノール、プロパツール、ブ
タノール等のアルコール類が好ましい。When separating and purifying 2-substituted-1,4-naphthoquinone by recrystallization, the solvent is distilled off from the reaction mixture obtained by the Diels-Alder reaction, and then the 2-substituted 1,4-naphthoquinone is separated and purified using the recrystallization solvent. -1,4-naphthoquinone is recrystallized, filtered and dried to obtain highly pure 2-substituted-1,4-naphthoquinone. As a recrystallization solvent, 2-substituted-
It is preferable that there is a difference in solubility between 1,4-naphthoquinone and the adduct, and alcohols such as methanol, ethanol, propatool, and butanol are preferable.
また、ディールス・アルダ−反応後得られた反応混合物
に例えば亜硫酸水素塩を加える２２−置換−１，４−ナ
フトキノンは亜硫酸水素塩として水相中に抽出さへ 付
加物は油相（ディールス・アルダ−反応に用いた溶媒の
相）中に残る。水相を取り出し、更に再結晶溶媒を加え
て再結晶させるか、塩析させることにより２−置換−１
，４−ナフトキノン亜硫酸水素塩として析出させ、濾別
・乾燥して高純度の２−置換−１，４−ナフトキノンが
得られる。Alternatively, for example, by adding bisulfite to the reaction mixture obtained after the Diels-Alder reaction, the 22-substituted-1,4-naphthoquinone is extracted as bisulfite into the aqueous phase. - remains in the phase of the solvent used in the reaction). The aqueous phase is taken out and recrystallized by adding a recrystallization solvent, or by salting out, 2-substituted-1
, 4-naphthoquinone bisulfite is precipitated, filtered and dried to obtain highly pure 2-substituted-1,4-naphthoquinone.
添付図面は本発明の公的な実施態様における工程を説明
するフローシート図である。第１図は、２−置換−ナフ
タリンを出発原料とする高純度の２−置換−１，４−ナ
フトキノンの一貫的な製造法を説明する。旅回では第１
工程（酸化反応）として第二セリウム塩の酸性水溶液を
使用する間接電解酸化反応が例示されているが、この第
１工程はクロム酸や過酸化水素等の酸化剤による方法な
ど他の酸化反応に置き換えてもよい。The accompanying drawings are flow sheet diagrams illustrating steps in a public embodiment of the invention. FIG. 1 illustrates a consistent process for the production of high purity 2-substituted-1,4-naphthoquinones starting from 2-substituted-naphthalenes. First in the travel series
As a process (oxidation reaction), an indirect electrolytic oxidation reaction using an acidic aqueous solution of ceric salt is exemplified, but this first step is not suitable for other oxidation reactions such as a method using an oxidizing agent such as chromic acid or hydrogen peroxide. May be replaced.
セリウム塩の酸性水溶液をタンク６から電解槽１９に供
給し、電解酸化して第二セリウム塩の酸性水溶液として
酸化・抽出槽４に供給する。一方、出発原料である２−
置換−ナフタリンをタンク１から酸化・抽出槽４に供給
し、攪拌しながら所定の温度に昇温し、酸化反応を行な
う（第１工程）。An acidic aqueous solution of cerium salt is supplied from tank 6 to electrolytic cell 19, electrolytically oxidized, and supplied to oxidation/extraction tank 4 as an acidic aqueous solution of ceric salt. On the other hand, the starting material 2-
Substituted naphthalene is supplied from tank 1 to oxidation/extraction tank 4, heated to a predetermined temperature while stirring, and subjected to an oxidation reaction (first step).
第１工程の酸化反応によって、２−置換−ナフタリンは
２−置換−１，４−ナフトキノンに転化されるが６−置
換−１，４−ナフトキノンも副生ずる。一方、酸化剤と
して消費された第二セリウム塩は還元されて第一セリウ
ム塩になる。By the oxidation reaction in the first step, 2-substituted naphthalene is converted to 2-substituted-1,4-naphthoquinone, but 6-substituted-1,4-naphthoquinone is also produced as a by-product. On the other hand, the ceric salt consumed as an oxidizing agent is reduced to become a cerous salt.
第１工程の酸化反応後、溶媒をタンク１２から酸化・抽
出槽４に供給し、２−置換−１，４−すフトキノン及び
６−置換−１，４−ナフトキノンを含む酸化反応生成物
を溶媒相に抽出して水相から分離する。一方、第１工程
で生成した第一セリウム塩および未反応の第二セリウム
塩は水相中に抽出される。酸化・抽出槽４の内容物を抜
き出し、油水分離槽５を経て溶媒相はタンク７に、セリ
ウム塩を含む水相はタンク６に移送する（第２工程）。After the oxidation reaction in the first step, the solvent is supplied from the tank 12 to the oxidation/extraction tank 4, and the oxidation reaction product containing 2-substituted-1,4-suphthoquinone and 6-substituted-1,4-naphthoquinone is removed from the solvent. The phases are extracted and separated from the aqueous phase. On the other hand, the cerous salt and unreacted ceric salt produced in the first step are extracted into the aqueous phase. The contents of the oxidation/extraction tank 4 are extracted, and the solvent phase is transferred to the tank 7 through the oil/water separation tank 5, and the aqueous phase containing cerium salt is transferred to the tank 6 (second step).
ここで用いられる溶媒は次の第３工程における溶媒とし
ても用い得るように、ディールス・アルダ−反応に使用
される溶媒として前述したものが好ましい。The solvent used here is preferably one mentioned above as a solvent used in the Diels-Alder reaction so that it can also be used as a solvent in the next third step.
なお、タンク６に移送されたセリウム塩を含む水相は電
解槽１９に送らへ ここで水相中の第一セリウム塩は第
二セリウム塩に電解酸化さ札 第二セリウム塩の酸性水
溶液として再使用される。The aqueous phase containing the cerium salt transferred to the tank 6 is sent to the electrolytic cell 19. Here, the cerous salt in the aqueous phase is electrolytically oxidized to ceric salt. used.
第２工程で抽出１分離した２−置換−１，４−ナフトキ
ノン及び６−置換−１，４−ナフトキノンを含む溶媒相
をタンク７から、ジエン化合物をタンク８からディール
ス・アルダ−反応槽９に供給し、ディールス・アルダ−
反応を行なう（第３工程）。前述したように、２−置換
−１，４−ナフトキノンは殆どジエン化合物と反応しな
いにも拘らず、６−置換−１，４−ナフトキノンはジエ
ン化合物と容易に反応して対応する付加物を生成する。The solvent phase containing the 2-substituted-1,4-naphthoquinone and 6-substituted-1,4-naphthoquinone separated in the second step is transferred from tank 7, and the diene compound is transferred from tank 8 to Diels-Alder reactor 9. Supply, Diels Alder
Perform the reaction (third step). As mentioned above, although 2-substituted-1,4-naphthoquinone hardly reacts with diene compounds, 6-substituted-1,4-naphthoquinone easily reacts with diene compounds to form the corresponding adduct. do.
ディールス・アルダ−反応後、反応混合物から溶媒を回
収する。第１図のフローシートの場合、ディールス・ア
ルダ−反応混合物を蒸留塔１０に供給して蒸留し、溶媒
をタンク１２に回収する。After the Diels-Alder reaction, the solvent is recovered from the reaction mixture. For the flow sheet of FIG. 1, the Diels-Alder reaction mixture is fed to distillation column 10 for distillation and the solvent is collected in tank 12.
なお、溶媒とともに未反応の２−置換−ナフタリンも一
緒に回収してもよい。蒸留塔１０の底部から２−置換−
１，４−ナフトキノン及び６−置換−１，４−ナフトキ
ノンとジエン化合物との付加物を含む混合物を抜き出す
（第４工程）。次いで、この混合物を減圧乾燥機１１に
供給し、残存する溶媒を更に完全に除去する。Incidentally, unreacted 2-substituted naphthalene may also be recovered together with the solvent. 2-substitution from the bottom of the distillation column 10
A mixture containing 1,4-naphthoquinone and an adduct of 6-substituted-1,4-naphthoquinone and a diene compound is extracted (fourth step). This mixture is then fed to a vacuum dryer 11 to further completely remove the remaining solvent.
最後に、溶媒を除去した後に得られた混合物から６−置
換−１，４−ナフトキノンとジエン化合物とのディール
ス・アルダ−反応付加物を再結晶や抽出などの操作によ
り除去して高純度の２−置換−１，４−ナフトキノンを
得る（第５工程）。Finally, the Diels-Alder reaction adduct of 6-substituted-1,4-naphthoquinone and diene compound is removed from the mixture obtained after removing the solvent by operations such as recrystallization and extraction to obtain highly pure 2 -Substituted-1,4-naphthoquinone is obtained (fifth step).
即ち、減圧乾燥機１１から抜き出しな２−置換−１，４
−ナフトキノン及び６−置換−１，４−ナフトキノンと
ジエン化合物との付加物を含む混合物を晶析槽１５に供
給し、再結晶溶媒タンク１４から再結晶溶媒を加えて再
結晶を行ない、スラリーを濾過器１６にて濾過し、結晶
を減圧乾燥機１７にて乾燥して高純度の２−置換−１，
４−ナフトキノンの結晶を得る。一方、濾液は再結晶溶
媒回収塔１８に供給して蒸留し、溶媒を再結晶溶媒タン
ク１４に回収して再使用する。That is, 2-substituted-1,4 without being extracted from the vacuum dryer 11
A mixture containing -naphthoquinone and an adduct of 6-substituted-1,4-naphthoquinone and a diene compound is supplied to the crystallization tank 15, and recrystallization is performed by adding a recrystallization solvent from the recrystallization solvent tank 14 to form a slurry. Filter with a filter 16 and dry the crystals with a vacuum dryer 17 to obtain high purity 2-substituted-1,
Obtain crystals of 4-naphthoquinone. On the other hand, the filtrate is supplied to the recrystallization solvent recovery column 18 and distilled, and the solvent is recovered to the recrystallization solvent tank 14 and reused.
本発明において、飼料の添加物（止血剤）として有用な
高純度の２−メチル−１，４−ナフトキノン亜硫酸水素
塩を製造する場合には、前記と同様にして得られた６−
メチル−１，４−ナフトキノンとジエン化合物とのディ
ールス・アルダ−反応付加物を含有するディールス・ア
ルダ−反応混合物に亜硫酸水素塩水溶液を加えて２−メ
チル−１，４−ナフトキノン亜硫酸水素塩として水相中
に抽出すればよい。In the present invention, when producing high-purity 2-methyl-1,4-naphthoquinone bisulfite useful as a feed additive (hemostatic agent), 6-methyl-1,4-naphthoquinone bisulfite obtained in the same manner as described above is produced.
An aqueous bisulfite solution is added to a Diels-Alder reaction mixture containing a Diels-Alder reaction adduct of methyl-1,4-naphthoquinone and a diene compound to form 2-methyl-1,4-naphthoquinone bisulfite in water. It can be extracted into the phase.
亜硫酸水素塩水溶液としてはナトリウム、カリウム等の
アルカリ金属の亜硫酸塩やジメチルビリシミノール等の
アミンの亜硫酸塩が用いられる。As the aqueous bisulfite solution, sulfites of alkali metals such as sodium and potassium, and sulfites of amines such as dimethylbiliciminol are used.
ディールス・アルダ−反応混合物に亜硫酸水素塩水溶液
を加えることによって２−メチル−１，４−ナフトキノ
ンは亜硫酸水素塩となり、溶媒相から水相中に抽出され
、溶媒相中の６−メチル−１゜４−ナフトキノンとジエ
ン化合物との付加物から分離される。この後、例えば取
り出した水相に再結晶溶媒を加えて２−メチル−１，４
−ナフトキノン亜硫酸水素塩を析出させ、結晶として取
り出すことができる。By adding an aqueous bisulfite solution to the Diels-Alder reaction mixture, 2-methyl-1,4-naphthoquinone becomes bisulfite and is extracted from the solvent phase into the aqueous phase, resulting in 6-methyl-1° in the solvent phase. It is separated from the adduct of 4-naphthoquinone and diene compound. After this, for example, a recrystallization solvent is added to the aqueous phase taken out and 2-methyl-1,4
- Naphthoquinone bisulfite can be precipitated and taken out as crystals.
第２図は、２−メチル−１，４−ナフトキノン亜硫酸水
素塩結晶を得る方法を説明するフローシート図である。FIG. 2 is a flow sheet diagram illustrating a method for obtaining 2-methyl-1,4-naphthoquinone bisulfite crystals.
２−メチル−１，４−ナフトキノンの酸化反応からディ
ールス・アルダ−反応までは前記第１図の方法における
第１工程から第３工程までと同様である。第２図におい
ても記号１〜９は第１図と同じ装置、ラインを表わす。The steps from the oxidation reaction of 2-methyl-1,4-naphthoquinone to the Diels-Alder reaction are the same as those from the first step to the third step in the method shown in FIG. In FIG. 2, symbols 1 to 9 represent the same devices and lines as in FIG.
第３工程終了後、ディールズ・アルダー反応槽９中には
２−メチル−１，４−ナフトキノン、６−メチル−１，
４−ナフトキノンとジエン化合物との付加物、溶媒等を
含む反応混合物が入っている。亜硫酸水素塩水溶液をタ
ンク３０からディールス・アルダ−反応槽９に加え、２
−メチル−１，４−ナフトキノンを亜硫酸水素塩として
水相中に抽出する。内容物を油水分離槽３１に移送して
溶媒相を分離する。ついで、水相中の２−メチル−１，
４−ナフトキノン亜硫酸水素塩を、再結晶溶媒の添加あ
るいは塩析などの方法によって析出させ、分離し、結晶
を取り出す。After the third step, 2-methyl-1,4-naphthoquinone, 6-methyl-1,
Contains a reaction mixture containing an adduct of 4-naphthoquinone and a diene compound, a solvent, etc. Add the bisulfite aqueous solution from tank 30 to Diels-Alder reactor 9,
-Methyl-1,4-naphthoquinone is extracted as bisulfite into the aqueous phase. The contents are transferred to an oil-water separation tank 31 to separate the solvent phase. Then, 2-methyl-1,
4-naphthoquinone bisulfite is precipitated by a method such as addition of a recrystallization solvent or salting out, separated, and crystals are taken out.
再結晶溶媒の添加による場合には、水相を晶析槽３３に
供給し、再結晶溶媒をタンク３６から加えて２−メチル
−１，４−ナフトキノン亜硫酸水素塩を析出させ、濾過
器３４で濾過し、減圧乾燥機３５で乾燥して高純度の２
−メチル−１，４−ナフトキノン亜硫酸水素塩結晶を得
る。好ましい再結晶溶媒はメタノール、エタノール、プ
ロパツール、ブタノール等のアルコール類やアセトンな
どが挙げられるが、これらの再結晶溶媒には水が含まれ
ていてもよい。濾過器３４から排出された濾液は、好ま
しくは再結晶溶媒回収塔３８に移送し、蒸留してタンク
３６に回収、再使用する。また、油水分離槽３１で分離
した溶媒相はライン３２を経て抜き出し、好ましくは蒸
留して溶媒をタンク１２に回収し、再使用する。In the case of addition of a recrystallization solvent, the aqueous phase is supplied to the crystallization tank 33, the recrystallization solvent is added from the tank 36 to precipitate 2-methyl-1,4-naphthoquinone bisulfite, and the filter 34 Filter and dry in a vacuum dryer 35 to obtain high purity 2
-Methyl-1,4-naphthoquinone bisulfite crystals are obtained. Preferred recrystallization solvents include alcohols such as methanol, ethanol, propatool, butanol, and acetone, but these recrystallization solvents may also contain water. The filtrate discharged from the filter 34 is preferably transferred to a recrystallization solvent recovery column 38, distilled, and recovered in a tank 36 for reuse. Further, the solvent phase separated in the oil-water separation tank 31 is extracted through a line 32, preferably distilled, and the solvent is recovered in the tank 12 for reuse.
塩析によって２−メチル−１，４−ナフトキノン亜硫酸
水素塩結晶を得る場合には、水相を晶析槽３３に供給し
た後、再結晶溶媒の代わりに塩化ナトリウム、亜硫酸ナ
トリウム、硫酸アンモニウムなどの無機塩、クエン酸、
酒石酸、シュウ酸などの有機酸あるいはそれらの塩を晶
析槽３３に加えて２−メチル−１，４−ナフトキノン亜
硫酸水素塩を析出させ、以下前記と同様に濾過、乾燥し
て高純度の２−メチル−１，４−ナフトキノン亜硫酸水
素塩結晶を得る。When obtaining 2-methyl-1,4-naphthoquinone bisulfite crystals by salting out, after supplying the aqueous phase to the crystallization tank 33, an inorganic solution such as sodium chloride, sodium sulfite, or ammonium sulfate is added instead of the recrystallization solvent. salt, citric acid,
Organic acids such as tartaric acid and oxalic acid or their salts are added to the crystallization tank 33 to precipitate 2-methyl-1,4-naphthoquinone bisulfite, which is then filtered and dried in the same manner as above to obtain highly pure 2-methyl-1,4-naphthoquinone bisulfite. -Methyl-1,4-naphthoquinone bisulfite crystals are obtained.
本発明において、副生６〜置換−１，４−ナフトキノン
からバルブ蒸解助剤やアントラキノン誘導体合成の原料
として有用な２−置換−アントラキノン類［一般式（Ｆ
）で表される５、８−ジヒドロ−２−置換−アントラキ
ノンあるいは一般式（Ｇ）で表される２−置換−アント
ラキノン］を得る場合について次ぎに説明する。In the present invention, 2-substituted anthraquinones [general formula (F
The case of obtaining 5,8-dihydro-2-substituted anthraquinone represented by ) or 2-substituted anthraquinone represented by general formula (G)] will be described next.
一般式（Ｄ）で表わされる１、３−ブタジェンを用いて
上述してきたようにディールス・アルダ−反応を行ない
、２−置換−１，４−ナフトキノン類を取り出す一方、
６−置換−１，４−ナフトキノンと一般式（Ｄ）で表わ
される１、３−ブタジェンとのディールス・アルダ−反
応付加物を含む混合物を取り出し、該付加物を酸化して
、２−置換−アントラキノン類を得る。該付加物の酸化
方法としては特に限定はされないが、空気などの分子状
酸素を含む気体を酸化剤として用いると取扱いが容易で
ありコストの面でも有利なので好ましい。例えば、と−
置換−１，４−ナフトキノンを再結晶させて分離した後
に得られる６−置換−１，４−ナフトキノンと一般式（
Ｄ）で表わされる１、３−ブタジェンとのディールス・
アルダ−反応付加物を含む溶媒溶液に空気を吹き込んで
酸化して２−置換−アントラキノン類を形成させた後、
溶媒を濃縮して再結晶させるか溶媒を留去して別の適当
な溶媒を用いて再結晶させるなどして２−置換−アント
ラキノン類を得る。または、該付加物を含む溶媒溶液に
アルカリ水溶液を加えて水相中に抽出し、好ましくは３
５℃〜１５０℃の範囲の温度にて空気を吹き込むと容易
に該付加物が酸化されて２−置換−アントラキノン類の
沈澱が得られる。この方法は、酸化反応が容易に進行す
るという利点があるだけでなく、殆どの不純物が溶媒相
中に抽出されるため精製効率がよい。ディールス・アル
ダ−反応付加物を酸化して得られル５．８−ジヒドロ−
２−置換−アントラキノン２２−置換−アントラキノン
の比率は酸化条件により選択できる。A Diels-Alder reaction is carried out as described above using 1,3-butadiene represented by general formula (D) to extract 2-substituted-1,4-naphthoquinones, while
A mixture containing a Diels-Alder reaction adduct of 6-substituted-1,4-naphthoquinone and 1,3-butadiene represented by general formula (D) is taken out, and the adduct is oxidized to form a 2-substituted-1,4-naphthoquinone. Obtain anthraquinones. The method for oxidizing the adduct is not particularly limited, but it is preferable to use a gas containing molecular oxygen, such as air, as the oxidizing agent because it is easy to handle and is advantageous in terms of cost. For example, and-
6-substituted-1,4-naphthoquinone obtained after recrystallizing and separating substituted-1,4-naphthoquinone and the general formula (
D) with 1,3-butadiene represented by
After oxidizing the solvent solution containing the Alder reaction adduct with air to form 2-substituted anthraquinones,
The 2-substituted anthraquinones are obtained by concentrating the solvent and recrystallizing, or by distilling off the solvent and recrystallizing using another suitable solvent. Alternatively, an alkaline aqueous solution is added to a solvent solution containing the adduct and extracted into the aqueous phase, preferably 3
Blowing air at a temperature in the range of 5 DEG C. to 150 DEG C. easily oxidizes the adduct to yield a precipitate of 2-substituted anthraquinones. This method not only has the advantage that the oxidation reaction proceeds easily, but also has good purification efficiency because most impurities are extracted into the solvent phase. 5,8-dihydro- obtained by oxidizing the Diels-Alder reaction adduct
2-Substituted-Anthraquinone The ratio of 22-substituted-anthraquinone can be selected depending on the oxidation conditions.
６−置換−１，４−ナフトキノンと一般式（Ｄ）で表わ
される１、３−ブタジェンとのディールス・アルダ−反
応付加物もバルブ蒸解助剤として使用可能であるが、比
較的不安定で取扱いが容易でなく、２−置換−アントラ
キノン類の方が好適に用いられる。The Diels-Alder reaction adduct of 6-substituted-1,4-naphthoquinone and 1,3-butadiene represented by the general formula (D) can also be used as a valve cooking aid, but it is relatively unstable and difficult to handle. 2-substituted anthraquinones are more preferably used.
第３図は、後者の方法を説明するフローシート図である
。再結晶溶媒回収塔１８（第１図）の塔底から残渣２１
を、溶媒タンク４１（第３図）から溶媒を、それぞれ第
３図の酸化槽４０に供給する。または第２図における２
−置換−１，４−ナフトキノンを亜硫酸水素塩として水
相中に抽出した後の溶媒相３２を第３図の酸化槽４０に
供給する。次いでアルカリ水溶液タンク４２からアルカ
リ水溶液を加え、攪拌しながら空気を吹込み酸化する。FIG. 3 is a flow sheet diagram illustrating the latter method. Residue 21 from the bottom of recrystallization solvent recovery tower 18 (Fig. 1)
and a solvent are supplied from a solvent tank 41 (FIG. 3) to an oxidation tank 40 in FIG. 3, respectively. or 2 in Figure 2
The solvent phase 32 after extraction of the substituted-1,4-naphthoquinone as bisulfite into the aqueous phase is fed to the oxidation tank 40 of FIG. Next, an alkaline aqueous solution is added from the alkaline aqueous solution tank 42, and air is blown in while stirring to oxidize.
反応混合物を油水分離槽４３に供給して溶媒相２２−置
換−アントラキノン類を含む水相とを分離し、水相を濾
過器４４に供給して結晶を濾別し、乾燥機４５にて乾燥
して２−置換−アントラキノン類の結晶を得る。一方、
油水分離槽４３で分離した溶媒相は溶媒回収塔４６にて
蒸留して溶媒を溶媒タンク４１に回収し、再使用する。The reaction mixture is supplied to an oil-water separation tank 43 to separate the solvent phase from the aqueous phase containing the 22-substituted anthraquinones, the aqueous phase is supplied to a filter 44 to filter out crystals, and then dried in a drier 45. to obtain crystals of 2-substituted anthraquinones. on the other hand,
The solvent phase separated in the oil-water separation tank 43 is distilled in a solvent recovery column 46, and the solvent is recovered in a solvent tank 41 for reuse.
［実施例］
以下、実施例により本発明の詳細な説明するが本発明は
これらの実施例に限定されるものではない。なお、各表
においては各化合物名を下記の略号で表わす。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in each table, each compound name is represented by the following abbreviation.
２−Ｍ Ｎ Ｑ・・・２−メチル−１，４−ナフトキノ
ン６−Ｍ Ｎ Ｑ・・・６−メチル−１，４−ナフトキ
ノン合計ＭＮＱ・・・（２−ＭＮＱ）＋ （６−ＭＮＱ
＞実施例１
還流冷却法 撹拌装置を取り付けたガラス製の反応槽に
、２−メチル−ナフタリン５０．４ｇおよび０−キシレ
ン１５０ｇを仕込んで攪拌し、溶解させた後、硫酸第２
セリウムの硫酸水溶液６１２（硫酸６００ｇ、硫酸第２
セリウム６９３ｇを含む）を投入し、４０℃で４時間反
応させた。反応終了後、撹拌を停止し、反応液を分離槽
に移し、溶媒相（０−キシレン相）と水相とを分離した
。2-M N Q...2-Methyl-1,4-naphthoquinone 6-M N Q...6-Methyl-1,4-naphthoquinone total MNQ...(2-MNQ) + (6-MNQ
>Example 1 Reflux cooling method A glass reaction tank equipped with a stirring device was charged with 50.4 g of 2-methyl-naphthalene and 150 g of 0-xylene, stirred, and dissolved.
Cerium sulfuric acid aqueous solution 612 (sulfuric acid 600g, sulfuric acid 2nd
(containing 693 g of cerium) was added thereto, and the mixture was reacted at 40° C. for 4 hours. After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separation tank, and the solvent phase (0-xylene phase) and aqueous phase were separated.
水相については０−キシレンを用いて抽出し、〇−キシ
レン相を先の溶媒相に加えた。この溶媒相（２−メチル
−１，４−ナフトキノン１１ｇ、６−メチル−１，４−
ナフトキノン４ｇ、 未反応の２−メチル−ナフタリ
ン１．５ｇ、 Ｏ−キシレン１００ｇを含む）にブタ
ジェンを１．５ｇ（モル比でブタジェン／６−メチル−
１，４−ナフトキノン＝１．２）、重合禁止剤としての
ｐ −ｔｅｒｔ−ブチル−カテコールを３０ｍｇ入れ、
温度１２０℃で、撹拌下、オートクレーブにて４時間反
応した。所定時間ごとに反応液を液体クロマトグラフィ
ーにより分析し、２−メチル−１，４−ナフトキノン及
び６−メチル−１，４−ナフトキノンの定量を行って表
１の結果を得た。The aqueous phase was extracted using 0-xylene, and the 0-xylene phase was added to the previous solvent phase. This solvent phase (11 g of 2-methyl-1,4-naphthoquinone, 6-methyl-1,4-
1.5 g of butadiene (containing 4 g of naphthoquinone, 1.5 g of unreacted 2-methyl-naphthalene, and 100 g of O-xylene) (molar ratio of butadiene/6-methyl-
1,4-naphthoquinone = 1.2), 30 mg of p-tert-butyl-catechol as a polymerization inhibitor,
The reaction was carried out at a temperature of 120° C. for 4 hours in an autoclave while stirring. The reaction solution was analyzed by liquid chromatography at predetermined intervals to quantify 2-methyl-1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone, and the results shown in Table 1 were obtained.
反応後、反応混合物の一部（６０ｇ ）を蒸留し、更に
減圧乾燥した。乾燥後の反応生成物にメタノール８０ｇ
を加えて液温５０℃に保持して溶解した。次いで液温１
０℃に冷却して晶析を行ない、析出した結晶を濾別し、
減圧乾燥して純度９９゜５％の２−メチル−１，４−ナ
フトキノン結晶を得た。一方、濾液を蒸留してメタノー
ルを留去し、減圧乾燥して６−メチル−１，４−ナフト
キノンのブタジェン付加物（１，４，４ａ、９ａ−テト
ラヒドロ−６−メチル−アントラキノン）を固型物残渣
として得た。After the reaction, a portion (60 g) of the reaction mixture was distilled and further dried under reduced pressure. 80g of methanol to the reaction product after drying
was added and dissolved while maintaining the liquid temperature at 50°C. Next, liquid temperature 1
Crystallization is performed by cooling to 0°C, and the precipitated crystals are separated by filtration.
After drying under reduced pressure, 2-methyl-1,4-naphthoquinone crystals with a purity of 99.5% were obtained. Meanwhile, the filtrate was distilled to remove methanol and dried under reduced pressure to solidify the butadiene adduct of 6-methyl-1,4-naphthoquinone (1,4,4a,9a-tetrahydro-6-methyl-anthraquinone). Obtained as a residue.
実施例２
実施例１で得た溶媒相の一部を用い、ディールス・アル
ダ−反応の温度を１５０℃にした他は実施例１と同様に
反広 分析を行い、表１に示す結果を得た。Example 2 Using a portion of the solvent phase obtained in Example 1, a reaction analysis was carried out in the same manner as in Example 1, except that the temperature of the Diels-Alder reaction was 150°C, and the results shown in Table 1 were obtained. Ta.
実施例３
実施例１で得た溶媒相の一部を用い、ディールス・アル
ダ−反応の温度を８０℃にした他は実施例１と同様に反
応、分析を行い、表１に示す結果を得た。Example 3 Using a portion of the solvent phase obtained in Example 1, the reaction and analysis were carried out in the same manner as in Example 1, except that the temperature of the Diels-Alder reaction was 80°C, and the results shown in Table 1 were obtained. Ta.
実施例４
２−メチル−ナフタリン酸化反応生成物の使用量を少な
くすることによって溶媒相（０−キシレン相）中の６−
メチル−１，４−ナフトキノンの濃度を１重量％にし、
ディールス・アルダ−反応に用いたブタジェンを０．５
ｇ、 ｐ−ｔｅｒｔ−ブチル−カテコールを８１ｇ
にした他は実施例１と同様に反広 分析を行い、表１に
示す結果を得た。Example 4 6- in the solvent phase (0-xylene phase) by reducing the amount of 2-methyl-naphthalate oxidation reaction product.
The concentration of methyl-1,4-naphthoquinone is 1% by weight,
Butadiene used in Diels-Alder reaction was 0.5
g, 81 g of p-tert-butyl-catechol
A wide range analysis was conducted in the same manner as in Example 1, except that the results were shown in Table 1.
実施例５
２−メチル−ナフタリン酸化反応生成物の使用量を多く
することによって溶媒相（Ｏ−キシレン相）中の６−メ
チル−１，４−ナフトキノンの濃度を８．０重量％にし
、ディールス・アルダ−反応に用いたブタジェンを４，
０ｇ１ｐ−ｔｅｒｔ−ブチル−カテコールを７０＋ａｇ
にした他は実施例１と同様に反応、分析を行い、表２に
示す結果を得た。Example 5 Diels・Butadiene used in Alder reaction is 4,
0g1p-tert-butyl-catechol 70+ag
The reaction and analysis were carried out in the same manner as in Example 1, except that the results shown in Table 2 were obtained.
実施例６
ディールス・アルダ−反応において、ブタジェンの使用
量を６−メチル−１，４−ナフトキノンと等モルにした
他は実施例１と同様に度広 分析を行い、表２に示す結
果を得た。Example 6 Diversity analysis was carried out in the same manner as in Example 1, except that the amount of butadiene used in the Diels-Alder reaction was made equimolar with 6-methyl-1,4-naphthoquinone, and the results shown in Table 2 were obtained. Ta.
実施例７
ディールス・アルダ−反応において、ブタジェンの使用
量を６−メチル−１，４−ナフトキノンの２倍モルにし
た他は実施例１と同様に反応、分析を行い、表２に示す
結果を得た。Example 7 In the Diels-Alder reaction, the reaction and analysis were carried out in the same manner as in Example 1, except that the amount of butadiene used was twice the mole of 6-methyl-1,4-naphthoquinone, and the results shown in Table 2 were obtained. Obtained.
実施例８
ディールス・アルダ−反応において、ブタジェン１．５
ｇの代わりにメチルブタジェン１．９ｇ（モル比でメチ
ルブタジェン／６−メチル−１゜４−ナフトキノン＝１
．２）を用いた他は実施例１と同様に反ふ 分析を行い
、表２に示す結果を得た。Example 8 In the Diels-Alder reaction, butadiene 1.5
g instead of 1.9 g of methylbutadiene (molar ratio of methylbutadiene/6-methyl-1°4-naphthoquinone = 1)
．． The reflux analysis was carried out in the same manner as in Example 1, except that 2) was used, and the results shown in Table 2 were obtained.
実施例９
２−メチル−ナフタリンを硫酸中クロム酸で酸化し、２
−メチル−１，４−ナフトキノン９．０ｇ、 ６−メ
チル−１，４−ナフトキノン６．０ｇ。Example 9 Oxidation of 2-methyl-naphthalene with chromic acid in sulfuric acid to give 2-methyl-naphthalene
-Methyl-1,4-naphthoquinone 9.0 g, 6-methyl-1,4-naphthoquinone 6.0 g.
未反応の２−メチル−ナフタリン２．０ｇを〇−キシレ
ン１００ｇで抽出した。この６−メチル−１、４−ナフ
トキノンを５．１重量％含む溶液にブタジェンを２．３
ｇ（モル比でブタジェン／６−メチル−１，４−ナフト
キノン＝１．２）、重合禁止剤としてのｐ−ｔｅｒｔ−
ブチル−カテコール３０ｍｇを入札温度１２０℃で、撹
拌下、オートクレーブにて５時間反応した。所定時間ご
とに反応液の一部をサンプリングし、液体クロマトグラ
フィーにより、２−メチル−１，４−ナフトキノン及び
６−メチル−１，４−ナフトキノンの定量を行い、表３
に示す結果を得た。2.0 g of unreacted 2-methyl-naphthalene was extracted with 100 g of 0-xylene. Add 2.3% butadiene to this solution containing 5.1% by weight of 6-methyl-1,4-naphthoquinone.
g (molar ratio of butadiene/6-methyl-1,4-naphthoquinone = 1.2), p-tert- as a polymerization inhibitor
30 mg of butyl-catechol was reacted at a tender temperature of 120°C for 5 hours in an autoclave with stirring. A portion of the reaction solution was sampled at predetermined intervals, and 2-methyl-1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone were quantified by liquid chromatography.
The results shown are obtained.
実施例１０
攪拌機、還流冷却法 過酸化水素滴下装置を取り付けた
ガラス製の反応槽に２−メチル−ナフタリンを投入し、
強酸性スルホン型イオン交換樹脂の存在下、２時間にわ
たって６０％過酸化水素水を滴下添加し反応を行なった
。得られた２−メチル−１，４−ナフトキノン１０ｇ、
６−メチル−１，４−ナフトキノン５ｇ、 未反
応の２−メチル−ナフタレン３．８ｇをベンゼンｌ○○
ｇで抽出した。この６−メチル−１，４−ナフトキノン
を４．２重量％含む溶液にブタジェンを２．２ｇ（モル
比でブタジェン／６−メチル−１，４−ナフトキノン＝
１．２）、重合禁止剤としてのｐ −ｔｅｒｔ−ブチル
−カテコールを３０＋ａｇ入へ 温度１２０℃で撹拌下
、オートクレーブにて４時間反応した。Example 10 Stirrer, reflux cooling method 2-methyl-naphthalene was put into a glass reaction tank equipped with a hydrogen peroxide dropping device,
In the presence of a strongly acidic sulfone type ion exchange resin, 60% hydrogen peroxide solution was added dropwise over 2 hours to carry out the reaction. 10 g of the obtained 2-methyl-1,4-naphthoquinone,
5 g of 6-methyl-1,4-naphthoquinone and 3.8 g of unreacted 2-methyl-naphthalene were mixed with benzene l○○.
Extracted with g. Add 2.2 g of butadiene to this solution containing 4.2% by weight of 6-methyl-1,4-naphthoquinone (molar ratio: butadiene/6-methyl-1,4-naphthoquinone =
1.2) P-tert-butyl-catechol as a polymerization inhibitor was added to 30+ag and reacted at a temperature of 120° C. with stirring in an autoclave for 4 hours.
サンプリング及び分析は実施例１に従って行い、表３に
示す結果を得た。Sampling and analysis were performed according to Example 1, and the results shown in Table 3 were obtained.
実施例１１
２−メチル−ナフタリンを触媒存在下に気相酸化して得
られた２−メチル−１，４−ナフトキノン８ｇ、６−メ
チル−１，４−ナフトキノン７ｇ。Example 11 8 g of 2-methyl-1,4-naphthoquinone and 7 g of 6-methyl-1,4-naphthoquinone were obtained by gas-phase oxidation of 2-methyl-naphthalene in the presence of a catalyst.
未反応の２−メチル−ナフタリン１．０ｇをベンゼン１
ｏｏｇで抽出した。この６−メチル−１４−ナフトキ
ノンを６．０％含む溶液にブタジェンを３．１ｇ（モル
比でブタジェン／６−メチル−１，４−ナフトキノン＝
１．２）、重合禁止剤としての、ｐ−ｔｅｒｔ−ブチル
−カテコール３０ｍｇを入れ、温度１２０℃で、撹拌下
オートクレーブにて５時間反応した。分析結果を表３に
示した。1.0 g of unreacted 2-methyl-naphthalene was added to 1 part of benzene.
Extracted with oog. Add 3.1 g of butadiene to this solution containing 6.0% of 6-methyl-14-naphthoquinone (molar ratio: butadiene/6-methyl-1,4-naphthoquinone =
1.2) 30 mg of p-tert-butyl-catechol as a polymerization inhibitor was added, and the reaction was carried out in an autoclave at a temperature of 120° C. for 5 hours with stirring. The analysis results are shown in Table 3.
実施例１２
（第１工程）
濃硫酸１９６ｋｇ、蒸留水１．５ｍ’に硫酸第２セリウ
ムＣｅ （ＳＯ４） ２４６４．８ｋｇを溶解し、蒸留
水を加えて２ｍ３とした。この溶液を還流冷却器、撹拌
装置を取り付けたグラスライニング製の反応槽に入Ｌ
５０℃に保持した。これに２−メチル−ナフタリン２
０ｋｇ１０−キシレン７０ ｋｇを投入し、撹拌下、３
時間酸化反応させた。Example 12 (First step) 2464.8 kg of ceric sulfate Ce (SO4) was dissolved in 196 kg of concentrated sulfuric acid and 1.5 m' of distilled water, and distilled water was added to make the solution 2 m3. This solution was put into a glass-lined reaction tank equipped with a reflux condenser and a stirring device.
It was maintained at 50°C. To this, 2-methyl-naphthalene 2
0kg10-xylene 70kg was added, and while stirring,
The oxidation reaction was carried out for a period of time.
（第２工程）
酸化反応終了後、撹拌を停止し、反応生成物を分離槽に
移し、溶媒相（０−キシレン相）と水相とを分離した。(Second step) After the oxidation reaction was completed, stirring was stopped, the reaction product was transferred to a separation tank, and the solvent phase (0-xylene phase) and the aqueous phase were separated.
水相について１５ｋｇの０−キシレンを用いて３回抽出
した。The aqueous phase was extracted three times with 15 kg of 0-xylene.
（第３工程）
分離後の溶媒相及び抽出溶媒相を混合して、ディールス
・アルダ−反応槽に投入し、ブタジェン６、３ｋｇを加
えて、攪拌下、温度１２０℃で４時間反応した。(Third Step) The separated solvent phase and extraction solvent phase were mixed and charged into a Diels-Alder reaction tank, 6.3 kg of butadiene was added, and the mixture was reacted with stirring at a temperature of 120° C. for 4 hours.
（第４工程）
反応混合物を蒸留し、溶媒及び未反応２−メチル−ナフ
タレンを回収した。残った反応生成物を更に減圧乾燥し
た。(Fourth step) The reaction mixture was distilled to recover the solvent and unreacted 2-methyl-naphthalene. The remaining reaction product was further dried under reduced pressure.
（第５工程）
乾燥した反応生成物を晶析用の反応槽に投入し、メタノ
ール１７０ｋｇを加えて、液１５０℃に保持し、完全に
溶解した。ついで？？！温を１０℃まで冷却して晶析を
行ない、析出した結晶を濾過器にて分離し、減圧乾燥し
て２−メチル−１，４−ナフトキノン１１．９ｋｇ（仕
込２−メチル−ナフタレンに対するモル収率４９．１％
）を得た。その純度は９９．５％であった。一方、濾液
を蒸留してメタノールを回収することにより、６−メチ
ル−１，４−ナフトキノンのブタジェン付加物（１゜４
．４ａ、９ａ−テトラヒドロ−６−メチル−アントラキ
ノン）が固型物残渣として残った。(Fifth step) The dried reaction product was put into a reaction tank for crystallization, 170 kg of methanol was added, and the liquid was maintained at 150° C. to completely dissolve. Next? ? ! The temperature was cooled to 10°C to perform crystallization, and the precipitated crystals were separated using a filter and dried under reduced pressure to give 11.9 kg of 2-methyl-1,4-naphthoquinone (molar yield relative to the charged 2-methyl-naphthalene). Rate 49.1%
) was obtained. Its purity was 99.5%. On the other hand, by distilling the filtrate and recovering methanol, a butadiene adduct of 6-methyl-1,4-naphthoquinone (1°4
．． 4a,9a-tetrahydro-6-methyl-anthraquinone) remained as a solid residue.
実施例１３
実施例１２の第５工程で得られた６−メチル−１，４−
ナフトキノンのブタジェン付加物からなる固型物残渣に
ＩＮ水酸化ナトリウム水溶液と０−キシレンを加え、３
０分間攪拌した後、５０℃で２時間空気を吹き込んだ。Example 13 6-methyl-1,4- obtained in the fifth step of Example 12
IN sodium hydroxide aqueous solution and 0-xylene were added to the solid residue consisting of the butadiene adduct of naphthoquinone, and 3
After stirring for 0 minutes, air was blown into the mixture at 50° C. for 2 hours.
その後静置すると油相と沈澱物を含む水相とに分離した
。水相を分離し、濾過し、得られた沈澱物を減圧乾燥し
て２−メチル−アントラキノン類（５，８−ジヒドロ−
２−メチル−アントラキノン２２−メチル−アントラキ
ノンの混合物）５ｋｇを得た。仕込２−メチル−ナフタ
レンに対するモル収率は１６．０％であった。After that, when the mixture was allowed to stand still, it was separated into an oil phase and an aqueous phase containing a precipitate. The aqueous phase was separated and filtered, and the resulting precipitate was dried under reduced pressure to produce 2-methyl-anthraquinones (5,8-dihydro-
5 kg of 2-methyl-anthraquinone (22-methyl-anthraquinone mixture) was obtained. The molar yield based on the charged 2-methyl-naphthalene was 16.0%.
実施例１４ 実施例１２の第１〜３工程を繰り返し行なった。Example 14 The first to third steps of Example 12 were repeated.
第３工程で得られた反応液に３３重量％亜硫酸水素ナト
リウム水溶液３７．５ｋｇを加え、５０℃で３時間反応
した。その後静置して油相と水相（２−メチル−１，４
−ナフトキノンの亜硫酸水素ナトリウム塩水溶液）とに
分離させた。水相を分離し、イソプロパツール１２０ｋ
ｇを加え、２５℃で２時間攪拌し、析出した結晶を濾別
した後、５０℃で減圧乾燥し、１９．７ｋｇの２−メチ
ル−１゜４−ナフトキノン亜硫酸水素ナトリウム塩を得
た。37.5 kg of a 33% by weight aqueous sodium bisulfite solution was added to the reaction solution obtained in the third step, and the mixture was reacted at 50° C. for 3 hours. After that, it was left to stand and the oil phase and water phase (2-methyl-1,4
- Naphthoquinone sodium bisulfite aqueous solution). Separate the aqueous phase and add isopropanol 120k
After stirring at 25°C for 2 hours, the precipitated crystals were filtered off and dried under reduced pressure at 50°C to obtain 19.7 kg of 2-methyl-1°4-naphthoquinone bisulfite sodium salt.
実施例１５
実施例１４で得られた油相に０．５Ｎの水酸化ナトリウ
ム水溶液を添加し３０分間攪拌した後、７０℃で２時間
空気を吹き込んだ。続いて油相と沈澱物を含む水相とを
分離し、得られた水相を濾過し減圧乾燥して２−メチル
−アントラキノン類５、５ｋｇを得た。Example 15 A 0.5N aqueous sodium hydroxide solution was added to the oil phase obtained in Example 14, stirred for 30 minutes, and then air was blown at 70° C. for 2 hours. Subsequently, the oil phase and the aqueous phase containing the precipitate were separated, and the obtained aqueous phase was filtered and dried under reduced pressure to obtain 5.5 kg of 2-methyl-anthraquinones.
実施例１６ 実施例１２の第１〜３工程を繰り返し行なった。Example 16 The first to third steps of Example 12 were repeated.
第３工程で得られた反応液に３３重量％亜硫酸水素ナト
リウム水溶液３７．５ｋｇを加え、５０℃で３時間反応
した。その後静置して油相と水相（２−メチル−１，４
−ナフトキノンの亜硫酸水素ナトリウム塩水溶液）とに
分離させた。水相を分離し、塩化ナトリウム４ｋｇを加
え、２０℃で１時間攪拌し、析出した結晶を濾別した後
、５０℃で減圧乾燥し、２０．５ｋｇの２−メチル−１
，４−ナフトキノン亜硫酸水素ナトリウム塩を得た。37.5 kg of a 33% by weight aqueous sodium bisulfite solution was added to the reaction solution obtained in the third step, and the mixture was reacted at 50° C. for 3 hours. After that, it was left to stand and the oil phase and water phase (2-methyl-1,4
- Naphthoquinone sodium bisulfite aqueous solution). The aqueous phase was separated, 4 kg of sodium chloride was added, stirred at 20°C for 1 hour, the precipitated crystals were filtered off, dried under reduced pressure at 50°C, and 20.5 kg of 2-methyl-1
, 4-naphthoquinone bisulfite sodium salt was obtained.
実施例１７
還流冷却法 撹拌装置を取り付けたガラス製の反応槽に
、０−キシレンに溶解した２−エチル−ナフタリンおよ
び硫酸第２セリウムの硫酸水溶液を投入し、撹拌下５０
℃で９０分間反応させた。Example 17 Reflux cooling method A sulfuric acid aqueous solution of 2-ethyl-naphthalene and ceric sulfate dissolved in 0-xylene was charged into a glass reaction tank equipped with a stirring device, and the mixture was stirred for 50 minutes.
The reaction was carried out at ℃ for 90 minutes.
反応終了後、撹拌を停止し、反応液を分離槽に移し、溶
媒相（０−キシレン相）と水相とを分離した。水相につ
いてはＯ−キシレンを用いて抽出し、○−キシレン相を
先の溶媒相に加えた。この溶媒相の一部（２−エチル−
１，４−ナフトキノン８ｇ、 ６−エチル−１，４−
ナフトキノン５ｇ、 未反応の２−エチル−ナフタリ
ン１．５ｇ、 ｏ−キシレン１００ｇを含む）にブタ
ジェンを１．９ｇ（モル比でブタジェン／６−エチル−
１，４−ナフトキノン＝１．３Ｌ 重合禁止剤として
のｐ−ｔｅｒｔ−ブチル−カテコールを３０ｍｇ入札
温度１１０℃で、撹拌下、オートクレーブにて５時間反
応した。反応後、反応混合物の一部を蒸留し、更に減圧
乾燥した。乾燥後の反応生成物にメタノール１００ｇを
加えて５０℃にて攪拌した後冷却し、析出した結晶を濾
別し、純水にて洗浄した後、減圧乾燥して純度９９．２
％の２−エチル−１，４−ナフトキノンを得た。次に、
濾液を蒸留してメタノールを回収し主として６−エチル
−１，４−ナフトキノンの付加物（Ｌ ４＋ ４ａ
、９ａ−テトラヒドロ−６−ニチルーアントラキノン）
より成る固形残渣に０．５Ｎ水酸化ナトリウム水溶液と
０−キシレンを加え、３０分間攪拌した後、６０℃で３
時間空気を吹き込んだ。静置して得られた沈澱物を含む
水相を濾過し、濾過物を純水で洗浄し減圧乾燥して２−
エチル−アントラキノン５゜４ｇを得た。After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separation tank, and the solvent phase (0-xylene phase) and aqueous phase were separated. The aqueous phase was extracted using O-xylene, and the O-xylene phase was added to the previous solvent phase. A portion of this solvent phase (2-ethyl-
1,4-naphthoquinone 8g, 6-ethyl-1,4-
1.9 g of butadiene (containing 5 g of naphthoquinone, 1.5 g of unreacted 2-ethyl-naphthalene, and 100 g of o-xylene) (molar ratio of butadiene/6-ethyl-
1,4-naphthoquinone = 1.3L Bid 30mg of p-tert-butyl-catechol as a polymerization inhibitor
The reaction was carried out at a temperature of 110° C. for 5 hours in an autoclave under stirring. After the reaction, a portion of the reaction mixture was distilled and further dried under reduced pressure. 100 g of methanol was added to the dried reaction product, stirred at 50°C, cooled, the precipitated crystals were filtered off, washed with pure water, and dried under reduced pressure to obtain a purity of 99.2.
% of 2-ethyl-1,4-naphthoquinone was obtained. next,
The filtrate is distilled to recover methanol, which is mainly an adduct of 6-ethyl-1,4-naphthoquinone (L 4+ 4a
, 9a-tetrahydro-6-nityluanthraquinone)
0.5N aqueous sodium hydroxide solution and 0-xylene were added to the solid residue, stirred for 30 minutes, and then heated at 60°C for 3
Time aired. The aqueous phase containing the precipitate obtained by standing was filtered, the filtrate was washed with pure water and dried under reduced pressure to obtain 2-
5.4 g of ethyl-anthraquinone was obtained.
実施例１８
還流冷却法 撹拌装置を取り付けたガラス製の反応槽に
、０−キシレンに溶解した２−ｔ−アミルナフタリンお
よび硫酸第２セリウムの硫酸水溶液を投入し、撹拌下５
０℃で２時間反応させた。Example 18 Reflux cooling method A sulfuric acid aqueous solution of 2-t-amylnaphthalene and ceric sulfate dissolved in 0-xylene was charged into a glass reaction tank equipped with a stirring device, and the mixture was stirred for 5 minutes.
The reaction was carried out at 0°C for 2 hours.
反応終了後、撹拌を停止し、反応液を分離槽に移し、溶
媒型（０−キシレン相）と水相とを分離した。水相につ
いては０−キシレンを用いて抽出し、０−キシレン相を
先の溶媒相に加えた。この溶媒相の一部（２−ｔ−アミ
ル−１，４−ナフトキノン４．２ｇ、６−ｔ−アミル−
１，４−ナフトキノン３．１ｇ、 未反応の２−ｔ−
アミルナフタリン２．０ｇ、 Ｏ−キシレン８０ｇを
含む）にブタジェンを０．９５ｇ、 重合禁止剤とし
てのｐ −ｔｅｒｔ−ブチル−カテコールを１５ｍｇ入
れ、温度１−１０℃で、撹拌下、オートクレーブにて５
時間反応した。反応後、反応混合物の一部を蒸留し、更
に減圧乾燥した。乾燥後の反応生成物にメタノール１０
０ｇを加えて５０℃にて攪拌した後冷却し、析出した結
晶を濾別し、純水にて洗浄した後、減圧乾燥して純度９
９．１％の２−ｔ−アミル−１゜４−ナフトキノンを得
た。次に、濾液を蒸留してメタノールを回収し主として
６−ｔ−アミル−１゜４−ナフトキノンの付加物（１，
４，４ａ、 ９ａ−テトラヒドロ−６−ｔ−アミル−
アントラキノン）より成る固形残渣に０．５Ｎ水酸化ナ
トリウム水溶液と０−キシレンを加え、３０分間攪拌し
た後、８０℃で３時間空気を吹き込んだ。静置して得ら
れた沈澱物を含む水相を濾過し、得られた沈澱物を純水
で洗浄し減圧乾燥して２−ｔ−アミルーアントラキノン
３ｇを得た。After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separation tank, and the solvent type (0-xylene phase) and the aqueous phase were separated. The aqueous phase was extracted using 0-xylene, and the 0-xylene phase was added to the previous solvent phase. A portion of this solvent phase (4.2 g of 2-t-amyl-1,4-naphthoquinone, 6-t-amyl-1,4-naphthoquinone,
3.1 g of 1,4-naphthoquinone, unreacted 2-t-
0.95 g of butadiene and 15 mg of p-tert-butyl-catechol as a polymerization inhibitor were added to the mixture (containing 2.0 g of amylnaphthalene and 80 g of O-xylene), and the mixture was heated in an autoclave at a temperature of 1-10° C. with stirring for 50 minutes.
Time reacted. After the reaction, a portion of the reaction mixture was distilled and further dried under reduced pressure. 10% methanol to the reaction product after drying
0g was added, stirred at 50°C, cooled, the precipitated crystals were filtered out, washed with pure water, and dried under reduced pressure to obtain a purity of 9.
9.1% of 2-t-amyl-1°4-naphthoquinone was obtained. Next, the filtrate is distilled to recover methanol, which is mainly an adduct of 6-t-amyl-1°4-naphthoquinone (1,
4,4a,9a-tetrahydro-6-t-amyl-
0.5N aqueous sodium hydroxide solution and 0-xylene were added to the solid residue consisting of anthraquinone), and after stirring for 30 minutes, air was blown into the mixture at 80°C for 3 hours. The aqueous phase containing the precipitate obtained by standing was filtered, and the obtained precipitate was washed with pure water and dried under reduced pressure to obtain 3 g of 2-t-amyluanthraquinone.
実施例１９
硝酸第２セリウムアンモニウムの硝酸溶液（第２セリウ
ムイオン濃度は０．５モル／リットル、硝酸濃度は２．
０モル／リットル）を、還流冷却法攪拌装置を取り付け
たガラス容器に入れ７０℃に保持した。これに２−二ト
ローナフタレンを投入し、攪拌しながら２時間反応させ
た。反応復液を冷却晶析濾過して得られた沈澱を純水に
て洗浄し２−ニトロ−１，４−ナフトキノン１０ｇと６
−二トロー１．４−ナフトキノン１８ｇを含む結晶を得
た。この結晶をエチレングリコールモノメチルエーテル
１５０ｃｃに加え、８ｇの１，３−ブタジェンと共に攪
拌装置の付いたオートクレーブに投入し攪拌しながら７
０℃で６時間反応させた。反応復液を冷却して濾過し、
得られた結晶を純水およびメタノールで洗浄した後減圧
乾燥して純度９９％の２−ニトロ−１，４−ナフトキノ
ン７ｇを得た。次に、濾液に０．５Ｎの水酸化ナトリウ
ム水溶液を添加し、１５分間攪拌させた後、７０℃で４
時間空気を吹き込み、得られたスラリーを濾過して２−
ニトロ−アントラキノン１７ｇを得た。Example 19 Nitric acid solution of ceric ammonium nitrate (ceric ion concentration: 0.5 mol/liter, nitric acid concentration: 2.
0 mol/liter) was placed in a glass container equipped with a reflux cooling stirrer and maintained at 70°C. 2-nitronaphthalene was added to this, and the mixture was reacted for 2 hours with stirring. The precipitate obtained by cooling and crystallizing the reaction condensate was washed with pure water, and 10 g of 2-nitro-1,4-naphthoquinone and 6
-Crystals containing 18 g of ditro-1,4-naphthoquinone were obtained. These crystals were added to 150 cc of ethylene glycol monomethyl ether, and then put into an autoclave equipped with a stirring device along with 8 g of 1,3-butadiene, and while stirring,
The reaction was carried out at 0°C for 6 hours. Cool and filter the reaction condensate,
The obtained crystals were washed with pure water and methanol and then dried under reduced pressure to obtain 7 g of 2-nitro-1,4-naphthoquinone with a purity of 99%. Next, 0.5N aqueous sodium hydroxide solution was added to the filtrate, stirred for 15 minutes, and then heated to 70°C for 4 hours.
Blow air in for an hour and filter the resulting slurry for 2-
17 g of nitro-anthraquinone were obtained.
実施例２０
還流冷却器、撹拌装置を取り付けたガラス製の反応槽に
、０−キシレンに溶解した２−カルボキシ−ナフタリン
および硫酸第２セリウムの硫酸水溶液を投入し、撹拌下
６０℃で２．５時間反応させた。反応終了後、攪拌を停
止し、反応液を分離槽に移し、溶媒相（０−キシレン相
）と水相とを分離した。水相については０−キシレンを
用いて抽出し、０−キシレン相を先の溶媒相に加えた。Example 20 A sulfuric acid aqueous solution of 2-carboxy-naphthalene and ceric sulfate dissolved in 0-xylene was charged into a glass reaction tank equipped with a reflux condenser and a stirring device, and the mixture was stirred at 60°C for 2.5 min. Allowed time to react. After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separation tank, and a solvent phase (0-xylene phase) and an aqueous phase were separated. The aqueous phase was extracted using 0-xylene, and the 0-xylene phase was added to the previous solvent phase.
この溶媒相の一部（２−カルボキシ−１，４−ナフトキ
ノン７、２ｇ、 ６−カルボキシ−１，４−ナフトキ
ノン５．３ｇ１ 未反応の２−カルボキシ−ナフタリ
ン２．６ｇ、 ｏ−キシレン１００ｇを含む）にブタ
ジェンを１．９ｇ、 重合禁止剤としてのｐ−ｔｅｒ
ｔ−ブチル−カテコールを３０ｍｇ入れ、温度１１０℃
で、攪拌下、オートクレーブにて５時間反応した。反応
後、反応混合物の一部を蒸留し、更に減圧乾燥した。乾
燥後の反応生成物にメタノール１００ｇを加えて５０℃
にて攪拌した後冷却し、析出した結晶を濾別し、純水に
て洗浄した後、減圧乾燥して純度９８．５％の２−カル
ボキシ−１，４−ナフトキノンを得た。次に、濾液を蒸
留してメタノールを回収し主として６−カルボキシ−１
，４−ナフトキノンの付加物（１，４゜４ａ、９ａ−テ
トラヒドロ−６−カルボキシ−アントラキノン）より成
る固形残渣に０．５Ｎ水酸化ナトリウム水溶液と０−キ
シレンを加え、３０分間攪拌した後、８０℃で３時間空
気を吹き込んだ。静置して得られた沈澱物を含む水相を
濾過し、得られた沈澱物を純水で洗浄し減圧乾燥して２
−カルボキシ−アントラキノン５ｇを得た。A portion of this solvent phase (containing 7.2 g of 2-carboxy-1,4-naphthoquinone, 5.3 g of 6-carboxy-1,4-naphthoquinone, 2.6 g of unreacted 2-carboxy-naphthalene, and 100 g of o-xylene) ), 1.9 g of butadiene, and p-ter as a polymerization inhibitor.
Add 30 mg of t-butyl-catechol and heat to 110°C.
The mixture was reacted for 5 hours in an autoclave under stirring. After the reaction, a portion of the reaction mixture was distilled and further dried under reduced pressure. Add 100g of methanol to the dried reaction product and heat at 50°C.
The precipitated crystals were filtered, washed with pure water, and dried under reduced pressure to obtain 2-carboxy-1,4-naphthoquinone with a purity of 98.5%. Next, the filtrate is distilled to recover methanol, mainly 6-carboxy-1
, 4-naphthoquinone adduct (1,4°4a,9a-tetrahydro-6-carboxy-anthraquinone) was added with 0.5N aqueous sodium hydroxide solution and 0-xylene, and after stirring for 30 minutes, Air was bubbled for 3 hours at °C. The aqueous phase containing the precipitate obtained by standing was filtered, and the obtained precipitate was washed with pure water and dried under reduced pressure.
5 g of -carboxy-anthraquinone were obtained.
実施例２１
還流冷却器 撹拌装置を取り付けたガラス製の反応槽に
、０−キシレンに溶解した２−クロロ−ナフタリンおよ
び硫酸第２セリウムの硫酸水溶液を投入し、撹拌下６０
℃で９０分間反応させた。Example 21 Reflux condenser A sulfuric acid aqueous solution of 2-chloro-naphthalene and ceric sulfate dissolved in 0-xylene was charged into a glass reaction tank equipped with a stirring device, and the mixture was stirred for 60 minutes.
The reaction was carried out at ℃ for 90 minutes.
反応終了後、撹拌を停止し、反応液を分離槽に移し、溶
媒相（０−キシレン相）と水相とを分離した。水相につ
いては０−キシレンを用いて抽出し、０−キシレン相を
先の溶媒相に加えた。この溶媒相の一部（２−クロロ−
１，４−ナフトキノン４ｇ、 ６−クロロ−１，４−
ナフトキノン５ｇ、未反応の２−クロロ−ナフタリン２
．２ｇ、 ｏ−キシレン１００ｇを含む）にブタジェ
ンを１．９ｇ。After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separation tank, and the solvent phase (0-xylene phase) and aqueous phase were separated. The aqueous phase was extracted using 0-xylene, and the 0-xylene phase was added to the previous solvent phase. Part of this solvent phase (2-chloro-
1,4-naphthoquinone 4g, 6-chloro-1,4-
5 g naphthoquinone, 2 unreacted 2-chloro-naphthalene
．． 2 g, o-xylene (containing 100 g) and 1.9 g of butadiene.
重合禁止剤としてｐ−ｔｅｒｔ−ブチル−カテコールを
３０ｍｇ入札 反応温度１１０℃で、撹拌下、オートク
レーブにて５時間反応した。反応後、反応混合物の一部
を蒸留し、更に減圧乾燥した。乾燥後の反応生成物にメ
タノール１００ｇを加えて５０℃にて攪拌した後冷却し
、析出した結晶を濾別し、純水にて洗浄した後、減圧乾
燥して純度９８．７％の２−クロロ−１，４−ナフトキ
ノンを得た。30 mg of p-tert-butyl-catechol was used as a polymerization inhibitor. The reaction was carried out at a reaction temperature of 110°C for 5 hours in an autoclave with stirring. After the reaction, a portion of the reaction mixture was distilled and further dried under reduced pressure. 100 g of methanol was added to the dried reaction product, stirred at 50°C, and then cooled. The precipitated crystals were filtered off, washed with pure water, and dried under reduced pressure to obtain 2-2-2 with a purity of 98.7%. Chloro-1,4-naphthoquinone was obtained.
次に、濾液を蒸留してメタノールを回収し主として６−
クロロ−１，４−ナフトキノンの付加物（１、４，４ａ
、 ９ａ−テトラヒドロ−６−クロロ−アントラキノ
ン）より成る固形残渣に０．５Ｎ水酸化ナトリウム水溶
液と０−キシレンを加え、３０分間攪拌した後、８０℃
で３時間空気を吹き込んだ。静置して得られた沈澱物を
含む水相を濾過し、濾過物を純水で洗浄し減圧乾燥して
２−クロロ−アントラキノン５．１ｇを得た。Next, the filtrate is distilled to recover methanol, mainly 6-
Adduct of chloro-1,4-naphthoquinone (1,4,4a
, 9a-tetrahydro-6-chloro-anthraquinone), 0.5N aqueous sodium hydroxide solution and 0-xylene were added, stirred for 30 minutes, and heated to 80°C.
I blew air into it for 3 hours. The aqueous phase containing the precipitate obtained by standing was filtered, and the filtrate was washed with pure water and dried under reduced pressure to obtain 5.1 g of 2-chloro-anthraquinone.
実施例２２
還流冷却器、撹拌装置を取り付けたガラス製の反応槽に
、１０重量％の１−メチル−ナフタリンを含む２−メチ
ル−ナフタリン１９ｇおよび０−キシレン５０ｇを仕込
んで攪拌し、溶解させた後、硫酸第２セリウムの硫酸水
溶液を投入し、撹拌下４０℃で４時間反応させた。反応
終了後、撹拌を停止し、反応液を分離槽に移し、溶媒相
（Ｏ−キシレン相）と水相とを分離した。水相について
は０−キシレンを用いて抽出し、０−キシレン相を先の
溶媒相に加えた。この溶媒相（２−メチル−１，４−ナ
フトキノン１１ｇ、６−メチル−１゜４−ナフトキノン
４ｇ１５−メチル−１，４−ナフトキノン０．５ｇ、
未反応の２−メチル−ナフタリン１．７ｇ、 １−
メチル−ナフタリン０．８ｇ、 ｏ−キシレン１００
ｇを含む）にブタジェンを１．８ｇ、重合禁止剤として
のｐ−ｔｅｒｔ−ブチル−カテコールを３０ｍｇ入札
温度１２０℃で、撹拌下、オートクレーブにて４時間反
応した。反応後、反応混合物のうちから６０ｇをとって
蒸留し、更に減圧乾燥した。乾燥後の反応生成物にメタ
ノール８０ｇを加えて５０℃にて攪拌・溶解した。Example 22 A glass reaction tank equipped with a reflux condenser and a stirring device was charged with 19 g of 2-methyl-naphthalene containing 10% by weight of 1-methyl-naphthalene and 50 g of 0-xylene, and the mixture was stirred and dissolved. Thereafter, a sulfuric acid aqueous solution of ceric sulfate was added, and the mixture was reacted at 40° C. for 4 hours with stirring. After the reaction was completed, stirring was stopped, the reaction solution was transferred to a separation tank, and the solvent phase (O-xylene phase) and aqueous phase were separated. The aqueous phase was extracted using 0-xylene, and the 0-xylene phase was added to the previous solvent phase. This solvent phase (11 g of 2-methyl-1,4-naphthoquinone, 4 g of 6-methyl-1°4-naphthoquinone, 0.5 g of 15-methyl-1,4-naphthoquinone,
1.7 g of unreacted 2-methyl-naphthalene, 1-
Methyl-naphthalene 0.8g, o-xylene 100
(including g), 1.8 g of butadiene and 30 mg of p-tert-butyl-catechol as a polymerization inhibitor.
The reaction was carried out at a temperature of 120° C. for 4 hours in an autoclave while stirring. After the reaction, 60 g of the reaction mixture was distilled and further dried under reduced pressure. 80 g of methanol was added to the dried reaction product and stirred and dissolved at 50°C.
次いで１０℃に冷却し、析出した結晶を濾別し、純水に
て洗浄した後、減圧乾燥して純度９９．１％の２−メチ
ル−１，４−ナフトキノンを得た。The mixture was then cooled to 10° C., and the precipitated crystals were filtered, washed with pure water, and dried under reduced pressure to obtain 2-methyl-1,4-naphthoquinone with a purity of 99.1%.
［発明の効果］
以上のように、本発明に従えば、非常に物性が似ている
ため困難であった２−置換−１，４−ナフトキノンと６
−置換−１，４−ナフトキノンとの分離が効率良く行な
わ札 高純度の２−置換−１，４−ナフトキノンが得ら
れる。本発明によれば、また、バルブ蒸解助剤やアント
ラキノン誘導体合成の原料として有用な２−置換−アン
トラキノンを副生物として得ることができるので、原料
２−置換−ナフタレンの有効利用、製造コスト低下、有
機廃棄物の大幅な減少も可能である。本発明によれば、
更に、人体や環境を汚染する危険性のある従来のクロム
酸を使用することなく安全に２−置換−１，４−ナフト
キノンを製造することも可能である。[Effect of the invention] As described above, according to the present invention, 2-substituted-1,4-naphthoquinone and 6-substituted
Separation from -substituted-1,4-naphthoquinone can be efficiently performed.High purity 2-substituted-1,4-naphthoquinone can be obtained. According to the present invention, 2-substituted anthraquinone, which is useful as a valve cooking aid and a raw material for anthraquinone derivative synthesis, can be obtained as a by-product, so that the raw material 2-substituted naphthalene can be used effectively, production costs can be reduced, and Significant reductions in organic waste are also possible. According to the invention,
Furthermore, it is also possible to safely produce 2-substituted-1,4-naphthoquinone without using conventional chromic acid, which has the risk of contaminating the human body and the environment.
第１図〜第３図は各々本発明を実施する一実施態様を表
わすフローシート図である。
１・・・２−メチル−ナフタリンタンク２・・・第２セ
リウム塩の酸性水溶液
３・・−溶媒 ４−・・酸化・抽出槽５・・
・油水分離槽
６・・・セリウム塩の酸性水溶液タンク７・・・油相タ
ンク ８・・・ジエン化合物タンク９・−・ディー
ルズ・アルダー反応槽
１０−・・溶媒回収塔 １１・・・減圧乾燥機１２・
−・溶媒タンク
１３・・・ディールズ・アルダー反応混合物１４・−・
再結晶溶媒 １５・・・晶析槽１６・・・濾過Ｍ
１７・・・減圧乾燥機１８・・・再結晶溶媒回収塔
１９・・・電解槽２０・・・２−メチル−１，４−
ナフトキノン２１・・・残渣
３０・・・亜硫酸水素ナトリウム水溶液タンク３１・・
・油水分離槽
３２・・・溶媒相抜き出しライン
３３・・・晶析槽 ３４・・・濾過器３５・・・
減圧乾燥機 ３６・・・再結晶溶媒タンク３７・・・
２−メチル−１，４−ナフトキノン亜硫酸水素ナトリウ
ム塩結晶
３８・−・再結晶溶媒回収塔
３９・・・廃液抜き出しライン
４０・・・６−メチル−１，４−ナフトキノンのジエン
化合物付加物酸化槽
４１・−・溶媒タンク
４２・・・アルカリ水溶液タンク1 to 3 are flow sheet diagrams each representing one embodiment of carrying out the present invention. 1...2-Methyl-naphthalene tank 2...Acidic aqueous solution of ceric salt 3...-Solvent 4-...Oxidation/extraction tank 5...
・Oil/water separation tank 6...Cerium salt acidic aqueous solution tank 7...Oil phase tank 8...Diene compound tank 9--Diels-Alder reaction tank 10--Solvent recovery tower 11...Drying under reduced pressure Machine 12・
- Solvent tank 13... Diels-Alder reaction mixture 14...
Recrystallization solvent 15...Crystallization tank 16...Filtration M
17... Vacuum dryer 18... Recrystallization solvent recovery tower 19... Electrolytic cell 20... 2-methyl-1,4-
Naphthoquinone 21...Residue 30...Sodium hydrogen sulfite aqueous solution tank 31...
・Oil/water separation tank 32...Solvent phase extraction line 33...Crystallization tank 34...Filter 35...
Vacuum dryer 36... Recrystallization solvent tank 37...
2-Methyl-1,4-naphthoquinone sodium bisulfite crystal 38... Recrystallization solvent recovery tower 39... Waste liquid extraction line 40... Diene compound adduct oxidation tank of 6-methyl-1,4-naphthoquinone 41...Solvent tank 42...Alkaline aqueous solution tank
Claims (1)
，４−ナフトキノン及び６−置換−１，４−ナフトキノ
ンを含む反応生成物を得、該反応生成物にジエン化合物
を加えて加熱することにより該ジエン化合物と該反応生
成物中の６−置換−１，４−ナフトキノンとのディール
ズ・アルダー反応付加物を形成し、２−置換−１，４−
ナフトキノンを該付加物から分離することを特徴とする
２−置換−１，４−ナフトキノンの製造法。 ２ ２−置換−ナフタリンが一般式（Ａ） ▲数式、化学式、表等があります▼ （ここでＲ＾１は炭素数１〜５のアルキル基、ニトロ基
、カルボキシル基またはハロゲン原子のいずれかである
） で表される２−置換−ナフタリンであり、ジエン化合物
が一般式（Ｄ） ▲数式、化学式、表等があります▼ （ここでＲ＾２、Ｒ＾３は各々独立して水素原子、メチ
ル基またはエチル基のいずれかである）で表されるジエ
ン化合物である請求項１に記載の方法。 ３ ２−置換−ナフタリンを第二セリウム塩の酸性水溶
液により酸化反応させる第１工程；第１工程の酸化反応
によって得られた２−置換−１，４−ナフトキノン及び
６−置換−１，４−ナフトキノンを含む反応生成物を溶
媒で抽出してセリウム塩の酸性水溶液相から溶媒相を分
離する第２工程；第２工程で分離した反応生成物を含む
溶媒相にジエン化合物を加えて加熱することによりジエ
ン化合物と６−置換−１，４−ナフトキノンとのディー
ルズ・アルダー反応付加物を形成する第３工程；第３工
程で得られた反応混合物から溶媒を分離して回収する第
４工程；溶媒を分離した後の反応混合物からディールズ
・アルダー反応付加物を除去し、高純度の２−置換−１
，４−ナフトキノンを得る第５工程；の各工程を含んで
なる２−置換−１，４−ナフトキノンの製造法。 ４ ２−メチル−ナフタリンを酸化反応して２−メチル
−１，４−ナフトキノン及び６−メチル−１，４−ナフ
トキノンを含む反応生成物を得、該反応生成物にジエン
化合物を加えて加熱することにより該ジエン化合物と該
反応生成物中の６−メチル−１，４−ナフトキノンとの
ディールズ・アルダー反応付加物を形成し、得られた反
応混合物に亜硫酸水素塩水溶液を加えて２−メチル−１
，４−ナフトキノン亜硫酸水素塩として水相中に抽出す
ることを特徴とする２−メチル−１，４−ナフトキノン
亜硫酸水素塩の製造法。 ５ ２−置換−ナフタリンを酸化反応して２−置換−１
，４−ナフトキノン及び６−置換−１，４−ナフトキノ
ンを含む反応生成物を得、該反応生成物に１，３−ブタ
ジエン類を加えて加熱することにより該１，３−ブタジ
エン類と該反応生成物中の６−置換−１，４−ナフトキ
ノンとのディールズ・アルダー反応付加物を形成し、２
−置換−１，４−ナフトキノンを分離した後、該付加物
を酸化することを特徴とする５，８−ジヒドロ−２−置
換−アントラキノン及び／又は２−置換−アントラキノ
ンの製造法。 ６ デイールズ・アルダー反応を５０〜２００℃の範囲
で行なう請求項１〜５のいずれかに記載の方法。[Claims] 1 oxidation reaction of 2-substituted-naphthalene to produce 2-substituted-1
, 4-naphthoquinone and 6-substituted-1,4-naphthoquinone are obtained, and a diene compound is added to the reaction product and heated to convert the diene compound and the 6-substituted-1,4-naphthoquinone in the reaction product. Forms a Diels-Alder reaction adduct with 1,4-naphthoquinone to form a 2-substituted-1,4-
A method for producing 2-substituted-1,4-naphthoquinone, which comprises separating naphthoquinone from the adduct. 2 2-Substituted naphthalene is the general formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^1 is either an alkyl group having 1 to 5 carbon atoms, a nitro group, a carboxyl group, or a halogen atom. The diene compound is a 2-substituted naphthalene represented by the general formula (D) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^2 and R^3 are each independently a hydrogen atom, The method according to claim 1, wherein the diene compound is a diene compound represented by a methyl group or an ethyl group. 3 First step of oxidizing 2-substituted naphthalene with an acidic aqueous solution of ceric salt; 2-substituted-1,4-naphthoquinone and 6-substituted-1,4-naphthoquinone obtained by the oxidation reaction of the first step A second step of extracting the reaction product containing naphthoquinone with a solvent and separating the solvent phase from the acidic aqueous solution phase of the cerium salt; adding a diene compound to the solvent phase containing the reaction product separated in the second step and heating it; A third step of forming a Diels-Alder reaction adduct of a diene compound and a 6-substituted-1,4-naphthoquinone; a fourth step of separating and recovering the solvent from the reaction mixture obtained in the third step; The Diels-Alder reaction adduct was removed from the reaction mixture after separation of 2-substituted-1 with high purity.
, a fifth step of obtaining 4-naphthoquinone; a method for producing 2-substituted-1,4-naphthoquinone. 4 Oxidation reaction of 2-methyl-naphthalene to obtain a reaction product containing 2-methyl-1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone, and adding a diene compound to the reaction product and heating. By this, a Diels-Alder reaction adduct is formed between the diene compound and 6-methyl-1,4-naphthoquinone in the reaction product, and an aqueous bisulfite solution is added to the resulting reaction mixture to form a 2-methyl-1,4-naphthoquinone. 1
, 4-naphthoquinone bisulfite is extracted into an aqueous phase. 5 Oxidation reaction of 2-substituted naphthalene to form 2-substituted-1
, 4-naphthoquinone and 6-substituted-1,4-naphthoquinone are obtained, and 1,3-butadienes are added to the reaction product and heated to react with the 1,3-butadienes. Forming a Diels-Alder reaction adduct with 6-substituted-1,4-naphthoquinone in the product, 2
A method for producing 5,8-dihydro-2-substituted anthraquinone and/or 2-substituted anthraquinone, which comprises separating the substituted 1,4-naphthoquinone and then oxidizing the adduct. 6. The method according to any one of claims 1 to 5, wherein the Dales-Alder reaction is carried out at a temperature in the range of 50 to 200°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31304090A JPH0798773B2 (en) | 1989-11-28 | 1990-11-15 | Process for producing 2-substituted-1,4-naphthoquinone |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-306660 | 1989-11-28 | ||
| JP30666089 | 1989-11-28 | ||
| JP2-45530 | 1990-02-28 | ||
| JP4553090 | 1990-02-28 | ||
| JP31304090A JPH0798773B2 (en) | 1989-11-28 | 1990-11-15 | Process for producing 2-substituted-1,4-naphthoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03275642A true JPH03275642A (en) | 1991-12-06 |
| JPH0798773B2 JPH0798773B2 (en) | 1995-10-25 |
Family
ID=27292266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31304090A Expired - Lifetime JPH0798773B2 (en) | 1989-11-28 | 1990-11-15 | Process for producing 2-substituted-1,4-naphthoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798773B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239600A (en) * | 2007-03-01 | 2008-10-09 | Kawasaki Kasei Chem Ltd | Radical scavenger, polymerization inhibitor and method for inhibiting polymerization |
-
1990
- 1990-11-15 JP JP31304090A patent/JPH0798773B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239600A (en) * | 2007-03-01 | 2008-10-09 | Kawasaki Kasei Chem Ltd | Radical scavenger, polymerization inhibitor and method for inhibiting polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798773B2 (en) | 1995-10-25 |
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