Hydrochloric Acid → 2,4-Di-tert-butyl-5-nitrophenol

HRID 401319Notes

Reaction equation

HRID 401319 reaction equation
COC(=O)[O:4][C:5]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[C:8]([C:14]([CH3:17])([CH3:16])[CH3:15])=[CH:7][C:6]=1[C:18]([CH3:21])([CH3:20])[CH3:19].COC(=O)OC1C([N+]([O-])=O)=CC(C(C)(C)C)=CC=1C(C)(C)C.[OH-].[K+].Cl>CO>[C:18]([C:6]1[CH:7]=[C:8]([C:14]([CH3:16])([CH3:15])[CH3:17])[C:9]([N+:11]([O-:13])=[O:12])=[CH:10][C:5]=1[OH:4])([CH3:19])([CH3:20])[CH3:21]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 532497902,4-Di-tert-butyl-5-nitrophenyl methyl carbonateHCID 666762282,4-Bis(1,1-dimethylethyl)-6-nitrophenyl methyl carbonate

Product 1

HCID 441762252,4-Di-tert-butyl-5-nitrophenolYield 29%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

The mixture of carbonic acid 2,4-di-tert-butyl-5-nitro-phenyl ester methyl ester and carbonic acid 2,4-di-tert-butyl-6-nitro-phenyl ester methyl ester (4.2 g, 12.9 mmol) was dissolved in MeOH (65 mL) and KOH (2.0 g, 36 mmol) was added. The mixture was stirred at room temperature for 2 h. The reaction mixture was then made acidic (pH 2-3) by adding conc. HCl and partitioned between water and diethyl ether. The ether layer was dried (MgSO4), concentrated and purified by column chromatography (0-5% ethyl acetate-hexanes) to provide 2,4-di-tert-butyl-5-nitro-phenol (1.31 g, 29% over 2 steps) and 2,4-di-tert-butyl-6-nitro-phenol. 2,4-Di-tert-butyl-5-nitro-phenol: 1H NMR (400 MHz, DMSO-d6) δ 10.14 (s, 1H, OH), 7.34 (s, 1H), 6.83 (s, 1H), 1.36 (s, 9H), 1.30 (s, 9H). 2,4-Di-tert-butyl-6-nitro-phenol: 1H NMR (400 MHz, CDCl3) δ 11.48 (s, 1H), 7.98 (d, J=2.5 Hz, 1H), 7.66 (d, J=2.4 Hz, 1H), 1.47 (s, 9H), 1.34 (s, 9H).

Workup

  1. custompartitioned between water and diethyl ether
  2. dry with materialThe ether layer was dried (MgSO4)
  3. concentrationconcentrated
  4. custompurified by column chromatography (0-5% ethyl acetate-hexanes)

Sources & evidence

ORD record
ord-46c4a2c998c347828ab62b900f347b9f
Source dataset
uspto-grants-2014_06
Patent number
US08741925B2

Reaction notes

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