Benzoyl chloride → HCID 11463306, compound

HRID 1935665Notes

Reaction equation

HRID 1935665 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:16]([CH2:17][OH:18])[O:15][C@H:12]([O:13][CH3:14])[C@H:11]([O:19][CH2:20][O:21][CH3:22])[C@H:10]1[O:23][CH2:24][O:25][CH3:26])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.C(Cl)(=[O:41])C1C=CC=CC=1>C(Cl)Cl.CCOC(C)=O>[C:1]([O:8][CH2:9][C@H:16]1[O:15][C@H:12]([O:13][CH3:14])[C@H:11]([O:19][CH2:20][O:21][CH3:22])[C@@H:10]([O:23][CH2:24][O:25][CH3:26])[C@@H:17]1[OH:18])(=[O:41])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 7412Benzoyl chlorideHCID 8471TriethylamineHCID 12012110HCID 12012110, compound

Product 1

HCID 11463306HCID 11463306, compoundYield 61.2%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of methyl 4-O-benzyl-2,3-di-O-methoxymethyl-α-D-glucopyranoside (D. B. Berkowitz et al., J. Org. Chem. 1993, vol. 58, page 6174) (1.1 g, 2.96 mmol) in methylene chloride (10 mL) was added triethyl-amine (3.4 mL, 24.5 mmol), and benzoyl chloride (1.4 mL, 12.0 mmol). The reaction was stirred at room temperature for approximately 30 min and then diluted with EtOAc (100 mL) and washed with 0.5 N aqueous HCl (100 mL), saturated aqueous NaHCO3 (100 mL), and brine (100 mL). The aqueous layers were reextracted with EtOAc (100 mL) and the organics were combined, dried over Na2SO4, and then concentrated in vacuo. The crude product was taken up in ethanol (7 mL) and Pd/C-Degussa type (100 mg) was added. The reaction was stirred under an atmosphere of hydrogen for 12 h and then filtered through celite and concentrated in vacuo. The product was purified by flash chromatography (gradient 33% to 50% EtOAc/petroleum ether) to afford 2 (0.70 g, 61%) as a colorless oil: Rf=0.25 (40% EtOAc/petroleum ether); 1H NMR (CDCl3, 270 MHz) δ 8.06 (d, J=7.2 Hz, 2H), 7.56 (t, J=7.2 Hz, 1H), 7.44 (t, J=7.2 Hz, 2H), 4.84 (d, J=3.6 Hz, 1H), 4.7-4.8 (m, 4H), 4.65 (dd, J=2.3, 11.9 Hz, 1H), 4.57 (dd, J=5.3, 11.9 Hz, 1H), 4.23 (br s, 1H), 3.91 (ddd, J=2.3, 5.3, 9.5 Hz, 1H), 3.71 (dd, J=9.5, 9.5 Hz, 1H), 3.61 (dd, J=3.6, 9.5 Hz, 1H), 3.50 (dd, J=9.5, 9.5 Hz, 1H), 3.46 (s, 3H), 3.45 (s, 3H), 3.39 (s, 3H); 13C NMR (CD3COCD3, 67.5 MHz) δ 167.0, 134.2, 131.5, 130.5, 129.7, 100.1, 98.8, 98.1, 81.0, 79.2, 71.4, 70.7, 65.2, 56.1, 55.7, 55.5; HRFABMS calcd for C18H27O9 (M+H+) 387.1655, found 387.1656.

Workup

  1. washwashed with 0.5 N aqueous HCl (100 mL), saturated aqueous NaHCO3 (100 mL), and brine (100 mL)
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. additionPd/C-Degussa type (100 mg) was added
  5. stirringThe reaction was stirred under an atmosphere of hydrogen for 12 h
  6. filtrationfiltered through celite and
  7. concentrationconcentrated in vacuo
  8. customThe product was purified by flash chromatography (gradient 33% to 50% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-57b15e158f7d4bf696152fc894306b50
Source dataset
uspto-grants-2002_05
Patent number
US06388059B1

Reaction notes

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