Acetaldehyde → HCID 59262240, compound

HRID 644740Notes

Reaction equation

HRID 644740 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][N:9]2[CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C@@H:11]([CH3:22])[CH2:10]2)=[CH:4][CH:3]=1.[CH:23](=O)[CH3:24].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(N(CC)CC)C.C([O-])(O)=O.[Na+]>ClCCCl>[CH2:23]([NH:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][N:9]2[CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C@@H:11]([CH3:22])[CH2:10]2)=[CH:4][CH:3]=1)[CH3:24]

Participants

7

Reactant 5

HCID 177AcetaldehydeHCID 8471TriethylamineHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 592622171,1-Dimethylethyl (2S)-4-[(4-aminophenyl)methyl]-2-methyl-1-piperazinecarboxylate

Product 1

HCID 59262240HCID 59262240, compoundYield 71.7%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

1,1-dimethylethyl (2S)-4-[(4-aminophenyl)methyl]-2-methyl-1-piperazinecarboxylate (D2) (0.30 g, 1 mmol), acetaldehyde (0.055 mL, 1 mmol), sodium triacetoxyborohydride (0.417 g, 2 mmol) and triethylamine (0.151 mL, 1.1 mmol) were combined in dry 1,2-DCE (15 mL) and stirred under Ar at room temperature for 48 hours. Saturated NaHCO3 (15 mL) was added and reaction mixture stirred for a further 2 hours. The aqueous layer was then extracted with DCM (×3) and the combined organic layers were dried (Na2SO4) and concentrated in vacuo. The crude material was purified by column chromatography eluting with 0-100% ether/petroleum ether to give the title compound (0.239 g). δH (CDCl3, 400 MHz) 7.11 (2H, d), 6.56 (2H, dd), 4.16 (1H, br.s), 3.78 (1H, d), 3.51 (1H, br.s), 3.42 (1H, d), 3.29 (1H, d), 3.15 (2H, q), 3.08 (1H, td), 2.75 (1H, d), 2.59 (1H, d), 2.06 (1H, dd), 1.93 (1H, m), 1.45 (9H, s), 1.25 (3H, t), 1.21 (3H, d). MS (ES+): 234.2, no molecular ion (MH+) observed.

Workup

  1. customreaction mixture
  2. stirringstirred for a further 2 hours
  3. extractionThe aqueous layer was then extracted with DCM (×3)
  4. dry with materialthe combined organic layers were dried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customThe crude material was purified by column chromatography
  7. washeluting with 0-100% ether/petroleum ether

Sources & evidence

ORD record
ord-bda69ebd5c284678ab558d2f2136800a
Source dataset
uspto-grants-2010_04
Patent number
US07700599B2

Reaction notes

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