Hydrochloric Acid → HCID 10156640, compound

HRID 394932Notes

Reaction equation

HRID 394932 reaction equation
[CH3:1][C:2]([C:16]1[CH:25]=[CH:24][C:23]2[C:22]([CH3:27])([CH3:26])[CH2:21][CH2:20][C:19]([CH3:29])([CH3:28])[C:18]=2[CH:17]=1)([CH3:15])[CH2:3][O:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11]C)=[O:10])=[CH:7][CH:6]=1.O.[OH-].[Li+].Cl>C1COCC1>[CH3:15][C:2]([C:16]1[CH:25]=[CH:24][C:23]2[C:22]([CH3:27])([CH3:26])[CH2:21][CH2:20][C:19]([CH3:29])([CH3:28])[C:18]=2[CH:17]=1)([CH3:1])[CH2:3][O:4][C:5]1[CH:6]=[CH:7][C:8]([C:9]([OH:11])=[O:10])=[CH:13][CH:14]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 168937Lithium hydroxide, monohydrateHCID 18177875HCID 18177875, compound

Product 1

HCID 10156640HCID 10156640, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

305 mg of 2-methyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-propanol dissolved in 15 ml THF were treated with 338 mg of triphenylphosphine, 196 mg of methyl 4-hydroxybenzoate and 0.21 ml of diethyl azodicarboxylate. The reaction mixture was heated to reflux for 6 hours. The mixture was partitioned in 100 ml of 1:1 ethyl acetate/sat. aq. sodium chloride solution. The phases were separated and the organic phase was dried over MgSO4. The solvents were removed in vacuo and the resulting oil was purified by flash chromatography (SiO2, 20% ethyl acetate/hexanes), giving 160 mg of methyl 4-[2-methyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-propyloxy]-benzoate as a colorless oil. The ester (160 mg), dissolved in 4 ml THF/0.8 ml H2O, was treated with 50 mg of lithium hydroxide hydrate. The mixture was heated at 60° C. for two hours. The mixture was acidified to pH 2 with 1N hydrochloric acid then partitioned in 10 ml ethyl acetate/10 ml sat. aq. sodium chloride solution. The phases were separated and the organic phase was dried over MgSO4. The solvent was removed in vacuo and the crude product was purified by preparation tlc (SiO2, 40% ethyl acetate/hexanes), giving a white foam. 1H NMR (CDCl3): 8.03 (d, J=8.8 Hz, 2H), 7.35 (d, J=2.1 Hz, 1H), 7.26 (d, J=8.4 Hz, 1H), 7.17 (dd, J=8.4, 2.1 Hz, 1H), 6.91 (d, J=8.8 Hz, 2H), 3.96 (s, 2H), 1.67 (s, 4H), 1.46 (s, 6H), 1.27 (s, 12H).

Workup

  1. customthen partitioned in 10 ml ethyl acetate/10 ml sat. aq. sodium chloride solution
  2. customThe phases were separated
  3. dry with materialthe organic phase was dried over MgSO4
  4. customThe solvent was removed in vacuo
  5. customthe crude product was purified by preparation tlc (SiO2, 40% ethyl acetate/hexanes)
  6. customgiving a white foam

Sources & evidence

ORD record
ord-5242c8cf9a3a4f62a48355c6e1d95277
Source dataset
uspto-grants-2003_08
Patent number
US06603012B2

Reaction notes

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