Hydrochloric Acid → HCID 59264848, compound

HRID 646530Notes

Reaction equation

HRID 646530 reaction equation
[CH2:1]([C:3]1[C:4]([OH:20])=[CH:5][C:6]([OH:19])=[C:7]([C:9](=[O:18])[CH2:10][C:11]2[CH:16]=[CH:15][C:14]([F:17])=[CH:13][CH:12]=2)[CH:8]=1)[CH3:2].Cl[C:22](=[O:28])[C:23]([O:25][CH2:26][CH3:27])=[O:24].Cl.O1C2C(=CC=CC=2)C=CC1C([O-])=O>N1C=CC=CC=1.CCCCCC.CCOC(C)=O>[CH2:26]([O:25][C:23](=[O:24])[C:22](=[O:28])[CH:10]([C:11]1[CH:16]=[CH:15][C:14]([F:17])=[CH:13][CH:12]=1)[C:9]([C:7]1[CH:8]=[C:3]([CH2:1][CH3:2])[C:4]([OH:20])=[CH:5][C:6]=1[OH:19])=[O:18])[CH3:27]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 20884Ethoxalyl chlorideHCID 797333HCID 797333, compoundHCID 23176900HCID 23176900, compound

Product 1

HCID 59264848HCID 59264848, compound

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 1-(5-Ethyl-2,4-dihydroxy-phenyl)-2-(4-fluoro-phenyl)-ethanone (10.3 g, 37.6 mmol) in dried pyridine (100 ml) at 0° C., ethyl chlorooxoacetate (15.4 g, 112.8 mmol) was added. The solution was stirred at 0° C. for 4 hours and at room temperature for 16 hours. The aq. layer was neutralised with 1M HCl and extracted with DCM (2×100 ml). The combined DCM layers were then washed with 2M HCl (2×80 ml), sat. NaHCO3 (1×100 ml), brine (1×100 ml) and dried with Na2SO4. After filtration and evaporation of the solvent, dark brown oil was obtained (11.4 g). Rf=0.22 (EtOAc:n-hexane/1:2). LCMS shows it is a mixture of desired product [(M−1)−=373.1, RT=7.27) and the cyclised chromene carboxylate [(M−1)−=355.4, RT=7.83) in a ratio of ca. 6:1. A small amount of sample was purified by prep. TLC for spectroscopic analysis. 1H NMR (d6-acetone) δ=7.75 (1H, s); 7.30 (2H, m); 7.00 (1H, m); 6.45 (1H, s); 4.65 (1H, s); 4.25 (2H, q); 2.55 (2H, q) and 1.10 (6H, t)

Workup

  1. extractionextracted with DCM (2×100 ml)
  2. washThe combined DCM layers were then washed with 2M HCl (2×80 ml), sat. NaHCO3 (1×100 ml), brine (1×100 ml)
  3. dry with materialdried with Na2SO4
  4. filtrationAfter filtration and evaporation of the solvent
  5. customdark brown oil was obtained (11.4 g)

Sources & evidence

ORD record
ord-f0039c0087d24839aa630a943bc83da9
Source dataset
uspto-grants-2010_04
Patent number
US07705027B2

Reaction notes

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