Tetrahydrofuran → HCID 67240767, compound

HRID 1970282Notes

Reaction equation

HRID 1970282 reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([O:16][CH3:17])=[CH:9][CH:10]=3)[C:5](=O)[C:4]=2[CH:3]=1.[CH2:19]1COC[CH2:20]1.C([Mg]Br)C.CC1C=CC(S(O)(=O)=O)=CC=1.N1C=CC=CC=1>C(Cl)Cl>[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([O:16][CH3:17])=[CH:9][CH:10]=3)[C:5](=[CH:19][CH3:20])[C:4]=2[CH:3]=1

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 161440Pyridine 4-methylbenzene-1-sulfonateHCID 574756332-Bromo-7-methoxy-9H-xanthen-9-oneHCID 178418443HCID 178418443, compound

Product 1

HCID 67240767HCID 67240767, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A 250 mL RBF was charged with 2-bromo-7-methoxy-9H-xanthen-9-one (10.20 g, 33.4 mmol) and 100 mL dry THF. The mixture was stirred for 10 min at RT and the resulting suspension was placed in an ice-methanol bath for another 10 min. Ethylmagnesium bromide, 1.0 M in THF (43.5 mL, 43.5 mmol) was added to the mixture dropwise. After 30 min, the mixture was carefully quenched with saturated aqueous ammonium chloride (100 mL) at 0° C. and diluted with EtOAc. The organic layer was washed with brine, dried with sodium sulfate, and concentrated in vacuo. The crude material was dissolved in 100 mL of chloroform, treated with pyridine 4-methylbenzenesulfonate (0.115 g, 0.669 mmol), and heated to reflux for 4 hr then 50° C. overnight. The mixture was cooled to RT, diluted with DCM, and washed with saturated sodium bicarbonate and brine. The organic fraction was dried over sodium sulfate and concentrated in vacuo. The residue was purified by silica gel chromatography using 5-40% Hexanes:EtOAc to afford 2-bromo-9-ethylidene-7-methoxy-9H-xanthene as a yellow oil, MH+=317.0/[email protected] min.

Workup

  1. waitthe resulting suspension was placed in an ice-methanol bath for another 10 min
  2. waitAfter 30 min
  3. customthe mixture was carefully quenched with saturated aqueous ammonium chloride (100 mL) at 0° C.
  4. additiondiluted with EtOAc
  5. washThe organic layer was washed with brine
  6. dry with materialdried with sodium sulfate
  7. concentrationconcentrated in vacuo
  8. dissolutionThe crude material was dissolved in 100 mL of chloroform
  9. temperatureheated
  10. temperatureto reflux for 4 hr
  11. custom50° C. overnight
  12. temperatureThe mixture was cooled to RT
  13. washwashed with saturated sodium bicarbonate and brine
  14. dry with materialThe organic fraction was dried over sodium sulfate
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-5d739f7bbd8546acbb7aa87fe9945ad3
Source dataset
uspto-grants-2013_04
Patent number
US08426447B2

Reaction notes

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