Acetic Acid → HCID 86743498, compound

HRID 1638501Notes

Reaction equation

HRID 1638501 reaction equation
[CH:1]1[C:10]([OH:11])=[C:6]([CH:7]([CH3:9])[CH3:8])[CH:5]=[CH:4][C:2]=1[CH3:3].C(O)(=O)C.S(=O)(=O)(O)O.[C:21](O)([CH3:24])([CH3:23])[CH3:22]>O.CCCCCC>[CH3:22][C:21]([C:5]1[C:6]([CH:7]([CH3:9])[CH3:8])=[C:10]([OH:11])[CH:1]=[C:2]([CH3:3])[CH:4]=1)([CH3:24])[CH3:23]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 1118Sulfuric AcidHCID 6386tert-Butanol2×HCID 6989Thymol

Product 1

HCID 86743498HCID 86743498, compoundYield 43%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8058HexaneSolvent

Conditions

Temperature
25 °C

Procedure

Thymol (360.0 g, 2.4 mol) was added to a cooled (0° C.) mixture of acetic acid (600 mL) and sulfuric acid (144 mL). The mixture was allowed to warm to 20°-25° C., after which, t-butanol (228 mL, 2.4 mol) was added dropwise over a one hour period. The mixture was stirred at 25° C. for one hour. An additional portion of t-butanol (114 mL, 1.2 mol) was then added dropwise over a one hour period. The mixture was stirred at 25° C. for 4 hours after which the mixture was poured into hexane (1 L) and water (1 L) and the layers separated. The aqueous layer was extracted with hexane (2×100 mL). The combined extracts were washed with water (3×200 mL), saturated sodium bicarbonate solution (2×100 mL), water (200 mL) and brine (2×100 mL). The solvents were evaporated and the residue distilled to provide 262 g (bp 135°-145° C., 6 mm) of material which was crystallized from hexane to give 215.2 g (43% yield, GLC purity 99.5%) of 4-(1,1-dimethylethyl-2-(1-methylethyl)-5-methylphenol; mp 75.5°-76.5° C.; 1H-NMR (CDCl3)δ 1.24 (6H, d, J=7 Hz), 1.38 (9H, s), 2.42 (3H, s), 2.95-3.42 (1H, m), 4.67 (1H, broad s), 6.48 (1H, s), 7.13 (1H, s); IR (CHCl3)νmax 3575, 3340, 2940, 1605, 1670, 1490, 1450, 1400 cm-1 ; MS m/e 206, 191, 149, 121; UVλmax (ethanol) 223 nm (ε=5650), 253 nm (ε=2260).

Workup

  1. temperaturea cooled
  2. temperatureto warm to 20°-25° C.
  3. stirringThe mixture was stirred at 25° C. for 4 hours after which the mixture
  4. customthe layers separated
  5. extractionThe aqueous layer was extracted with hexane (2×100 mL)
  6. washThe combined extracts were washed with water (3×200 mL), saturated sodium bicarbonate solution (2×100 mL), water (200 mL) and brine (2×100 mL)
  7. customThe solvents were evaporated
  8. distillationthe residue distilled
  9. customto provide 262 g (bp 135°-145° C., 6 mm) of material which
  10. customwas crystallized from hexane

Sources & evidence

ORD record
ord-9742bd7a7c2d4a9d9d0d61478804b48a
Source dataset
uspto-grants-1989_11
Patent number
US04880775

Reaction notes

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