Benzoyl chloride → HCID 123299690, compound

HRID 1471365Notes

Reaction equation

HRID 1471365 reaction equation
[S:1]1[C:5]([CH2:6][C:7]2[C:8](C)=[CH:9][C:10]([OH:23])=[C:11]([CH:13]3[CH:18]([OH:19])[CH:17]([OH:20])[CH2:16][CH:15]([CH2:21][OH:22])[O:14]3)[CH:12]=2)=[CH:4][C:3]2[CH:25]=[CH:26][CH:27]=[CH:28][C:2]1=2.[C:29](Cl)(=[O:36])C1C=CC=CC=1>N1C=CC=CC=1>[S:1]1[C:5]([CH2:6][C:7]2[C:8]([O:36][CH3:29])=[CH:9][C:10]([OH:23])=[C:11]([CH:13]3[CH:18]([OH:19])[CH:17]([OH:20])[CH2:16][CH:15]([CH2:21][OH:22])[O:14]3)[CH:12]=2)=[CH:4][C:3]2[CH:25]=[CH:26][CH:27]=[CH:28][C:2]1=2

Participants

4

Reactant 2

HCID 7412Benzoyl chlorideHCID 123746885HCID 123746885, compound

Product 1

HCID 123299690HCID 123299690, compoundYield 70.7%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a solution of allyl α-D-glactonpyranoside (1, 5.0 g, 22.7 mmol) in 100 mL of dry pyridine at −35˜−30° C. was added benzoyl chloride dropwise with stirring. The reaction mixture was stirred at that temperature for 20 mins, then warmed to room temperature and stirred at room temperature for 48 h. The reaction was quenched by the dropwise addition of the reaction mixture to 200 ml of ice-cold saturated aqueous sodium bicarbonate with stirring. The aqueous mixture was extracted with EtOAc three times (150 ml each time). The combined extracts were washed with 1N HCl six times, brine, dried over Na2SO4, then evaporated to dryness in vacuo to give the crude product as light orange oil, which was purified by flash column chromatography on silica gel (150 g AnaLogix column, EtOAc/heptane: 0>>>5%>>>15%>>>35%) to yield compound 2 (8.55 g, 70.7%) as a white solid. 1H NMR (CDCl3) δ 8.07 (s, 1H), 8.05 (d, J=1.01 Hz, 1H), 8.01 (dd, J=3.03, 1.52 Hz, 2H), 7.99 (dd, J=3.03, 1.52 Hz, 2H), 7.59 (m, 1H), 7.52 (m, 2H), 7.46 (t, J=7.58 Hz, 2H), 7.35-7.42 (4H), 5.86 (ddd, J=16.67, 11.12, 5.56 Hz, 1H), 5.79 (dd, J=11.12, 0.03 Hz, 1H), 5.70 (dd, J=10.61, 3.54 Hz, 1H), 5.35 (d, J=3.54 Hz, 1H), 5.27 (dq, J=17.18, 1.52 Hz, 1H), 5.12 (dq, J=10.61, 1.52 Hz, 1H), 4.68 (dd, J=11.62, 6.57 Hz, 1H), 4.55 (dd, J=11.12, 6.57 Hz, 1H), 4.42 (m, 2H), 4.25 (m, 1H), 4.10 (m, 1H), 2.47 (d, J=4.04 Hz, 1H). MS (ES) 554.8 (M+Na+).

Workup

  1. stirringThe reaction mixture was stirred at that temperature for 20 mins
  2. stirringstirred at room temperature for 48 h
  3. customThe reaction was quenched by the dropwise addition of the reaction mixture to 200 ml of ice-cold saturated aqueous sodium bicarbonate
  4. stirringwith stirring
  5. extractionThe aqueous mixture was extracted with EtOAc three times (150 ml each time)
  6. washThe combined extracts were washed with 1N HCl six times, brine
  7. dry with materialdried over Na2SO4
  8. customevaporated to dryness in vacuo
  9. customto give the crude product as light orange oil, which
  10. customwas purified by flash column chromatography on silica gel (150 g AnaLogix column, EtOAc/heptane: 0>>>5%>>>15%>>>35%)

Sources & evidence

ORD record
ord-770774dd6057480d9d1df8ec42de950e
Source dataset
uspto-grants-2015_04
Patent number
US09012412B2

Reaction notes

Loading…