Perchloric Acid → Ethyl 2-tert-butoxy-2-(1-hydroxy-3-methylnaphthalen-2-yl)acetate

HRID 514111Notes

Reaction equation

HRID 514111 reaction equation
[OH:1][CH:2]([C:8]1[C:17]([CH3:18])=[CH:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:9]=1[OH:19])[C:3]([O:5][CH2:6][CH3:7])=[O:4].Cl(O)(=O)(=O)=O.C([O-])(O)=O.[Na+]>C(OC(C)(C)C)(=O)C>[C:8]([O:1][CH:2]([C:8]1[C:17]([CH3:18])=[CH:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:9]=1[OH:19])[C:3]([O:5][CH2:6][CH3:7])=[O:4])([CH3:17])([CH3:9])[CH3:2]

Participants

5

Reactant 3

HCID 24247Perchloric AcidHCID 516892Sodium BicarbonateHCID 67126334Ethyl 2-hydroxy-2-(1-hydroxy-3-methylnaphthalen-2-yl)acetate

Product 1

HCID 67126272Ethyl 2-tert-butoxy-2-(1-hydroxy-3-methylnaphthalen-2-yl)acetateYield 75.6%

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetateSolvent

Procedure

A solution of ethyl 2-hydroxy-2-(1-hydroxy-3-methylnaphthalen-2-yl)acetate (622 mg, 2.39 mmol) in tert-butyl acetate (12 mL) was treated with 70% HClO4 (20 μL) at 23° C.). After 3 h, the reaction was added slowly over 5 min to saturated NaHCO3 (25 mL). The resulting system was extracted with DCM (3×15 mL). The combined organic layers were dried (Na2SO4), filtered, and concentrated. Hexane (10 mL) was added, and the mixture was concentrated again. The residue was dissolved in benzene. The solution was wet-loaded onto a 24 g “gold” ISCO silica gel column and purified by flash chromatography (hexane→ethyl acetate) giving the desired product (286 mg, 38% yield). 1H NMR (400 MHz, CDCl3) δ 9.00 (s, 1H), 8.26 (d, J=8.2 Hz, 1H), 7.65 (d, J=8.8 Hz, 1H), 7.44 (dd, J=8.2, 8.0 Hz, 1H), 7/39 (dd, J=8.8, 8.0 Hz, 1H), 7.17 (s, 1H), 5.52 (s, 1H), 4.25-4.06 (m, 2H), 2.59 (s, 3H), 1.33 (s, 9H), 1.20 (t, J=7.0 Hz, 3H).

Workup

  1. extractionThe resulting system was extracted with DCM (3×15 mL)
  2. dry with materialThe combined organic layers were dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. additionHexane (10 mL) was added
  6. concentrationthe mixture was concentrated again
  7. dissolutionThe residue was dissolved in benzene
  8. custompurified by flash chromatography (hexane→ethyl acetate)

Sources & evidence

ORD record
ord-bd227591104a409e9b77a6f33a5f45e7
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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