Estrone → 3-Hydroxy-13-methyl-16-pyridin-3-ylmethylene-6,7,8,9,11,12,13,14,15,16-decahydro-cyclopenta[a]phenanthren-17-one

HRID 1675916Notes

Reaction equation

HRID 1675916 reaction equation
[OH-].[Na+].[CH3:3][C@@:4]12[C:20](=[O:21])[CH2:19][CH2:18][C@H:17]1[C@H:16]1[C@@H:7]([C:8]3[CH:9]=[CH:10][C:11]([OH:22])=[CH:12][C:13]=3[CH2:14][CH2:15]1)[CH2:6][CH2:5]2.[N:23]1[CH:28]=[CH:27][CH:26]=[C:25]([CH:29]=O)[CH:24]=1.CC(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O>C(O)C>[OH:22][C:11]1[CH:10]=[CH:9][C:8]2[CH:7]3[CH:16]([CH2:15][CH2:14][C:13]=2[CH:12]=1)[CH:17]1[C:4]([CH3:3])([C:20](=[O:21])[C:19](=[CH:29][C:25]2[CH:24]=[N:23][CH:28]=[CH:27][CH:26]=2)[CH2:18]1)[CH2:5][CH2:6]3

Participants

6

Reactant 4

HCID 5870EstroneHCID 103713-PyridinecarboxaldehydeHCID 14798Sodium HydroxideHCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl ester

Product 1

HCID 673496973-Hydroxy-13-methyl-16-pyridin-3-ylmethylene-6,7,8,9,11,12,13,14,15,16-decahydro-cyclopenta[a]phenanthren-17-one

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium hydroxide (1.0 g, 25 mmol) was added to a suspension of estrone (1.35 g, 5.0 mmol) and pyridine-3-carbaldehyde (595 mg, 5.0 mmol) in ethanol (40 mL) at room temperature. The resulting dark orange solution was stirred at room temperature for 4 hours. Then glacial acetic (ca. 10 mL) acid was added with stirring. The colour changed to light yellow and a light yellow solid precipitated. The solid was filtered off and washed with water (50 mL), ethanol (20 mL), diethyl ether (50 mL) and hexane (50 mL) and dried under high vacuum. Yield: 1.6313 g (90%) yellow powder. 1H-NMR (DMSO-d6, 400 MHz), δ: 0.90 (s, 3H, —CH3), 1.26-1.66 (m, 5H), 1.82-1.90 (m, 1H), 1.95-2.02 (m, 1H), 2.14-2.22 (m, 1H), 2.30-2.38 (m, 1H), 2.57-2.66 (m, 1H), 2.70-2.81 (m, 2H), 2.83-2.92 (m, 1H), 6.45 (d, J=2.3 Hz, 1H), 6.51 (dd, J=8.2, 2.3 Hz, 1H), 7.04 (d, J=8.2 Hz, 1H), 7.34 (s, 1H), 7.47 (dd, J=8.2, 5.1 Hz, 1H), 8.06 (d, J=8.2 Hz, 1H), 8.56 (dd, J=4.7, 1.2 Hz, 1H), 8.82 (d, J=1.6 Hz, 1H), 9,03 (s, 1H, —OH). LRMS (FAB+): 360.2 (100, [M+H]+). LRMS (FAB−): 276.1 (100), 358.2 (90, [M−H]−). HRMS (FAB+): 360.196434 C24H26NO2 requires 360.196354

Workup

  1. stirringwith stirring
  2. customprecipitated
  3. filtrationThe solid was filtered off
  4. washwashed with water (50 mL), ethanol (20 mL), diethyl ether (50 mL) and hexane (50 mL)
  5. customdried under high vacuum

Sources & evidence

ORD record
ord-997694d3ba704bd4969010d67783e17f
Source dataset
uspto-grants-2011_08
Patent number
US08003783B2

Reaction notes

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