Bromobenzene → Methyl 4-[2-(4-bromophenyl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate

HRID 30850Notes

Reaction equation

HRID 30850 reaction equation
Cl[C:2](=[O:14])[CH2:3][C:4]1([C:10]([O:12][CH3:13])=[O:11])[CH2:9][CH2:8][O:7][CH2:6][CH2:5]1.[Br:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[Cl-].[Al+3].[Cl-].[Cl-]>ClCCl>[Br:15][C:16]1[CH:21]=[CH:20][C:19]([C:2](=[O:14])[CH2:3][C:4]2([C:10]([O:12][CH3:13])=[O:11])[CH2:9][CH2:8][O:7][CH2:6][CH2:5]2)=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 7961BromobenzeneHCID 6451240Aluminum(III) ChlorideHCID 21985713methyl 4-(2-chloro-2-oxoethyl)tetrahydro-2H-pyran-4-carboxylate

Product 1

HCID 21985831Methyl 4-[2-(4-bromophenyl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylateYield 55%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Step 5 To a solution of methyl 4-(2-chloro-2-oxoethyl)tetrahydro-2H-pyran-4-carboxylate (1.06 g, 4.8 mmol) and bromobenzene (1.13 g, 7.21 mmol) in dichloromethane (20 mL) at 0° C. was added aluminum chloride (1.92 g, 14.4 mmol). The ice-water bath was removed and the reaction mixture was stirred at rt for 16 h. The mixture was then cooled at 0° C. and quenched by the addition of 1 N HCl solution and water. The mixture was extracted with dichloromethane, and the combined organic phases were dried over sodium sulfate. The crude material was then purified by flash chromatography (Biotage Flash 40 M, 2:1 hexane/ethyl acetate, to afford methyl 4-[2-(4-bromo-phenyl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate (900 mg, 55%). LC-MS ret. time 2.76 min; m/z 342.9 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.58-1.69 (m, 2H), 2.12-2.18 (m, 2H), 3.28 (s, 2H), 3.64 (s, 3H), 3.69-3.77 (m, 4H), 7.59 (d, 2H), 7.77 (d, 2H).

Workup

  1. customThe ice-water bath was removed
  2. temperatureThe mixture was then cooled at 0° C.
  3. customquenched by the addition of 1 N HCl solution and water
  4. extractionThe mixture was extracted with dichloromethane
  5. dry with materialthe combined organic phases were dried over sodium sulfate
  6. customThe crude material was then purified by flash chromatography (Biotage Flash 40 M, 2:1 hexane/ethyl acetate

Sources & evidence

ORD record
ord-d527912d91024514961c0daf5e7d19af
Source dataset
uspto-grants-2008_09
Patent number
US07423156B2

Reaction notes

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