Benzyl Alcohol → HCID 67043395, compound

HRID 1258137Notes

Reaction equation

HRID 1258137 reaction equation
[C:1]([CH:5]1[O:9][C:8]([CH2:15][C:16]([OH:18])=[O:17])([CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13])[C:7](=[O:19])[O:6]1)([CH3:4])([CH3:3])C.[CH2:20](O)[C:21]1C=CC=C[CH:22]=1.[H-].[Na+]>C1COCC1>[CH2:5]([O:6][C:7](=[O:19])[C:8]([OH:9])([CH2:10][CH:11]=[C:12]([CH3:13])[CH3:14])[CH2:15][C:16]([OH:18])=[O:17])[C:1]1[CH:3]=[CH:22][CH:21]=[CH:20][CH:4]=1

Participants

5

Reactant 3

HCID 244Benzyl AlcoholHCID 24758Sodium hydrideHCID 67043626HCID 67043626, compound

Product 1

HCID 67043395HCID 67043395, compoundYield 88%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of dioxolanone 74 (120 mg, 0.444 mmol, 1.00 equiv) in THF (4.5 mL) was cooled to 0° C. and benzyl alcohol (69 μL, 0.67 mmol, 1.5 equiv) was added via syringe followed by a 60% dispersion of NaH in mineral oil (45 mg, 1.1 mmol, 2.5 equiv) which resulted in vigorous evolution of gas. The solution was allowed to stir at 0° C. for 30 min, at which time the reaction was quenched with 4.5 mL NaHCO3, removed from the cold bath and allowed to warm to room temperature. The solution was then poured into H2O (4.5 mL), washed with CH2Cl2 (1×6 mL), acidified to pH<5 with 1N HCl, and then extracted with Et2O (4×6 mL). The combined ethereal phases were dried over MgSO4 and solvent removal by rotary evaporation yielded a white solid which was purified by silica gel column chromatography (70:28:2 hex:EtOAc:HOAc) to yield 75 (114 mg, 88%) as a white solid. Rf=0.39 (60:38:2 EtOAc:Hex:HOAc); 1H NMR (500 MHz, CDCl3) δ 7.35 (m, 5H, ArH), 5.20 (s, 2H, PhCH2), 5.07 (m, 1H, vinyl H), 3.00 (d, 1H, J=16.7 Hz, C(O)CH2), 2.76 (d, 1H, J=16.7 Hz, C(O)CH2), 2.41 (m, 2H, CHCH2), 1.67 (d, 3H, J=0.7 Hz, CH3), 1.54 (d, 3H, J=0.7 Hz, CH3); 13C NMR (100 MHz, CDCl3) δ 176.43, 174.60, 136.79, 135.21, 128.71, 128.64, 128.61, 116.45, 75.41, 67.95, 42.69, 38.14, 26.06, 18.09; IR (neat film) 3483 (br m), 2968 (m), 1736 (s), 1498 (w), 1195 (s) cm−1; HRMS (ESI) m/z calcd for C16H20O5Na (M++Na+) 315.1208; observed 315.1214; [α]D=−18° (c 2.98, CHCl3).

Workup

  1. customresulted in vigorous evolution of gas
  2. customwas quenched with 4.5 mL NaHCO3
  3. customremoved from the cold bath
  4. temperatureto warm to room temperature
  5. additionThe solution was then poured into H2O (4.5 mL)
  6. washwashed with CH2Cl2 (1×6 mL)
  7. extractionextracted with Et2O (4×6 mL)
  8. dry with materialThe combined ethereal phases were dried over MgSO4 and solvent removal by rotary evaporation
  9. customyielded a white solid which
  10. customwas purified by silica gel column chromatography (70:28:2 hex:EtOAc:HOAc)

Sources & evidence

ORD record
ord-69b3fb8e2d884a329a77bf7c4619eab4
Source dataset
uspto-grants-2013_06
Patent number
US08466142B2

Reaction notes

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