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CAS No. : | 2174-59-6 | MDL No. : | MFCD08458849 |
Formula : | C20H20O8 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DOFJNFPSMUCECH-UHFFFAOYSA-N |
M.W : | 388.37 | Pubchem ID : | 358832 |
Synonyms : |
5-Demethylnobiletin
|
Chemical Name : | 2-(3,4-Dimethoxyphenyl)-5-hydroxy-6,7,8-trimethoxy-4H-chromen-4-one |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With aluminum (III) chloride; In acetonitrile; at 60℃; for 3h; | General procedure: 5-Hydroxy-6,7,8,4?-tetramethoxyflavone (9): Tangeretin (45 mg)was dissolved in anhydrous acetonitrile (13 mL) and anhydrous AlCl3(128 mg, 0.96 mmol, 8 equiv.) was added to the mixture which was keptat 60 C for 3 h. Then acetonitrile was evaporated, and hydrochloricacid (3%, 15 mL) was added. The mixture was heated under reflux for30 min. The mixture was cooled and then extracted with ethyl acetate(3 × 5 mL) and dried with anhydrous MgSO4. Filtration and evaporationof the solvent afforded the crude solid which was purified by silica gelchromatography with petroleum ether/ethyl acetate (2 : 1) to affordyellow crystals of 9: 40 mg; 93% |
88% | To a solution of 1 (111 mg, 0.276 mmol) in dichloromethane (5 mL) was added a solution of BCl3 in toluene (1.0 M, 0.30 mL, 0.30 mmol) at -78 C. The reaction mixture was allowed to warm to rt over a period of 15 h, to which was added 1 M aq. NaOH (10 mL). The mixture was stirred at rt for additional 1 h, acidified with 2 M HCl (10 mL), and extracted with chloroform (2 × 15 mL). The combined organic layer was dried (MgSO4) and concentrated. The residue (108 mg) was chromatographed (silica gel, toluene/ethyl acetate = 10/1-8/1-6/1) to afford 12 as yellow solids (95.0 mg, 0.244 mmol, 88% yield): mp 147-148 C (Lit.refPreviewPlaceHolder21 mp 144-145 C); IR (KBr) 3443, 2936, 2837, 1651, 1596 cm-1; 1H NMR (CDCl3) delta: 12.55 (1H, s, OH), 7.59 (1H, dd, J = 2.0, 8.5 Hz), 7.43 (1H, d, J = 2.0 Hz), 7.01 (1H, d, J = 8.5 Hz), 6.62 (1H s), 4.12 (3H, s), 3.990 (3H, s), 3.985 (3H, s), 3.979 (3H, s), 3.96 (3H, s); 13C NMR (CDCl3) delta: 182.9, 163.8, 152.9, 152.4, 149.5, 149.3, 145.7, 136.5, 132.9, 123.6, 120.1, 111.2, 108.6, 106.9, 103.9, 62.0, 61.7, 61.1, 56.1, 55.9; HRMS calcd. for [M-H]- of C20H20O8: 387.1085, found: 387.1079. | |
76% | With aluminum (III) chloride; In dichloromethane; ethanethiol; at 0 - 20℃; for 1h;Inert atmosphere; | To a solution of 3 (50 mg, 0.13 mmol) in CH2Cl2 (40 mL) was added AlCl3 (33 mg, 0.26 mmol, 2.0equiv) in EtSH (0.66 mL) at 0 C. The reaction mixture was stirred at room temperature for 1 h. Theresulting mixture was quenched with 6 M HCl aq. at 0 C, and extracted with CH2Cl2. The organic layerwas washed with brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure. Thecrude residue was purified by silica gel column chromatography (n-hexane/EtOAc = 2/1, 1/1) to afford 24(36 mg, 76%) as a yellow powder. Spectral data for 24 were in good agreement with those reported in reference.19 |
With hydrogenchloride; In ethanol; at 105℃;Microwave irradiation; | Microwave Heating - Open Condensing System 50 mg of <strong>[478-01-3]Nobiletin</strong> or Tangeretin was placed in a round bottom flask, The mixture was treated with 20 mL of 6N HCl and 100% EtOH (1: 1, v / v) And the focusing microwave synthesizer was connected with the condensation tube to conduct the demethylation reaction in an open system, Set the power to 150W, The temperature was 105 C, The microwave reaction times were 0.5, 1, 1.5 and 2 hours ,After completion of the reaction, The reaction solution was allowed to cool to room temperature, And then with the equivalent concentration of 6N NaOH for acid-base neutralization, And the solvent was removed by concentration under reduced pressure, 20 mL of distilled water was added, The reaction solution was acidified with 20 mL of EtOAc, and the reaction solution was subjected to fractional extraction. After the extraction, the EtOAc extract was concentrated under reduced pressure to remove the extract, The extraction step was repeated twice, The EtOAc extracts were concentrated under reduced pressure to give a dry extract powder (EtOAc extracts). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; ethanol; at 80℃; for 18 - 70h;Heating / reflux;Product distribution / selectivity; | 54 g of the above obtained fraction were refluxed in 500 ml of a HCl solution in ethanol (1.25 M, Fluka) for 70 h. The ethanol was evaporated. About 100 ml of fresh ethanol <n="8"/>were added and evaporated to dryness. This was repeated two times. 46.5 g of 5-hydroxy polymethoxyflavones-rich fraction were obtained. This fraction contained at least 85% w/w of 5-desmethyl polymethoxyflavones, relative to total flavone fraction (HPLC- UV-MS). Further HPLC purification work and NMR analyses showed the presence of 5-desmethylsinensetin, 5-desmethyl<strong>[478-01-3]nobiletin</strong>, 5-desmethyltangeretin, 5-desmethyl-TOM- scutellarein, 5-desmethyl-HOM-quercetagenin and 5-hydroxy-3,6,7,8,34'- hexamethoxyflavone; 300 mg of a polymethoxyflavone-rich extract obtained in Example 3 were reacted at 8O0C in the presence of ethanolic HCl solutions having different amounts of water. All the different experiments were analysed by HPLC after 18 hours of reaction to monitor the progression. The results (UV-peak area) are shown in Table 1 hereinbelow: | |
With hydrogenchloride; ethanol; water; at 80℃; for 18h;Heating / reflux;Conversion of starting material; | The same result was obtained in 1.6 ml of ethanol and 0.4 ml of concentrated HCl; 300 mg of a polymethoxyflavone-rich extract obtained in Example 3 were reacted at 8O0C in the presence of ethanolic HCl solutions having different amounts of water. All the different experiments were analysed by HPLC after 18 hours of reaction to monitor the progression. The results (UV-peak area) are shown in Table 1 hereinbelow: <n="9"/>PMF: polymethoxyflavoneAs it can be seen easily, if the water content of the alcoholic HCl solution is above 50% w/w, the yield of conversion is very low and preferably said water content should be below 33% or 20%. | |
With ethanol; water; for 24h;Heating / reflux;Product distribution / selectivity; | 165 mg of the PMF rich fraction were refluxed over 24 hours in 1.8 ml of ethanol and 0.2 ml of concentrated aqueous. About 15 ml of water were added and the mixture was extracted two times with 5 ml of dichloromethane. The organic phase was dried over Na2SO4 and the solvent was evaporated. 124 mg (yield: 75%) of 5-hydroxy polymethoxyflavones-rich fraction were obtained. This fraction contained a proportion of 5-desmethyl polymethoxyflavones, relative to total flavones, higher than 95 % (HPLC- UV-MS). |