JPS62289595A - Production of alpha,beta-nuclear substituted phenylglucoside and alpha,beta-nuclear substituted phenylmalto oligoside - Google Patents
Production of alpha,beta-nuclear substituted phenylglucoside and alpha,beta-nuclear substituted phenylmalto oligosideInfo
- Publication number
- JPS62289595A JPS62289595A JP13438486A JP13438486A JPS62289595A JP S62289595 A JPS62289595 A JP S62289595A JP 13438486 A JP13438486 A JP 13438486A JP 13438486 A JP13438486 A JP 13438486A JP S62289595 A JPS62289595 A JP S62289595A
- Authority
- JP
- Japan
- Prior art keywords
- nuclear substituted
- beta
- alpha
- nuclear
- acetylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- NEZJDVYDSZTRFS-RMPHRYRLSA-N Phenyl beta-D-glucopyranoside Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1 NEZJDVYDSZTRFS-RMPHRYRLSA-N 0.000 title description 3
- 150000002989 phenols Chemical class 0.000 claims abstract description 8
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 239000002798 polar solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- FYGDTMLNYKFZSV-DZOUCCHMSA-N alpha-D-Glcp-(1->4)-alpha-D-Glcp-(1->4)-D-Glcp Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](OC(O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-DZOUCCHMSA-N 0.000 claims description 10
- 229930182478 glucoside Natural products 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 150000008131 glucosides Chemical class 0.000 claims description 7
- HXBYBCASAVUYKF-GVYWOMJSSA-N (4r,5s,6r,7r)-4,5,6,7,8-pentahydroxyoctane-2,3-dione Chemical compound CC(=O)C(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO HXBYBCASAVUYKF-GVYWOMJSSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 14
- 229910015900 BF3 Inorganic materials 0.000 abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 6
- 230000026030 halogenation Effects 0.000 abstract description 5
- 238000005658 halogenation reaction Methods 0.000 abstract description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- UMDMFPMJBPQCHS-UHFFFAOYSA-N methylsilane trifluoromethanesulfonic acid Chemical compound C[SiH3].FC(S(=O)(=O)O)(F)F UMDMFPMJBPQCHS-UHFFFAOYSA-N 0.000 abstract description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 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 9
- 239000008103 glucose Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 phenyl glucosides Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 102000004139 alpha-Amylases Human genes 0.000 description 4
- 108090000637 alpha-Amylases Proteins 0.000 description 4
- 229940024171 alpha-amylase Drugs 0.000 description 4
- 102000006995 beta-Glucosidase Human genes 0.000 description 4
- 108010047754 beta-Glucosidase Proteins 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YXGBAQKCCMQLGH-VQSBMGSQSA-N (2r,3r,4s,5s,6r)-2-[(2r,3s,4r,5r,6r)-6-[(2r,4r,5r,6r)-6-[(2r,3s,4r,5r,6r)-6-[(2r,3s,4r,5r,6r)-4,5-dihydroxy-2-(hydroxymethyl)-6-(4-nitrophenoxy)oxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-4,5-dih Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](OC2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O[C@@H]4[C@H](O[C@H](OC=5C=CC(=CC=5)[N+]([O-])=O)[C@H](O)[C@H]4O)CO)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O YXGBAQKCCMQLGH-VQSBMGSQSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 102100024295 Maltase-glucoamylase Human genes 0.000 description 3
- FTNIPWXXIGNQQF-UHFFFAOYSA-N UNPD130147 Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(OC3C(OC(OC4C(OC(O)C(O)C4O)CO)C(O)C3O)CO)C(O)C2O)CO)C(O)C1O FTNIPWXXIGNQQF-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 108010028144 alpha-Glucosidases Proteins 0.000 description 3
- FJCUPROCOFFUSR-UHFFFAOYSA-N malto-pentaose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 FJCUPROCOFFUSR-UHFFFAOYSA-N 0.000 description 3
- FJCUPROCOFFUSR-GMMZZHHDSA-N maltopentaose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O[C@H]([C@H](O)CO)[C@H](O)[C@@H](O)C=O)O[C@H](CO)[C@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O[C@@H]2[C@@H]([C@@H](O)[C@H](O[C@@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)[C@@H](CO)O2)O)[C@@H](CO)O1 FJCUPROCOFFUSR-GMMZZHHDSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- BNABBHGYYMZMOA-AHIHXIOASA-N alpha-maltoheptaose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O[C@@H]4[C@H](O[C@H](O[C@@H]5[C@H](O[C@H](O[C@@H]6[C@H](O[C@H](O)[C@H](O)[C@H]6O)CO)[C@H](O)[C@H]5O)CO)[C@H](O)[C@H]4O)CO)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O BNABBHGYYMZMOA-AHIHXIOASA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- DRQFBCMQBWNTNV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;trifluoroborane Chemical compound FB(F)F.OCCN(CCO)CCO DRQFBCMQBWNTNV-UHFFFAOYSA-N 0.000 description 1
- BOFRXDMCQRTGII-UHFFFAOYSA-N 619-08-9 Chemical compound OC1=CC=C([N+]([O-])=O)C=C1Cl BOFRXDMCQRTGII-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 102000008579 Transposases Human genes 0.000 description 1
- 108010020764 Transposases Proteins 0.000 description 1
- LUEWUZLMQUOBSB-UHFFFAOYSA-N UNPD55895 Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(OC3C(OC(O)C(O)C3O)CO)C(O)C2O)CO)C(O)C1O LUEWUZLMQUOBSB-UHFFFAOYSA-N 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- UGJVZXBXVRMUSG-UHFFFAOYSA-K [B+3].[F-].[F-].[F-] Chemical compound [B+3].[F-].[F-].[F-] UGJVZXBXVRMUSG-UHFFFAOYSA-K 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- OCIBBXPLUVYKCH-QXVNYKTNSA-N alpha-maltohexaose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O[C@@H]4[C@H](O[C@H](O[C@@H]5[C@H](O[C@H](O)[C@H](O)[C@H]5O)CO)[C@H](O)[C@H]4O)CO)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O OCIBBXPLUVYKCH-QXVNYKTNSA-N 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
- DJMVHSOAUQHPSN-UHFFFAOYSA-N malto-hexaose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(OC4C(C(O)C(O)C(CO)O4)O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 DJMVHSOAUQHPSN-UHFFFAOYSA-N 0.000 description 1
- UYQJCPNSAVWAFU-UHFFFAOYSA-N malto-tetraose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(O)C(CO)O2)O)C(CO)O1 UYQJCPNSAVWAFU-UHFFFAOYSA-N 0.000 description 1
- RUJILUJOOCOSRO-WJMYNTJYSA-N maltooctaose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O[C@@H]4[C@H](O[C@H](O[C@@H]5[C@H](O[C@H](O[C@@H]6[C@H](O[C@H](O[C@@H]7[C@H](O[C@H](O)[C@H](O)[C@H]7O)CO)[C@H](O)[C@H]6O)CO)[C@H](O)[C@H]5O)CO)[C@H](O)[C@H]4O)CO)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O RUJILUJOOCOSRO-WJMYNTJYSA-N 0.000 description 1
- LUEWUZLMQUOBSB-OUBHKODOSA-N maltotetraose Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O[C@@H]3[C@@H](O[C@@H](O)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-OUBHKODOSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Saccharide Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〔産業上の利用分野〕
本発明はα、β−核置換フェニルグルコシドおよびα、
β−核置換フェニルマルトオリゴシドの新規な製造法に
関するものである。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention provides α,β-nucleosubstituted phenyl glucosides and α,
The present invention relates to a novel method for producing β-nucleus substituted phenyl malto-oligoside.
α、β−核置換フェニルグルコシドはα−またはβ−グ
ルコシダーゼ測定用基質として用いられる。又該グルコ
シドは、α−アミラーゼ活性測定用基質として有用なα
−核置換フェニルマルトオリ−ｆ’シト、例えばｐ−ニ
トロフェニルα−Ｄ−マルトヘプタオシド等の転位酵素
を用いる酵素法による合成の際の原料としても有用なも
のである。α, β-nuclear substituted phenyl glucosides are used as substrates for α- or β-glucosidase measurements. The glucoside is also useful as a substrate for measuring α-amylase activity.
It is also useful as a raw material for synthesis by an enzymatic method using a transposase such as p-nitrophenyl α-D-maltoheptaoside.
さらにα、β−核置換フェニルマルトオリコシドは血液
、尿等の体液中のα−アミラーゼ活性測定のための基質
として有用なものである。具体的には、例えばｐ−ニト
ロフェニルマルトペンタオシド、ｐ−ニトロフェニール
マルトへキサオシド、ｐ−ニトロフェニールマルトへブ
タオシド、２．４−ジクロロフェニルマルトペンタオシ
ド、２−１０口、４−ニトロフェニルマルトペンタオシ
ド等を挙げることができる。Further, the α,β-substituted phenyl malto-olicoside is useful as a substrate for measuring α-amylase activity in body fluids such as blood and urine. Specifically, for example, p-nitrophenylmaltopentaoside, p-nitrophenylmaltohexaoside, p-nitrophenylmaltohexaoside, 2,4-dichlorophenylmaltopentaoside, 2-10, 4-nitrophenyl Maltopentaoside and the like can be mentioned.
これらのグルコシドの内、酵素の転位反応を利用して合
成されるｐ−ニトロフェニルα−Ｄ−マルトヘプタオシ
ド以外は主に化学合成法によって調製されている。しか
し、該化学合成法は工程が繁雑で収率も低いものであっ
た。Among these glucosides, except for p-nitrophenyl α-D-maltoheptaoside, which is synthesized using an enzymatic rearrangement reaction, these glucosides are mainly prepared by chemical synthesis. However, this chemical synthesis method involved complicated steps and had a low yield.
すなわち、従来法はグルコースまたはマルトペンタオー
ス等のマルトオリゴ糖をアセチル化し、ハロゲン化し、
次いで脱アセチル化するものであった。That is, the conventional method acetylates malto-oligosaccharides such as glucose or maltopentaose, halogenates them,
This was followed by deacetylation.
より詳しくはグルコースまたはマルトオリゴ塘に酢酸無
水物を作用させて水酸基をアセチル化し、アセチル化グ
ルコースまたはアセチル化マルトオリゴ糖、例えばペン
タアセチルグルコース、ヘプタデカアセチルマルトペン
タオース等を得る。次いでアセチル化グルコースまたは
アセチル化マルトオリゴ糖の末端基をハロゲン化する。More specifically, acetic anhydride is applied to glucose or malto-oligosaccharide to acetylate the hydroxyl group to obtain acetylated glucose or acetylated malto-oligosaccharide, such as pentaacetylglucose, heptadecaacetylmaltopentaose, and the like. The terminal group of the acetylated glucose or acetylated maltooligosaccharide is then halogenated.
ハロゲン化はクロロホルム、ジクロロメタン等の非極性
溶媒中で無水塩化亜鉛、塩化第二錫、無水匹ハロゲン化
チタン、無水ハロゲン化水素等を作用させて行われる。Halogenation is carried out by reacting anhydrous zinc chloride, stannic chloride, anhydrous titanium halide, anhydrous hydrogen halide, etc. in a nonpolar solvent such as chloroform or dichloromethane.
このようにして得られるハロゲン化アセチルグルコース
またはハロゲン化アセチルマルトオリゴ糖にα、β−核
装フエノールをピリジン等の溶媒の存在下に作用させる
とα、β−核置換フェニルグルコシドまたはマルトオリ
ゴシトのアセチル化物が得られる。（尋られたアセチル
化物をナトリウムメトキサイド等を用いて脱水メタノー
ル溶媒中で脱アセチル化して目的とするα、β−核核置
換ユニニルグルコシドたはα、β−核置換フェニルマル
トオリゴシドを得るものであった。When halogenated acetylglucose or halogenated acetylmaltooligosaccharide thus obtained is treated with α,β-nucleated phenol in the presence of a solvent such as pyridine, an acetylated α,β-nuclear substituted phenylglucoside or maltooligosite is produced. is obtained. (The desired acetylated product is deacetylated in a dehydrated methanol solvent using sodium methoxide or the like to obtain the desired α,β-nucleus substituted uninyl glucoside or α,β-nucleus substituted phenyl malto-oligoside. Met.
Ｓ発明が解決しようする問題点〕
以上の如〈従来法はアセチル化グルコースまたはアセチ
ル化マルトオリゴ糖のハロゲン化工程が必要であるため
工程が複雑となり、また収率も低く問題があった。本発
明者等はα、β−核亙換フェニルグルコシドまたばば、
β−核２７０フェニルマルトオリゴシトの効率的な合成
法について検討した。その結果アセチル化グルコースま
たはアセチル化マルトオリゴ糖と核置換フェノールとを
三フッ化ホウ素、三フッ化メタンスルホン酸メチルシラ
ン等のルイス酸の存在下に直接反応させることにより、
ハロゲン化工程を経由することなく、α、β−核置換フ
ェニルグルコシド及びα、β−核置換フェニルマルトオ
リゴシドを効率よく合成することができることを見出し
、本発明を完成した。Problems to be Solved by the Invention S] As described above, the conventional method requires a halogenation step of acetylated glucose or acetylated malto-oligosaccharide, which complicates the process and causes problems in that the yield is low. The present inventors have discovered that α, β-transformed phenyl glucosides,
An efficient method for synthesizing β-nuclear 270 phenyl maltooligosites was investigated. As a result, by directly reacting acetylated glucose or acetylated malto-oligosaccharide with a nuclear-substituted phenol in the presence of a Lewis acid such as boron trifluoride or methylsilane trifluoromethanesulfonate,
The present invention has been completed by discovering that α,β-nucleus-substituted phenylglucosides and α,β-nucleus-substituted phenyl malto-oligosides can be efficiently synthesized without going through a halogenation step.
即ち本発明は、アセチルグルコースおよび／またはアセ
チルグ化マルトオリゴ糖と核置換フェノールとをルイス
酸の存在下に反応させることを特徴とする、
一般式
（式中Ｒ１及びＲ２はそれぞれ別々に水素原子、ヒドロ
キシ基、低級アルキル基、アミノ基、ニトロ基、または
ハロゲン原子を表し、ｎは０から７の整数を意味する）
で示されるα、β−核置換フェニルグルコシドおよびα
、β−核置換フェニルマルトオリゴシドの新規な製造方
法を提供するものである。That is, the present invention is characterized by reacting acetyl glucose and/or acetyl glylated maltooligosaccharide with a nuclear-substituted phenol in the presence of a Lewis acid. group, lower alkyl group, amino group, nitro group, or halogen atom, n means an integer from 0 to 7)
α,β-nuclear substituted phenyl glucoside and α
, provides a novel method for producing β-nucleus substituted phenyl malto-oligoside.
即ち本発明はα、β−グルコシダーゼ活性測定用の基質
として有用なα、β−核置換フェニルグルコシダーゼ、
またはα−アミラーゼ活性測定用基質として有用なα、
β−核置換フェニルマルトオリゴシドの新規な製造法に
関するものである。That is, the present invention provides α,β-nucleus-substituted phenylglucosidase useful as a substrate for measuring α,β-glucosidase activity,
or α useful as a substrate for measuring α-amylase activity;
The present invention relates to a novel method for producing β-nucleus substituted phenyl malto-oligoside.
以下に上記化合物を製造する方法について更に詳細に説
明する。The method for producing the above compound will be explained in more detail below.
先ず本発明において使用するグルコースまたはマルトオ
リゴ糖としては、無水α−グルコース、無水β−グルコ
ース、マルトテトラオース、マルトペンタオース、マル
トヘキサオース、マルトヘプタオース、マルトオクタオ
ース等が挙げられる。First, the glucose or malto-oligosaccharide used in the present invention includes anhydrous α-glucose, anhydrous β-glucose, maltotetraose, maltopentaose, maltohexaose, maltoheptaose, maltooctaose, and the like.
より好ましくは、これらを出来るだけ乾燥した後アセチ
ル化を行う。アセチル化は、公知の方法で行えばよい。More preferably, acetylation is performed after drying these as much as possible. Acetylation may be performed by a known method.
−例えば、上記のグルコースまたはマルトオリゴ糖を無
水酢酸に溶解し、無水酢酸ナトリウムを加え１，００〜
１１０℃で４〜５時間還流冷却管付きの容器に入れ撹拌
する。反応終了後常法により精製し、濃縮乾燥してアセ
チル化物を得る。- For example, dissolve the above glucose or maltooligosaccharide in acetic anhydride, add anhydrous sodium acetate and
Stir at 110°C for 4 to 5 hours in a container equipped with a reflux condenser. After the reaction is completed, the product is purified by a conventional method and concentrated to dryness to obtain an acetylated product.
アセチルグルコースまたはアセチル化オリゴ糖を脱水し
たトルエン−ジクロロエタン混液等の低極性溶媒に溶解
し、核置換フェノールを加え、更に触媒としてルイス酸
を加える。ルイス酸としては、例えば三フッ化ホウ素、
三フッ化メタンスルホン酸メチルシラン、塩化第二スズ
、三臭化アルミニウム等を挙げることができる。Acetyl glucose or acetylated oligosaccharide is dissolved in a low polar solvent such as a dehydrated toluene-dichloroethane mixture, a nuclear substituted phenol is added, and a Lewis acid is further added as a catalyst. Examples of Lewis acids include boron trifluoride,
Examples include methylsilane trifluoromethanesulfonate, stannic chloride, and aluminum tribromide.
触媒として用いる三フッ化ホウ真または三フッ化ホウ素
コンプレックスとしては通常三フッ化ホｔＳエチルエー
テルコンプレックスが用いられるが、その他、三フプ化
ホウ素フェノールコンプレックス、三フッ化ホウ素酢酸
コンプレックス、三フッ化ホウ毒モノエチルコンプレッ
クス、三フッ化ホウ素ヒベリジンコンプレックス、三フ
フ化ホウ素ｎ−ブチルエーテルコンプレックス、三フッ
化ホウ素トリエタノールアミンコンプレックス等を用い
ることが出来る。As the boron trifluoride true or boron trifluoride complex used as a catalyst, a trifluoride tS ethyl ether complex is usually used, but in addition, boron trifluoride phenol complex, boron trifluoride acetic acid complex, trifluoride Boron poison monoethyl complex, boron trifluoride hiberidine complex, boron trifluoride n-butyl ether complex, boron trifluoride triethanolamine complex, etc. can be used.
アセチル化グルコースまたはアセチル化マルトオリゴ糖
とα、β−核置換フェノールとの反応温度は１０〜１０
０℃、好ましくは３０〜６０℃である。反応時間は１〜
５０時間、好ましくは５〜４０時間である。The reaction temperature between acetylated glucose or acetylated maltooligosaccharide and α,β-nucleus substituted phenol is 10-10
The temperature is 0°C, preferably 30-60°C. Reaction time is 1~
50 hours, preferably 5 to 40 hours.
反応に用いる溶媒としては低極性溶媒であれば何れを用
いてもよいが、トルエンまたは／およびジクロロエタン
を用いるのが好ましい。As the solvent used for the reaction, any low polarity solvent may be used, but it is preferable to use toluene and/or dichloroethane.
ハロゲン化工程を径由す−る従来法においてはβ一体が
多く生成し、α一体を多（生成することは一般に困難で
あった。またα一体、β一体の生成比工を自由に調節す
ることも困難であった。しかし本発明においては、熱力
学的に安定なα体と反応速度的に有利なβ体との生成比
を反応温度、反応時間、触媒量等の条件を選択すること
によりある程度まで調節できる。In conventional methods that involve a halogenation process, a large amount of β-units is produced, and it is generally difficult to generate a large number of α-units.Also, the production ratio of α-units and β-units can be freely adjusted. However, in the present invention, it is necessary to select conditions such as reaction temperature, reaction time, amount of catalyst, etc. so that the production ratio of the thermodynamically stable α-form and the β-form that is advantageous in terms of reaction rate is determined. It can be adjusted to a certain extent.
反応終了後、反応液を無水状態のま＼冷却し、氷を加え
て冷却した炭酸ナトリウム溶液１こ反応液を加え撹拌す
る。After the reaction is completed, the reaction solution is cooled in an anhydrous state, and 1 portion of a sodium carbonate solution cooled with ice is added to the reaction solution and stirred.
これを分液ロートに移し、クロロホルムを加えてフェノ
ール類を抽出した後、硫酸ナトリウムで脱水、濃縮乾固
するとα、β−核置換フェニールグルコシドアセチル化
物またはα、β−核置換フェニルマルトオリゴシドアセ
チル化物が得られる。Transfer this to a separating funnel, add chloroform to extract the phenols, dehydrate with sodium sulfate, concentrate and dry. is obtained.
これをクロロホルムを展開溶媒とするシリカゲルカラム
でＩ′ｉ′製し、各面分を乾固した後脱水メタノールに
溶解し、ナトリウムメトキサイドを加えて常法により脱
アセチル化し、メタノールを溜去すると目的とするα、
β−核置換フェニルグルコシドまたはα、β−核置換フ
ェニルマルトオシドが得られる。This was prepared using a silica gel column using chloroform as a developing solvent, and after drying each surface, it was dissolved in dehydrated methanol, and sodium methoxide was added to deacetylate it by a conventional method, and the methanol was distilled off. Target α,
β-nucleus substituted phenylglucosides or α,β-nucleus substituted phenyl maltoosides are obtained.
以下に実施例を挙げて更に具体的に説明するが、本発明
は以下の実施例に限定されるものではない。The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples.
実施例１ ｐ−＝）ロフニニル−α−Ｄ −クルコシトノ合成 ペンタアセチル−β−Ｄ−グルコシド９．３ｇ。Example 1 p-=)lovninyl-α-D-curcocytonosynthesis 9.3 g of pentaacetyl-β-D-glucoside.
ｐ−ニトロフェノール５．Ｏｇをトルエン３６ｍ！、ジ
クロロエタン６ｍｌの混合溶媒に加え触媒として三フッ
化ホウ素エチルエーテルコンプレックス１２ｇを加えて
５０℃で３０時間換押した。反応終了後、反応液を冷却
し氷冷した炭酸す） ＩＪウム溶液に加えて撹拌した後
クロロホルムで抽出し、抽畠液を飽和重炭酸ナトリウム
水溶液及び水で洗浄し、クロロホルム層を無水硫酸ナト
リウムで脱水した後、クロロホルムを減圧で溜去すると
９．８ｇのα−β−（ｐ−二トロフェニル）−テトラア
セチルグルコシドの粗生成物が得られた。次いでこの粗
生成物５ｇをクロロホルムを展開溶媒とするシリカゲル
のカラムクロマトグラフィーにより精製し、クロロホル
ムを溜去すると粗ｐ−ニトロフェニルーα−Ｄ−テトラ
アセチルグルコシド２．５ｇが得られた。この生成物を
７０ｍ１の脱水メタノールに溶解し、撹拌しつつ０．５
Ｎナトリウムメトキシド１０ｍ１を添加して５時間反応
し、脱アセチル化ヲ行すった。ｐ−ニトロフニニルーα
−Ｄグルコシド１．２ｇが得られた。本物質がα配位で
あることは、α−グルコシダーゼおよびβ−グルコシダ
ーゼを反応させる事により確認した。p-Nitrophenol5. Og to toluene 36m! In addition to a mixed solvent of 6 ml of dichloroethane, 12 g of boron trifluoride ethyl ether complex was added as a catalyst, and the mixture was pressurized at 50° C. for 30 hours. After the reaction was completed, the reaction solution was cooled and added to an ice-cooled carbonic acid solution. After stirring, the mixture was extracted with chloroform. The extracted solution was washed with a saturated aqueous sodium bicarbonate solution and water, and the chloroform layer was dissolved in anhydrous sodium sulfate. After dehydration, chloroform was distilled off under reduced pressure to obtain 9.8 g of a crude product of α-β-(p-nitrophenyl)-tetraacetylglucoside. Next, 5 g of this crude product was purified by column chromatography on silica gel using chloroform as a developing solvent, and chloroform was distilled off to obtain 2.5 g of crude p-nitrophenyl-α-D-tetraacetyl glucoside. This product was dissolved in 70 ml of dehydrated methanol and, with stirring, 0.5
10 ml of N sodium methoxide was added and reacted for 5 hours to perform deacetylation. p-Nitrophini-alpha
1.2 g of -D glucoside was obtained. The α-coordination of this substance was confirmed by reacting α-glucosidase and β-glucosidase.
（ｐ−＝）ロフェニルーα−グルコシド）融点 ２１
２〜２１４℃
旋光度 ［α］。”＋２０３．３ 。(p-=)rophenyl-α-glucoside) Melting point 21
2-214°C Optical rotation [α]. ”+203.3.
（メタノーノベＣ；０．３３）
赤外吸収スペクトルｃｍ−’
： ３４８０．３３２０（ＯＨ）、 １５９０． ｒ５
００１３５０（ＰｈＮＯ２）、 ７５０．７１０． ６
９０（Ｐｈ）２７０ ！Ｊ Ｈｚ核磁気共鳴スペクトル
（重メタノール）δ３．４８〜３．９３ （ｍ、 ６Ｈ
，Ｈ−２〜６）５．６５ （ｄ、 ＩＨ，ＪＩ２３．６
６ｉｆ、 Ｈ−１）？、 ２８．８．２２ （ｍ、
４Ｈ，Ｐｈ）実施例２
ｐ−ニトロ７ニニルα−Ｄ−マルトペンタオシド
マルトペンタオース１４．３ ｇを用いて常法によりア
セチル化を行いヘプタデカアセチルマルトペンタオース
２２． Ｏｇを得た。これにｐ−ニトロフェノール９．
８ｇ、）ルエン１００ｍｆジクロロエタン２０ｍｆ！０
）混合溶媒を加え触媒として三フッ化ホウ素エチルエー
テルコンプレックス４ｍｌを加えて４５℃で２４時間撹
拌反応した。反応終了後実施例１と同様にクロロホルム
を抽出し、クロロホルムヲ溜去スると粗ｐニトロフェニ
ルα−ヘキサデカアセチルマルトペンタオシド２６．０
ｇが得られた。次いで上記生成物をクロロホルムを溶
媒としてシリカゲルクロマトグラフィーにより精製し、
クロロホルムを溜去後、脱水メタノールに溶解し、ナト
リウムメトキシドを用いて、常法により脱アセチル化す
ると、ｐ−ニトロフェニル−α−Ｄ−マルトペンタオシ
ド３ｇが得られた。(Methananobe C; 0.33) Infrared absorption spectrum cm-': 3480.3320 (OH), 1590. r5
001350 (PhNO2), 750.710. 6
90 (Ph) 270! J Hz nuclear magnetic resonance spectrum (heavy methanol) δ3.48-3.93 (m, 6H
, H-2~6) 5.65 (d, IH, JI23.6
6if, H-1)? , 28.8.22 (m,
4H, Ph) Example 2 p-Nitro7ninyl α-D-maltopentaose 14.3 g of maltopentaose was acetylated by a conventional method to produce heptadecaacetylmaltopentaose 22. Obtained Og. To this, p-nitrophenol 9.
8g, ) toluene 100mf dichloroethane 20mf! 0
) A mixed solvent was added, 4 ml of boron trifluoride ethyl ether complex was added as a catalyst, and the reaction was stirred at 45° C. for 24 hours. After the reaction was completed, chloroform was extracted in the same manner as in Example 1, and the chloroform was distilled off to give 26.0 g of crude p-nitrophenyl α-hexadecaacetylmaltopentaoside.
g was obtained. The above product was then purified by silica gel chromatography using chloroform as a solvent,
After distilling off chloroform, the residue was dissolved in dehydrated methanol and deacetylated using sodium methoxide in a conventional manner to obtain 3 g of p-nitrophenyl-α-D-maltopentaoside.
（ｐ−ニトロフェニル−α−マルトペンタオシド）融点
２０２〜２０６℃
旋光度 ［α］。”、−２０３，１゜
（メタノール、ｃ； ０．３９）
赤外吸収スペクトルイ：ｍ−１
： ３４８０．３３２０（Ｏｆｔ）、 １５９０．１
５００゜１３５Ｑ（ＰｈＮＯ２）、 ７５ＣＬ ７１０
．６９０（Ｐｈ）６３．４３〜４．ｉ６ （ｍ、
３０）１． Ａ −ＢＨ−２〜６）５．１２〜５．１
４ （ｍ、 ４Ｈ，Ｃ−ＤＨ−１）５．２０（ｄ、
ＬＨ，ＪＢｌ、Ｂ２゜３、 ｂ７Ｈｚ、 ８ｆｌ
ｌ）
）、６７ （ｄ、 ＬＨ，ｊｈｌ。(p-nitrophenyl-α-maltopentaoside) Melting point 202-206°C Optical rotation [α]. ", -203.1° (methanol, c; 0.39) Infrared absorption spectrum m-1: 3480.3320 (Oft), 1590.1
500°135Q (PhNO2), 75CL 710
．． 690 (Ph) 63.43-4. i6 (m,
30)1. A-BH-2-6) 5.12-5.1
4 (m, 4H, C-DH-1) 5.20 (d,
LH, JBl, B2゜3, b7Hz, 8fl
l) ), 67 (d, LH, jhl.
３、６６ Ｈｚ 、Ａ Ｈｉ ）
７．３２． ８．２２ （ｍ、 ４Ｈ，Ｐｈ）実施
例３
２−クロロ−４−ニトロフェニル−β−Ｄ−マルトヘプ
タオシドの合成
マルトヘプタオース１９．７ ｇを常法によりアセチル
化し、アセチル化物３５．５ｇ ％得た。得られたマル
トヘプクオースアセチル化１勿３５ｙ５ ｇ、２−クロ
ロ−４ニトロフェノール９．４ ｇ ）ルエン１５０ｍ
１を混合し触媒として三フブ化ホウ累エチルエーテルコ
ンプレックス９ｒｒ＋ｊ７を加えて４０℃で２０時間撹
拌した。反応終了後、実施例１と同様にクロロホルムで
抽出し、クロロホルムを溜去すると粗−２−クロロ−４
−ニトロフェニル−β−Ｄ−マルトヘプタオシドのアセ
チル化物３６．０ｇが得られた。次いで上記生成物をク
ロロホルムを展開溶媒とするシリカゲルカラムクロマト
グラフィーにより精製し、クロロホルムを溜去後、脱水
メタノールに溶解し、ナトリウムメトキシサイドを用い
て常法により脱アセチル化し、脱塩すると２−クロロ−
４−ニトロフェニル−β−Ｄ−マルトヘプタオシド１．
９ｇが得られた。本島がβ体であることはα−アミラー
ゼ（Ａｍｙｌａｓｅ）をｆ［させた後α−およびβ−グ
ルコシダーゼを作用させる事により確認した。3, 66 Hz, A Hi ) 7.32. 8.22 (m, 4H, Ph) Example 3 Synthesis of 2-chloro-4-nitrophenyl-β-D-maltoheptaoside 19.7 g of maltoheptaose was acetylated by a conventional method, and the acetylated product 35. 5g% was obtained. Obtained maltohepquase acetylated 1 ml (35y5 g, 2-chloro-4 nitrophenol 9.4 g) toluene 150m
1 was mixed, and boric trifubide ethyl ether complex 9rr+j7 was added as a catalyst, followed by stirring at 40°C for 20 hours. After the reaction was completed, extraction was performed with chloroform in the same manner as in Example 1, and when the chloroform was distilled off, crude 2-chloro-4
36.0 g of acetylated product of -nitrophenyl-β-D-maltoheptaoside was obtained. The above product was then purified by silica gel column chromatography using chloroform as a developing solvent, and after distilling off the chloroform, it was dissolved in dehydrated methanol, deacetylated using sodium methoxide in a conventional manner, and desalted to give 2-chloro −
4-Nitrophenyl-β-D-maltoheptaoside 1.
9g was obtained. It was confirmed that the main island was in the β-form by subjecting it to f[α-amylase and then applying α- and β-glucosidase.
融点 ２１５〜２２０℃
旋光度 ［αコＤ” ＋ １０７．４゜（メタノール、
ｃ； ０．４３）
赤外吸収スペクトルＣｍ７’
： ３３８０（叶）、 １５９０．１５１０．１３５０
゜８５０ （ＰｈＮＯ□Ｃ） ７５０． ７１０． ６
９０（Ｐｈ）６３．４１〜３．９５ （ｍ、 ４９
Ｈ，Ａ−ＧＨ−２〜６）４、６５〜５．２５ （ｍ、
７Ｈ，Ａ−Ｇ）Ｉ ｌ）？、４５，８．２１，８
，３０ （ｍ、 ３Ｈ，Ｐｈ）融点 ２１４〜２
１９℃
融点 １４３〜１４５℃Melting point 215-220°C Optical rotation [αcoD” + 107.4° (methanol,
c; 0.43) Infrared absorption spectrum Cm7': 3380 (Kano), 1590.1510.1350
゜850 (PhNO□C) 750. 710. 6
90 (Ph) 63.41-3.95 (m, 49
H, A-GH-2-6) 4, 65-5.25 (m,
7H,A-G)I l)? ,45,8.21,8
,30 (m, 3H, Ph) Melting point 214~2
19℃ Melting point 143-145℃
Claims (3)
ルトオリゴ糖と核置換フェノールとをルイス酸の存在下
に反応させることを特徴とする、一般式 ▲数式、化学式、表等があります▼（ I ） （式中Ｒ＿１及びＲ＿２はそれぞれ別々に水素原子、ヒ
ドロキシ基、低級アルキル基、アミノ基、ニトロ基、ま
たはハロゲン原子を表し、ｎは０から７の整数を意味す
る）で示されるα，β−核置換フェニルグルコシドおよ
びα，β−核置換フェニルマルトオリゴシドの製造方法
。(1) General formula ▲Mathematical formula, chemical formula, table, etc., characterized by reacting acetyl glucose and/or acetylated malto-oligosaccharide with a nuclear-substituted phenol in the presence of a Lewis acid▼(I) (in the formula R_1 and R_2 each independently represent a hydrogen atom, a hydroxy group, a lower alkyl group, an amino group, a nitro group, or a halogen atom, and n means an integer from 0 to 7) α,β-nuclear substituted phenyl A method for producing a glucoside and an α,β-substituted phenyl malto-oligoside.
特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, characterized in that the reaction is carried out in a low polar solvent.
徴とする特許請求の範囲第１項記載の製造方法。(3) The manufacturing method according to claim 1, wherein the reaction is carried out at a temperature of 10 to 100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13438486A JPS62289595A (en) | 1986-06-10 | 1986-06-10 | Production of alpha,beta-nuclear substituted phenylglucoside and alpha,beta-nuclear substituted phenylmalto oligoside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13438486A JPS62289595A (en) | 1986-06-10 | 1986-06-10 | Production of alpha,beta-nuclear substituted phenylglucoside and alpha,beta-nuclear substituted phenylmalto oligoside |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62289595A true JPS62289595A (en) | 1987-12-16 |
Family
ID=15127136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13438486A Pending JPS62289595A (en) | 1986-06-10 | 1986-06-10 | Production of alpha,beta-nuclear substituted phenylglucoside and alpha,beta-nuclear substituted phenylmalto oligoside |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62289595A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498602A (en) * | 1991-09-13 | 1996-03-12 | Dainippon Ink And Chemicals, Inc. | Oligosaccharide aromatic glycoside and sulfate thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5312831A (en) * | 1976-07-13 | 1978-02-04 | Du Pont | Nitro aromatic glycoside and process for preparation thereof |
-
1986
- 1986-06-10 JP JP13438486A patent/JPS62289595A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5312831A (en) * | 1976-07-13 | 1978-02-04 | Du Pont | Nitro aromatic glycoside and process for preparation thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498602A (en) * | 1991-09-13 | 1996-03-12 | Dainippon Ink And Chemicals, Inc. | Oligosaccharide aromatic glycoside and sulfate thereof |
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