Carbon tetrabromide → tert-Butyl (2S)-2-(bromomethyl)morpholine-4-carboxylate

HRID 1864006Notes

Reaction equation

HRID 1864006 reaction equation
O[CH2:2][C@H:3]1[O:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:4]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@H:3]1[O:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:4]1

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 1512577tert-Butyl (2S)-2-(hydroxymethyl)morpholine-4-carboxylate

Product 1

HCID 69388802tert-Butyl (2S)-2-(bromomethyl)morpholine-4-carboxylateYield 55%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

1,1-Dimethylethyl (2S)-2-(hydroxymethyl)-4-morpholinecarboxylate (18.5 g, 0.080 mol) and carbon tetrabromide (34.5 g, 0.104 mol) were dissolved in methylene chloride (400 mL) and cooled in an ice bath. A solution of triphenylphosphine (22 g, 0.084 mol) in methylene chloride (150 ml) was added dropwise over 30 min. After 1 hr at 0° C., the reaction was allowed warm to room temp and was stirred overnight. The reaction volume was reduced by ½ in vacuo and poured onto a pad of silica gel and the product eluted with 15% ethyl acetate in hexane. The filtrate was concentrated in vacuo to afford the desired compound as an oil (12 g, 55%). MS (ES)+ m/e 281 [M+H]+.

Workup

  1. temperaturecooled in an ice bath
  2. additionpoured onto a pad of silica gel
  3. washthe product eluted with 15% ethyl acetate in hexane
  4. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-30262ed140f749d0944ff945b8fb32b4
Source dataset
uspto-grants-2009_12
Patent number
US07625890B2

Reaction notes

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