Diisopropylethylamine → Tert-butyl 4-(3-(2-methyl-1-phenylpropylamino)-4-nitrophenyl)piperazine-1-carboxylate

HRID 1910554Notes

Reaction equation

HRID 1910554 reaction equation
F[C:2]1[CH:3]=[CH:4][C:5]([N+:19]([O-:21])=[O:20])=[C:6]([NH:8][CH:9]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:10]([CH3:12])[CH3:11])[CH:7]=1.[C:22]([N:29]1[CH2:34][CH2:33][NH:32][CH2:31][CH2:30]1)([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23].C(N(CC)C(C)C)(C)C>C(#N)C>[CH3:11][CH:10]([CH3:12])[CH:9]([NH:8][C:6]1[CH:7]=[C:2]([N:32]2[CH2:31][CH2:30][N:29]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:34][CH2:33]2)[CH:3]=[CH:4][C:5]=1[N+:19]([O-:21])=[O:20])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 143452tert-Butyl piperazine-1-carboxylateHCID 587072515-Fluoro-n-(2-methyl-1-phenylpropyl)-2-nitrobenzenamine

Product 1

HCID 58707253Tert-butyl 4-(3-(2-methyl-1-phenylpropylamino)-4-nitrophenyl)piperazine-1-carboxylateYield 86.9%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of 5-fluoro-N-(2-methyl-1-phenylpropyl)-2-nitrobenzenamine (1.79 g, 6.2 mmol), N-Boc-piperazine (1.16 g, 6.2 mmol) and N,N-diisopropylethylamine (2.2 mL, 12.4 mmol) in acetonitrile was stirred at reflux for 24 h. The reaction mixture was cooled down and concentrated under reduced pressure. The residue was taken up in dichloromethane, washed with water, dried and concentrated in vacuo to yield 2.45 g of the crude aniline. The crude product was purified by PTLC (15% ethyl acetate in hexanes) to yield 1.75 g (62%) of tert-butyl 4-(3-(2-methyl-1-phenylpropylamino)-4-nitrophenyl)piperazine-1-carboxylate: 1H NMR (400 MHz, CD3OD): δ 9.01 (br d, 1H), 7.96 (dd, 1H), 7.33-7.32 (m, 4H), 7.25-7.24 (m, 1H), 6.27 (br d, 1H), 5.72 (s, 1H), 4.40 (t, 1H), 3.42-3.34 (m, 4H), 3.27-3.23 (m, 2H), 3.16-3.11 (m, 2H), 2.13 (m, 1H), 1.07 (d, 3H), 0.96 (d, 3H). MS (ESI) m/z: Calculated: 454.26; Observed: 477.3 (M++Na).

Workup

  1. temperatureat reflux for 24 h
  2. temperatureThe reaction mixture was cooled down
  3. concentrationconcentrated under reduced pressure
  4. washwashed with water
  5. customdried
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-09a6a796942b403dab633768d0169701
Source dataset
uspto-grants-2013_12
Patent number
US08604021B2

Reaction notes

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