Ammonia → 1,3-Di-tert-butylbenzene

HRID 401414Notes

Reaction equation

HRID 401414 reaction equation
N.C(OP(=O)(OCC)O[C:7]1[CH:12]=[CH:11][C:10]([C:13]([CH3:16])([CH3:15])[CH3:14])=[CH:9][C:8]=1[C:17]([CH3:20])([CH3:19])[CH3:18])C.[Li]>CCOCC>[C:13]([C:10]1[CH:11]=[CH:12][CH:7]=[C:8]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH:9]=1)([CH3:16])([CH3:15])[CH3:14]

Participants

5

Reactant 3

HCID 222AmmoniaHCID 3028194LithiumHCID 57567401Phosphoric acid 2,4-di-tert-butyl-phenyl ester diethyl ester

Product 1

HCID 1368101,3-Di-tert-butylbenzene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

To NH3 (liquid, 250 mL) was added a solution of phosphoric acid 2,4-di-tert-butyl-phenyl ester diethyl ester (51 g, crude from last step, about 0.2 mol) in Et2O (anhydrous, 150 mL) at −78° C. under N2 atmosphere. Lithium metal was added to the solution in small pieces until a blue color persisted. The reaction mixture was stirred at −78° C. for 15 min and then quenched with sat. NH4Cl solution until the mixture turned colorless. Liquid NH3 was evaporated and the residue was dissolved in water, extracted with Et2O (300 mL×2). The combined organic phases were dried over Na2SO4 and concentrated to give crude 1,3-di-tert-butyl-benzene as a yellow oil (30.4 g, 94% over 2 steps, contaminated with some mineral oil), which was used directly in next step.

Workup

  1. customquenched with sat. NH4Cl solution until the mixture
  2. customLiquid NH3 was evaporated
  3. dissolutionthe residue was dissolved in water
  4. extractionextracted with Et2O (300 mL×2)
  5. dry with materialThe combined organic phases were dried over Na2SO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-1d674f6e2a814159ac3b7daf951b0998
Source dataset
uspto-grants-2014_06
Patent number
US08741925B2

Reaction notes

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