Hexane → HCID 59152646, compound

HRID 1947496Notes

Reaction equation

HRID 1947496 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:10]2[CH:11]=[CH:12][C:13]([O:15]C)=[CH:14][C:9]=2[O:8][CH:7]=1)=[O:5])[CH3:2].B(Br)(Br)Br.CCCCCC>C(Cl)Cl.CCOC(C)=O>[CH2:1]([O:3][C:4]([C:6]1[C:10]2[CH:11]=[CH:12][C:13]([OH:15])=[CH:14][C:9]=2[O:8][CH:7]=1)=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 8058HexaneHCID 25134Boron tribromideHCID 45489697Ethyl 6-methoxybenzofuran-3-carboxylate

Product 1

HCID 59152646HCID 59152646, compoundYield 89.7%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
10 °C

Procedure

To a cooled (0° C.) solution of 6-methoxy-benzofuran-3-carboxylic acid ethyl ester (90.0 g, 408.67 mmol) in DCM (700 mL) was slowly added BBr3 (159.0 g, 634.67 mmol) in DCM (200 mL) maintaining a controlled temperature (<5° C.). The resulting mixture was stirred (10° C., 6 h). The reaction mixture was slowly poured into ice/water with vigorous stirring followed by stirring in a temperature gradient (0° C.−rt, 18 h). The solids were filtered off and the filtrate was extracted with EtOAc (2×250 mL). The solids were dissolved (required heat) with the combined organic phase. The organic phase was washed with saturated NaHCO3 (700 mL), H2O (700 mL), dried, filtered and concentrated in vacuo to provide a yellow solid. The crude solid was suspended in EtOAc:hexane (20%), stirred (24 h) and filtered to provide the title compound as a solid (75.6 g). The filtrate was concentrated in vacuo and the resulting residue was purified by flash column chromatography using EtOAc:hexanes (20%) to provide the title compound (2.4 g) as a white solid (93% combined yield). MS (ESI): mass calcd. for C11H10O4, 206.2; m/z found, 207.1 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.15 (s, 1H), 7.88 (d, J=8.5, 1H), 7.01 (s, 1H), 6.90 (dd, J=8.5, 2.3, 1H), 5.05 (s, 1H), 4.4 (q, J=7.1, 2H) 1.42 (t, J=7.2, 3H).

Workup

  1. temperaturemaintaining a controlled temperature (<5° C.)
  2. stirringwith vigorous stirring
  3. stirringby stirring in a temperature gradient (0° C.−rt, 18 h)
  4. filtrationThe solids were filtered off
  5. extractionthe filtrate was extracted with EtOAc (2×250 mL)
  6. dissolutionThe solids were dissolved
  7. temperature(required heat) with the combined organic phase
  8. washThe organic phase was washed with saturated NaHCO3 (700 mL), H2O (700 mL)
  9. customdried
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customto provide a yellow solid
  13. filtrationfiltered

Sources & evidence

ORD record
ord-7e94d97dfb594e5ea67eb820bd669a45
Source dataset
uspto-grants-2013_03
Patent number
US08399465B2

Reaction notes

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