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CAS No. : | 6559-91-7 | MDL No. : | MFCD00189421 |
Formula : | C21H20O8 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | YVCVYCSAAZQOJI-JHQYFNNDSA-N |
M.W : | 400.38 | Pubchem ID : | 122797 |
Synonyms : |
4'-O-demethylepipodophyllotoxin;4'-DMEP;(?)-4′-Demethylepipodophyllotoxin;DMEP;VM-26;NSC-122819;4-Demethylepipodophyllotoxin
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-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 |
---|---|---|
1) Synthesis of 4-N-(<strong>[7149-75-9]4-chloro-3-methylaniline</strong>)-4-deoxy-4 ?-demethylepipodophyllotoxin: taking 1 mol of activated product of position 4 of C-ring of 4?-demethylepipodophyllotoxin (prepared in preparatory test example 1), which is then dried in vacuo at 45° C. for 2 hours; under protection of nitrogen, dried dichloromethane were added into a 4-necked flask, then adding dried activated product of position 4 of C-ring of 4?-demethylepipodophyllotoxin and 2 mol of <strong>[7149-75-9]4-chloro-3-methylaniline</strong>, adding 0.36 g of BaCO3, stirring for reaction at 25° C. for 24 hours; reaction liquid is rotary dried, then obtaining crude product of 4-N-(<strong>[7149-75-9]4-chloro-3-methylaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin. (0042) (2) Separation and purification of 4-N-(<strong>[7149-75-9]4-chloro-3-methylaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin: Separation and purification using silica gel column chromatography and gel column chromatography: (0043) (A) using normal phase silica gel column (normal phase silica gel: China Qingdao Haiyang Chemical Co., Ltd, HG/T2354-92; separation system: Swiss Buchi isocratic fast chromatography system; chromatographic column: Swiss Buchi glass column C-690 with length of 460 mm and inner diameter of 15 mm) or a similar polar column separation; taking system of chloroform:acetone=10:1 as eluent, with sample volume of 2 ml, constant flow rate of 1.0 ml/min; each of 2 ml of eluent as a fraction were collected. Using normal phase silica gel thin layer (efficient silica gel thin layer by Merck, Germany) or thin layer with similar polarity, each of fractions are viewed; taking system of chloroform:acetone=10:1 as a developing agent, fractions with Rf value of 0.5 are merged; the sample after merged is subjected to vacuum drying, stored at 4° C. in the refrigerator under dark conditions, as samples to be purified. (B) separating by gel column chromatography (gel: Sephadex LH-20; Separation column: glass column with length 480 mm and inner diameter of 30 mm); loading processed gel Sephadex LH-20 into column by wet method to be balanced with methanol. The sample to be purified is dissolved in 6 ml of methanol, adsorbed at flow rate of 0.6 ml/min of sample and then eluted at flow rate of 0.6 ml/min with 600 ml of methanol, eluate was collected to a bottle every 10 ml, each fraction is checked with normal phase silica gel thin layer (effective silica gel thin layer by Merck, Germany) or thin layer with similar polar; adopting system with chloroform:acetone=5:1 as developing solvent, fractions with Rf value of 0.5 are combined; sample of white powder from vacuum drying is 4-N-(<strong>[7149-75-9]4-chloro-3-methylaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin. (0045) 4-N-(<strong>[7149-75-9]4-chloro-3-methylaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin: white powder: C28H26ClNO7; 523, 1H NMR (300 MHz, CDCl3): delta 2.303 (s, 3H, ?CH3), 2.965-3.012 (m, 1H, 2-H), 3.071 (dd, J=4.8 Hz, 1H, 3-H), 3.775 (s, 6H, 3?, 5?-OCH3), 3.950 (t, J=9.3 Hz, 1H, 11-H), 4.349 (t, J=7.8 Hz, 1H, 11-H), 4.556 (dd, J=4.8 Hz, 2H, 4-H, 1-H), 5.937 (d, J=6.6 Hz 2H, OCH2O), 6.316 (s, 3H, ArH), 6.421 (s, 1H, ArH), 6.508 (s, 1H, ArH), 6.740 (s, 1H, ArH), 7.126 (d, J=8.1 Hz, 1H, ArH)13C NMR (75 MHz, CDCl3): delta 20.614, 38.855, 42.090, 43.604, 52.836, 56.695, 69.103, 101.785, 108.152, 109.369, 110.126, 111.076, 114.935, 123.484, 130.029, 130.682, 130.816, 132.122, 134.289, 137.243, 146.356, 146.682, 147.781, 148.463, 175.120 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1) Synthesis of 4-N-(<strong>[20191-74-6]2-ethyl-5-nitroaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin: taking 1 mol of activated product of position 4 of C-ring of 4?-demethylepipodophyllotoxin (prepared in preparatory test example 1), which is then dried in vacuo at 45° C. for 2 hours; under protection of nitrogen, dried dichloromethane were added into a 4-necked flask, then adding dried activated product of position 4 of C-ring of 4?-demethylepipodophyllotoxin and 2 mol of <strong>[20191-74-6]2-ethyl-5-nitroaniline</strong>, adding 0.36 g of BaCO3, stirring for reaction at 25° C. for 24 hours; reaction liquid is rotary dried, then obtaining crude product of 4-N-(<strong>[20191-74-6]2-ethyl-5-nitroaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin. (0134) (2) Separation and purification of 4-N-(<strong>[20191-74-6]2-ethyl-5-nitroaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin: (0135) Separation and Purification Using Silica Gel Column Chromatography and Gel Column Chromatography: (0136) (A) using normal phase silica gel column (normal phase silica gel: China Qingdao Haiyang Chemical Co., Ltd, HG/T2354-92; separation system: Swiss Buchi isocratic fast chromatography system; chromatographic column: Swiss Buchi glass column C-690 with length of 460 mm and inner diameter of 15 mm) or a similar polar column separation; taking system of chloroform:acetone=10:1 as eluent, with sample volume of 2 ml, constant flow rate of 1.0 ml/min; each of 2 ml of eluent as a fraction were collected. Using normal phase silica gel thin layer (efficient silica gel thin layer by Merck, Germany) or thin layer with similar polarity, each of fractions are viewed; taking system of chloroform:acetone=5:1 as a developing agent, fractions with Rf value of 0.5 are merged; the sample after merged is subjected to vacuum drying, stored at 4° C. in the refrigerator under dark conditions, as samples to be purified. (0137) (B) separating by gel column chromatography (gel: Sephadex LH-20; Separation column: glass column with length 480 mm and inner diameter of 30 mm); loading processed gel Sephadex LH-20 into column by wet method to be balanced with methanol. The sample to be purified is dissolved in 6 ml of methanol, adsorbed at flow rate of 0.6 ml/min of sample and then eluted at flow rate of 0.6 ml/min with 600 ml of methanol, eluate was collected to a bottle every 10 ml, each fraction is checked with normal phase silica gel thin layer (effective silica gel thin layer by Merck, Germany) or thin layer with similar polar; adopting system with chloroform:acetone=5:1 as developing solvent, fractions with Rf value of 0.5 are combined; sample of white powder from vacuum drying is 4-N-(<strong>[20191-74-6]2-ethyl-5-nitroaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin. 4-N-(<strong>[20191-74-6]2-ethyl-5-nitroaniline</strong>)-4-deoxy-4?-demethylepipodophyllotoxin: white powder: C28H26N2O7; 502, 1H NMR (300 MHz, CDC13): delta 1.248 (s, 3H), 2.549 (d, J=7.2 Hz, 2H), 3.129 (s, 2H), 3.809 (s, 6H), 4.004 (s, 1H), 4.453 (s, 1H), 4.631 (s, 1H), 4.849 (s, 1H), 5.986 (d, J=2.4 Hz, 2H), 6.339 (s, 2H), 6.563 (s, 1H), 6.724 (s, 1H), 7.231 (d, J=9.3 Hz, 1H), 7.342 (s, 1H), 7.634 (d, J=9.6 Hz, 1H)13C NMR (75 MHz, CDCl3): delta 12.571, 24.340, 38.599, 42.293, 43.667, 52.672, 56.710, 68.879, 101.950, 103.282, 108.063, 109.037, 110.354, 113.518, 128.894, 129.911, 130.440, 132.662, 134.377, 134.778, 145.544, 146.733, 147.678, 148.079, 148.809, 174.779 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With trifluoroacetic acid; In dichloromethane; at 0 - 20℃; for 3h; | General procedure: A mixture of 4?-demethylepipodophyllotoxin (DMEP) (400mg 1mmol) and SH-containing building blocks in dichloromethane (15mL) at 0C was mixed with 1mL of TFA as the catalyst. After stirring the reaction mixture for 2-3hat room temperature and maximal conversion was reached (3h, monitored by TLC), the resultant mixture was washed with saturated NaHCO3 (20mL×2) and extracted with CH2Cl2 (45mL×2). The organic layer was dried over MgSO4, and the solvent was evaporated to give a crude residue, which was purified by flash column chromatography (petroleum ether: dichloromethane: ethyl acetate, 3:2:1) to afford the target compounds. The purity of compounds was determined by HPLC with a thermo-C18 (250mm×4.6mm, 5mum) column as the stationary phase and methanol-water (35:65) as the mobile phase at ambient temperature and a flow rate of 2.0mL/min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With trifluoroacetic acid; In dichloromethane; at 0 - 20℃; for 3h; | General procedure: A mixture of 4?-demethylepipodophyllotoxin (DMEP) (400mg 1mmol) and SH-containing building blocks in dichloromethane (15mL) at 0C was mixed with 1mL of TFA as the catalyst. After stirring the reaction mixture for 2-3hat room temperature and maximal conversion was reached (3h, monitored by TLC), the resultant mixture was washed with saturated NaHCO3 (20mL×2) and extracted with CH2Cl2 (45mL×2). The organic layer was dried over MgSO4, and the solvent was evaporated to give a crude residue, which was purified by flash column chromatography (petroleum ether: dichloromethane: ethyl acetate, 3:2:1) to afford the target compounds. The purity of compounds was determined by HPLC with a thermo-C18 (250mm×4.6mm, 5mum) column as the stationary phase and methanol-water (35:65) as the mobile phase at ambient temperature and a flow rate of 2.0mL/min. |