Ammonium Hydroxide → Ethyl 2-amino-2-methyl-4-oxo-4-p-tolylbutanoate

HRID 1629785Notes

Reaction equation

HRID 1629785 reaction equation
[CH3:1]/[C:2](=[CH:8]\[C:9](=[O:17])[C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=1)/[C:3]([O:5][CH2:6][CH3:7])=[O:4].[NH4+:18].[OH-]>CS(C)=O.CCOC(C)=O>[NH2:18][C:2]([CH3:1])([CH2:8][C:9](=[O:17])[C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=1)[C:3]([O:5][CH2:6][CH3:7])=[O:4]

Participants

5

Reactant 2

HCID 14923Ammonium HydroxideHCID 86685877(E)-Ethyl 2-methyl-4-oxo-4-p-tolylbut-2-enoate

Product 1

HCID 86685876Ethyl 2-amino-2-methyl-4-oxo-4-p-tolylbutanoateYield 55.2%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of Intermediate 102A (1.067 g, 4.59 mmol) in DMSO (20 mL) under argon was added NH4OH (18.04 mL, 271 mmol) and the reaction mixture was stirred at rt overnight. The reaction mixture was diluted with EtOAc (75 mL) and washed sequentially with water (40 mL) and brine (20 mL). The organic phase was dried over MgSO4 and concentrated in vacuo to give a yellow oil. The oil was purified by silica gel chromatography (120 g silica gel) to provide the desired product (0.632 g, 55%) as a clear oil. LCMS Anal. Calc'd for C14H19NO3 249.14, found [M+H] 250.1. 1H NMR (500 MHz, CDCl3) δ 7.83 (d, J=8.25 Hz, 2H), 7.24 (d, J=7.98 Hz, 2H), 4.14 (dd, J=7.15, 2.75 Hz, 2H), 3.65 (d, J=17.61 Hz, 1H), 3.20 (d, J=17.61 Hz, 1H), 2.40 (s, 3H), 2.18-2.27 (m, 2H), 1.39 (s, 3H), 1.19 (t, J=7.01 Hz, 3H).

Workup

  1. washwashed sequentially with water (40 mL) and brine (20 mL)
  2. dry with materialThe organic phase was dried over MgSO4
  3. concentrationconcentrated in vacuo
  4. customto give a yellow oil
  5. customThe oil was purified by silica gel chromatography (120 g silica gel)

Sources & evidence

ORD record
ord-83a9b17334c149558e2297885d4429fc
Source dataset
uspto-grants-2014_07
Patent number
US08791091B2

Reaction notes

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