Phosphate → HCID 15678068, compound

HRID 1198800Notes

Reaction equation

HRID 1198800 reaction equation
COC1[CH:16]=[CH:15][C:14]2[C:5](=[C:6]3[C:11](=[CH:12][N:13]=2)[CH2:10][CH2:9][CH2:8][CH2:7]3)C=1.C([S-])C.[Na+].[C:21]([O:24][C:25](=[O:27])[CH3:26])(=O)[CH3:22].P([O-])([O-])([O-])=O>CN(C=O)C>[C:25]([O:24][C:21]1[CH:16]=[CH:15][C:14]2[C:5](=[C:6]3[C:11](=[CH:12][N:13]=2)[CH2:10][CH2:9][CH2:8][CH2:7]3)[CH:22]=1)(=[O:27])[CH3:26]

Participants

6

Reactant 4

HCID 1061PhosphateHCID 7918Acetic AnhydrideHCID 4459711Sodium ethanethiolateHCID 10856826HCID 10856826, compound2×

Product 1

HCID 15678068HCID 15678068, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
160 °C

Procedure

A mixture of 2-methoxy-7,8,9,10-tetrahydrophenanthridine (Compound 273, 48.17 g, 226 mmol) and sodium ethanethiolate (43.69 g, 520 mmol) in dry DMF was heated at 160° C. for 4 hours. After the reaction mixture was cooled to zero degrees C., acetic anhydride (63.9 mL, 678 mmol) was added and the reaction mixture was stirred for 30 minutes. The resulting thick white slurry was poured into 0.1M pH 7.5 phosphate buffer (1.6 L) and extracted with ether (3×400 mL). The combined organic layers were washed with water (3×300 mL) and brine (300 mL), dried (MgSO4), filtered through a 3 cm×3 cm plug of silica, and evaporated in vacuo. The residue was purified by recrystallization from ethyl acetate-hexanes to give 45.70 g (86 percent) of Compound 274: white crystalline solid; mp 118°-119° C.; Rf =0.39 (silica, 50 percent ethyl acetate in dichloromethane); IR (CHCl3) νmax 3018, 2938, 2861, 1758, 1507, 1369, 1193, 1174 cm-1 ; 1H NMR (300 MHz, CDCl3), 8.60 (s, 1 H, H6), 8,06 (d, J=9.0 Hz, 1 H, H4), 7.61 (d, J=2.5 Hz, 1 H, H1), 7.36 (dd, J=9.0, 2.5 Hz, 1 H, H3), 3.03 (t, J=6.0 Hz, 2 H, H7 or H10), 2.89 (t, J=6.0 Hz, 2 H, H7 or H10), 2.37 (s, 3 H, OCOCH3), 1.98-1.86 (m, 4 H, H8 and H9); 13C NMR (125 Mz, CDCl3) δ 169.5, 152.3, 148.4, 144.3, 140.9, 131.3, 130.1, 128.0, 122.9, 113.8, 27.0, 24.8, 22.2, 22.1, 21.1; MS (FAB+) m/e (rel intensity) 242 (M+H, 100), 200 (25); HRMS for C15H16NO2 (M+H), calcd 242.1181, found 242,1181. Anal. Calcd for C15H15NO2 : C, 74.67; H, 6.27; N, 5.80. Found: C, 74.66; H, 6.37; N, 5.64.

Workup

  1. temperatureAfter the reaction mixture was cooled to zero degrees C
  2. extractionextracted with ether (3×400 mL)
  3. washThe combined organic layers were washed with water (3×300 mL) and brine (300 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered through a 3 cm×3 cm plug of silica
  6. customevaporated in vacuo
  7. customThe residue was purified by recrystallization from ethyl acetate-hexanes

Sources & evidence

ORD record
ord-693f3d03bbcc48f8b6b3f5783167f965
Source dataset
uspto-grants-1994_01
Patent number
US05281710

Reaction notes

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