Dichloromethane → HCID 67367535, compound

HRID 714508Notes

Reaction equation

HRID 714508 reaction equation
C[O:2][C:3]1[CH:8]=[C:7]([O:9]C)[CH:6]=[CH:5][C:4]=1[C:11](=[O:23])[CH2:12][C:13]1[CH:22]=[CH:21][C:16]([C:17]([O:19][CH3:20])=[O:18])=[CH:15][CH:14]=1.B(Br)(Br)Br.[CH2:28](Cl)Cl>>[OH:2][C:3]1[CH:8]=[C:7]([OH:9])[CH:6]=[CH:5][C:4]=1[C:11](=[O:23])[CH2:12][C:13]1[CH:22]=[CH:21][C:16]([C:17]([O:19][CH2:20][CH3:28])=[O:18])=[CH:15][CH:14]=1

Participants

4

Reactant 3

HCID 6344DichloromethaneHCID 25134Boron tribromideHCID 67366210HCID 67366210, compound

Product 1

HCID 67367535HCID 67367535, compoundYield 58%

Procedure

To a solution of methyl 4-(2-(2,4-dimethoxyphenyl)-2-oxoethyl)benzoate (55 g, 141.6 mmol) in DCM (600 ml) was added dropwise BBr3 (164 ml, 1.7 mol) at −10° C. When the addition was complete, the mixture was stirred at room temperature overnight and poured into crashed ice (700 g) with stirring. The volatiles were evaporated to afford a yellow solid, which was dried in high vacuo and dissolved in absolute ethanol (500 ml). To the solution was added dropwise thionyl chloride (80 ml) at 0˜10° C. When the addition was complete, the resultant mixture was heated to reflux for 3 hours. The volatiles were evaporated and the residue was partitioned between EtOAc (600 ml) and saturated sodium carbonate (200 ml). The organic phase was separated, washed with brine (200 ml), dried with anhydrous sodium sulfate, filtered and concentrated to afford brown slurry, which was purified by column chromatography (PE/EtOAc=3/1) to afford product (24.5 g, 58%) as a yellow solid. 1H NMR (CDCl3 500 MHz TMS): δ 12.58 (s, 1H), 8.01 (d, J=8.5 Hz, 2H), 7.69 (d, J=9.0 Hz, 1H), 7.33 (d, J=8.0 Hz, 2H), 7.05 (brs, 1H), 6.41 (d, J=8.0 Hz, 1H), 6.37 (s, 1H), 4.38 (q, J=7.0 Hz, 2H), 4.26 (s, 2H), 1.38 (t, J=7 Hz, 3H). MS (ESI): m/z 301.1 [M+1]+.

Workup

  1. additionWhen the addition
  2. additionpoured
  3. stirringwith stirring
  4. customThe volatiles were evaporated
  5. customto afford a yellow solid, which
  6. customwas dried in high vacuo
  7. dissolutiondissolved in absolute ethanol (500 ml)
  8. additionTo the solution was added dropwise thionyl chloride (80 ml) at 0˜10° C
  9. additionWhen the addition
  10. temperaturethe resultant mixture was heated
  11. temperatureto reflux for 3 hours
  12. customThe volatiles were evaporated
  13. customthe residue was partitioned between EtOAc (600 ml) and saturated sodium carbonate (200 ml)
  14. customThe organic phase was separated
  15. washwashed with brine (200 ml)
  16. dry with materialdried with anhydrous sodium sulfate
  17. filtrationfiltered
  18. concentrationconcentrated
  19. customto afford brown slurry, which
  20. customwas purified by column chromatography (PE/EtOAc=3/1)

Sources & evidence

ORD record
ord-3747bc8411534d2e9487dd327999e1fb
Source dataset
uspto-grants-2015_11
Patent number
US09187447B2

Reaction notes

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