Iodine → ethyl 6-chloro-8-(methylthio)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 854937Notes

Reaction equation

HRID 854937 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([S:12](Cl)(=O)=O)[CH:11]=1)[O:8][CH:7]([C:16]([F:19])([F:18])[F:17])[C:6]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:5]2.II.[C:27]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCN(CC)CC.CI>C1C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([S:12][CH3:27])[CH:11]=1)[O:8][CH:7]([C:16]([F:19])([F:18])[F:17])[C:6]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:5]2

Participants

7

Reactant 5

HCID 807IodineHCID 6328Methyl iodideHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 86599472ethyl 6-chloro-8-(chlorosulfonyl)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 69517271ethyl 6-chloro-8-(methylthio)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To benzene (solvent) was added ethyl 6-chloro-8-(chlorosulfonyl)-2-(trifluoromethyl)-2H-chromene-3-carboxylate (Step 2, 0.68 g, 1.68 mmol), iodine (0.11 g, 0.84 mmol), and triphenyl phosphine (4.41 g, 16.8 mmol) amd the resulting mixture heated to reflux for 4 h and allowed to cool to RT and stand for 48 h. To this crude reaction was added Et3N (0.58 mL, 0.424 g, 4.20 mmol) and methyl iodide (0.06 mL, 0.13 g, 0.92 mmol). After extractive workup and silica chromatography the title compound was obtained as a yellow, crystalline mass (0.215 g, 36%). 1HNMR (CDCl3-d6/300 MHz) 7.59 (s, 1H), 7.07 (d, J=2.4 Hz, 1H), 6.98 (d, J=2.4 Hz, 1H), 5.78 (q, 1H, J=6.8 Hz), 4.20-4.40 (m, 3H), 2.42 (s, 3H), 1.33 (t, 3H, J=7.3 Hz).

Workup

  1. temperatureheated
  2. temperatureto reflux for 4 h
  3. customTo this crude reaction

Sources & evidence

ORD record
ord-854dacd5a15945869312c701ece08c5d
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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