Methanol → HCID 86749209, compound

HRID 2257937Notes

Reaction equation

HRID 2257937 reaction equation
Cl.C[O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:19]=[CH:18][C:17]3[C:12](=[CH:13][CH:14]=[C:15]([O:20]C)[CH:16]=3)[C:11]=2[C:22]2[CH:27]=[C:26]([O:28][CH2:29][CH2:30][N:31]3[CH2:35][CH2:34][CH2:33][CH2:32]3)[CH:25]=[CH:24][C:23]=2[CH3:36])=[CH:6][CH:5]=1.B(Cl)(Cl)Cl.CO>ClCCCl>[OH:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:19]=[CH:18][C:17]3[C:12](=[CH:13][CH:14]=[C:15]([OH:20])[CH:16]=3)[C:11]=2[C:22]2[CH:27]=[C:26]([O:28][CH2:29][CH2:30][N:31]3[CH2:32][CH2:33][CH2:34][CH2:35]3)[CH:25]=[CH:24][C:23]=2[CH3:36])=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 887MethanolHCID 25135Boron TrichlorideHCID 86749210HCID 86749210, compound

Product 1

HCID 86749209HCID 86749209, compoundYield 29.8%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a solution of the product of Example 18 (1.61 g, 2.60 mmol) in 1,2-dichloroethane (30 mL) stirring at 0° C. was added boron trichloride (10 ml, 117 mmol). The resulting dark purple solution was stirred overnight at ambient temperature in a sealed tube. After cooling the solution to 0° C., methanol (25 mL) was carefully added over a period of 30 minutes (caution, gas evolution). The solution was subsequently concentrated and the resulting material dissolved in 30% isopropanol/chloroform then washed with saturated sodium bicarbonate, brine, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude material was purified by radial chromatography (methanol/chloroform gradient) to give 0.34 g (27%) of the desired product as a white foam: 1H-NMR (300 MHz, DMSO-d6) δ 9.45 (s, 1H), 9.36 (s, 1H), 7.72 (d, J=8.8 Hz, 1H), 7.62 (d, J=9.2 Hz, 1H), 7.28 (d, J=8.7 Hz, 1H), 7.00-7.10 (m, 2H), 6.80-6.90 (m, 2H), 6.70-6.80 (m, 4H), 5.45 (s, 1H), 4.84 (s, 1H), 4.25 (s, 2H), 3.90-4.05 (m, 2H), 2.75-2.90 (m, 2H), 2.50-2.65 (m, 4H), 1.60-1.80 (m, 4H); 13C-NMR (75 MHz, DMSO-d6) δ 203.32, 191.97, 188.16, 186.14, 185.95, 177.43, 173.46, 169.60, 167.74, 163.48, 162.30, 159.87, 158.14, 154.98, 152.43, 60.50, 56.25, 54.00, 45.05, 41.00, 37.50, 35.00, 30.05, 27.50, 26.00, 22.50, 20.00; Anal. Calc'd. for: C, 79.24; H, 6.65; N, 3.19. Found: C, 78.99; H, 6.51; N, 2.92; MS (FD) m/e 440 (M+); IR (KBr) 3382.61, 2964.00, 1610.77, 1509.49 cm-1.

Workup

  1. temperatureAfter cooling the solution to 0° C.
  2. concentrationThe solution was subsequently concentrated
  3. dissolutionthe resulting material dissolved in 30% isopropanol/chloroform
  4. washthen washed with saturated sodium bicarbonate, brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude material was purified by radial chromatography (methanol/chloroform gradient)

Sources & evidence

ORD record
ord-e054d7f7492442cab915d4819f3ca41e
Source dataset
uspto-grants-1997_08
Patent number
US05658931

Reaction notes

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