Acetic Acid → 1-(3-Hydroxy-5,6,7,8-tetrahydronaphthalen-2-yl)ethan-1-one

HRID 1869563Notes

Reaction equation

HRID 1869563 reaction equation
[CH:1]1[C:10]2[CH2:9][CH2:8][CH2:7][CH2:6][C:5]=2[CH:4]=[CH:3][C:2]=1[OH:11].[C:12](O)(=[O:14])[CH3:13]>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[OH:11][C:2]1[C:3]([C:12](=[O:14])[CH3:13])=[CH:4][C:5]2[CH2:6][CH2:7][CH2:8][CH2:9][C:10]=2[CH:1]=1

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 143055,6,7,8-Tetrahydro-2-naphthol

Product 1

HCID 109432711-(3-Hydroxy-5,6,7,8-tetrahydronaphthalen-2-yl)ethan-1-oneYield 59.9%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

To 5,6,7,8-tetrahydro-2-naphthol 14 (10 mmol, 1.48 g) placed in a flask flushed with argon at room temperature, was slowly added TiCl4 (11 mmol, 1.2 mL). The resulting dark cherry-colored mixture was stirred at room temperature, and when gas evolution ceased, 15 mmol (1.07 mL) of acetic acid was added to the solid. The resulting thick solution was stirred at room temperature for 15 min, then brought to 120° C. and left to stir at this temperature for an additional hour. The reaction mixture was then cooled to room temperature, diluted with CH2Cl2 (30 mL) and quenched with H2O (30 mL). A cloudy solution was obtained which was easily extracted with CH2Cl2. The organic layer was washed with H2O (2×30 mL), dried (Na2SO4), and concentrated under reduced pressure. The crude material was purified by silica gel column chromatography using a mixture of hexanes/EtOAc (95/5) to give 15 as a yellowish solid (1.14 g, 59% yield). mp 70-72° C.; 1H NMR (CDCl3) δ 1.77 (m, 4H), 2.59 (s, 3H), 2.76 (m, 4H), 6.68 (s, 1H), 7.41 (s, 1H), 11.96 (s, 1H); 13C NMR (CDCl3) δ 22.87, 23.42, 26,72, 28.82, 30.17, 117.82, 118.21, 128.10, 131.04, 147.71, 160.09, 204.16; IR (KBr, ν cm−1) 2934, 1621, 1491, 1344; MS (ESI) 191 (M+1). Anal. Calcd for C12H14O2: C, 75.76; H, 7.42. Found: C, 75.91; H, 7.46.

Workup

  1. customflushed with argon at room temperature
  2. stirringThe resulting thick solution was stirred at room temperature for 15 min
  3. custombrought to 120° C.
  4. waitleft
  5. stirringto stir at this temperature for an additional hour
  6. temperatureThe reaction mixture was then cooled to room temperature
  7. customquenched with H2O (30 mL)
  8. customA cloudy solution was obtained which
  9. extractionwas easily extracted with CH2Cl2
  10. washThe organic layer was washed with H2O (2×30 mL)
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated under reduced pressure
  13. customThe crude material was purified by silica gel column chromatography
  14. additiona mixture of hexanes/EtOAc (95/5)

Sources & evidence

ORD record
ord-6540ef290a9b483d9cdff08ff3596e25
Source dataset
uspto-grants-2009_12
Patent number
US07638554B2

Reaction notes

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