Methanol → HCID 59756060, compound

HRID 1360329Notes

Reaction equation

HRID 1360329 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5](C)[C:6]([C:12]([O:14][CH3:15])=[O:13])=[C:7]([CH:11]=1)[C:8](O)=O.C[OH:18].C([N:21]([CH2:24]C)CC)C.C1C=C[C:29]([O:32]P(OC2C=CC=CC=2)(N=[N+]=[N-])=O)=CC=1>O1CCOCC1.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[CH:11]=[C:7]([CH3:8])[C:6]([C:12]([O:14][CH3:15])=[O:13])=[C:5]([NH:21][C:24]([O:32][CH3:29])=[O:18])[CH:4]=1

Participants

7

Reactant 4

HCID 887MethanolHCID 8471TriethylamineHCID 123414Diphenylphosphoryl azideHCID 14207577HCID 14207577, compound

Product 1

HCID 59756060HCID 59756060, compoundYield 64.5%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a suspension of compound M (45.4 g, 202 mmol) in 1,4-dioxane (420 mL) was added MeOH (40.9 mL, 1010 mmol) and triethylamine (56.3 mL, 404 mmol). The mixture was heated at 100° C. and diphenylphosphonic azide (65.3 mL, 303 mmol) was dropped into the mixture over 15 minutes. The mixture was stirred at 100° C. for 1 hour and concentrated. The residue was diluted with saturated aqueous NaHCO3 and extracted with ethyl acetate 3 times. The combined organic layers were washed with saturated brine and dried over anhydrous Na2SO4. The combined organic layers were then filtered and evaporated. The resulting residue was crystallized from iPrOH to give a white solid. The solid was dissolved in ethyl acetate and the resulting solution was washed with water and saturated brine and dried over anhydrous Na2SO4. Filtration and evaporation of the solvent gave compound N (33.0 g). In addition, the mother liquid was diluted with ethyl acetate and washed with water and saturated brine, dried over anhydrous Na2SO4, filtered, and evaporated. The resulting residue was recrysatallized from iPrOH to give compound N (4.29 g, 73% total yield) as a white powder. 1H NMR (CDCl3, 400 MHz): δ 2.45 (3H, s), 3.77 (3H, s), 3.84 (3H, s), 3.90 (3H, s), 6.45 (1H, d, J=2.4 Hz), 7.84 (1H, d, J=2.4 Hz), 9.97 (1H, s). EIMS (+): 253 [M]+

Workup

  1. concentrationconcentrated
  2. additionThe residue was diluted with saturated aqueous NaHCO3
  3. extractionextracted with ethyl acetate 3 times
  4. washThe combined organic layers were washed with saturated brine
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationThe combined organic layers were then filtered
  7. customevaporated
  8. customThe resulting residue was crystallized from iPrOH
  9. customto give a white solid
  10. washthe resulting solution was washed with water and saturated brine
  11. dry with materialdried over anhydrous Na2SO4
  12. filtrationFiltration and evaporation of the solvent

Sources & evidence

ORD record
ord-554af5c3c13447b980ff963588d84c94
Source dataset
uspto-grants-2011_02
Patent number
US07879846B2

Reaction notes

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