2,4-Di-tert-butyl-5-nitrophenyl methyl carbonate → Carbonic acid, 5-amino-2,4-bis(1,1-dimethylethyl)phenyl methyl este

HRID 1261788Notes

Reaction equation

HRID 1261788 reaction equation
[C:1](=[O:22])([O:20][CH3:21])[O:2][C:3]1[CH:8]=[C:7]([N+:9]([O-])=O)[C:6]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:5][C:4]=1[C:16]([CH3:19])([CH3:18])[CH3:17]>[Pd].CO>[C:1](=[O:22])([O:20][CH3:21])[O:2][C:3]1[CH:8]=[C:7]([NH2:9])[C:6]([C:12]([CH3:13])([CH3:14])[CH3:15])=[CH:5][C:4]=1[C:16]([CH3:19])([CH3:18])[CH3:17]

Participants

4

Reactant 1

HCID 532497902,4-Di-tert-butyl-5-nitrophenyl methyl carbonate

Product 1

HCID 46927778Carbonic acid, 5-amino-2,4-bis(1,1-dimethylethyl)phenyl methyl este

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

2,4-Di-tert-butyl-5-nitrophenyl methyl carbonate (1.00 eq) was charged to a suitable hydrogenation reactor, followed by 5% Pd/C (2.50 wt % dry basis, Johnson-Matthey Type 37). MeOH (15.0 vol) was charged to the reactor, and the system was closed. The system was purged with N2 (g), and was then pressurized to 2.0 Bar with H2 (g). The reaction was performed at a reaction temperature of 25° C.+/−5° C. When complete, the reaction was filtered, and the reactor/cake was washed with MeOH (4.00 vol). The resulting filtrate was distilled under vacuum at no more than 50° C. to 8.00 vol. Water (2.00 vol) was added at 45° C.+/−5° C. The resultant slurry was cooled to 0° C.+/−5. The slurry was held at 0° C.+/−5° C. for no less than 1 hour, and filtered. The cake was washed once with 0° C.+/−5° C. MeOH/H2O (8:2) (2.00 vol). The cake was dried under vacuum (−0.90 bar and −0.86 bar) at 35° C.-40° C. to give compound 32. 1H NMR (400 MHz, DMSO-d6) δ 7.05 (s, 1H), 6.39 (s, 1H), 4.80 (s, 2H), 3.82 (s, 3H), 1.33 (s, 9H), 1.23 (s, 9H).

Workup

  1. customthe system was closed
  2. customThe system was purged with N2 (g)
  3. customwas performed at a reaction temperature of 25° C.+/−5° C
  4. filtrationWhen complete, the reaction was filtered
  5. washthe reactor/cake was washed with MeOH (4.00 vol)
  6. distillationThe resulting filtrate was distilled under vacuum at no more than 50° C. to 8.00 vol. Water (2.00 vol)
  7. additionwas added at 45° C.+/−5° C
  8. waitwas held at 0° C.+/−5° C. for no less than 1 hour
  9. filtrationfiltered
  10. washThe cake was washed once with 0° C.+/−5° C
  11. customThe cake was dried under vacuum (−0.90 bar and −0.86 bar) at 35° C.-40° C.

Sources & evidence

ORD record
ord-3f7ccfe8af7b4dd29b9121986211321b
Source dataset
uspto-grants-2013_06
Patent number
US08471029B2

Reaction notes

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