Perchloric Acid → HCID 67126141, compound

HRID 513998Notes

Reaction equation

HRID 513998 reaction equation
[C:1]([O:7][CH2:8][C@H:9]([C:11]1[C:20]([CH3:21])=[CH:19][C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:12]=1[C:22]1[CH:27]=[CH:26][C:25]([Cl:28])=[CH:24][CH:23]=1)[OH:10])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].Cl(O)(=O)(=O)=O>C(OC(C)(C)C)(=O)C>[C:1]([O:7][CH2:8][C@@H:9]([O:10][C:2]([CH3:4])([CH3:3])[CH3:1])[C:11]1[C:20]([CH3:21])=[CH:19][C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:12]=1[C:22]1[CH:23]=[CH:24][C:25]([Cl:28])=[CH:26][CH:27]=1)(=[O:6])[C:2]([CH3:4])([CH3:5])[CH3:3]

Participants

4

Reactant 2

HCID 24247Perchloric AcidHCID 67126116HCID 67126116, compound

Product 1

HCID 67126141HCID 67126141, compound

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetateSolvent

Procedure

A solution of (S)-2-(1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-hydroxyethyl pivalate (3H) (0.4582 g, 1.15 mmol) and perchloric acid, (70%, 0.138 mL, 2.3 mmol) in tert-butyl acetate (10 mL) was stirred at room temperature for 3 h. The reaction mixture was quenched with solid sodium bicarbonate (0.5 g) for 1 h. Saturated sodium bicarbonate solution was added and extracted with ethyl acetate (3×). The combined organic layer was dried (MgSO4), filtered and concentrated to give (S)-2-tert-butoxy-2-(1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)ethyl pivalate (3I) that was used in next step without further purification. (S)-2-tert-butoxy-2-(1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)ethyl pivalate (31) from above reaction was dissolved in MeOH (1 mL) and THF (7 mL). Sodium hydroxide (2 M, 0.75 mL, 1.5 mmol) was added and the reaction mixture was stirred at room temperature overnight. Additional sodium hydroxide (2 M, 0.75 mL, 1.5 mmol) was added and reaction mixture was stirred for an additional 24 hours. The reaction mixture was then diluted with ethyl acetate and washed with brine. The aqueous layer was back-extracted with ethyl acetate and combined organic layer was dried (MgSO4), filtered, concentrated and purified by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes) to give 3J as a white solid (0.1889 g). 1H-NMR: 300 MHz, (CDCl3) δ 7.72 (d, J=8.1 Hz, 1H), 7.63 (s, 1H), 7.46-7.05 (m, 7H), 4.60 (dd, J=10.5, 4.5 Hz, 1H), 3.77 (dd, J=11.4, 4.2 Hz, 1H), 3.46 (dd, J=11.4, 4.2 Hz, 1H), 2.71 (s, 3H), 1.00 (s, 9H).

Workup

  1. customThe reaction mixture was quenched with solid sodium bicarbonate (0.5 g) for 1 h
  2. additionSaturated sodium bicarbonate solution was added
  3. extractionextracted with ethyl acetate (3×)
  4. dry with materialThe combined organic layer was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-83c4335a286a40d29c69684cbb30dd7e
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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