Hydrochloric Acid → HCID 10325243, compound

HRID 742117Notes

Reaction equation

HRID 742117 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:15]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:14]([CH2:33][O:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][NH:40]C(=O)C(F)(F)F)[O:13][C@H:10]1[O:11][CH3:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl>C(O)C>[NH2:40][CH2:39][CH2:38][CH2:37][CH2:36][CH2:35][O:34][CH2:33][C@H:14]1[O:13][C@@H:10]([O:11][CH3:12])[C@H:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C@@H:16]([O:17][CH2:18][C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C@@H:15]1[O:25][CH2:26][C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

4

Reactant 2

HCID 313Hydrochloric AcidHCID 15384539HCID 15384539, compound2×

Product 1

HCID 10325243HCID 10325243, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a stirred solution of methyl 2,3,4-tri-O-benzyl-6-O-(N-trifluoroacetyl-5-aminopentyl)-β-D-glucopyranoside (799 mg, theoretically 1.71 mmol, structure (13) from Example 4) in 10 mL of ethanol at room temperature was added a solution of 5M (3 mL, 15 mmol). The solution was heated to reflux for 2 hours. The solvents were removed under reduced pressure. The reaction mixture was diluted with dichloromethane (70 mL) and washed with aqueous HCl (25 mL, 15 mmol). The water layer was re-extracted with dichloromethane (3×50 mL), and the combined organic layers were washed with saturated aqueous NaCl (1×75 mL) and dried over magnesium sulfate. Concentration and crystallization from ethyl acetate/petroleum ether provided pure analog having structure (8), methyl 6-O-(5-aminopentyl)-2,3,4-tri-O-benzyl-β-D-glucopyranoside, (675 mg, 72% from methyl 2,3,4-tri-O-benzyl-6-O-trifluoromethylsulfonyl-β-D-glucopyranoside) as a white solid: m.p. 95°-95.5° C.; RF 0.19 (6% methanol in dichloromethane); 1H NMR (500 MHz, CDCl3) δ7.35-7.24 (m, 15H), 4.92 (d, J=7.5 Hz 1H), 4.90 (d, J=7.6 Hz, 1H), 4.85 (d, J=11.0 Hz, 1H), 4.78 (d, J=11.0 Hz, 1H), 4.70 (d, J=11.0 Hz, 1H), 4.60 (d, J=11.0 Hz, 1H), 4.32 (7.8, 1H), 3.66-3.59 (m, 3H), 3.56 (s, 3H), 3.48-3.36 (m, 3H), 2.94 (dd, J=12.5, 2.1 Hz, 1H), 2.68 (dd, J=12.0, 6.8 Hz, 1H), 2.64-2.53 (m, 2H), 1.71 (s, 2H), 1.59-1.53 (m. 2H), 1.51-1.45 (m, 2H), 1.42-1.36 (m, 2H), 13C NMR (500 MHz, CDCl3) δ138.55, 138.47, 138.17, 128.39, 128.33, 128.03, 127.95, 127.85, 127.77, 127.60, 127.57, 104.72, 84.56, 82.45, 79.74, 75.66, 75.02, 74.74, 74.16, 62.62, 57.20, 50.69, 49.72, 32.49, 29.65, 23.37; IR (thin film) 3280(m), 3095(w), 3065(w), 3035(w), 2935(s), 2915(s), 2860(s), 1496(w), 1454(m), 1404(w), 1393(w), 1358(m), 1214(m), 1115(s), 1072(s), 1037(m), 1027(m), 1009(m), 911(w), 826(s), 747(s), 696(s) cm-1 ; HRMS m/e calc'd for C33H43O6N (M+H): 550.3168, found 550.3179; [α]D20 +9.3° (c=0.15, acetonitrile).

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 2 hours
  3. customThe solvents were removed under reduced pressure
  4. additionThe reaction mixture was diluted with dichloromethane (70 mL)
  5. extractionThe water layer was re-extracted with dichloromethane (3×50 mL)
  6. washthe combined organic layers were washed with saturated aqueous NaCl (1×75 mL)
  7. dry with materialdried over magnesium sulfate
  8. concentrationConcentration and crystallization from ethyl acetate/petroleum ether provided pure analog

Sources & evidence

ORD record
ord-b05c39c369cb4e67892fed942edc3684
Source dataset
uspto-grants-1996_09
Patent number
US05552534

Reaction notes

Loading…