Hydrochloric Acid → HCID 9797005, compound

HRID 1466703Notes

Reaction equation

HRID 1466703 reaction equation
[O:1]=[C:2]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]([CH3:22])([CH3:21])[CH2:19][OH:20])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]([CH3:12])([CH3:11])[CH2:9][OH:10].[BH4-].[Na+].C(OCC)(=O)C.Cl>C(O)(C)C.O>[CH3:21][C:18]([CH3:22])([CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH:2]([OH:1])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]([CH3:12])([CH3:11])[CH2:9][OH:10])[CH2:19][OH:20]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 4311764Sodium borohydride2×HCID 11738551HCID 11738551, compound

Product 1

HCID 9797005HCID 9797005, compoundYield 44.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3776IsopropanolSolvent2×

Procedure

Under nitrogen atmosphere, a solution of 8-oxo-2,2,14,14-tetramethylpentadecane-1,15-diol (0.9 g, 2.5 mmol) in iso-propanol (10 mL) was added dropwise to a stirred suspension of sodium borohydride (0.1 g, 2.7 mmol) in iso-propanol (10 mL) at room temperature. The reaction progress was monitored by thin layer chromatography (silica, hexanes:ethyl acetate=1:1). Additional sodium borohydride was added after each hour (0.36 g, 10 mmol, six times). The reaction mixture was stirred for additional 20 h, hydrolyzed with water (10 mL), acidified with 1 N hydrochloric acid (25 mL) to pH 1, and extracted with dichloromethane (4×15 mL). The combined organic phases were washed with saturated sodium chloride solution (15 mL), dried over magnesium sulfate, and concentrated in vacuo to furnish the crude product (1.0 g) as a white solid in oil, which was purified by column chromatography (silica; hexanes, then hexanes:ethyl acetate=2:1 to 1:2) to give the pure product (0.35 g, 43%) as nice white crystals. M.p.: 71-75° C. 1H NMR (300 MHz, CD3COCD3/CD3OD/TMS): δ (ppm): 4.32-4.03 (m, 3H), 3.52 (s, 1H), 3.22 (s, 4H), 1.63-1.20 (m, 20H), 0.83 (s, 12H). 13C NMR (75 MHz, CD3COCD3/CD3OD/TMS): δ (ppm): 72.0, 71.7, 39.8, 38.4, 35.8, 31.8, 26.7, 24.8, 24.6. HRMS (LSLMS, gly): Calcd. for C19H41O3 (MH+): 317.3056. found: 317.3026. HPLC: 97.1% purity.

Workup

  1. extractionextracted with dichloromethane (4×15 mL)
  2. washThe combined organic phases were washed with saturated sodium chloride solution (15 mL)
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customto furnish the crude product (1.0 g) as a white solid in oil, which
  6. customwas purified by column chromatography (silica

Sources & evidence

ORD record
ord-b83c26c68ec84215b4d22399f4b345ba
Source dataset
uspto-grants-2015_04
Patent number
US09000041B2

Reaction notes

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