Sodium hydride → HCID 90238743, compound

HRID 1478756Notes

Reaction equation

HRID 1478756 reaction equation
[CH:1]1([CH2:4][CH:5]([OH:9])[CH2:6][CH:7]=[CH2:8])[CH2:3][CH2:2]1.[H-].[Na+].Br[CH2:13][CH:14]([O:18][CH2:19][CH3:20])[O:15][CH2:16][CH3:17]>O1CCCC1>[CH2:16]([O:15][CH:14]([O:18][CH2:19][CH3:20])[CH2:13][O:9][CH:5]([CH2:6][CH:7]=[CH2:8])[CH2:4][CH:1]1[CH2:3][CH2:2]1)[CH3:17]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 74852Ethane, 2-bromo-1,1-diethoxy-HCID 80483439HCID 80483439, compound

Product 1

HCID 90238743HCID 90238743, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 1-cyclopropylpent-4-en-2-ol (C65) (16 g, 0.127 mmol) in tetrahydrofuran (200 mL) was added to a 0° C. suspension of sodium hydride (60% in mineral oil, 15.2 g, 0.38 mol) in tetrahydrofuran (400 mL). After stirring at room temperature for 10 minutes, 2-bromo-1,1-diethoxyethane (97%, 75 g, 0.38 mol) was added drop-wise at room temperature. The reaction mixture was heated to 70° C. for 24 hours. It was then cooled to 0° C., slowly quenched with water (200 mL) and extracted with dichloromethane (3×500 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo; purification via silica gel chromatography (Gradient: 0% to 10% ethyl acetate in petroleum ether) afforded the product as a yellow oil. Yield: 20 g, 83 mmol, 65%. 1H NMR (400 MHz, CDCl3) δ 5.79-5.89 (m, 1H), 5.04 (dt, J=14.0, 1.6 Hz, 2H), 4.60 (t, J=5.2 Hz, 1H), 3.64-3.73 (m, 2H), 3.51-3.62 (m, 4H), 3.45 (quintet, J=6.0 Hz, 1H), 2.31 (t, J=6.4 Hz, 1H), 1.50 (quintet, J=6.8 Hz, 1H), 1.20-1.30 (m, 2H), 1.21 (dt, J=6.8, 1.2 Hz, 6H), 0.72-0.80 (m, 1H), 0.38-0.49 (m, 2H), −0.02-0.10 (m, 2H).

Workup

  1. temperatureThe reaction mixture was heated to 70° C. for 24 hours
  2. temperatureIt was then cooled to 0° C.
  3. customslowly quenched with water (200 mL)
  4. extractionextracted with dichloromethane (3×500 mL)
  5. dry with materialThe combined organic layers were dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. custompurification via silica gel chromatography (Gradient: 0% to 10% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-46ddf316ff114b0b84f1f45ed1d29876
Source dataset
uspto-grants-2016_08
Patent number
US09403846B2

Reaction notes

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