Ethylene Glycol → HCID 71116097, compound

HRID 1423853Notes

Reaction equation

HRID 1423853 reaction equation
[N+:1]([CH2:4][C@H:5]1[CH2:10][CH2:9][CH2:8][C:7](=[O:11])[CH2:6]1)([O-:3])=[O:2].[CH2:12]([OH:15])[CH2:13][OH:14].Cl>C1COCC1>[N+:1]([CH2:4][C@H:5]1[CH2:10][CH2:9][CH2:8][C:7](=[O:11])[CH2:6]1)([O-:3])=[O:2].[N+:1]([CH2:4][C@H:5]1[CH2:10][CH2:9][CH2:8][C:7]2([O:15][CH2:12][CH2:13][O:14]2)[CH2:6]1)([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 174Ethylene GlycolHCID 313Hydrochloric AcidHCID 11252145HCID 11252145, compound

Product 2

HCID 11252145HCID 11252145, compoundHCID 71116097HCID 71116097, compoundYield 67%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

(S)-3-(nitromethyl)cyclohexanone was synthesized according to the general procedure found in Mei, K.; et al Org. Lett. 2009, 11, 2864-2867. A rt solution containing (3S)-3-(nitromethyl)cyclohexanone (64.6 g, 411 mmol) and ethylene glycol (68.8 mL, 1233 mmol) in THF (741 mL) was treated with HCl (12.5 mL, 411 mmol) under nitrogen. After stirring for 18 h the reaction mixture was concentrated. The residue was dissolved in Et2O and washed with water and saturated aqueous sodium bicarbonate. The combined aqueous layers were washed with Et2O. The combined organics were washed with brine, dried over Na2SO4, filtered, and concentrated. The crude residue was purified on two 330 g silica gel columns (0-35% EtOAc/hexanes, 35 min gradient; 100 mL/min elution; 254 nm detection) to provide the title compound (27.7 g, 34% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 4.29 (dd, J=7.03, 11.80 Hz, 2H), 3.94 (d, J=3.01 Hz, 4H), 2.44-2.57 (m, J=3.51, 7.26, 7.26, 11.18, 14.95 Hz, 1H), 1.68-1.83 (m, 4H), 1.54-1.68 (m, 1H), 1.42-1.53 (m, 1H), 1.34 (t, J=12.17 Hz, 1H), 1.09 (ddd, J=3.76, 12.80, 24.59 Hz, 1H). MS (m/z) 202.1 (M+H+).

Workup

  1. concentrationwas concentrated
  2. dissolutionThe residue was dissolved in Et2O
  3. washwashed with water and saturated aqueous sodium bicarbonate
  4. washThe combined aqueous layers were washed with Et2O
  5. washThe combined organics were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude residue was purified on two 330 g silica gel columns (0-35% EtOAc/hexanes, 35 min gradient; 100 mL/min elution; 254 nm detection)

Sources & evidence

ORD record
ord-71bc5813d07b44959c3bea63e5f97f67
Source dataset
uspto-grants-2015_01
Patent number
US08927585B2

Reaction notes

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