JP2008543818A - アントシアニンの合成方法 - Google Patents
アントシアニンの合成方法 Download PDFInfo
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- JP2008543818A JP2008543818A JP2008516401A JP2008516401A JP2008543818A JP 2008543818 A JP2008543818 A JP 2008543818A JP 2008516401 A JP2008516401 A JP 2008516401A JP 2008516401 A JP2008516401 A JP 2008516401A JP 2008543818 A JP2008543818 A JP 2008543818A
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- Japan
- Prior art keywords
- compound
- general formula
- groups
- opg
- anthocyanins
- 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
- 239000004410 anthocyanin Substances 0.000 title claims abstract description 65
- 235000010208 anthocyanin Nutrition 0.000 title claims abstract description 65
- 229930002877 anthocyanin Natural products 0.000 title claims abstract description 65
- 150000004636 anthocyanins Chemical class 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 239000000543 intermediate Substances 0.000 claims abstract description 33
- 235000000346 sugar Nutrition 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims description 75
- 125000006239 protecting group Chemical group 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 29
- -1 diphenylmethylenedioxy Chemical group 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 23
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000007858 starting material Substances 0.000 claims description 17
- VEVZSMAEJFVWIL-UHFFFAOYSA-O cyanidin cation Chemical compound [O+]=1C2=CC(O)=CC(O)=C2C=C(O)C=1C1=CC=C(O)C(O)=C1 VEVZSMAEJFVWIL-UHFFFAOYSA-O 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 13
- 239000012312 sodium hydride Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 11
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 10
- 235000007336 cyanidin Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 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 claims description 6
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- GCPYCNBGGPHOBD-UHFFFAOYSA-N Delphinidin Natural products OC1=Cc2c(O)cc(O)cc2OC1=C3C=C(O)C(=O)C(=C3)O GCPYCNBGGPHOBD-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 235000007242 delphinidin Nutrition 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- OVVGHDNPYGTYIT-VHBGUFLRSA-N Robinobiose Natural products O(C[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](C)O1 OVVGHDNPYGTYIT-VHBGUFLRSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims 1
- OVVGHDNPYGTYIT-BNXXONSGSA-N rutinose Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1 OVVGHDNPYGTYIT-BNXXONSGSA-N 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 22
- 239000002243 precursor Substances 0.000 abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 59
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 34
- 238000005481 NMR spectroscopy Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 235000019439 ethyl acetate Nutrition 0.000 description 24
- QSGHCNKMLLWXLM-UHFFFAOYSA-N CC(=O)C1=CC2=C(C=C1)OC(O2)(C3=CC=CC=C3)C4=CC=CC=C4 Chemical compound CC(=O)C1=CC2=C(C=C1)OC(O2)(C3=CC=CC=C3)C4=CC=CC=C4 QSGHCNKMLLWXLM-UHFFFAOYSA-N 0.000 description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 15
- 238000010168 coupling process Methods 0.000 description 15
- 230000008878 coupling Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- ZJWIIMLSNZOCBP-BTTVDUMLSA-N delphinidin-3-glucoside Chemical compound [Cl-].O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC(O)=C(O)C(O)=C1 ZJWIIMLSNZOCBP-BTTVDUMLSA-N 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 238000001953 recrystallisation Methods 0.000 description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 12
- FTCXFVDHYVIFPN-UHFFFAOYSA-N 2-iodo-1-[3,4,5-tris(phenylmethoxy)phenyl]ethanone Chemical compound C=1C=CC=CC=1COC=1C(OCC=2C=CC=CC=2)=CC(C(=O)CI)=CC=1OCC1=CC=CC=C1 FTCXFVDHYVIFPN-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- IULYROKRCRZRES-UHFFFAOYSA-N (3-acetyloxy-4-formyl-5-hydroxyphenyl) acetate Chemical compound CC(=O)OC1=CC(O)=C(C=O)C(OC(C)=O)=C1 IULYROKRCRZRES-UHFFFAOYSA-N 0.000 description 9
- IEOLRPPTIGNUNP-RKQHYHRCSA-N [(2r,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-hydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@H]1O[C@@H](O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O IEOLRPPTIGNUNP-RKQHYHRCSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000004809 thin layer chromatography Methods 0.000 description 9
- WLOXXFQUTQZLLO-UHFFFAOYSA-N 2-bromo-1-[3,4,5-tris(phenylmethoxy)phenyl]ethanone Chemical compound C=1C=CC=CC=1COC=1C(OCC=2C=CC=CC=2)=CC(C(=O)CBr)=CC=1OCC1=CC=CC=C1 WLOXXFQUTQZLLO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- RWRBIBPUKWHJDB-TZEVNULSSA-N [(2r,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-[2-oxo-2-[3,4,5-tris(phenylmethoxy)phenyl]ethoxy]oxan-2-yl]methyl acetate Chemical compound CC(=O)O[C@@H]1[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(=O)C)O[C@H]1OCC(=O)C(C=C1OCC=2C=CC=CC=2)=CC(OCC=2C=CC=CC=2)=C1OCC1=CC=CC=C1 RWRBIBPUKWHJDB-TZEVNULSSA-N 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 238000003818 flash chromatography Methods 0.000 description 5
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- LWTJEJCZJFZKEL-UHFFFAOYSA-N 2-chloro-3',4'-dihydroxyacetophenone Chemical compound OC1=CC=C(C(=O)CCl)C=C1O LWTJEJCZJFZKEL-UHFFFAOYSA-N 0.000 description 4
- NRCGMEJBEDWPMG-UHFFFAOYSA-N 3,4,5-tris(phenylmethoxy)benzoic acid Chemical compound C=1C=CC=CC=1COC=1C(OCC=2C=CC=CC=2)=CC(C(=O)O)=CC=1OCC1=CC=CC=C1 NRCGMEJBEDWPMG-UHFFFAOYSA-N 0.000 description 4
- 0 C*c1c(*)c(*)cc(C(CC*)=O)c1 Chemical compound C*c1c(*)c(*)cc(C(CC*)=O)c1 0.000 description 4
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000010511 deprotection reaction Methods 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000006206 glycosylation reaction Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- MAUSJTNDKNFSEU-UHFFFAOYSA-N methyl 3,4,5-tris(phenylmethoxy)benzoate Chemical compound C=1C=CC=CC=1COC=1C(OCC=2C=CC=CC=2)=CC(C(=O)OC)=CC=1OCC1=CC=CC=C1 MAUSJTNDKNFSEU-UHFFFAOYSA-N 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 150000002772 monosaccharides Chemical class 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000009518 sodium iodide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000006257 total synthesis reaction Methods 0.000 description 4
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- TWCMVXMQHSVIOJ-UHFFFAOYSA-N Aglycone of yadanzioside D Natural products COC(=O)C12OCC34C(CC5C(=CC(O)C(O)C5(C)C3C(O)C1O)C)OC(=O)C(OC(=O)C)C24 TWCMVXMQHSVIOJ-UHFFFAOYSA-N 0.000 description 3
- PLMKQQMDOMTZGG-UHFFFAOYSA-N Astrantiagenin E-methylester Natural products CC12CCC(O)C(C)(CO)C1CCC1(C)C2CC=C2C3CC(C)(C)CCC3(C(=O)OC)CCC21C PLMKQQMDOMTZGG-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012039 electrophile Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000013595 glycosylation Effects 0.000 description 3
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- KZMACGJDUUWFCH-UHFFFAOYSA-O malvidin Chemical compound COC1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O)=C1 KZMACGJDUUWFCH-UHFFFAOYSA-O 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- KADXVMRYQRCLAH-UHFFFAOYSA-N n'-iodobutanediamide Chemical compound NC(=O)CCC(=O)NI KADXVMRYQRCLAH-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- 235000016357 Mirtillo rosso Nutrition 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 240000001890 Ribes hudsonianum Species 0.000 description 2
- 235000016954 Ribes hudsonianum Nutrition 0.000 description 2
- 235000001466 Ribes nigrum Nutrition 0.000 description 2
- 244000281247 Ribes rubrum Species 0.000 description 2
- 235000002355 Ribes spicatum Nutrition 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 244000078534 Vaccinium myrtillus Species 0.000 description 2
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 2
- 244000077923 Vaccinium vitis idaea Species 0.000 description 2
- 235000017606 Vaccinium vitis idaea Nutrition 0.000 description 2
- OJOBTAOGJIWAGB-UHFFFAOYSA-N acetosyringone Chemical compound COC1=CC(C(C)=O)=CC(OC)=C1O OJOBTAOGJIWAGB-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 235000009584 malvidin Nutrition 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
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- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
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- HKUHOPQRJKPJCJ-UHFFFAOYSA-N pelargonidin Natural products OC1=Cc2c(O)cc(O)cc2OC1c1ccc(O)cc1 HKUHOPQRJKPJCJ-UHFFFAOYSA-N 0.000 description 1
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- OGBSHLKSHNAPEW-UHFFFAOYSA-N peonidin chloride Chemical compound [Cl-].C1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O)=C1 OGBSHLKSHNAPEW-UHFFFAOYSA-N 0.000 description 1
- QULMBDNPZCFSPR-UHFFFAOYSA-N petunidin chloride Chemical compound [Cl-].OC1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O)=C1 QULMBDNPZCFSPR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 description 1
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- 239000012925 reference material Substances 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 210000000614 rib Anatomy 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 description 1
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 description 1
- 235000005493 rutin Nutrition 0.000 description 1
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- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/18—Acyclic radicals, substituted by carbocyclic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
のα−官能性ケトン出発物質を、一般式:XO-
[式中、XO-は、糖のアノマー酸素原子からプロトンを除去することにより形成される陰イオンであり、前記糖の他のヒドロキシ基は適切な保護基によって保護されている]
の糖陰イオンと反応させることと、任意に前記保護基の一部またはすべてを除去することとを含み、一般式E−1:
の東半分中間体を得る方法である。
の西半分(Western half)中間体と反応させることと、それにより、中間体E−1およびW−1をカップリングし、且つ、任意に1個、数個、またはすべての保護基を除去し、一般式P−1:
のアントシアニン生成物を得ることとを含む。
水素化ナトリウムとを反応させることが所望の陰イオンを得る簡便な方法である。水素化ナトリウムは、安価且つ入手が容易であるため有利である。他の適切な陽イオンとして、カリウムおよびリチウムが挙げられるが、これに限定されない。
例えば、ジフェニルメチレンジオキシ誘導体:
実験の詳細
核磁気共鳴300MHz1H−NMRスペクトルおよび75MHz13C−NMRスペクトルは、バリアン(Varian)300MHz分光計で記録した。テトラメチルシラン(TMS)を内部基準物質として使用した。1H−NMRスペクトルの化学シフトは低磁場におけるTMSからのppmで表示する。13C−NMRスペクトルは、重クロロホルム(δ=76.9ppm)またはDMSO−d6(δ=39.5ppm)またはMeOH−d4(δ=49.0ppm)を基準としてppmで表す。高圧/高速液体クロマトグラフィー(HPLC)分析は、ウォーターズ(Waters)996(フォトダイオードアレイ検出器)と接続したウォーターズ2695(分離モジュール)で実施した。使用したカラムは、ヒューレットパッカード(Hewlett Packard)のHP ODS ハイパーシル(Hypersil)(4.6×200mm、粒径5μm)であった。溶離液は水―アセトニトリルであった。質量分析(MS)による分析は、ポジティブモードで作動しているエレクトロスプレーイオン化を用いたマイクロマス・プラットフォーム(Micromass Platform)LCZ質量分析計で実施した。ドライフラッシュクロマトグラフィーは、シリカゲル(フルカ(Fluka):シリカゲル60、粒径0.040〜0.063mm(230〜400メッシュ))を用いて実施した。水流アスピレーターで真空状態とした。薄層クロマトグラフィー(TLC)は、フルカのシリカゲルプレート(シリカゲル/蛍光指示薬付きdc−alufolien−kieselgel、製品番号60778)を用いて実施した。スポットは、UVP−UVキャビネット内でのUV(λ=254nmにおける吸光度またはλ=366nmにおける蛍光)によるか、および/またはMOP(エタノール(125ml)中リンモリブデン酸(14g))またはCER−MOP(水(180ml)中リンモリブデン酸(molybdato phosphoric acid)(5g)、硫酸セリウム(IV)(2g)および98%H2SO4(16ml))による染色によって検出し、スポットが現れるまでヒートガンで加熱して展開した。アントシアニンについての薄層クロマトグラフィーは、セルロースシート(メルク(Merck)、1.05565、セルロースF)上でFHW(98%ギ酸−37%HCl−水、4:1:8)を溶離剤として使用し実施した。市販の化学薬品は、フルカ、アルドリッチ(Aldrich)、アクロス(Acros)、メルクおよびランカスター(Lancaster)から購入した。必要に応じて標準的な精製方法を適用した。さらに、乾燥アセトン、アセトニトリル、DCM、DMSO、THF、DMEおよび乾燥EtOAcはフルカから購入した。
方法A:2−ブロモ−3’,4’−ジフェニルメチレンジオキシアセトフェノン(5)(1.98g、5mmol)およびβ−D−グルコース−2,3,4,6−テトラアセテート(8)(C. M. McCloskey, G. H. Coleman, Organic Syntheses, Coll. Vol. 3 434)(1.74g、5mmol)を乾燥DCM(50mL)に溶解し、水素化ナトリウム(0.18g、7.5mmol(オイル中60%NaH懸濁液0.3g))を少量ずつ添加した。この反応混合物を室温で一夜撹拌した。水(50mL)を添加し、水相をDCM(3×25mL)で抽出した。有機層を一つにまとめ、水(2×50mL)で洗浄し、乾燥させ(MgSO4)、蒸発させることにより、黄色油を得た。この粗生成物をドライフラッシュクロマトグラフィー(PE/EtOAc 6:4)(PE=石油エーテル)によって単離することにより、1.22g(37%)の黄色粘稠油を得たが、これは放置により緩慢に固化した。DCMの代わりに乾燥テトラヒドロフラン(THF)を溶媒として用いてこの反応を反復することにより、収率は51%となった。乾燥DMEを溶媒として用いてこの反応を反復することにより、収率は63%となった。1H NMR(300MHz、CDCl3):δ=1.90(3H、s)、1.92(3H、s)、1.94(3H、s)、1.95(3H、s)、4.01〜4.07(2H、m)、4.61〜4.75(5H、m)、5.01〜5.10(1H、m)、5.15〜5.25(1H、m)、6.80(1H、d、J=8.4Hz)、7.27〜7.48(12H、m);13C NMR(75MHz):δ=20.4(4×CH3)、61.5(CH2)、68.0(CH2)、70.1(CH)、70.7(CH)、71.6(CH)、72.3(CH)、99.9(CH)、107.8(2×CH)、108.0(C)、118.4(C)、124.3(CH、C)、125.9(2×CH)、128.1(4×CH)、128.2(C)、129.2(4×CH)、139.2(2×C)、147.5(C)、151.4(C)、169.1(C=O)、169.4(C=O)、169.8(C=O)、170.3(C=O)、192.6(C=O)。
方法A:3,4,5−トリヒドロキシ安息香酸メチル(16)(55.24g、0.3mol)、塩化ベンジル(113.93g、0.9mol)、乾燥炭酸カリウム(124.39g、0.9mol)およびヨウ化カリウム(触媒量)を乾燥アセトン(600mL)還流下で12時間撹拌した。冷却後、このアセトンを蒸発させ、溶液を水(250mL)に溶解した。水相をジエチルエーテル(4×100mL)で抽出し、有機相をブライン(2×50mL)で洗浄し、乾燥させ(MgSO4)、溶媒を真空下で除去した。石油エーテルおよび酢酸エチルからの再結晶化により、標題の化合物が白色結晶(融点102〜103℃)として得られた。収量121.4g(89%)。分光学的データは、文献(J. Barbera, R. Iglesias, J. L. Serrano, T. Sierra, M. R. de la Fuente, B. Palacios, M. A. Perez-Jubindo, J. T. Vazquez, J. Am. Chem. Soc. 1998, 120, 2908)どおりであった。
方法A:2−ブロモ−3’,4’,5’−トリベンジルオキシアセトフェノン(5.17g、10.0mmol)(11)およびヨウ化ナトリウム(2.25g、15mmol)を乾燥アセトニトリル(50mL)に溶解し、室温で一夜撹拌した。この溶液をろ過し、アセトニトリルを真空下で除去した。水(30mL)を添加し、この溶液をジエチルエーテル(4×25mL)で抽出した。有機相を乾燥させ(MgSO4)、溶媒を真空下で除去した。メチルシクロヘキサンからの再結晶化により、標題の化合物が黄色結晶(融点110〜112℃)として得られた。収量:3.6g(64%)。1H NMR(300MHz、CDCl3):δ=4.21(2H、s)、5.15(6H、s)、7.22〜7.48(17H、m);13C NMR(75MHz):δ=1.0、71.3、75.1、109.0、127.4、127.9、128.0、128.1、128.3、128.4、128.5、136.3、137.1、143.4、152.6、191.5。
方法A:2−ブロモ−3’,4’,5’−トリベンジルオキシアセトフェノン(11)(2.59g、5mmol)およびβ−D−グルコース−2,3,4,6−テトラアセテート(8)(1.74g、5mmol)を乾燥DME(50mL)に溶解し、水素化ナトリウム(0.18g、7.5mmol)(オイル中60%NaH懸濁液0.3g)を少量ずつ添加した。この反応混合物を室温で一夜撹拌した。水(50mL)を添加し、水相をDCM(3×25mL)で抽出した。有機層を一つにまとめ、水(2×50mL)で洗浄し、乾燥させ(MgSO4)、蒸発させることにより、粘稠性の暗色油が得られた。この生成物をドライフラッシュクロマトグラフィー(PE/EtOAc 6:4)(PE=石油エーテル)によって単離した。メチルシクロヘキサンおよび酢酸エチルの混合物からの再結晶化により、所望の化合物が白色結晶(融点156〜158℃)として得られた。収量:0.51g(13%)。1H NMR(300MHz、CDCl3):δ=1.98(3H、s)、2.00(3H、s)、2.02(3H、s)、2.06(3H、s)、3.63〜3.73(2H、m)、4.08〜4.30(5H、m)、4.62〜4.94(1H、m)、5.02〜5.34(7H、m)、7.20〜7.56(17H、m);13C NMR(75MHz):δ=20.5、20.6、61.6、68.2、70.5、70.8、71.2、71.8、72.4、75.0、100.1、107.9、127.4、127.9、128.0、128.1、128.4、128.5、129.6、136.4、137.1、143.2、152.6、169.3、169.5、170.0、170.5、193.4。
Claims (16)
- アントシアニンの東(Eastern)部分を製造する方法であって、前記方法は、一般式S−1:
R1はH、OMeまたはOPGであり、
R2はOPGであり、
R3はH、OMeまたはOPGであり、且つ、
PGは、それぞれ独立に保護基を示し、PGが一つの化合物の異なった部分に存在する場合は、同一の保護基を示してもよいが、必ずしもそうではなく、隣接した2つのOPG基は任意に一緒になって環状部分を形成してもよい]
のα−官能性ケトン出発物質を、一般式:XO-
[式中、XO-は、糖のアノマー酸素原子からプロトンを除去することにより形成される陰イオンであり、前記糖の他のヒドロキシ基は適切な保護基によって保護されている]
の糖陰イオンと反応させることと、任意に前記保護基の一部またはすべてを除去することとを含み、一般式E−1:
の東半分中間体を得る方法。 - LGが、BrまたはIである請求項1に記載の方法。
- XO-が由来する前記糖が、グルコースまたはルチノースである請求項1または請求項2に記載の方法。
- XOHとヒドリド試薬との反応により、XO-がその場で調製される前記請求項のいずれかに記載の方法。
- 前記ヒドリド試薬が、水素化ナトリウムである請求項4に記載の方法。
- PG基が、それぞれ独立にアセチル、ベンジルおよびベンゾイルから選択され、且つ/または、
隣接した2つのOPG基が、一緒になってジフェニルメチレンジオキシを示す前記請求項のいずれかに記載の方法。 - 前記反応が行われる溶媒が、THF、DMEまたはDCMである、前記請求項のいずれかに記載の方法。
- アントシアニンの製造方法であって、
前記方法は、アントシアニンの東部分を調製する前記いずれかの請求項に記載の方法に続いて、
任意に、R1’、R2’、R3’またはX’のいずれかが、それぞれR1、R2、R3またはXの脱保護類似体である場合、
R1’、R2’、R3’およびX’の一つ以上を再保護することと、その後、
一般式E−1の東半分(Eastern half)中間体またはその再保護誘導体を、一般式W−1:
R5はOPGであり、
R6はHであり、および
R7はOHもしくはOPGであるか、または
R4はOHであり、
R5はHであり、
R6はOHもしくはOPGであり、およびR7はHである]
の西半分(Western half)中間体と反応させることと、それにより、
中間体E−1およびW−1をカップリングし、且つ、任意に1個、数個、またはすべての保護基を除去し、一般式P−1:
Y-は対イオンであり、好ましくは生理学的に許容し得る対イオンである]
のアントシアニン生成物を得ることとを含む方法。 - 一般式P−1の前記アントシアニン生成物が、天然シアニジンまたはデルフィニジンアントシアニンである、請求項8に記載の方法。
- 請求項1に記載の一般式S−1の化合物。
- アントシアニンの「東(Eastern)」部分の製造における、請求項1に記載の一般式S−1の化合物の使用。
- LGが、BrまたはIである、請求項10に記載の化合物または請求項11に記載の使用。
- PG基が、それぞれ独立にアセチル、ベンジルおよびベンゾイルから選択され、且つ/または、隣接した2つのOPG基が、一緒になってジフェニルメチレンジオキシを示す、請求項12に記載の化合物または使用。
- R1、R2およびR3のそれぞれが、ベンジルオキシを示すか、またはR1がHを示し、R2およびR3が、一緒になってジフェニルメチレンジオキシを示す、請求項12に記載の化合物。
- R5’およびR7’がHであり、ならびにR6’がOH、O−アセチル、O−ベンジルまたはO−ベンゾイルである、請求項8に記載の一般式P−1の化合物。
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