4-Methylmorpholine → 1,1-Dimethylethyl N-[1,1-dimethyl-2-(methylamino)-2-oxoethyl]carbamate

HRID 1867767Notes

Reaction equation

HRID 1867767 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]([CH3:14])([C:11](O)=[O:12])[CH3:10])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:15][N:16]1CCOCC1.C(OC(Cl)=O)C(C)C>C1COCC1>[C:1]([O:5][C:6]([NH:8][C:9]([CH3:14])([C:11]([NH:16][CH3:15])=[O:12])[CH3:10])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 79724-MethylmorpholineHCID 62365Isobutyl chloroformateHCID 2733845N-((1,1-dimethylethoxy)carbonyl)-2-methyl-alanine

Product 1

HCID 474517541,1-Dimethylethyl N-[1,1-dimethyl-2-(methylamino)-2-oxoethyl]carbamateYield 42.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

N-(tert-butoxycarbonyl)-2-methylalanine (2.87 g, 14.13 mmol) was dissolved in THF (20 ml) and cooled to −10° C. (acetone/ice). N-methylmorpholine (2.14 g, 21.2 mmol) was added followed by iso-butylchloroformate (2.12 g, 15.5 mmol, 1.1 equivalents) over a period of 3 minutes. The reaction mixture was allowed to stir for 10 minutes, split in two equal halves (approximately 12 ml each). One sample was treated with methylamine in THF (5 ml of 2.0M solution) and the resulting mixture was evaporated to dryness. The residues were re-dissolved in dichloromethane (30 ml), washed with water, saturated aqueous sodium hydrogen carbonate, water, dried over magnesium sulfate and evaporated to dryness to give N2-(tert-butoxycarbonyl)-N1,2-dimethylalaninamide (0.67 g, 42.6%), which was used without further purification, 1H NMR Spectrum: (DMSO-d6) 1.29 (s, 6H), 1.37 (s, 9H), 2.50 (s, 3H), 6.57 (br s, 1H), 6.93 (br s, 1H)

Workup

  1. customsplit in two equal halves (approximately 12 ml each)
  2. additionOne sample was treated with methylamine in THF (5 ml of 2.0M solution)
  3. customthe resulting mixture was evaporated to dryness
  4. dissolutionThe residues were re-dissolved in dichloromethane (30 ml)
  5. washwashed with water, saturated aqueous sodium hydrogen carbonate, water
  6. dry with materialdried over magnesium sulfate
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-9e6a431dfa874bad9b13db3e75d6a929
Source dataset
uspto-grants-2009_12
Patent number
US07632840B2

Reaction notes

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