Triphenylphosphine → Methyl 3-bromo-5-(bromomethyl)benzoate

HRID 391435Notes

Reaction equation

HRID 391435 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([CH2:12]O)[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:33]N1C(=O)CCC1=O>O1CCCC1.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([CH2:12][Br:33])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 67184N-bromobutanimideHCID 11356988Methyl 3-bromo-5-(hydroxymethyl)benzoate

Product 1

HCID 58993494Methyl 3-bromo-5-(bromomethyl)benzoate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Methyl 3-bromo-5-(hydroxymethyl)benzoate (2.0 g, 8.2 mmol) and triphenylphosphine (4.28 g, 16.3 mmol) were combined in tetrahydrofuran (20 mL) and cooled to 0° C. N-Bromosuccinimide (3.05 g, 17.1 mmol) was introduced in portions and the reaction allowed to warm to room temperature. After 16 h, the reaction mixture was diluted with ethyl acetate, washed with concentrated sodium bicarbonate (2×), then brine (2×), dried over sodium sulfate, and concentrated. Column chromatography on silica gel (10% ethylacete/hexanes) gave 2.1 g (83%) as a light brown oil. 1H-NMR (CDCl3, 300 MHz) δ 8.07 (s, 1H), 7.96 (s, 1H), 7.70 (s, 1H), 4.42 (s, 2H), 3.90 (s, 3H). Mass spec.: 308.93 (MH)+.

Workup

  1. temperatureto warm to room temperature
  2. washwashed with concentrated sodium bicarbonate (2×)
  3. dry with materialbrine (2×), dried over sodium sulfate
  4. concentrationconcentrated
  5. customColumn chromatography on silica gel (10% ethylacete/hexanes) gave 2.1 g (83%) as a light brown oil

Sources & evidence

ORD record
ord-750b1855582a4a9eb97de14f3654e90c
Source dataset
uspto-grants-2013_02
Patent number
US08383821B2

Reaction notes

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