Carbon Dioxide → HCID 45100640, compound

HRID 861647Notes

Reaction equation

HRID 861647 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[C:13](=[O:15])=O.[CH3:16][C@H:17]1[CH2:34][CH2:33][C@@:32]2([CH3:35])[C:19](=[CH:20][CH2:21][C@@H:22]3[C@@H:31]2[CH2:30][CH2:29][C@@:27]2([CH3:28])[C@H:23]3[CH2:24][CH2:25][C:26]2=O)[CH2:18]1.CI>O1CCCC1.CCCCCC.C(Cl)(Cl)(Cl)Cl>[CH3:16][C@H:17]1[CH2:34][CH2:33][C@@:32]2([CH3:35])[C:19](=[CH:20][CH2:21][C@@H:22]3[C@@H:31]2[CH2:30][CH2:29][C@@:27]2([CH3:28])[C@H:23]3[CH2:24][C@@H:25]([CH3:26])[C:13]2=[O:15])[CH2:18]1

Participants

9

Reactant 5

HCID 280Carbon DioxideHCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 1289153-Methylandrost-5-en-17-oneHCID 178418339Butyllithium

Product 1

HCID 45100640HCID 45100640, compoundYield 74%

Reagents, catalysts & solvents 3

HCID 5943Carbon TetrachlorideSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

Diisopropyl amine (1.165 g, 11.5 mmol) was dissolved in dry tetrahydrofuran (30 mL) at -78° C. under N2. n-Butyl lithium (4.44 mL of a 2.6M solution in hexane, 11.5 mmol) was added via syringe and the solution warmed to -23° C. (CO2, CCl4) for 0.25 h. 3β-Methylandrost-5-en-17-one (3.0 g, 10.4 mmol) in dry tetrahydrofuran (30 mL) was added via syringe and the solution stirred for 0.25 h. Methyl iodide (7.0 g, 49.33 mmol) in dry tetrahydrofuran (30 mL) was added dropwise and the mixture stirred at room temperature for 1.5 h. The solution was quenched with saturated ammonium chloride and the organic layer separated, dried over magnesium sulfate, filtered, and evaporated. The residual solid was chromatographed on flash silica gel (120 g) and eluted with 1/99 (v/v) ether hexane to give 3β,16α-dimethylandrost-5-en-17-one (2.32 g, 74%). mp 109°-110° C. (recrystallized from methanol); NMR (CDCl3) δ 5.29 (br s, J=5 Hz, 1H, H-6), 2.52 (m, 1-H, H-16), 1.07 (d J=8 Hz, 3H, C-16 Me), 0.99 (s, 3H, C-19 Me), 0.91 (s, 3H, C-18 Me); IR (KBr) 2900, 1730, 1450, 1430, 1370; MS 300 (M+, 100), 285(62), 282(2), 272(12), 267(17), 229(20), 217(30), 159(17); Anal. Calcd for C21H32O: C, 83.93; H, 10.73. Found: C, 83.79; H, 10.52.

Workup

  1. stirringthe mixture stirred at room temperature for 1.5 h
  2. customThe solution was quenched with saturated ammonium chloride
  3. customthe organic layer separated
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customThe residual solid was chromatographed on flash silica gel (120 g)
  8. washeluted with 1/99 (v/v) ether hexane

Sources & evidence

ORD record
ord-70c5ea8a8eff438ea27a18e2bab05d2b
Source dataset
uspto-grants-1998_02
Patent number
US05714481

Reaction notes

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