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

HRID 76794Notes

Reaction equation

HRID 76794 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-7497cdf20e844817ab45f8044e35c234
Source dataset
uspto-grants-2014_09
Patent number
US08835639B2

Reaction notes

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