Formaldehyde → HCID 178439838, compound

HRID 2228397Notes

Reaction equation

HRID 2228397 reaction equation
[Mg].C(I)C.[CH2:5]([C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11](Br)=[CH:10][C:9]=1[SiH:19]([CH3:21])[CH3:20])[CH:6]=[CH2:7].[CH2:22]=[O:23].[NH4+].[Cl-]>C1COCC1>[CH2:5]([C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]([CH2:22][OH:23])=[CH:10][C:9]=1[SiH:19]([CH3:21])[CH3:20])[CH:6]=[CH2:7]

Participants

7

Reactant 5

HCID 712FormaldehydeHCID 6340IodoethaneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 178439836HCID 178439836, compound

Product 1

HCID 178439838HCID 178439838, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
65 °C

Procedure

To a vigorously stirred suspension of activated magnesium turning (480 mg, 20 mmol) in dry THF (70 mL) were added a piece of 12 and ethyl iodide (50 μL). The reaction mixture was heated to reflux until the red color disappeared. Heating (65° C.) of the suspension was continued while a solution of 1-allyldimethylsilyl-4-bromo-naphthalene (1 Scheme 26, 3.0 g, 10 mmol) in THF (20 mL) was added over a period of 15 min. Upon completion of the addition, the gray solution was heated further for 10 min and transferred to a separate flask containing. paraformaldehyde (700 mg) in THF (20 mL) via cannula. After stirring the reaction mixture at 50° C. for 30 min, concentrated NH4Cl (10 mL) was added to the solution, and the reaction mixture was concentrated. The residue was extracted with ethyl acetate (70 mL) and brine (30 mL), and the organic layer was dried (Na2SO4), concentrated. The crude product was purified by column chromatography (1:5 ethyl acetate/hexanes) to afford a colorless oil (1.8 g, 75%); 1H NMR (300 MHz, CDCl3) δ 0.58 (s, 6 H), 2.08 (d, J=7.50 Hz, 2 H), 3.21 (s, OH, 1 H), 4.93-5.03 (2 H), 5.04 (s, 2 H), 5.89 (m, 1 H), 7.47 (d, J=7.20 Hz, 2 H), 7.53-7.64 (2 H), 7.69 (d, J=6.90 Hz, 1 H), 8.11 (d, J=8.80 Hz, 1 H), 8.23 (d, J=8.80 Hz, 1 H), 13C NMR (75 MHz, CDCl3) −1.50 (2 C), 24.6, 63.5, 114.1, 124.5, 124.8, 125.9, 126.8, 129.1, 131.4, 133.7, 135.0, 137.3, 137.5, 138.3.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux until the red color
  3. additionwas added over a period of 15 min
  4. additionUpon completion of the addition
  5. temperaturethe gray solution was heated further for 10 min
  6. customtransferred to a separate flask
  7. additioncontaining
  8. concentrationthe reaction mixture was concentrated
  9. extractionThe residue was extracted with ethyl acetate (70 mL) and brine (30 mL)
  10. dry with materialthe organic layer was dried (Na2SO4)
  11. concentrationconcentrated
  12. customThe crude product was purified by column chromatography (1:5 ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-00400a4925ab49e2bf3e849880da033b
Source dataset
uspto-grants-2002_07
Patent number
US06416861B1

Reaction notes

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