Tert-Butylamine → Methyl 1-tert-butyl-2-azetidinecarboxylate

HRID 1449326Notes

Reaction equation

HRID 1449326 reaction equation
Br[CH:2]([CH2:7][CH2:8]Br)[C:3]([O:5][CH3:6])=[O:4].[C:10]([NH2:14])([CH3:13])([CH3:12])[CH3:11]>C(#N)C>[C:10]([N:14]1[CH2:8][CH2:7][CH:2]1[C:3]([O:5][CH3:6])=[O:4])([CH3:13])([CH3:12])[CH3:11]

Participants

4

Reactant 2

HCID 6385Tert-ButylamineHCID 296716Methyl 2,4-dibromobutanoate

Product 1

HCID 419968Methyl 1-tert-butyl-2-azetidinecarboxylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

The procedure of Cromwell described in J. Heterocyclic Chem. 6: 435 (1969) and 5: 309 (1968) was followed for the preparation of this ester. To a 200 ml round bottom flask was added 5.20 g (0.02 mol) methyl 2,4-dibromobutyrate, 80 ml acetonitrile and 4.69 g (0.06 mol) of t-butylamine. After stirring at room temperature for 5 minutes, heat was applied and the temperature raised to and maintained at reflux for 24 hours. The yellowish mixture was cooled to room temperature and filtered. The filtrate was concentrated in vacuo, giving a yellow liquid to which dry ether was added. The pot was vigorously shaken and the ether solution decanted. This was repeated three times. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to give a pale yellow liquid. Kugelrohr distillation at 65° (1.8 mm) afforded 2.3 g (70%) of a water-white liquid: IR (liquid film) cm-1 1750, 1725, 1275, 1230, 1200, 1175, 1130, 1060; NMR (CDCl3) delta 3.70 (3H, s), 3.93 (1H, t, J=8 Hz), 3.15 (2H, m), 2.13 (2H, m), 0.93 (9H, s).

Workup

  1. temperatureheat
  2. temperaturethe temperature raised to and
  3. temperaturemaintained
  4. temperatureat reflux for 24 hours
  5. temperatureThe yellowish mixture was cooled to room temperature
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated in vacuo
  8. customgiving a yellow liquid to which dry ether
  9. additionwas added
  10. stirringThe pot was vigorously shaken
  11. customthe ether solution decanted
  12. dry with materialThe combined extracts were dried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. customrotary evaporated
  15. customto give a pale yellow liquid
  16. distillationKugelrohr distillation at 65° (1.8 mm)
  17. customafforded 2.3 g (70%) of a water-white liquid

Sources & evidence

ORD record
ord-8ae606ec34b847848388d5b65198002d
Source dataset
uspto-grants-1980_02
Patent number
US04190579

Reaction notes

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