4-Chlorobenzaldehyde → tert-Butyl (2-((4-chlorobenzyl)amino)ethyl)carbamate

HRID 1192414Notes

Reaction equation

HRID 1192414 reaction equation
[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][NH2:10])([CH3:4])([CH3:3])[CH3:2].[Cl:12][C:13]1[CH:20]=[CH:19][C:16]([CH:17]=O)=[CH:15][CH:14]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl>[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][NH:10][CH2:17][C:16]1[CH:19]=[CH:20][C:13]([Cl:12])=[CH:14][CH:15]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 77264-ChlorobenzaldehydeHCID 187201N-BOC-ethylenediamineHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 67134877tert-Butyl (2-((4-chlorobenzyl)amino)ethyl)carbamateYield 61%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

The (2-amino-ethyl)-carbamic acid tert-butyl ester (5.00 g, 31.2 mmol) and 4-chloro-benzaldehyde (4.61 g, 32.77 mmol) were dissolved in 60 mL of 1,2-dichloroethane at room temperature. The reaction mixture was allowed to stir for 40 minutes prior to treatment with sodium triacetoxyborohydride (9.90 g, 46.8 mmol). The mixture was allowed to stir overnight to completion and quenched with a saturated NaHCO3 solution. The aqueous was extracted with DCM, separated, dried over MgSO4, and concentrated in vacuo. The residue was purified by chromatography (silica gel eluted with hexanes/EtOAc plus 2% triethyl amine) to afford the pure [2-(4-chlorobenzylamino)-ethyl]-carbamic acid tert-butyl ester as a viscous yellow oil (5.38 g, 61%). 1H NMR (CDCl3, 400 MHz) δ 7.29 (d, J=8.0 Hz, 2H), 7.25 (d, J=8.0 Hz, 2H), 4.92 (brs, 1H), 3.75 (s, 2H), 3.23 (appd, J=5.6 Hz, 2H), 2.73 (appt, J=6.0 Hz, 2H), 1.44 (s, 9H), 1.36 (brs, 1H). LCMS (APCI+) m/z 285 [M+H]+; Rt=2.30 min.

Workup

  1. stirringto stir overnight to completion
  2. customquenched with a saturated NaHCO3 solution
  3. extractionThe aqueous was extracted with DCM
  4. customseparated
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by chromatography (silica gel eluted with hexanes/EtOAc plus 2% triethyl amine)

Sources & evidence

ORD record
ord-aeb0b06f393049d4b1832de79f20fec2
Source dataset
uspto-grants-2014_03
Patent number
US08680114B2

Reaction notes

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