Acetic Acid → (R)-N-(4-Chloro-3-nitrobenzyl)-1-(3-chlorophenyl)ethanamine

HRID 1801573Notes

Reaction equation

HRID 1801573 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[Cl:13][C:14]1[CH:15]=[C:16]([C@H:20]([NH2:22])[CH3:21])[CH:17]=[CH:18][CH:19]=1.C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>ClCCCl>[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][NH:22][C@@H:20]([C:16]2[CH:17]=[CH:18][CH:19]=[C:14]([Cl:13])[CH:15]=2)[CH3:21])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 855054-Chloro-3-nitrobenzaldehydeHCID 2507697(R)-1-(3-chlorophenyl)ethanamineHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 24953403(R)-N-(4-Chloro-3-nitrobenzyl)-1-(3-chlorophenyl)ethanamineYield 87%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a solution of 4-chloro-3-nitrobenzaldehyde 1 (1.71 g, 9.2 mmol) and (R)-1-(3-chlorophenyl)ethanamine (1.115 g, 7.2 mmol) in DCE (15 mL) at room temperature was added acetic acid (2.0 mL, 35 mmol) and NaBH(OAc)3 (2.23 g, 11 mmol). The reaction mixture was stirred at room temperature for 2 d, quenched with saturated NaHCO3, and diluted with EtOAc. The organic phase was washed with NaHCO3 (1×), brine (1×), dried over MgSO4, filtered, and concentrated in vacuo. Purification by flash column chromatography on silica gel (eluted with 10% to 40% EtOAc in hexanes) gave (R)—N-(4-chloro-3-nitrobenzyl)-1-(3-chlorophenyl)ethanamine 30 (2.03 g, 87% yield) as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 1.37 (d, J=6.7 Hz, 3H), 3.66 (s, 2H), 3.77 (q, J=6.7 Hz, 1H), 7.18-7.32 (m, 5H), 7.44-7.48 (m, 2H), 7.83 (s, 1H). Mass spectrum: calculated for C15H14Cl2N2O2 324.0. found 325.1 (M++1).

Workup

  1. customquenched with saturated NaHCO3
  2. additiondiluted with EtOAc
  3. washThe organic phase was washed with NaHCO3 (1×), brine (1×)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash column chromatography on silica gel (eluted with 10% to 40% EtOAc in hexanes)

Sources & evidence

ORD record
ord-2204a5a9b845402e81d7f629c63d0427
Source dataset
uspto-grants-2013_01
Patent number
US08349831B2

Reaction notes

Loading…