Ethyl Acetate → HCID 87329412, compound

HRID 1367611Notes

Reaction equation

HRID 1367611 reaction equation
Cl.[NH2:2][O:3][CH2:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][CH:6]=1.C([O-])([O-])=O.[Na+].[Na+].[C:20](Cl)([O:22][CH2:23][CH:24]1[C:36]2[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:30]2[C:25]1=[CH:26][CH:27]=[CH:28][CH:29]=2)=[O:21].C(OCC)(=O)C>O1CCOCC1>[C:20]([NH:2][O:3][CH2:4][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][CH:6]=1)([O:22][CH2:23][CH:24]1[C:25]2[C:30](=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:31]2[C:36]1=[CH:35][CH:34]=[CH:33][CH:32]=2)=[O:21]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 343679-Fluorenylmethyl chloroformateHCID 196926191-[(Ammoniooxy)methyl]-4-carboxybenzene chloride

Product 1

HCID 87329412HCID 87329412, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 4-aminooxymethyl-benzoic acid, hydrochloride 111 (2.0 g, 0.010 mol) in dioxane (20 mL) and half saturated Na2CO3 solution (20 mL) was added Fmoc-Cl (2.8 g, 0.011 mol) and the mixture was stirred for 2 h. Ethyl acetate (100 mL) was added and the pH of the aqueous phase was adjusted to 1-3 by careful addition of HCl(conc.). The mixture was poured in to a separating funnel and the organic phase was isolated, washed once with water (100 mL), dried over Na2SO4 and the solvent was removed on a rotavap to give an oil that solidified upon standing. The crude product was purified by flash column chromatography (petroleum ether, ethyl acetate, AcOH 60:40:1). Yield: 3.5 g (92%) 1H-NMR (250 MHz, DMSO-d6) =4.05 (1H, t, J=6.3 Hz), 4.27 (2H, d, J=6.3 Hz), 4.51 (2H, s), 7.08-7.22 (6H, m), 7.46 (2H, d, J=7.4 Hz), 7.66 (2H, d, J=7.1 Hz), 7.72 (2H, d, J=8.4 Hz), 10.29 (1H, br. s), 12.78 (1H, br. s). 13C-NMR (63 MHz, DMSO-d6) =47.04, 66.03, 76.91, 120.51, 125.41, 127.45, 128.03, 128.89, 129.33, 129.63, 130.82, 141.19, 144.01, 157.12, 167.48. MS (ES) m/z=389 (MH+). 1The material was prepared as previously described: Deles, J. et al.; PJCHDQ; Pol. J. Chem.; EN; 53; 1979; 1025-1032

Workup

  1. additionThe mixture was poured in to a separating funnel
  2. customthe organic phase was isolated
  3. washwashed once with water (100 mL)
  4. dry with materialdried over Na2SO4
  5. customthe solvent was removed on a rotavap
  6. customto give an oil that
  7. customThe crude product was purified by flash column chromatography (petroleum ether, ethyl acetate, AcOH 60:40:1)
  8. custom1The material was prepared

Sources & evidence

ORD record
ord-4b973e38a1af4badb1a376133063f29a
Source dataset
uspto-grants-2011_02
Patent number
US07893253B2

Reaction notes

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