Tetrabutylammonium Fluoride → HCID 118572844, compound

HRID 59053Notes

Reaction equation

HRID 59053 reaction equation
[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][C:13]([CH:25]=[O:26])=[C:14]2Cl)[CH2:6]1)(=[O:3])[CH3:2].[Cl:27][C:28]1[N:36]=[CH:35][N:34]=[C:33]2[C:29]=1[NH:30][CH:31]=[N:32]2.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][C:13]([CH:25]=[O:26])=[C:14]2[N:32]2[CH:31]=[N:30][C:29]3[C:33]2=[N:34][CH:35]=[N:36][C:28]=3[Cl:27])[CH2:6]1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 2724141Tetrabutylammonium FluorideHCID 53592776-ChloropurineHCID 1047470117-Chloro-16-formylandrosta-5,16-dien-3beta-yl acetate

Product 1

HCID 118572844HCID 118572844, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of 13 (2.43 g, 6.46 mmol), 6-chloropurine (0.5 g, 3.23 mmol) and TBAF (1.69 g, 6.46) in dry THF (40 mL) was stirred at 50° C. under Ar for 48 h. After cooling to room temperature, the reaction mixture concentrated and poured onto ice-cold water (250 mL) and the resulting precipitate was filtered, washed with water and dried to give a crude product. Purification by FCC [DCM/Methanol (9.7:0.3)] and then recrystallized with hot ethanol to give 0.82 g (51.3%) of pure 21a: mp 140-142° C.; IR (Neat) 2943, 2853, 1729, 1672, 1584, 1556, 1435, 1236, 1032, 939, cm-1; 1H NMR (500 MHz, CDCl3) δ 1.07 (s, 3H, 18-CH3), 1.09 (s, 3H, 19-CH3), 2.04 (s, 3H, 3β-OCOCH3), 4.61 (m, 1H, 3α-H), 5.43 (br, 1H, 6-H), 8.20 (s, 1H, 2′-H), 8.79 (s, 1H, aromatic-H), and 9.53 (s, 1H, 16-CHO).

Workup

  1. temperatureAfter cooling to room temperature
  2. concentrationthe reaction mixture concentrated
  3. additionpoured onto ice-cold water (250 mL)
  4. filtrationthe resulting precipitate was filtered
  5. washwashed with water
  6. customdried
  7. customto give a crude product
  8. customPurification by FCC [DCM/Methanol (9.7:0.3)]
  9. customrecrystallized with hot ethanol

Sources & evidence

ORD record
ord-2f83b4028cf648b7b996082481bfdf89
Source dataset
uspto-grants-2016_09
Patent number
US09439912B2

Reaction notes

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