Acetic Acid → N,N-Dimethyl-5-nitro-2-indanamine

HRID 1159976Notes

Reaction equation

HRID 1159976 reaction equation
Cl.[N+:2]([C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[CH2:10][CH:9](N)[CH2:8]2)([O-:4])=[O:3].C=O.[BH3-][C:18]#[N:19].[Na+].[C:21](O)(=O)C>ClCCCl>[CH3:21][N:19]([CH3:18])[CH:9]1[CH2:8][C:7]2[C:11](=[CH:12][CH:13]=[C:5]([N+:2]([O-:4])=[O:3])[CH:6]=2)[CH2:10]1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 223193245-Nitro-indan-2-ylamine hydrochloride

Product 1

HCID 25138868N,N-Dimethyl-5-nitro-2-indanamineYield 52%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

(5-Nitro-2,3-dihydro-1H-inden-2-yl)amine hydrochloride (5.52 g, 26 mmol), paraformaldehyde (4.1 g, 128 mmol), NaCNBH3 (8.1 g, 128 mmol), and acetic acid (7.4 mL, 128 mmol) were combined in 1,2-dichloroethane (200 mL) and the suspension was heated to reflux for 15 h. The reaction was cooled and quenched with saturated aqueous NaHCO3. The organic layer was separated, washed with brine dried with MgSO4 and concentrated to an oil. The crude material was purified by silica gel flash column chromatography (0-100% (90% DCM/9% MeOH/1% NH4OH)/DCM) and yielded 2.7 g (52%) of a yellow oil that crystallized while stored on the bench top. 1H NMR (400 MHz, CDCl3) δ 8.07 (m, 2H), 7.36 (d, J=8.1 Hz, 1H), 4.13 (m, 1H), 3.34 (m, 4H), 2.74 (s, 6H).

Workup

  1. temperaturethe suspension was heated
  2. temperatureto reflux for 15 h
  3. temperatureThe reaction was cooled
  4. customquenched with saturated aqueous NaHCO3
  5. customThe organic layer was separated
  6. washwashed with brine
  7. dry with materialdried with MgSO4
  8. concentrationconcentrated to an oil
  9. customThe crude material was purified by silica gel flash column chromatography (0-100% (90% DCM/9% MeOH/1% NH4OH)/DCM)

Sources & evidence

ORD record
ord-29d544bc67924cc7a6abc45482d45b5d
Source dataset
uspto-grants-2010_10
Patent number
US07812022B2

Reaction notes

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