Chlorosulfonic acid → HCID 21883691, compound

HRID 722293Notes

Reaction equation

HRID 722293 reaction equation
[Cl:1][S:2]([OH:5])(=O)=[O:3].[F:6][C:7]([F:24])([F:23])[CH:8]1[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:12][C:11]2[CH:19]=[CH:20][CH:21]=[CH:22][C:10]=2[O:9]1>>[Cl:1][S:2]([C:20]1[CH:21]=[CH:22][C:10]2[O:9][CH:8]([C:7]([F:24])([F:23])[F:6])[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:12][C:11]=2[CH:19]=1)(=[O:5])=[O:3]

Participants

3

Reactant 2

HCID 24638Chlorosulfonic acidHCID 218835922H-1-Benzopyran-3-carboxylic acid, 2-(trifluoromethyl)-, ethyl ester

Product 1

HCID 21883691HCID 21883691, compoundYield 87%

Conditions

Temperature
-15 °C

Procedure

Chlorosulfonic acid (50.0 mL) was cooled to 15° C. and ethyl 2-trifluoromethyl-2H-1-benzopyran-3-carboxylate (Example 10, Step 2) (6.21 g, 22.83 mmol) was added. After stirring at −15° C. for 1 hour, the solution was warmed to room temperature and stirred for 16 hours. The solution was added dropwise onto ice (500 mL) with vigorous stirring and extracted with diethyl ether (2×250 mL). The ether layers were combined, washed with water (2×250 mL), saturated sodium bicarbonate (2×250 mL), and brine (2×250 mL). Hexanes (50 mL) were added and the solution was dried over sodium sulfate. The solvent was removed in vacuo to afford the ester as a yellow solid (7.41 g, 87%): mp 97.2–98.4° C. 1H NMR (CDCl3, 300 MHz) 7.97 (dd, 1H, J=8.6, 2.2. Hz), 7.92 (d, 1H, J=2.2 Hz), 7.73 (s, 1H), 7.17 (d, 1H, J=2.2 Hz), 5.82 (qH-F, 1H, J=7.2 Hz), 4.28–4.39 (m, 2H), 1.35 (t, 3H, J=7.0 Hz). FABLRMS m/z 376 (M+Li+).

Workup

  1. temperaturethe solution was warmed to room temperature
  2. stirringstirred for 16 hours
  3. additionThe solution was added dropwise onto ice (500 mL)
  4. stirringwith vigorous stirring
  5. extractionextracted with diethyl ether (2×250 mL)
  6. washwashed with water (2×250 mL), saturated sodium bicarbonate (2×250 mL), and brine (2×250 mL)
  7. additionHexanes (50 mL) were added
  8. dry with materialthe solution was dried over sodium sulfate
  9. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-1280c9f94a054650bf391e11721189b1
Source dataset
uspto-grants-2006_11
Patent number
US07138411B2

Reaction notes

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