3-Hydroxybenzaldehyde → 3-Prop-2-ynyloxy-benzaldehyde

HRID 1858119Notes

Reaction equation

HRID 1858119 reaction equation
[CH3:1][C:2](C)([O-])[CH3:3].[K+].[OH:7][C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)[CH:11]=[O:12].C(Br)C#C>CN(C)C=O>[CH2:3]([O:7][C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)[CH:11]=[O:12])[C:2]#[CH:1]

Participants

5

Reactant 3

HCID 1013-HydroxybenzaldehydeHCID 7842Propargyl bromideHCID 23665647Potassium tert-butoxide

Product 1

HCID 31612423-Prop-2-ynyloxy-benzaldehyde

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
110 °C

Procedure

Potassium tert-butoxide (6.16 g, 0.055 mole), 3-hydroxybenzaldehyde (6.1 g, 0.05 mole), and dry dimethylformamide (DMF, over Na2SO4 ; 30 mL) were stirred briefly at 25° C., and then propargyl bromide (6.6 g, 0.055 mole) was added in 30 mL of dry DMF according to the method of F. Albericio et al., "Preparation and Application of the5-(4-(9-Fluorenylmethyloxycarbonyl)-Aminomethyl-3,5-Dimethoxyphenoxy)-ValericAcidHandle for the Solid Phase Synthesis of C-Terminal Peptide Amides under Mild Conditions," J. Org. Chem. vol. 55, pp. 3730-3743 (1990). The reaction mixture was heated to 110° C. for 8 h, and the solvent was then removed under high vacuum. Ethyl acetate was added, inorganic salts were removed by filtration, and the organic extract was washed sequentially with water, 2 M NaOH, and saturated aqueous NaCl. The organic phase was dried overnight (MgSO4), and the solvent was removed to yield a yellow liquid that was purified by silica gel chromatography using hexane-ethyl acetate (8.5:1.5) as the eluting solvent. Yield: 6.5 g (81%). 1H NMR (CDCl3): d 2.54 (t, 1H, CH), 4.73 (t, 2H,--OCH2 --), 7.2-7.48 (m, 4H, Aromatics), 9.96 (s, 1H, CHO). GC-MS (m/z): M+ =160.

Workup

  1. customAlbericio et al., "Preparation and Application of the5-(4-(9-Fluorenylmethyloxycarbonyl)-Aminomethyl-3,5-Dimethoxyphenoxy)-ValericAcidHandle
  2. customthe solvent was then removed under high vacuum
  3. additionEthyl acetate was added
  4. custominorganic salts were removed by filtration
  5. extractionthe organic extract
  6. washwas washed sequentially with water, 2 M NaOH, and saturated aqueous NaCl
  7. dry with materialThe organic phase was dried overnight (MgSO4)
  8. customthe solvent was removed
  9. customto yield a yellow liquid that
  10. customwas purified by silica gel chromatography

Sources & evidence

ORD record
ord-91f2737e71ac47b99628b138020cd607
Source dataset
uspto-grants-2000_11
Patent number
US06150404

Reaction notes

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