Acetic Acid → 3-Hydroxy-13-methyl-16-(3,4,5-trimethoxy-benzylidene)-6,7,8,9,11,12,13,14,15,16-decahydro-cyclopenta[a]phenanthren-17-one

HRID 1675922

Reaction equation

HRID 1675922 reaction equation
[OH-].[K+].[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.[CH3:23][O:24][C:25]1[CH:26]=[C:27]([CH:30]=[C:31]([O:35][CH3:36])[C:32]=1[O:33][CH3:34])[CH:28]=O.C(O)(=O)C>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:28][C:27]2[CH:30]=[C:31]([O:35][CH3:36])[C:32]([O:33][CH3:34])=[C:25]([O:24][CH3:23])[CH:26]=2)[CH2:18]1)[CH2:5][CH2:6]3

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 5870EstroneHCID 68583,4,5-TrimethoxybenzaldehydeHCID 14797Potassium Hydroxide

Product 1

HCID 50130353-Hydroxy-13-methyl-16-(3,4,5-trimethoxy-benzylidene)-6,7,8,9,11,12,13,14,15,16-decahydro-cyclopenta[a]phenanthren-17-one

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Potassium hydroxide (1.0 g) was added to a solution of estrone (1.350 g, 2.0 mmol) and 3,4,5-trimethoxybenzaldehyde (1.00 g, 5.10 mmol) in ethanol (50 ml) at room temperature. The resulting dark brown solution was stirred at this temperature for 4 h, then glacial acetic acid (ca. 2.5 ml) was added with stirring. The colour changed to yellow and a white solid precipitated. The solid was filtered off and washed with water (50 ml), ethanol (20 ml), diethyl ether (50 ml) and hexane and recrystallised from ethanol. Yield: 2.063 g (92%) light yellow crystals. 1H-NMR (CDCl3, 400 MHz), δ: 1.00 (s, 3H), 1.40-1.78 (m, 5H), 2.00-2.11 (m, 2H), 2.26-2.34 (m, 1H), 2.38-2.56 (m, 2H), 2.84-3.04 (m, 3H), 3.90 (s, 3H), 3.91 (s, 6H), 4.93 (s, 1H, —OH), 6.60 (d, J=2.3 Hz, 1H), 6.66 (dd, J=8.2, 2.3 Hz, 1H), 6.80 (s, 2H), 7.17 (d, J=8.2 Hz, 1H), 7.40 (s, 1H). 13C-NMR (CDCl3, 100 MHz), δ: 15.0, 26.4, 27.2, 29.4, 32.1, 38.4, 44.4, 48.2, 49.0, 56.6, 61.3, 108.2, 113.2, 115.6, 126.6, 131.3, 131.9, 133.9, 135.2, 137.9, 139.7, 153.4, 154.0, 209.9. LRMS (FAB+): 449.3 (100, [M+H]+). LRMS (FAB−): 447.3 (100, [M−H]−). HRMS (FAB+): 448.223763.

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
  5. customrecrystallised from ethanol

Sources & evidence

ORD record
ord-44e32c34f08e4d2a8284e59d14ca5d91
Source dataset
uspto-grants-2011_08
Patent number
US08003783B2

Linked notes

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