Carbon tetrabromide → Ethyl 2-[4-(bromomethyl)phenoxy]acetate

HRID 1459434Notes

Reaction equation

HRID 1459434 reaction equation
O[CH2:2][C:3]1[CH:15]=[CH:14][C:6]([O:7][CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:5][CH:4]=1.C(Br)(Br)(Br)[Br:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[Br:17][CH2:2][C:3]1[CH:15]=[CH:14][C:6]([O:7][CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 11413157Acetic acid, [4-(hydroxymethyl)phenoxy]-, ethyl ester

Product 1

HCID 12870369Ethyl 2-[4-(bromomethyl)phenoxy]acetateYield 74.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a 1 L round bottomed flask with a stirring bar, addition funnel and an argon inlet was added ethyl 2-(4-hydroxymethylphenoxy)acetate 35-4 (7.47 g, 35.53 mmol), CBr4 (13.26 g, 39.97 mmol) and dry CH2Cl2 (300 mL). This solution was cooled in an ice bath and and a solution of triphenyl phosphine (10.48 g, 39.97 mmol) in CH2Cl2 (100 mL) was added dropwise over 1 h. The ice bath was allowed to expire and and the mixture was stirred at ambient temperature 18 h. The solvent was removed in vacuo and the residue was chromatographed directly on 200 g of silica gel useing 15% EtOAc-hexane as eluant. There was obtained ethyl 2-(4-bromomethylphenoxy)acetate 35-5 (7.2 g, 74%) as a low melting solid, mp.: 44°-45° C. 1H NMR (CDCl3): δ 1.29 (t, J=7 Hz, 3H), 4.26 (q, J=7 Hz, 2H), 4.48 (s, 2H), 4.61 (s, 2H), 6.86 (d, J=9 Hz, 2H), 7.32 (d, J=9HZ, 2H).

Workup

  1. additionTo a 1 L round bottomed flask with a stirring bar, addition funnel and an argon inlet
  2. temperatureThis solution was cooled in an ice bath
  3. customThe solvent was removed in vacuo
  4. customthe residue was chromatographed directly on 200 g of silica gel useing 15% EtOAc-hexane as eluant

Sources & evidence

ORD record
ord-0e09a5f283984d4ab65d8843efe6c82e
Source dataset
uspto-grants-1998_12
Patent number
US05854245

Reaction notes

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