Tetrahydrofuran → HCID 69381053, compound

HRID 2217054Notes

Reaction equation

HRID 2217054 reaction equation
[CH2:1](Cl)[C:2](=[CH2:4])[CH3:3].C(=O)=O.Cl[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[CH3:16]CCCCC.CCOC(C)=O.[O:28]1[CH2:32][CH2:31][CH2:30][CH2:29]1>>[CH:30](=[C:31]1[CH2:10][CH:15]2[CH2:14][CH:13]([C:12]2([CH3:11])[CH3:16])[C:32]1([CH2:3][C:2]([CH3:1])=[CH2:4])[OH:28])[CH3:29]

Participants

6

Reactant 5

HCID 8028Tetrahydrofuran3×HCID 8058HexaneHCID 8857Ethyl AcetateHCID 112413-Chloro-2-methyl-1-propeneHCID 86608553HCID 86608553, compound

Product 1

HCID 69381053HCID 69381053, compoundYield 92%

Procedure

A solution of methallylchloride (0.692 g, 7.64 mmol) in freshly distilled tetrahydrofuran (THF) (2.5 mL) was added to a suspension of flame-dried Mg metal turnings (0.28 g, 11.5 mmol) in THF (2.5 mL) over 30 minutes at 60° C. The resulting Grignard solution darkened during heating at reflux for an additional 20 minutes. The mixture was then cooled to −42° C. (dry ice/chlorobenzene bath), and a solution of the enone Compound 3 (0.4182 g, 2.6 mmol) in THF (2.5 mL) was added dropwise. After 5 minutes, the cooling bath was removed, and the reaction was stirred for 1.5 hours as it warmed to room temperature. The mixture was then decanted into ice-cold 0.1 N HCl (50 mL) and extracted with ether. The combined organic fractions were washed with water and brine, dried over Na2SO4, filtered, and concentrated. Column chromatography (with 90:10/Hexane: EtOAc) provided Compound 4a (0.52 g, 92% yield) as a colorless liquid. 1H NMR: (250 MHz, CDCl3), δ 0.973 (s 3H), 1.05–1.01 (d 1H), 1.21 (s 3H), 1.60–1.57 (d of t, 3H), 1.61 (s 3H), 1.92 (s 3H), 2.63–2.18 (m 5H), 4.82–4.65 (m 2H), 5.79–5.77 (m 1H); 13C NMR (62.5 MHz, CDCl3) δ 13.1, 22.4, 24.7, 27.3, 30.1, 31.6, 37.9, 38.7, 48.9, 49.8, 78.7, 114.4, 122.0, 143.2, 143.4.

Workup

  1. temperatureduring heating
  2. temperatureat reflux for an additional 20 minutes
  3. customthe cooling bath was removed
  4. customThe mixture was then decanted into ice-cold 0.1 N HCl (50 mL)
  5. extractionextracted with ether
  6. washThe combined organic fractions were washed with water and brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-33d2cd5b381e4e2d820d059c30a14621
Source dataset
uspto-grants-2006_09
Patent number
US07112700B1

Reaction notes

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