Diisopropylamine → HCID 18177822, compound

HRID 394950Notes

Reaction equation

HRID 394950 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][C:14]1([CH3:30])[CH2:23][C:22]([CH3:25])([CH3:24])[C:21]2[C:16](=[CH:17][CH:18]=[C:19]([CH2:26][C:27]([OH:29])=[O:28])[CH:20]=2)[O:15]1.[CH2:31](I)[CH2:32][CH2:33][CH2:34][CH3:35]>C1COCC1>[CH3:13][C:14]1([CH3:30])[CH2:23][C:22]([CH3:24])([CH3:25])[C:21]2[C:16](=[CH:17][CH:18]=[C:19]([CH:26]([CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[C:27]([OH:29])=[O:28])[CH:20]=2)[O:15]1

Participants

6

Reactant 4

HCID 7912DiisopropylamineHCID 123351-IodopentaneHCID 18177797HCID 18177797, compoundHCID 178418339Butyllithium

Product 1

HCID 18177822HCID 18177822, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

2.55 ml of diisopropylamine were dissolved in 60 ml THF and treated dropwise, at 0° C., with 7.2 ml of butyl lithium (2.5M). After 30 min. at 0° C., a solution of 1.8 g of (2,2,4,4-tetramethyl-chroman-6-yl)-acetic acid in 8 ml of THF was dropped in. The reaction mixture was stirred at 0° C. for one hour then at room temperature for 30 min. After cooling back to 0° C., a solution of 1.42 ml of pentyl iodide in 4 ml THF was added dropwise. The mixture was kept at 0° C. for one hour then at room temperature for two hours. The mixture was quenched with the addition of 50 ml of water and the pH was adjusted to 2 with HCl 1N. The mixture was extracted with three portions of 50 ml of ether. The combined organic extracts were washed with two portions of 50 ml of water and one portion of 50 ml of saturated aqueous sodium chloride solution. The organic phase was dried over MgSO4 and concentrated in vacuo. The crude product was purified by flash chromatography (SiO2, 20% ethyl acetate/hexanes), yielding 1.2 g of a pale yellow oil. 1H NMR (CDCl3): 7.17 (d, J=2.2 Hz, 1H), 7.03 (dd, J=8.4, 2.2 Hz, 1H), 6.73 (d, J=8.4 Hz, 1H), 3.45 (t, J=7.7 Hz, 1H), 2.10-1.90 (m, 1H), 1.81 (s, 2H), 1.80-1.65 (m, 1H), 1.33 (s, 6H), 1.32 (s, 6H), 1.40-1.20 (m, 6H), 0.85 (t, J=6.9 Hz, 3H).

Workup

  1. waitat room temperature for 30 min
  2. temperatureAfter cooling back to 0° C.
  3. waitThe mixture was kept at 0° C. for one hour
  4. waitat room temperature for two hours
  5. customThe mixture was quenched with the addition of 50 ml of water
  6. extractionThe mixture was extracted with three portions of 50 ml of ether
  7. washThe combined organic extracts were washed with two portions of 50 ml of water and one portion of 50 ml of saturated aqueous sodium chloride solution
  8. dry with materialThe organic phase was dried over MgSO4
  9. concentrationconcentrated in vacuo
  10. customThe crude product was purified by flash chromatography (SiO2, 20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-a974c17ce0964238a6dce84eaf14bd5e
Source dataset
uspto-grants-2003_08
Patent number
US06603012B2

Reaction notes

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