tert-Butoxy bis(dimethylamino)methane → tert-butyl 3-[(dimethylamino)methylene]-4-oxotetrahydro-1(2H)-pyridinecarboxylate

HRID 394519Notes

Reaction equation

HRID 394519 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(O[CH:20](N(C)C)[N:21]([CH3:23])[CH3:22])(C)(C)C>CN(C)C=O.O>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH2:10][C:11](=[O:14])[C:12](=[CH:20][N:21]([CH3:23])[CH3:22])[CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 2

HCID 79885tert-Butoxy bis(dimethylamino)methaneHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 53395404tert-butyl 3-[(dimethylamino)methylene]-4-oxotetrahydro-1(2H)-pyridinecarboxylateYield 72%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-oxo-piperidine-1-carboxylic acid tert-butyl ester (prepared according to the method of Example 101, Step A, 4.0 g, 20.0 mmol) in dimethylformamide (40 mL) was added tert-butoxybis(dimethylamino)methane (4.35 mL, 22 mmol). This mixture was stirred at reflux for 15 h, cooled to room temperature, diluted with water, and extracted with ethyl acetate (5×). The combined organic extracts were washed with water (3×) and brine (1×), dried over sodium sulfate, filtered, and evaporated to give 3.64 g (72%) of the title compound of Example 101, Step B as a brown oil that was sufficiently pure to carry on to the next step. 1H NMR (CDCl3, 400 MHz) δ 7.47 (s, 1H), 4.53 (s, 2H), 3.58 (t, 2H), 3.09 (s, 6H), 2.43 (t, 2H), 1.46 (s, 9H); MS (APCI) 255 (MH+).

Workup

  1. temperatureat reflux for 15 h
  2. extractionextracted with ethyl acetate (5×)
  3. washThe combined organic extracts were washed with water (3×) and brine (1×)
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated

Sources & evidence

ORD record
ord-49240ca3960b4a1b8b76d8a88078c707
Source dataset
uspto-grants-2003_08
Patent number
US06602875B2

Reaction notes

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