Phosphorus oxychloride → HCID 69272498, compound

HRID 1892623Notes

Reaction equation

HRID 1892623 reaction equation
P(Cl)(Cl)(Cl)=O.[O:6]1[C:10]2[CH:11]=[CH:12][C:13]([CH2:15][CH2:16][NH:17][C:18](=O)[CH2:19][C:20]3[CH:25]=[CH:24][C:23]([Br:26])=[CH:22][CH:21]=3)=[CH:14][C:9]=2[O:8][CH2:7]1.[BH4-].[Na+].O.O.[C:32]([OH:37])(=[O:36])[C:33]([OH:35])=[O:34]>C(#N)C.CO.CCOCC>[C:32]([OH:37])(=[O:36])[C:33]([OH:35])=[O:34].[Br:26][C:23]1[CH:24]=[CH:25][C:20]([CH2:19][CH:18]2[C:12]3[CH:11]=[C:10]4[O:6][CH2:7][O:8][C:9]4=[CH:14][C:13]=3[CH2:15][CH2:16][NH:17]2)=[CH:21][CH:22]=1

Participants

8

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 61373Oxalic acid dihydrateHCID 4311764Sodium borohydrideHCID 18117857HCID 18117857, compound

Product 1

HCID 69272498HCID 69272498, compoundYield 84%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

Phosphorus oxychloride (119.372 g, 778.83 mmol) was added to a stirred solution of N-(2-benzo[1,3]dioxol-5-yl-ethyl)-2-(4-bromophenyl)acetamide 35 (9.400 g, 25.951 mmol) in anhydrous acetonitrile (225 mL) and refluxed for 6 h. The reaction mixture was concentrated under reduced pressure, methanol was added to it, and again concentrated the solvent under reduced pressure. The obtained residue was dissolved in methanol, to this solution was added sodium borohydride (17.700 g, 467.118 mmol) and the mixture was stirred overnight at room temperature. The solvent was removed under reduced pressure, the residue was dissolved in CHCl3, washed with 1N NaOH solution, water and dried over Na2SO4. The organic layer was evaporated under reduced pressure and the oily mass was dissolved in CHCl3. A solution of oxalicacid dihydrate (6.543 g, 51.902 mmol) in methanol was added to above solution with stirring at room temperature followed by addition of ether. The mixture was stirred for 2 h at the same temperature and kept in the refrigerator overnight. Filtered the solid and washed with ether, and air dried to afford 37 as white solid (9.5 g, 84%). 1H NMR (300 MHz, DMSO-d6) δ 7.55 (d, J=7.5 Hz, 2H, ArH), 7.31 (d, J=7.8 Hz, 2H, ArH), 6.79 (s, 1H, ArH), 6.73 (s, 1H, ArH), 5.99 (s, 2H, CH2), 4.63 (t, J=6.3 Hz, 1H, —CH), 3.36-3.32 (m, 2H, CH2), 3.18-3.06 (m, 2H, CH2), 2.96-2.82 (m, 2H, —CH2). MS (ES+) m/z 346 [M-(COOH)2+H]+.

Workup

  1. temperaturerefluxed for 6 h
  2. concentrationThe reaction mixture was concentrated under reduced pressure, methanol
  3. additionwas added to it
  4. concentrationagain concentrated the solvent under reduced pressure
  5. dissolutionThe obtained residue was dissolved in methanol, to this solution
  6. customThe solvent was removed under reduced pressure
  7. dissolutionthe residue was dissolved in CHCl3
  8. washwashed with 1N NaOH solution, water
  9. dry with materialdried over Na2SO4
  10. customThe organic layer was evaporated under reduced pressure
  11. dissolutionthe oily mass was dissolved in CHCl3
  12. stirringwith stirring at room temperature
  13. stirringThe mixture was stirred for 2 h at the same temperature
  14. customkept in the refrigerator overnight
  15. filtrationFiltered the solid
  16. washwashed with ether, and air
  17. customdried

Sources & evidence

ORD record
ord-48187822928041a18aa10a90b6232945
Source dataset
uspto-grants-2013_08
Patent number
US08507523B2

Reaction notes

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