Toluene → Tert-butyl 4-(3-(4-amino-5-chloro-2-methylphenoxy)propyl)piperazine-1-carboxylate

HRID 415066Notes

Reaction equation

HRID 415066 reaction equation
[Cl:1][C:2]1[C:3]([N+:26]([O-])=O)=[CH:4][C:5]([CH3:25])=[C:6]([CH:24]=1)[O:7][CH2:8][CH2:9][CH2:10][N:11]1[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]1.C([O-])=O.[NH4+].C1(C)C=CC=CC=1>[Fe].O>[NH2:26][C:3]1[C:2]([Cl:1])=[CH:24][C:6]([O:7][CH2:8][CH2:9][CH2:10][N:11]2[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:21])[CH3:22])=[O:18])[CH2:13][CH2:12]2)=[C:5]([CH3:25])[CH:4]=1

Participants

6

Reactant 3

HCID 1140TolueneHCID 2723923Ammonium formateHCID 59349539Tert-butyl 4-(3-(5-chloro-2-methyl-4-nitrophenoxy)propyl)piperazine-1-carboxylate

Product 1

HCID 59349545Tert-butyl 4-(3-(4-amino-5-chloro-2-methylphenoxy)propyl)piperazine-1-carboxylateYield 89%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Procedure

A flask was charged with tert-butyl 4-(3-(5-chloro-2-methyl-4-nitrophenoxy)propyl)-piperazine-1-carboxylate (1.2 g, 2.9 mmol), ammonium formate (0.84 g, 13 mmol), and iron powder (0.74 g, 13 mmol). Toluene (20 mL) and water (20 mL) were added to the flask and the mixture was heated to reflux for 6 hours, after which time, the mixture was filtered through a plug of Celite. The supernatant was extracted with ethyl acetate and water. The organic solvent was removed on a rotary evaporator under reduced pressure to yield tert-butyl 4-(3-(4-amino-5-chloro-2-methylphenoxy)propyl)piperazine-1-carboxylate as a brown oil (0.99 g, 89% yield). 1H-NMR (400 MHz, DMSO-d6): δ 6.77 (s, 1H), 6.61 (s, 1H), 4.76 (s, 2H), 3.86 (t, 6.1 Hz, 2H), 3.30 (s, br, 4H), 2.50 (m, 2H), 2.31 (m, 2H), 2.03 (s, 3H), 1.82 (m, 2H), 1.39 (s, 9H). MS (EI): 384 (MH+).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 6 hours
  3. filtrationafter which time, the mixture was filtered through a plug of Celite
  4. extractionThe supernatant was extracted with ethyl acetate and water
  5. customThe organic solvent was removed on a rotary evaporator under reduced pressure

Sources & evidence

ORD record
ord-c74f2c53dd3f4283aa304b5c9a8fb654
Source dataset
uspto-grants-2012_01
Patent number
US08088767B2

Reaction notes

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