Cesium carbonate → Di-tert-butyl N-3-butenyliminodicarboxylate

HRID 37776Notes

Reaction equation

HRID 37776 reaction equation
[CH3:1][C:2]([O:5][C:6]([NH:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[O:7])([CH3:4])[CH3:3].C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:23][CH2:24][CH:25]=[CH2:26]>CC(=O)CC.[I-].[Li+]>[CH2:26]([N:8]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[C:6]([O:5][C:2]([CH3:1])([CH3:3])[CH3:4])=[O:7])[CH2:25][CH:24]=[CH2:23]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 21241Homoallyl bromideHCID 279800Di-tert-butyl Iminodicarboxylate

Product 1

HCID 12186469Di-tert-butyl N-3-butenyliminodicarboxylateYield 93%

Reagents, catalysts & solvents 2

HCID 66321Lithium iodideCatalystHCID 6569Methyl Ethyl KetoneSolvent

Procedure

To a solution of di-tert-butyliminodicarboxylate (868 mg, 4 mmol), cesium carbonate (2.61 g, 8 mmol), and lithium iodide (28 mg, 0.2 mmol) in 2-butanone (20 mL) was added 4-bromobutene (812 mg, 6 mmol) and the mixture was heated at reflux for 48 h. The reaction was allowed to cool and was quenched with brine (40 mL) and extracted with diethyl ether (3×20 mL). The combined organic fractions were washed with brine (30 mL), dried, and evaporated to yield the title compound (1.01 g, 3.7 mmol, 93%) as a light brown oil. 1H NMR (CDCl3, 300 MHz): δ 5.77 (m, 1H, H3); 5.04 (m, 2H, H4); 3.62 (dd, J=6.0, 8.7 Hz, 2H, H1); 2.30 (m, 2H, H2); 1.51 (s, 18H, 2×(CH3)3). Mass Spectrum (ES, +ve) m/z 310 (55%) [MK+]1, 294 (30%) [MNa+], 272 (40%) [MH+]. HRMS calcd for C14H26NO4 272.1862, found 272.1848.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 48 h
  3. temperatureto cool
  4. customwas quenched with brine (40 mL)
  5. extractionextracted with diethyl ether (3×20 mL)
  6. washThe combined organic fractions were washed with brine (30 mL)
  7. customdried
  8. customevaporated

Sources & evidence

ORD record
ord-bc28d4d86cdc405780710f5621499f1e
Source dataset
uspto-grants-2013_09
Patent number
US08524657B2

Reaction notes

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