Dimethylformamide → ethyl 8-iodo-7-methoxy-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855023Notes

Reaction equation

HRID 855023 reaction equation
[OH:1][C:2]1[C:9]([I:10])=[C:8]([O:11][CH3:12])[CH:7]=[CH:6][C:3]=1[CH:4]=O.[F:13][C:14](/[C:17](=C\C)/C(OCC)=O)([F:16])[F:15].C(=O)([O-])[O-].[Cs+].[Cs+].CN(C)C=O.[C:36]([O:39][CH2:40][CH3:41])(=[O:38])[CH3:37]>>[I:10][C:9]1[C:8]([O:11][CH3:12])=[CH:7][CH:6]=[C:3]2[C:2]=1[O:1][CH:17]([C:14]([F:16])([F:15])[F:13])[C:37]([C:36]([O:39][CH2:40][CH3:41])=[O:38])=[CH:4]2

Participants

6

Reactant 5

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 190890572-Hydroxy-3-iodo-4-methoxybenzaldehydeHCID 23051828Ethyl trifluoromethylcrotonate

Product 1

HCID 58934894ethyl 8-iodo-7-methoxy-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 14%

Conditions

Temperature
90 °C

Procedure

To the mixture of 1.5 g (5.4 mmol) of 2-hydroxy-3-iodo-4-methoxybenzaldehyde, 3.1 mL (20.6 mmol) of ethyl trifluoromethylcrotonate, and 4.2 g(12.9 mmol) of cesium carbonate was added 8 mL of anhydrous N,N-dimethylformamide. The mixture was heated to 90° C. overnight. After cooling to room temperature, to the reaction was added 150 mL of ethyl acetate. The organic solution was filtered, washed with brine and dried over anhydrous magnesium sulfate. After removing the volatiles, the residue was purified by silica chromatography with ethyl acetate/hexane (2:8) to give 0.3 g (14%) a light yellow solid: 1H NMR(CDCl3/400 MHz) 7.65(s, 1H), 7.17(d, J=8.4 Hz, 1H), 6.50(d, J=8.4 Hz, 1H), 5.80(q, J=6.8 Hz,1H), 4.30(m, 2H), 3.92(s, 3H), 1.33(t, J=7.6 Hz, 3H). MS (ESI+) 429.0(M+1, 100). HRMS (EI+) m/z calcd for (C14H12F3O4) 427.9732, found 427.9715.

Workup

  1. temperatureAfter cooling to room temperature, to the reaction
  2. filtrationThe organic solution was filtered
  3. washwashed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customAfter removing the volatiles
  6. customthe residue was purified by silica chromatography with ethyl acetate/hexane (2:8)

Sources & evidence

ORD record
ord-85b4db35c8b64128bac6b94fbe2ef3c4
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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