Methanol → HCID 10684223, compound

HRID 619695Notes

Reaction equation

HRID 619695 reaction equation
[CH3:1][O:2][C:3]1[C:29]([O:30][CH3:31])=[CH:28][CH:27]=[C:26]2[C:4]=1[CH2:5][C:6]1[C:7]3[CH:8]2[CH2:9][N:10](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:11][C:12]=3[CH:13]=[CH:14][CH:15]=1.CO.P([O-])([O-])(O)=O.[Na+].[Na+]>O>[CH3:1][O:2][C:3]1[C:29]([O:30][CH3:31])=[CH:28][CH:27]=[C:26]2[C:4]=1[CH2:5][C:6]1[C:7]3[CH:8]2[CH2:9][NH:10][CH2:11][C:12]=3[CH:13]=[CH:14][CH:15]=1

Participants

5

Reactant 3

HCID 887MethanolHCID 24203Sodium Phosphate, DibasicHCID 10741550HCID 10741550, compound

Product 1

HCID 10684223HCID 10684223, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of compound 14 (440 mg, 1.01 mmol), dry methanol (10 mL) and disodium hydrogen phosphate (574 mg, 4.04 mmol) was stirred under nitrogen at room temperature. To this mixture was added 6.20 g of 6% Na--Hg in three portions and the reaction was heated at reflux for 2 h. After cooling, water (200 mL) was added and the mixture was extracted with ether (3×200 mL). The ether layers were combined, dried (MgSO4), filtered (Celite), and evaporated to give an oil that solidified under vacuum. After rotary chromatography 142 mg (50%) of compound 15 was obtained as an oil. The oil quickly darkened on exposure to air and was used immediately for the next step. A small portion of the oil was treated with ethereal HCl and the hydrochloride salt of compound 15 was recrystallized from ethanol-ether: mp (HCl salt) 190° C. (dec); 1H NMR (CDCl3, base) δ3.13 (dd, 1H, J=10.8, 12 Hz, H-1a), 3.50 (dd, 1H, J=3.4, 17.4 Hz, H-1b), 3.70 (m, 1H, H-11b), 3.839 (s, 3H, OCH3), 3.842 (s, 3H, OCH3), 4.03 (dd, 1H, J=6, 12 Hz, H-7a), 4.08 (s, 2H, H-3), 4.33 (d, 1H, J=17.4 Hz, H-7b), 6.78 (d, 1H, J=8.24 Hz, ArH), 6.92 (m, 3H, ArH), 7.11 (t, 1H, J=7.5 Hz, ArH), 7.18 (d, 1H, J=7.5 Hz, ArH); MS (CI) m/z 282 (100); HRCIMS Calculated for C18H19NO2 : 282.1494; Found 282.1497.

Workup

  1. temperaturethe reaction was heated
  2. temperatureat reflux for 2 h
  3. temperatureAfter cooling
  4. extractionthe mixture was extracted with ether (3×200 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered (Celite)
  7. customevaporated
  8. customto give an oil that

Sources & evidence

ORD record
ord-2464cc0ee03e43ae85d331fc851723e4
Source dataset
uspto-grants-1999_09
Patent number
US05959110

Reaction notes

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