Ethyl Acetate → 1-Naphthalenecarboxylic acid, 4-(bromomethyl)-, methyl ester

HRID 1950719Notes

Reaction equation

HRID 1950719 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]([CH3:15])=[CH:7][CH:6]=1)=[O:4].[Br:16]NC(=O)CCC(N)=O.CCOC(C)=O>C(Cl)(Cl)(Cl)Cl.CCCCCC.CC(N=NC(C#N)(C)C)(C#N)C>[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]([CH2:15][Br:16])=[CH:7][CH:6]=1)=[O:4]

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 9834204N-BromosuccinamideHCID 21973653Methyl 4-methylnaphthalene-1-carboxylate

Product 1

HCID 103338131-Naphthalenecarboxylic acid, 4-(bromomethyl)-, methyl esterYield 69.4%

Reagents, catalysts & solvents 3

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolventHCID 8058HexaneSolvent

Procedure

To a stirred solution of 4-methyl-naphthalene-1-carboxylic acid methyl ester (Preparation 50, 10.85 g, 54.18 mmol) in CCl4 (500 mL) was added N-bromosuccinamide (9.93 gm, 55.81 mmol) followed by AIBN (0.1 g, 0.612 mmol) at room temperature. Resulting reaction mixture was refluxed for 3 hours. Progress of reaction was monitored by TLC using 5% EtOAc in hexane. Rf of new spot and starting material was 0.8 and 0.7 respectively. After consumption of starting material, reaction mixture was concentrated in vacuo to residue. Residue was dissolved in EtOAc (300 mL) and washed with water (2×300 mL), brine (300 mL), dried over sodium sulphate and evaporated in vacuo to get pale yellow semisolid. Crude was purified by column chromatography using 100-200 mesh silica gel. Desired product was eluted in 4% EtOAc in hexane to afford white solid (10.5 g, 69.39%). 1H NMR (400 MHz, CDCl3) δ: 4.00 (s, 3H), 4.93 (s, 2H), 7.56 (d, J=7.48 Hz, 1H), 7.62-7.68 (m, 2H), 8.06 (d, J=7.4 Hz, 1H), 8.17-8.20 (m, 1H), 8.90-8.93 (m, 1H).

Workup

  1. customResulting
  2. customreaction mixture
  3. temperaturewas refluxed for 3 hours
  4. customProgress of reaction
  5. customAfter consumption of starting material, reaction mixture
  6. concentrationwas concentrated in vacuo to residue
  7. dissolutionResidue was dissolved in EtOAc (300 mL)
  8. washwashed with water (2×300 mL), brine (300 mL)
  9. dry with materialdried over sodium sulphate
  10. customevaporated in vacuo
  11. customto get pale yellow semisolid
  12. customCrude was purified by column chromatography
  13. washDesired product was eluted in 4% EtOAc in hexane

Sources & evidence

ORD record
ord-f23be8481b0f4fb2b547ecd3f9732f87
Source dataset
uspto-grants-2013_03
Patent number
US08404649B2

Reaction notes

Loading…