Sodium Azide → 17-(2-((5-Azidopentyl)oxy)acetyl)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3(2H)-one

HRID 2039395Notes

Reaction equation

HRID 2039395 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][O:7][CH2:8][C:9]([CH:11]1[C:27]2([CH3:28])[CH:14]([CH:15]3[CH:24]([CH2:25][CH2:26]2)[C:23]2([CH3:29])[C:18](=[CH:19][C:20](=[O:30])[CH2:21][CH2:22]2)[CH2:17][CH2:16]3)[CH2:13][CH2:12]1)=[O:10].[N-:31]=[N+:32]=[N-:33].[Na+]>CN(C)C=O>[N:31]([CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][O:7][CH2:8][C:9]([CH:11]1[C:27]2([CH3:28])[CH:14]([CH:15]3[CH:24]([CH2:25][CH2:26]2)[C:23]2([CH3:29])[C:18](=[CH:19][C:20](=[O:30])[CH2:21][CH2:22]2)[CH2:17][CH2:16]3)[CH2:13][CH2:12]1)=[O:10])=[N+:32]=[N-:33]

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 8667556417-(2-((5-Bromopentyl)oxy)acetyl)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3(2H)-one

Product 1

HCID 7118308317-(2-((5-Azidopentyl)oxy)acetyl)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3(2H)-oneYield 68%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
65 °C

Procedure

To a solution of 7 (125 mg, 0.261 mmol) in anhydrous N,N-dimethylformamide (7 mL) was added sodium azide (169 mg, 2.61 mmol). The reaction mixture was heated to 65° C. and stirred overnight. Excess sodium azide was filtered off and the solvent was removed by rotary evaporation. The crude residue was dissolved in ethyl acetate and washed with water three times. The organic layer was dried over sodium sulfate and concentrated followed by flash chromatography in hexanes/ethyl acetate (2:1) to give 9 (78 mg, 68%). 1H NMR (500 MHz, CD3OD) δ 5.61 (d, J=4.9 Hz, 1H), 3.39 (t, J=6.4 Hz, 2H), 3.25-3.17 (m, 4H), 2.60 (t, J=9.1 Hz, 1H), 2.45-2.33 (m, 2H), 2.25-2.15 (m, 2H), 2.12-2.03 (m, 1H), 1.99 (m, 1H), 1.89-1.76 (m, 2H), 1.70-1.29 (m, 15H), 1.29-1.15 (m, 2H), 1.13 (d, J=11.0 Hz, 4H), 1.04-0.87 (m, 2H), 0.60 (s, 3H). 13C NMR (125 MHz, CD3OD) δ 210.81, 202.29, 174.92, 124.24, 78.00, 72.34, 62.71, 59.71, 57.39, 55.16, 52.43, 45.67, 39.99, 39.72, 36.81, 34.72, 33.90, 33.20, 30.15, 29.75, 25.52, 24.46, 24.17, 23.76, 22.15, 17.67, 13.96. ESI-MS m/z [M+Na]+ observed: 464.2, calculated: 464.3.

Workup

  1. filtrationExcess sodium azide was filtered off
  2. customthe solvent was removed by rotary evaporation
  3. dissolutionThe crude residue was dissolved in ethyl acetate
  4. washwashed with water three times
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-d2b7005f53774e9db978ec53c7fc41cb
Source dataset
uspto-grants-2013_11
Patent number
US08580231B2

Reaction notes

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