Eicosanoic acid, 3-oxo-, ethyl ester → 6,8-Difluoro-4-heptadecyl-7-hydroxycoumarin

HRID 355414Notes

Reaction equation

HRID 355414 reaction equation
[F:1][C:2]1[C:8]([OH:9])=[C:7]([F:10])[CH:6]=[CH:5][C:3]=1[OH:4].[C:11]([CH2:30][C:31](OCC)=[O:32])(=O)[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]>CS(O)(=O)=O>[F:10][C:7]1[CH:6]=[C:5]2[C:3](=[C:2]([F:1])[C:8]=1[OH:9])[O:4][C:31](=[O:32])[CH:30]=[C:11]2[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]

Participants

4

Reactant 2

HCID 81566Eicosanoic acid, 3-oxo-, ethyl esterHCID 108445152,4-Difluororesorcinol2×

Product 1

HCID 57067496,8-Difluoro-4-heptadecyl-7-hydroxycoumarinYield 11.2%

Reagents, catalysts & solvents 1

HCID 6395Methanesulfonic AcidSolvent

Procedure

A mixture of 2,4-difluororesorcinol (Compound 4, 0.15 g, 1.0 mmol) and ethyl stearoylacetate (354 mg, 1.03 mmol) in methanesulfonic acid (4 mL) is stirred at room temperature overnight. The reaction mixture is partitioned between ethyl acetate and water. The ethyl acetate layer is washed with brine (1×) and dried over sodium sulfate, then concentrated to 0.67 g of a pale brown solid, which is purified by silica gel chromatography to give 49 mg of Compound 30 as a colorless powder: Rf =0.64 (EtOAc/hexanes 3:2). 1H NMR (CDCl3) δ 7.12 (dd, 1H), 6.22 (s, 1H), 1.7-0.7 (m, 70H). 19F NMR (CDCl3) Φ 139.8 (t, 1F), 153.5 (d, 1F).

Workup

  1. customThe reaction mixture is partitioned between ethyl acetate and water
  2. washThe ethyl acetate layer is washed with brine (1×)
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated to 0.67 g of a pale brown solid, which
  5. customis purified by silica gel chromatography

Sources & evidence

ORD record
ord-8b46a6f2918a46c1ad688fd1a3b30920
Source dataset
uspto-grants-1998_11
Patent number
US05830912

Reaction notes

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