Aniline → 2-sec-Butyl-6-iospropylphenol

HRID 1922560Notes

Reaction equation

HRID 1922560 reaction equation
[CH:1]([C:5]1[CH:11]=[CH:10][CH:9]=[C:8]([CH:12]([CH3:14])[CH3:13])[C:6]=1N)([CH2:3][CH3:4])[CH3:2].N([O-])=[O:16].[Na+].NC1C=CC=CC=1>OS(O)(=O)=O.O.[O-]S([O-])(=O)=O.[Cu+2]>[CH:1]([C:5]1[CH:11]=[CH:10][CH:9]=[C:8]([CH:12]([CH3:14])[CH3:13])[C:6]=1[OH:16])([CH2:3][CH3:4])[CH3:2]

Participants

7

Reactant 3

HCID 6115AnilineHCID 20347035HCID 20347035, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 30582992-sec-Butyl-6-iospropylphenol

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1118Sulfuric AcidSolventHCID 24462Copper SulfateSolvent

Conditions

Temperature
0 °C

Procedure

(−)-2-Sec-butyl-6-isopropylaniline (3) (1.92 g, 10 mmol) was dissolved in 20 ml 15% H2SO4 at 60° C., and then cooled to 0° C. A solution of NaNO2 (0.76 g, 11 mmol) in 8 ml water was added to the reaction mixture rapidly (˜30 sec) with vigorous stirring keeping temperature below 0° C. The solution was stirred for an additional 2 minutes, and then added in one portion to the suspension of Cu2O (1.5 g), in aqueous CuSO4×5H2O (10 g in 220 ml) with vigorous stirring at 50° C. Reaction mixture was stirred 30 min. and cooled to room temperature. The reaction was repeated five times with the same scale (total 9.13 g of aniline was used), and all reaction mixtures were combined. Organic material was extracted twice with ether (400 ml). The solvent was evaporated, and the compound purified by silica gel chromatography. CombiFlash chromatography (Hexane/EtAc) was performed and final product distilled (105-110*C/˜3 mm) (4.1 g (45%). Optical rotation: α20D=−7.58° (c=5, pentane). 1H NMR (250 MHz, chloroform-d1) δ 0.84-0.90 (t. 3H), δ 1.21-1.26 (m. 11H), δ 2.85-2.89 (m. 1H), δ 3.11-3.16 (m. 1H), δ 4.74 (s, 1H), δ 6.87-6.90 (t, 1H) δ 6.987-7.05 (m 2H).

Workup

  1. customtemperature below 0° C
  2. stirringThe solution was stirred for an additional 2 minutes
  3. stirringwith vigorous stirring at 50° C
  4. customReaction mixture
  5. stirringwas stirred 30 min.
  6. temperaturecooled to room temperature
  7. customall reaction mixtures
  8. extractionOrganic material was extracted twice with ether (400 ml)
  9. customThe solvent was evaporated
  10. customthe compound purified by silica gel chromatography
  11. distillationfinal product distilled (105-110*C/˜3 mm) (4.1 g (45%)

Sources & evidence

ORD record
ord-aa1e76336cc2438b9cc03325a3ae10ad
Source dataset
uspto-grants-2012_05
Patent number
US08173849B2

Reaction notes

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