JPH0432834B2 - - Google Patents
Info
- Publication number
- JPH0432834B2 JPH0432834B2 JP58223187A JP22318783A JPH0432834B2 JP H0432834 B2 JPH0432834 B2 JP H0432834B2 JP 58223187 A JP58223187 A JP 58223187A JP 22318783 A JP22318783 A JP 22318783A JP H0432834 B2 JPH0432834 B2 JP H0432834B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- ribose
- arabinose
- boric acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 86
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 77
- PYMYPHUHKUWMLA-LMVFSUKVSA-N aldehydo-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 76
- 239000004327 boric acid Substances 0.000 claims description 28
- SRBFZHDQGSBBOR-OWMBCFKOSA-N L-ribopyranose Chemical compound O[C@H]1COC(O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-OWMBCFKOSA-N 0.000 claims description 26
- -1 molybdate ions Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 235000000346 sugar Nutrition 0.000 description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 238000006345 epimerization reaction Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 10
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000003957 anion exchange resin Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 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 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical group CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- SRBFZHDQGSBBOR-SOOFDHNKSA-N D-ribopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@@H]1O SRBFZHDQGSBBOR-SOOFDHNKSA-N 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 229920001429 chelating resin Polymers 0.000 description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- QXKAIJAYHKCRRA-BXXZVTAOSA-N D-ribonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-BXXZVTAOSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011716 vitamin B2 Substances 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- CUOKHACJLGPRHD-BXXZVTAOSA-N D-ribono-1,4-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H]1O CUOKHACJLGPRHD-BXXZVTAOSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- PYMYPHUHKUWMLA-MROZADKFSA-N aldehydo-L-ribose Chemical compound OC[C@H](O)[C@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-MROZADKFSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- QXKAIJAYHKCRRA-JJYYJPOSSA-N D-arabinonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(O)=O QXKAIJAYHKCRRA-JJYYJPOSSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229910004844 Na2B4O7.10H2O Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IAZJBPYVKVBVSI-UHFFFAOYSA-N phenyl-(2-phenylphenyl)diazene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1C1=CC=CC=C1 IAZJBPYVKVBVSI-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はＤ−アラビノースからＤ−リボースを
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing D-ribose from D-arabinose.
Ｄ−リボースは核酸の構成成分として、ビタミ
ンB2の合成原料として重要な化合物である。従
来、Ｄ−リボースの製造方法としては、天然物か
ら抽出する方法、微生物による醗酵法、フランま
たはグルコースを原料として化学合成する方法な
どが知られているが、方法が繁雑である、収率が
低いなどの欠点があり、工業的に安価にＤ−リボ
ースを製造する方法としては必ずしも満足すべき
ものではなかつた。 D-ribose is an important compound as a constituent of nucleic acids and a raw material for the synthesis of vitamin B2 . Conventionally, known methods for producing D-ribose include extraction from natural products, fermentation using microorganisms, and chemical synthesis using furan or glucose as raw materials, but these methods are complicated and have low yields. However, it was not always satisfactory as a method for industrially producing D-ribose at low cost.
通常、工業的規模で行なわれるＤ−リボースの
製造方法は原料としてＤ−グルコースを使用し、
これをアルカリ水溶液中で酸素で酸化して得られ
るＤ−アラボン酸をカルシウム塩として分離し、
ついでアルカリ水溶液中で加熱することによりエ
ピメリ化して生じるＤ−リボン酸を水銀または亜
鉛などの金属塩として分離した後、ラクトン化し
てＤ−リボノラクトンとし、次にこれをナトリウ
ムアマルガムで還元してＤ−リボースとする方法
である。この方法ではＤ−アラボン酸をアルカリ
水溶液中で加熱するとＤ−アラボン酸70：Ｄ−リ
ボン酸30の平衝混合物になり、Ｄ−リボン酸比率
は30％以上にならず、また、アマルガム還元に大
量の水銀を使用する欠点がある。 Usually, the production method of D-ribose carried out on an industrial scale uses D-glucose as a raw material,
D-araboxylic acid obtained by oxidizing this with oxygen in an alkaline aqueous solution is separated as a calcium salt,
Next, the D-ribonic acid produced by epimerization by heating in an alkaline aqueous solution is separated as a metal salt such as mercury or zinc, and then lactonized to D-ribonolactone, which is then reduced with sodium amalgam to form D-ribonolactone. This is a method of converting it into ribose. In this method, when D-araboxylic acid is heated in an alkaline aqueous solution, it becomes an equilibrium mixture of 70 parts D-araboxylic acid and 30 parts D-ribonic acid, and the ratio of D-ribonic acid does not exceed 30%, and it is difficult to reduce the amalgam. It has the disadvantage of using large amounts of mercury.
その後、ビリクらにより種々の糖が水溶液中モ
リブデン酸を触媒としてエピメリ化されること、
例えばＬ型のアラビノースの約33％がＬ−リボー
スにエピメリ化されることが報告された（チエコ
スロバキア特許第149472号、ケミカル・アブスト
ラクツ81，78189K）。これを応用して、原料とし
てＤ−グルコースを使用するが、Ｄ−アラボン酸
およびＤ−リボン酸を経由せずに、酸化してＤ−
グルコン酸を製造し、これを次亜塩素酸によりＤ
−アラビノースとし、次に水溶液中モリブデン酸
化合物を触媒としてエピメリ化してＤ−リボー
スを製造する方法が提案された（特開昭55−
164699号公報）。この方法ではエピメリ化率（平
衝混合物中のリボースの比率）が約25％である
が、水銀を使用しない点および工程数が短い点で
前記方法より優れている。モリブデン酸（モリブ
デン酸化合物）を触媒として用いるエピメリ化
反応では、反応終了水溶液中のモリブデン酸の分
離を簡単にするため、モリブデン酸にかえてモリ
ブデン酸を担持したイオン交換樹脂（特公昭56−
40700号公報）、モリブデン酸を担持したイオン交
換繊維（特開昭55−76894号公報、Ｄ−アラビノ
ースからＤ−リボースへのエピメリ化率30.6％、
特開昭57−54197号公報、Ｄ−アラビノースから
Ｄ−リボースへのエピメリ化率27.2％）が提案さ
れた。 Later, Birik et al. reported that various sugars were epimerized using molybdic acid as a catalyst in an aqueous solution.
For example, it has been reported that about 33% of L-type arabinose is epimerized to L-ribose (Ciekoslovakia Patent No. 149472, Chemical Abstracts 81, 78189K). Applying this, D-glucose is used as a raw material, but it is oxidized to D-glucose without passing through D-arabonic acid and D-ribonic acid.
Gluconic acid is produced and D is treated with hypochlorous acid.
- A method was proposed for producing D-ribose by epimerizing arabinose and then epimerizing it in an aqueous solution using a molybdic acid compound as a catalyst (Japanese Patent Application Laid-Open No. 1985-1999-
Publication No. 164699). Although this method has an epimerization rate (ratio of ribose in the equilibrium mixture) of about 25%, it is superior to the previous method in that it does not use mercury and requires fewer steps. In the epimerization reaction using molybdic acid (molybdic acid compound) as a catalyst, in order to simplify the separation of molybdic acid in the aqueous solution after the reaction, an ion exchange resin supporting molybdic acid instead of molybdic acid
40700), ion exchange fiber supporting molybdic acid (JP-A-55-76894, epimerization rate of D-arabinose to D-ribose 30.6%,
JP-A-57-54197 proposed an epimerization rate of 27.2% from D-arabinose to D-ribose.
Ｌ型のアラビノースではジメチルホルムアミド
中ジオクソビス（２，４−ペンタン）ジオノート
−Ｏ，O′−）モリブデニウムの存在下に加熱
すると、Ｌ−アラビノースの36％がＬ−リボース
にエピメリ化することが知られている〔アベら：
ケミカル アンド フアームシユーテイカル ブ
リチン 28，1324（1980）〕。 It is known that when L-type arabinose is heated in the presence of dioxobis(2,4-pentane)dionot-O,O'-)molybdenium in dimethylformamide, 36% of L-arabinose epimerizes to L-ribose. [Abe et al.:
Chemical and Pharmaceutical Bulletin 28, 1324 (1980)].
上記の技術水準下、エピメリ化率を高め、工業
的に安価にＤ−リボースを製造するため研究した
結果、本発明者らはＤ−アラビノースを水溶液中
モリブデン酸イオンを触媒としてエピメリ化して
Ｄ−リボースを製造する公知の反応系にホウ酸化
合物を加えることにより、エピメリ化率が70％ま
で向上することを見出し先に特許出願した（特願
昭58−189976号）。本発明者らは更に研究した結
果、前記の公知の反応系において、溶媒を水に代
えて有機溶媒とし、ホウ酸化合物を添加すること
により、エピメリ化率が約94％まで向上すること
を見出し、本発明を完成した。 Under the above-mentioned state of the art, as a result of research to increase the epimerization rate and industrially produce D-ribose at low cost, the present inventors epimerized D-arabinose in an aqueous solution using molybdate ions as a catalyst. They discovered that by adding a boric acid compound to a known reaction system for producing ribose, the epimerization rate could be improved to 70%, and filed a patent application (Japanese Patent Application No. 189976/1982). As a result of further research, the present inventors found that in the above-mentioned known reaction system, by replacing water with an organic solvent and adding a boric acid compound, the epimerization rate could be improved to approximately 94%. , completed the invention.
本発明で使用する溶媒としてはメタノール、エ
タノール、ｎ−プロパノール、イソプロパノー
ル、ｎ−ブタノール、イソブタノール、sec−ブ
タノール、ｔ−ブタノール、ｎ−アミルアルコー
ル、イソアミルアルコール、sec−アミルアルコ
ール、ｎ−ヘキサノール、メチルアミルアルコー
ル、２−エチル−ヘキサノール、シクロヘキサノ
ール、エチレングリコール、ジエチレングリコー
ル、プロピレングリコール、エチレングリコール
モノメチルエーテル（メチルセロソルブ）、ジエ
チレングリコールモノエチルエーテル（カルビト
ール）、ジエチレングリコールモノメチルエーテ
ル（メチルカルビトール）などのアルコール類、
アセトン、メチルアセトン、メチルエチルケト
ン、１，４−ジオキサン、ピリジン、α−ピコリ
ン、２，６−ルチジン、アセトニトリル、Ｎ，Ｎ
−ジメチルホルムアミド（DMF）、Ｎ，Ｎ−ジメ
チルアセトアミド（DMA）、ジメチルスルホキ
シド（DMSO）などＤ−アルビノースおよびホ
ウ酸化合物を溶解する溶媒であればよいが、これ
らの溶媒に限定されるものではない。 Solvents used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexanol, Alcohols such as methyl amyl alcohol, 2-ethyl-hexanol, cyclohexanol, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monomethyl ether (methyl cellosolve), diethylene glycol monoethyl ether (carbitol), diethylene glycol monomethyl ether (methyl carbitol) kind,
Acetone, methylacetone, methyl ethyl ketone, 1,4-dioxane, pyridine, α-picoline, 2,6-lutidine, acetonitrile, N,N
- Any solvent that can dissolve D-albinose and boric acid compounds such as dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and dimethyl sulfoxide (DMSO) may be used, but it is not limited to these solvents. do not have.
溶媒の使用量はＤ−アラビノースに対して10倍
量（ｗ／ｗ）以下、好ましくは0.5〜３倍量であ
る。 The amount of the solvent used is 10 times or less (w/w), preferably 0.5 to 3 times the amount of D-arabinose.
溶媒として含水溶媒を用いることもできるが、
含水率が上るに従いエピメリ化率が下るので含水
率の低い溶媒または無水溶媒を用いることが望ま
しい。 Although a water-containing solvent can be used as the solvent,
Since the epimerization rate decreases as the water content increases, it is desirable to use a solvent with a low water content or an anhydrous solvent.
モリブデン酸イオンの供給源としては、糖類の
エピメリ化に使用するモリブデン酸化合物であ
れば使用でき、例えばモリブデン酸、モリブデン
酸アンモニウム、モリブデン酸カリウム、モリブ
デン酸ナトリウム、モリブデン酸カルシウム、ア
セチルアセトンモリブデン酸塩などが挙げられ、
またイオン交換樹脂に担持されたモリブデン酸、
イオン交換繊維に担持されたモリブデン酸を用い
てもよく、その使用量はモリブデン酸イオンとし
てＤ−アラビノースに対し１〜10％（ｗ／ｗ）、
好ましくは５〜10％である。 As a source of molybdate ions, any molybdate compound used for epimerization of sugars can be used, such as molybdic acid, ammonium molybdate, potassium molybdate, sodium molybdate, calcium molybdate, acetylacetone molybdate, etc. are mentioned,
In addition, molybdic acid supported on ion exchange resin,
Molybdic acid supported on ion-exchange fibers may be used, and the amount used is 1 to 10% (w/w) as molybdate ions relative to D-arabinose.
Preferably it is 5 to 10%.
ホウ酸化合物としては、溶媒として無水溶媒を
用いる場合にはホウ酸を用いることが好ましく、
溶媒として含水溶媒を用いる場合にはホウ酸、酸
化ホウ素、ホウ酸メチル；ホウ酸エチル、ホウ酸
アンモニウム、ホウ酸カリウムなどのホウ酸塩が
用いられる。ホウ酸塩を用いる場合には有機また
は無機の酸で加水分解してホウ酸を生成させてか
ら使用する。ホウ酸化合物の使用量はＤ−アラビ
ノースに対し0.5倍モル以上、好ましくは1.5〜３
倍モル程度である。 As the boric acid compound, it is preferable to use boric acid when an anhydrous solvent is used as the solvent,
When a water-containing solvent is used as the solvent, borates such as boric acid, boron oxide, methyl borate; ethyl borate, ammonium borate, and potassium borate are used. When a boric acid salt is used, it is hydrolyzed with an organic or inorganic acid to produce boric acid before use. The amount of boric acid compound to be used is 0.5 times or more mole relative to D-arabinose, preferably 1.5 to 3 times
It is about double the mole.
反応温度は沸点90℃未満の溶媒を用いる場合は
還流下で、沸点90℃以上の溶媒を用いる場合は90
〜95℃でよく常圧下でよい。反応時間は30〜60分
である。反応終了液を室温まで冷却するとホウ酸
の一部が析出する。この析出物を除去することに
より後処理の負担を軽減することができる。 The reaction temperature is reflux when using a solvent with a boiling point of less than 90°C, and 90°C when using a solvent with a boiling point of 90°C or higher.
It can be used at ~95°C or under normal pressure. Reaction time is 30-60 minutes. When the reaction-completed liquid is cooled to room temperature, a portion of boric acid is precipitated. By removing this precipitate, the burden of post-treatment can be reduced.
本発明により製造されたＤ−リボース含有反応
液中にはＤ−リボース以外にＤ−アラビノース、
微量のＤ−キシロースとＤ−リクソース、モリブ
デン酸イオンおよびホウ酸が含まれており、その
他反応溶媒や使用した原料に基づくイオン、副生
物が含まれていることもある。 In addition to D-ribose, D-arabinose,
It contains trace amounts of D-xylose, D-lyxose, molybdate ions, and boric acid, and may also contain other ions and by-products based on the reaction solvent and raw materials used.
上記のＤ−リボース含有反応液から溶媒を留去
後、触媒であるモリブデン酸を公知の方法、例え
ばイオン交換または電気透析により除去すること
ができ、触媒除去液からホウ酸またはその塩を公
知の方法、例えばメタノールなどの低級アルキル
アルコールを加えて加熱乾固をり返すか、イオン
交換樹脂（弱塩基性）で処理することにより除去
することができる。 After distilling off the solvent from the D-ribose-containing reaction solution, molybdic acid as a catalyst can be removed by a known method such as ion exchange or electrodialysis, and boric acid or its salt can be removed from the catalyst removal solution by a known method. For example, it can be removed by adding a lower alkyl alcohol such as methanol and repeating heating to dryness, or by treatment with an ion exchange resin (weakly basic).
触媒およびホウ酸またはホウ酸塩を除去した溶
液からＤ−リボースを公知の方法、例えばカルシ
ウムイオンまたはバリウムイオンを負荷した陽イ
オン交換樹脂で分離することができる。 D-ribose can be separated from the solution free of catalyst and boric acid or borate by known methods, for example with a cation exchange resin loaded with calcium or barium ions.
本発明によれば最高約94％のエピメリ化率が達
成され、しかもＤ−キシロースおよびＤ−リクソ
ースの生成率が低い利点がある。本発明ではエピ
メリ化率が高い（反応溶液中のＤ−リボースの含
有率が高く、それ以外の糖の含有率が低い）の
で、Ｄ−リボースを高収率で単離することができ
る。Ｄ−リボースをビタミンB2製造の原料とす
る場合には、本発明により製造されたＤ−リボー
ス含有溶液からＤ−リボースを単離せずに、触媒
のみを除去した溶液を４−ニトロ−Ｏ−キシレン
または３，４−キシリジンの存在下接触還元し、
生成した混合物を結晶化することにより純粋なＮ
−Ｄ−リビチル−３，４−キシリジンが得られ
る。この場合、Ｄ−リボース以外の糖およびこれ
らの糖との反応で消費される副原料の損失はＤ−
リボースの単離に要する費用に比べ非常に小さい
ものであり、この点も本発明の利点の一つであ
る。上記のＮ−Ｄ−リビチル−３，４−キシリジ
ンをジアゾニウム塩溶液とカツプリング反応して
１−Ｄ−リビチルアミノ−３，４−ジメチル−６
−フエニルアゾベンゼンを製造し、ついでバルビ
ツール酸と縮合すればビタミンB2が得られる。 According to the present invention, an epimerization rate of up to about 94% can be achieved, and the production rate of D-xylose and D-lyxose is low. In the present invention, since the epimerization rate is high (the content of D-ribose in the reaction solution is high and the content of other sugars is low), D-ribose can be isolated in high yield. When D-ribose is used as a raw material for producing vitamin B2 , D-ribose is not isolated from the D-ribose-containing solution produced according to the present invention, and the solution from which only the catalyst is removed is converted into 4-nitro-O- Catalytic reduction in the presence of xylene or 3,4-xylidine,
Pure N is obtained by crystallizing the resulting mixture.
-D-ribityl-3,4-xylidine is obtained. In this case, the loss of sugars other than D-ribose and the auxiliary raw materials consumed in the reaction with these sugars is
The cost is very small compared to the cost required for isolation of ribose, and this point is also one of the advantages of the present invention. The above N-D-ribityl-3,4-xylidine was coupled to a diazonium salt solution to produce 1-D-ribitylamino-3,4-dimethyl-6
- Preparation of phenylazobenzene and subsequent condensation with barbituric acid yields vitamin B2 .
実施例中の糖分の組成は試料溶液中の糖分をホ
ウ素化水素ナトリウムで還元し対応する糖アルコ
ールとし、ついで無水トリフルオル酢酸でアセチ
ル化し、これがガスクロマトグラフイーにより測
定した。 The sugar composition in the examples was determined by reducing the sugar content in the sample solution with sodium borohydride to give the corresponding sugar alcohol, followed by acetylation with trifluoroacetic anhydride, and measuring this by gas chromatography.
実施例 １
Ｄ−アラビノース15.0ｇにエチルアルコール15
ml、モリブデン酸アンモニウム1.2ｇおよびホウ
酸18.5ｇを加え、78℃で60分間攪拌下加熱した。
Ｄ−アラビノースおよびホウ酸は常温ではあまり
溶解しないが加温すると徐々に溶解した。反応液
を冷却し、析出物を別し、溶媒を減圧下留去し
た。残存物に水30mlを加え弱塩基性陰イオン交換
樹脂〔アンバーライトIRA−99，オルガノ(株)製〕
で処理してモリブデン酸を除いた。更に弱塩基性
陰イオン交換樹脂〔アンバーライトIRA−743，
オルガノ(株)製〕で処理してホウ酸イオンを除去
し、処理済みの溶液を糖濃度が約50％になるまで
減圧下濃縮した。この溶液中の糖分を測定すると
Ｄ−リボース 94.0％
Ｄ−アラビノース 4.2％
Ｄ−キシロースとＤ−リクソース 1.8％
であつた。Example 1 15.0g of D-arabinose and 15% of ethyl alcohol
ml, 1.2 g of ammonium molybdate and 18.5 g of boric acid, and heated at 78°C for 60 minutes with stirring.
D-arabinose and boric acid did not dissolve much at room temperature, but gradually dissolved when heated. The reaction solution was cooled, the precipitate was separated, and the solvent was distilled off under reduced pressure. Add 30ml of water to the residue and use a weakly basic anion exchange resin [Amberlite IRA-99, manufactured by Organo Co., Ltd.]
to remove molybdic acid. In addition, weakly basic anion exchange resin [Amberlite IRA-743,
(manufactured by Organo Co., Ltd.) to remove boric acid ions, and the treated solution was concentrated under reduced pressure until the sugar concentration was about 50%. When the sugar content in this solution was measured, it was found to be 94.0% D-ribose, 4.2% D-arabinose, and 1.8% D-xylose and D-lyxose.
この溶液をカルシウム型にした陽イオン交換樹
脂〔MK−31、三菱化成工業(株)製〕を充填したカ
ラムに120ml／hrの流速で通液し、フラクシヨン
コレクターにより分画した。Ｄ−リボースの分画
を集めて減圧下濃縮してエタノールを加え冷所に
一夜放置するとＤ−リボースの結晶12.6ｇが得ら
れた。融点84〜85℃、比旋光度〔α〕24 D＝−18.4°
（Ｃ＝１，H2Ｏ）。 This solution was passed through a column packed with a calcium-type cation exchange resin [MK-31, manufactured by Mitsubishi Chemical Industries, Ltd.] at a flow rate of 120 ml/hr, and fractionated using a fraction collector. D-ribose fractions were collected and concentrated under reduced pressure, ethanol was added, and the mixture was left in a cold place overnight to obtain 12.6 g of D-ribose crystals. Melting point 84-85℃, specific optical rotation [α] 24 D = -18.4°
(C=1, H2O ).
実施例 ２
Ｄ−アラビノース15ｇに５％含水エチレングリ
コール37.5ml、モリブデン酸（80％）2.3ｇおよ
びホウ酸ナトリウム（Na2B4O7・10H2Ｏ）76.3
ｇを加え、硫酸を加えてPH3.5に調整した。90℃
で60分間攪拌下加熱した後、冷却しエチレングリ
コール15mlを加え一夜放置し析出物を別した。
液から溶媒を減圧下留去し、残存物にメタノー
ル100mlを加えてホウ酸の大部分と硫酸ナトリウ
ムを別除去した。この操作を３回くり返した。
ついで溶液中のメタノールを留去し、水30mlを加
えてMR型弱塩基性陰イオン交換樹脂〔IRA−
743，オルガノ(株)製〕で処理してモリブデン酸イ
オンを除き、更にダイヤイオンCRBO2〔三菱化成
工業（製）〕でホウ酸を除いた後、糖濃度が約50
％になるまで濃縮した。この溶液中の糖分を測定
すると
Ｄ−リボース 89.3％
Ｄ−アラビノース 7.8％
Ｄ−キシロースとＤ−リクソース 2.9％
であつた。Example 2 15 g of D-arabinose , 37.5 ml of 5% hydrated ethylene glycol, 2.3 g of molybdic acid (80% ) and 76.3 g of sodium borate ( Na2B4O7.10H2O )
g, and sulfuric acid was added to adjust the pH to 3.5. 90℃
After heating with stirring for 60 minutes, the mixture was cooled, 15 ml of ethylene glycol was added, and the mixture was allowed to stand overnight to separate the precipitate.
The solvent was distilled off from the solution under reduced pressure, and 100 ml of methanol was added to the residue to separately remove most of the boric acid and sodium sulfate. This operation was repeated three times.
Next, methanol in the solution was distilled off, 30 ml of water was added, and MR type weakly basic anion exchange resin [IRA-
743 (manufactured by Organo Co., Ltd.) to remove molybdate ions, and further remove boric acid with Diaion CRBO2 (manufactured by Mitsubishi Chemical Industries, Ltd.), the sugar concentration was approximately 50.
It was concentrated to %. When the sugar content in this solution was measured, it was found to be 89.3% D-ribose, 7.8% D-arabinose, and 2.9% D-xylose and D-lyxose.
この溶液をホウ酸型とした陰イオン交換樹脂
（Dowex １−X4，100〜200メツシユ）に2.0ml／
minの流速で通液し、フラクシヨンコレクターで
分画した。Ｄ−リボースの分画を集めて減圧下濃
縮し、メクノールを加えてホウ酸を留去し、エタ
ノール２：１アセトン溶液35mlを加えて一夜冷所
に放置するとＤ−リボースの結晶11.8ｇが得られ
た。融点84℃、比旋光度〔α〕24 D＝−18.6°（Ｃ＝
１，H2Ｏ）。 Add 2.0 ml of this solution to an anion exchange resin (Dowex 1-X4, 100-200 mesh) in boric acid form.
The solution was passed through the solution at a flow rate of min and fractionated using a fraction collector. The D-ribose fractions were collected and concentrated under reduced pressure, Meknol was added to distill off the boric acid, 35 ml of ethanol 2:1 acetone solution was added, and the mixture was left in a cool place overnight to obtain 11.8 g of D-ribose crystals. It was done. Melting point 84℃, specific optical rotation [α] 24 D = -18.6° (C =
1, H2O ).
実施例 ３
Ｄ−アラビノース20ｇにイソプロパノール20
ml、モリブデン酸カリウム2.2ｇおよびホウ酸
25.0ｇを加え、82.3℃で40分間攪拌下加熱した。
反応後イソプロパノール20mlを加え一夜冷所に放
置するとホウ酸の一部が析出した。これを別後
溶媒を減圧下留去し、水を加えて電気透析により
モリブデン酸を除去し、更にイオン交換体〔ダイ
ヤイオンCRBO2、三菱化成工業(株)製〕でホウ酸
を除去し、糖濃度が約50％となるまで減圧下濃縮
した。この溶液の糖分を測定すると
Ｄ−リボース 91.9％
Ｄ−アラビノース 6.9％
Ｄ−キシロースとＤ−リクソース 1.0％
であつた。Example 3 20 g of D-arabinose and 20 g of isopropanol
ml, potassium molybdate 2.2g and boric acid
25.0g was added and heated at 82.3°C for 40 minutes with stirring.
After the reaction, 20 ml of isopropanol was added and the mixture was left in a cool place overnight to precipitate some of the boric acid. After separating this, the solvent was distilled off under reduced pressure, water was added, molybdic acid was removed by electrodialysis, boric acid was removed with an ion exchanger [Diaion CRBO2, manufactured by Mitsubishi Chemical Industries, Ltd.], and the sugar It was concentrated under reduced pressure until the concentration was about 50%. When the sugar content of this solution was measured, it was found to be 91.9% D-ribose, 6.9% D-arabinose, and 1.0% D-xylose and D-lyxose.
この溶液を実施例１と同様に操作してＤ−リボ
ースの結晶16.3ｇを得た。融点84〜85℃、比旋光
度〔α〕24 D＝−18.3°（Ｃ＝１，H2Ｏ）。 This solution was operated in the same manner as in Example 1 to obtain 16.3 g of D-ribose crystals. Melting point: 84-85°C, specific optical rotation [α] 24 D = -18.3° (C = 1, H 2 O).
実施例 ４
Ｄ−アラビノース15.0ｇにアセトン15ml、アセ
チルアセトンモリブデン酸塩〔MoO2（CH2
COCH2COCH3）2〕2.5ｇおよびホウ酸12.4ｇを加
え、40分間攪拌下還流した。反応後溶媒を減圧下
留去し、残存物にメタノール60mlを加え、生成し
た不溶物を除去し、メタノールを留去し水30mlを
加えて弱塩基性陰イオン交換樹脂〔アンバーライ
トIRA−99およびIRA−743、オルガノ(株)製〕で
処理してモリブデン酸イオンおよびホウ酸イオン
を除去した。処理済み溶液を糖濃度が約50％にな
るまで濃縮した。この溶液中の糖分を測定すると
Ｄ−リボース 90.5％
Ｄ−アラビノース 7.7％
Ｄ−キシロースとＤ−リクソース 1.8％
であつた。Example 4 15.0 g of D-arabinose, 15 ml of acetone, acetylacetone molybdate [MoO 2 (CH 2
2.5 g of COCH 2 COCH 3 ) 2 ] and 12.4 g of boric acid were added, and the mixture was stirred and refluxed for 40 minutes. After the reaction, the solvent was distilled off under reduced pressure, 60 ml of methanol was added to the residue, the formed insoluble matter was removed, the methanol was distilled off, 30 ml of water was added, and weakly basic anion exchange resins [Amberlite IRA-99 and IRA-743, manufactured by Organo Co., Ltd.] to remove molybdate ions and borate ions. The treated solution was concentrated to a sugar concentration of approximately 50%. When the sugar content in this solution was measured, it was found to be 90.5% D-ribose, 7.7% D-arabinose, and 1.8% D-xylose and D-lyxose.
この溶液をカルシウムを負荷したイオン交換樹
脂〔ダイヤイオンMK−31、三菱化成工業(株)製〕
で処理して、Ｄ−リボースの分画を集めて濃縮し
エタノール２：１アセトン溶液を加えて一夜冷蔵
庫中に放置してＤ−リボースの結晶12.1ｇを得
た。融点83〜84℃、比旋光度〔α〕24 D＝−18.4°（Ｃ
＝１，H2Ｏ）。 Ion exchange resin loaded with this solution with calcium [Diaion MK-31, manufactured by Mitsubishi Chemical Industries, Ltd.]
The fractions of D-ribose were collected and concentrated, a 2:1 acetone solution of ethanol was added, and the mixture was left in the refrigerator overnight to obtain 12.1 g of D-ribose crystals. Melting point 83-84℃, specific optical rotation [α] 24 D = -18.4° (C
= 1, H 2 O).
実施例 ５
Ｄ−アラビノース15ｇに10％含水イソプロパノ
ール45ml、ホウ酸メチル31.0ｇおよびモリブデン
酸アンモニウム1.2ｇを加え、50％硫酸でPH3.3に
調整した。この溶液を60分間還流下反応した。反
応液を除冷後析出物を過後、減圧下溶媒を留去
した。この溶液を弱塩基性陰イオン交換樹脂〔ア
ンバーライトIRA−99およびIRA−743、オルガ
ノ(株)製〕で処理してモリブデン酸イオンおよびホ
ウ酸イオンを除去した。このイオン交換処理液を
糖濃度が約50％になるまで濃縮した。この溶液の
糖分を測定すると
Ｄ−リボース 89.6％
Ｄ−アラビノース 8.3％
Ｄ−キシロースとＤ−リクソース 2.1％
であつた。Example 5 45 ml of 10% hydrous isopropanol, 31.0 g of methyl borate and 1.2 g of ammonium molybdate were added to 15 g of D-arabinose, and the pH was adjusted to 3.3 with 50% sulfuric acid. This solution was reacted under reflux for 60 minutes. After cooling the reaction solution and removing the precipitate, the solvent was distilled off under reduced pressure. This solution was treated with a weakly basic anion exchange resin (Amberlite IRA-99 and IRA-743, manufactured by Organo Co., Ltd.) to remove molybdate ions and borate ions. This ion exchange treated solution was concentrated until the sugar concentration was approximately 50%. When the sugar content of this solution was measured, it was found to be 89.6% D-ribose, 8.3% D-arabinose, and 2.1% D-xylose and D-lyxose.
この溶液をカルシウム型陽イオン交換樹脂
〔MK−31、三菱化成工業(株)製〕に通液してクロ
マトグラフイーによりＤ−リボースの分画を集め
て濃縮しエタノール２：１アセトン溶液50mlを加
えて冷蔵庫中に一夜放置するとＤ−リボースの結
晶12.0ｇが得られた。融点86℃、比旋光度〔α〕
24 D＝−18.7°（Ｃ＝１，H2Ｏ）。 This solution was passed through a calcium-type cation exchange resin [MK-31, manufactured by Mitsubishi Chemical Industries, Ltd.], and the D-ribose fraction was collected and concentrated by chromatography, and 50 ml of an ethanol 2:1 acetone solution was added. In addition, when the mixture was left in the refrigerator overnight, 12.0 g of D-ribose crystals were obtained. Melting point 86℃, specific optical rotation [α]
24 D = -18.7° (C = 1, H 2 O).
実施例 ６
Ｄ−アラビノース20ｇにｎ−プロパノール18
ml、モリブデン酸アンモニウム1.5ｇおよびホウ
酸23.0ｇを加え、90℃で60分間攪拌下加熱した。
反応液を冷却後、ｎ−プロパノール20mlを加え冷
所に放置するとホウ酸の一部が析出した。これを
別した後、実施例１と同様に操作してモリブデ
ン酸およびホウ酸を弱塩基性陰イオン交換樹脂で
除去し、減圧下糖濃度が約50％になるまで濃縮し
た。この溶液の糖分を測定すると
Ｄ−リボース 91.3％
Ｄ−アラビノース 7.3％
Ｄ−キシロースとＤ−リクソース 1.4％
であつた。この溶液の還元糖の定量値は53.5％で
あつた。この溶液500mlをオートクレーブに入れ、
メタノール137ml、３，４−キシリジン16.3ｇ、
ラネーニツケル（含水）11.7ｇおよび酢酸ナトリ
ウム0.5ｇを加え、水素を40Kg／cm2まで充填し、
攪拌下60℃まで昇温し80分間反応した。反応液か
らラネーニツケルを別し、液を約200mlまで
濃縮し、徐々に冷却すると結晶が析出した。この
結晶を別し水−メタノール（メタノール50％）
で２回再結晶してＮ−Ｄ−リビチル−３，４−キ
シリジン24.8ｇを得た。融点145℃、比旋光度
〔α〕20 D＝−21.8°（Ｃ＝１，H2Ｏ）。Example 6 20 g of D-arabinose and 18 n-propanol
ml, 1.5 g of ammonium molybdate and 23.0 g of boric acid, and heated at 90° C. for 60 minutes with stirring.
After cooling the reaction solution, 20 ml of n-propanol was added and the solution was left in a cool place to precipitate a portion of boric acid. After separating this, molybdic acid and boric acid were removed using a weakly basic anion exchange resin in the same manner as in Example 1, and the mixture was concentrated under reduced pressure until the sugar concentration was about 50%. When the sugar content of this solution was measured, it was found to be 91.3% D-ribose, 7.3% D-arabinose, and 1.4% D-xylose and D-lyxose. The quantitative value of reducing sugar in this solution was 53.5%. Put 500ml of this solution into an autoclave,
137ml of methanol, 16.3g of 3,4-xylidine,
Add 11.7g of Raney Nickel (hydrated) and 0.5g of sodium acetate, fill with hydrogen to 40Kg/ cm2 ,
The temperature was raised to 60°C while stirring, and the reaction was carried out for 80 minutes. The Raney nickel was separated from the reaction solution, the solution was concentrated to about 200 ml, and when it was gradually cooled, crystals were precipitated. Separate the crystals and water-methanol (methanol 50%)
The product was recrystallized twice to obtain 24.8 g of N-D-ribityl-3,4-xylidine. Melting point: 145°C, specific optical rotation [α] 20 D = -21.8° (C = 1, H 2 O).
実施例 ７
Ｄ−アラビノース20ｇにジエチレングリコール
モノエチルエーテル（カルビトール）20ml、モリ
ブデン酸アンモニウム1.5ｇおよびホウ酸23.0ｇ
を加え、92℃で80分間攪拌下加熱した。反応液に
水60mlを加え減圧下溶媒を留去した。この溶液を
減圧下乾固し、メタノール150mlを加え、析出物
を別した後メタノールを留去し、水50mlを加
え、弱塩基性陰イオン交換樹脂〔アンバーライト
IRA−99、オルガノ(株)製〕に通液してモリブデン
酸を除去した。この溶液を約50％になるまで減圧
下濃縮し糖分を測定すると
Ｄ−リボース 92.8％
Ｄ−アラビノース 5.3％
Ｄ−キシロースとＤ−リクソース 1.9％
であつた。この溶液34.6ｇの還元糖の定量値は
54.6％であつた。この溶液500mlをオートクレー
ブに入れ、メタノール135ml、３，４−キシリジ
ン15.8ｇ、ラネーニツケル（含水）11.4ｇおよび
酢酸ナトリウム0.5ｇを加え、水素を40Kg／cm2ま
で充填し、攪拌下60℃まで昇温し80分間反応し
た。反応液からラネーニツケルを別し、液を
約200mlまで濃縮し徐々に冷却すると結晶が析出
した。この結晶を別し50％メタノールで再結晶
するとＮ−Ｄ−リビチル−３，４−キシリジンの
結晶25.1ｇを得た。融点142〜143℃。Example 7 20 g of D-arabinose, 20 ml of diethylene glycol monoethyl ether (carbitol), 1.5 g of ammonium molybdate and 23.0 g of boric acid
was added and heated at 92°C for 80 minutes with stirring. 60 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. This solution was dried under reduced pressure, 150 ml of methanol was added, the precipitate was separated, the methanol was distilled off, 50 ml of water was added, and a weakly basic anion exchange resin [Amberlite
IRA-99, manufactured by Organo Co., Ltd.] to remove molybdic acid. This solution was concentrated under reduced pressure to about 50%, and the sugar content was measured: D-ribose 92.8%, D-arabinose 5.3%, D-xylose and D-lyxose 1.9%. The quantitative value of reducing sugar in 34.6g of this solution is
It was 54.6%. Put 500ml of this solution into an autoclave, add 135ml of methanol, 15.8g of 3,4-xylidine, 11.4g of Raney nickel (hydrated) and 0.5g of sodium acetate, fill with hydrogen to 40Kg/ cm2 , and raise the temperature to 60℃ while stirring. and reacted for 80 minutes. The Raney nickel was separated from the reaction solution, and the solution was concentrated to about 200 ml and gradually cooled to precipitate crystals. The crystals were separated and recrystallized with 50% methanol to obtain 25.1 g of N-D-ribityl-3,4-xylidine crystals. Melting point 142-143℃.
元素分析値 （C13H21NO4として）
計算値 Ｃ：61.15％、Ｈ：8.29％、Ｏ：25.07
％、Ｎ：5.49％
実測値 Ｃ：61.1％、Ｈ：8.1％、Ｏ：25.2％、
Ｎ：5.4％
実施例 ８
Ｄ−アラビノース15ｇにｎ−ヘキサノール15
ml、アセチルアセトンモリブデン酸塩〔MoO2
（CH2COCH2COCH3）2〕3.2ｇおよびホウ酸15.4
ｇを加え、90℃で60分間攪拌した。反応液に水を
加え減圧下共沸蒸留して溶媒を留去した。この溶
液中のモリブデン酸およびホウ酸を電気透析によ
り除去した。この処理液を糖濃度が約50％になる
まで濃縮し、糖分を測定すると
Ｄ−リボース 91.7％
Ｄ−アラビノース 6.8％
Ｄ−キシロースとＤ−リクソース 1.5％
であつた。この溶液27.8ｇの還元糖の定量値は
50.2％であつた。この溶液500mlを実施例７と同
様に操作してＮ−Ｄ−リビチル−３，４−キシリ
ジンの結晶16.8ｇを得た。融点145℃、比旋光度
〔α〕24 D＝−21.8°（Ｃ＝0.4、メタノール）。 Elemental analysis value (as C 13 H 21 NO 4 ) Calculated value C: 61.15%, H: 8.29%, O: 25.07
%, N: 5.49% Actual value C: 61.1%, H: 8.1%, O: 25.2%,
N: 5.4% Example 8 15g of D-arabinose and 15g of n-hexanol
ml, acetylacetone molybdate [MoO 2
(CH 2 COCH 2 COCH 3 ) 2 ] 3.2 g and boric acid 15.4
g and stirred at 90°C for 60 minutes. Water was added to the reaction solution, and the solvent was removed by azeotropic distillation under reduced pressure. Molybdic acid and boric acid in this solution were removed by electrodialysis. This treated solution was concentrated to a sugar concentration of approximately 50%, and the sugar content was measured to be 91.7% D-ribose, 6.8% D-arabinose, and 1.5% D-xylose and D-lyxose. The quantitative value of reducing sugar in 27.8g of this solution is
It was 50.2%. 500 ml of this solution was treated in the same manner as in Example 7 to obtain 16.8 g of N-D-ribityl-3,4-xylidine crystals. Melting point: 145°C, specific optical rotation [α] 24 D = -21.8° (C = 0.4, methanol).
Claims (1)
機溶媒中、モリブデン酸イオンの存在下、ホウ酸
化合物を共存させてエピメリ化することを特徴と
するＤ−リボースの製造方法。1. A method for producing D-ribose, which comprises epimerizing D-arabinose in an organic solvent that may contain water in the presence of molybdate ions and in the presence of a boric acid compound.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22318783A JPS60115595A (en) | 1983-11-29 | 1983-11-29 | Production of solution containing d-ribose |
| US06/659,272 US4602086A (en) | 1983-10-13 | 1984-10-10 | Method of producing solution containing D-ribose |
| DE3437571A DE3437571A1 (en) | 1983-10-13 | 1984-10-11 | METHOD FOR PRODUCING A D-RIBOSE-CONTAINING SOLUTION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22318783A JPS60115595A (en) | 1983-11-29 | 1983-11-29 | Production of solution containing d-ribose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60115595A JPS60115595A (en) | 1985-06-22 |
| JPH0432834B2 true JPH0432834B2 (en) | 1992-06-01 |
Family
ID=16794162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22318783A Granted JPS60115595A (en) | 1983-10-13 | 1983-11-29 | Production of solution containing d-ribose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60115595A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140498A (en) * | 1998-11-17 | 2000-10-31 | Xyrofin Oy | Process for the continuous production of high purity L-ribose |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6081196A (en) * | 1983-10-13 | 1985-05-09 | Tokyo Tanabe Co Ltd | Production of aqueous solution containing d-ribose |
-
1983
- 1983-11-29 JP JP22318783A patent/JPS60115595A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6081196A (en) * | 1983-10-13 | 1985-05-09 | Tokyo Tanabe Co Ltd | Production of aqueous solution containing d-ribose |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60115595A (en) | 1985-06-22 |
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