tert-Butyl 7-nitro-3,4-dihydroisoquinoline-2(1H)-carboxylate → tert-Butyl 7-amino-3,4-dihydroisoquinoline-2(1H)-carboxylate

HRID 423891Notes

Reaction equation

HRID 423891 reaction equation
[N+:1]([C:4]1[CH:13]=[C:12]2[C:7]([CH2:8][CH2:9][N:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:11]2)=[CH:6][CH:5]=1)([O-])=O>CO.[OH-].[OH-].[Pd+2]>[NH2:1][C:4]1[CH:13]=[C:12]2[C:7]([CH2:8][CH2:9][N:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:11]2)=[CH:6][CH:5]=1

Participants

4

Reactant 1

HCID 6420695tert-Butyl 7-nitro-3,4-dihydroisoquinoline-2(1H)-carboxylate

Product 1

HCID 22061016tert-Butyl 7-amino-3,4-dihydroisoquinoline-2(1H)-carboxylateYield 69%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent

Procedure

Pd(OH)2 (330.0 mg) was added to a stirring solution of tert-butyl 3,4-dihydro-7-nitroisoquinoline-2(1H)-carboxylate (3.3 g, 12.0 mmol) in MeOH (56 mL) under N2 atmosphere. The reaction mixture was stirred under H2 (1 atm) at room temperature for 72 h. The solid was removed by filtration through Celite. The filtrate was concentrated and purified by column chromatography (15-35% EtOAc-Hexanes) to provide tert-butyl 7-amino-3,4-dihydroisoquinoline-2(1H)-carboxylate (DC-6) as a pink oil (2.0 g, 69%). 1H NMR (400 MHz, DMSO-d6) δ 6.79 (d, J=8.1 Hz, 1H), 6.40 (dd, J=8.1, 2.3 Hz, 1H), 6.31 (s, 1H), 4.88 (s, 2H), 4.33 (s, 2H), 3.48 (t, J=5.9 Hz, 2H), 2.58 (t, J=5.9 Hz, 2H), 1.42 (s, 9H); HPLC ret. time 2.13 min, 10-99% CH3CN, 5 min run; ESI-MS 249.0 m/z (MH+).

Workup

  1. customThe solid was removed by filtration through Celite
  2. concentrationThe filtrate was concentrated
  3. custompurified by column chromatography (15-35% EtOAc-Hexanes)

Sources & evidence

ORD record
ord-f8a8e28f37bc4b18b529e408faaef1d0
Source dataset
uspto-grants-2012_01
Patent number
US08101767B2

Reaction notes

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