Dimethylformamide → HCID 86652900, compound

HRID 1260136Notes

Reaction equation

HRID 1260136 reaction equation
[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][C:12]=1[OH:13])[CH:8]=[O:9])[C:2]#[CH:3].C([O-])([O-])=O.[K+].[K+].CN(C=O)C.[Br:25][CH:26](Br)[CH3:27]>O>[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][C:12]=1[O:13][CH2:27][CH2:26][Br:25])[CH:8]=[O:9])[C:2]#[CH:3]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 112011,1-DibromoethaneHCID 11430Potassium CarbonateHCID 529215204-Hydroxy-3-(2-propyn-1-yloxy)benzaldehyde

Product 1

HCID 86652900HCID 86652900, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a dry two-neck flask, compound 8 (4.3 g, 24 mmol, 1 equiv) and K2CO3 (16 g, 120 mmol, 5 equiv) were added into anhydrous DMF (50 mL) under nitrogen. The mixture was stirred at rt for 30 min. Dibromoethane (21 mL, 240 mmol, 10 equiv) was then added in one portion and the resulting mixture was heated overnight at 55° C. under a nitrogen atmosphere. The mixture was poured into water (400 mL) and the product was extracted with ethyl acetate (3×200 mL). The combined organic extracts were concentrated to about 250 mL and were washed subsequently with 1 M NaOH (2×200 mL), water (250 mL) and brine (5×250 mL). The organic layer was dried over MgSO4, filtered and the solvent was removed under vacuum. The crude product as yellow oil was chromatographed on a silica gel column with the eluent of ethyl acetate/hexane (20/80) to give pure product as a white solid (5.2 g, yield: 77%). 1H NMR δ=9.88 (s, 1H, —CHO), 7.58 (d, J=1.8, 1H), 7.54 (dd, J1=1.8, J2=8, 1H), 7.02 (d, J=8, 1H), 4.83 (d, J=2.3, 2H, —OCH2), 4.43 (t, J=6.6, 2H, —OCH2CH2Br), 3.72 (t, J=6.6, 2H, —OCH2CH2Br), 2.54 (t, J=2.3, 1H, —C≡CH). 13C NMR δ=190.68 (—CHO), 153.70, 147.77, 130.79, 127.01, 113.95, 113.19, 78.01 (—C≡CH), 76.63 (—C≡CH), 68.98 (—OCH2CH2Br), 57.16 (—OCH2C≡CH), 28.45 (—OCH2CH2Br). HRMS calculated for C12H11BrO3 (M+), 281.9892; found, 281.9903.

Workup

  1. temperaturethe resulting mixture was heated overnight at 55° C. under a nitrogen atmosphere
  2. extractionthe product was extracted with ethyl acetate (3×200 mL)
  3. concentrationThe combined organic extracts were concentrated to about 250 mL
  4. washwere washed subsequently with 1 M NaOH (2×200 mL), water (250 mL) and brine (5×250 mL)
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. customthe solvent was removed under vacuum
  8. customThe crude product as yellow oil was chromatographed on a silica gel column with the eluent of ethyl acetate/hexane (20/80)

Sources & evidence

ORD record
ord-054cb2389f2f402ca5fec2db648ef4fa
Source dataset
uspto-grants-2013_06
Patent number
US08470587B2

Reaction notes

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