Hydrogen Bromide → Methyl 2-bromo-3-{4-[2-hydroxy-2-(5-methyl-2-phenyl-4-oxazolyl)ethoxy] phenyl}propionate

HRID 4404

Reaction equation

HRID 4404 reaction equation
[OH:1][CH:2]([C:12]1[N:13]=[C:14]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[O:15][C:16]=1[CH3:17])[CH2:3][O:4][C:5]1[CH:11]=[CH:10][C:8](N)=[CH:7][CH:6]=1.[BrH:24].N([O-])=O.[Na+].[C:29]([O:33][CH3:34])(=[O:32])[CH:30]=[CH2:31]>CO.CC(C)=O.O>[Br:24][CH:30]([CH2:31][C:8]1[CH:10]=[CH:11][C:5]([O:4][CH2:3][CH:2]([OH:1])[C:12]2[N:13]=[C:14]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[O:15][C:16]=2[CH3:17])=[CH:6][CH:7]=1)[C:29]([O:33][CH3:34])=[O:32]

Participants

8

Reactant 4

HCID 260Hydrogen BromideHCID 7294Methyl AcrylateHCID 150263484-[2-Hydroxy-2-(5-methyl-2-phenyl-4-oxazolyl)ethoxy]anilineHCID 23668193Sodium Nitrite

Product 1

HCID 54435832Methyl 2-bromo-3-{4-[2-hydroxy-2-(5-methyl-2-phenyl-4-oxazolyl)ethoxy] phenyl}propionate

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

4-[2-Hydroxy-2-(5-methyl-2-phenyl-4-oxazolyl)ethoxy]aniline (18.5 g) was dissolved in methanol (50 ml)-acetone (150 ml), and 47% aqueous HBr (41.0 g) was added to the solution. Then, a solution of NaNO2 (4.5 g) in water (10 ml) was added dropwise to the mixture at a temperature of not higher than 5° C. The whole was stirred at 5° C. for 15 minutes, and methyl acrylate (30.4 g) was added to the mixed solution, followed by warming at 38° C. Cuprous oxide (2.0 g) was added in small portions to the reaction solution with vigorous stirring, and stirring was continued until evolution of nitrogen gas stopped. After concentration, the residue was made basic with aqueous ammonia, and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried (MgSO4) concentrated to give methyl 2-bromo-3-{4-[2-hydroxy-2-(5-methyl-2-phenyl-4-oxazolyl)ethoxy] phenyl}propionate as a crude oily material (27.0 g, 98.5%). IR (Neat) cm-1 : 3300, 1735. NMR δ (ppm) in CDCl3 : 2.40(3H, s), 3.0(1H, broad), 3.11(1H, d.d, J=14 and 7 Hz), 3.39(1H, d.d, J=14 and 7 Hz), 3.68(3H, s), 4.0 to 4.5(3H, m), 5.05(1H, d.d, J=8 and 5 Hz), 6.0 to 7.2(4H, m), 7.4 (3H, m), 7.9(2H, m).

Workup

  1. additionwas added to the solution
  2. temperatureby warming at 38° C
  3. stirringstirring
  4. concentrationAfter concentration
  5. extractionextracted with ethyl acetate
  6. washThe ethyl acetate layer was washed with water
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-edc4b3f2acff4e9497253a46d41f09ff
Source dataset
uspto-grants-1988_02
Patent number
US04725610

Linked notes

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