4-Fluoroaniline → HCID 68154261, compound

HRID 73632Notes

Reaction equation

HRID 73632 reaction equation
[F:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.C[Al](C)C.[O:13]1[C@@:23]23[C@H:18]([CH2:19][CH2:20][O:21][CH2:22]2)[CH2:17][CH2:16][CH2:15][CH:14]13>C(Cl)Cl>[F:1][C:2]1[CH:8]=[CH:7][C:5]([NH:6][C@H:14]2[C@:23]3([OH:13])[C@H:18]([CH2:19][CH2:20][O:21][CH2:22]3)[CH2:17][CH2:16][CH2:15]2)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 97314-FluoroanilineHCID 16682925TrimethylaluminumHCID 86668658HCID 86668658, compound

Product 1

HCID 68154261HCID 68154261, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a mixture of 4-fluoroaniline (0.721 g, 6.48 mmol) in CH2Cl2 (6 mL) at 0° C. was added trimethylaluminum (2M in toluene, 3.24 mL) dropwise. The mixture was warmed and stirred to rt for 30 min. (1aS,5aS)-hexahydro-4H-oxireno[i]isochromene (0.200 g, 1.30 mmol) in CH2Cl2 2 mL+0.5 mL rinse) was then added and the mixture was stirred at rt overnight. The reaction was cooled to 0° C. and treated with 50% NaOH (1 mL) then water (1 mL) The mixture was diluted with more water and extracted 3× with CH2Cl2. The combined organics were dried (anhd. Na2SO4), filtered, and concentrated. The residue was purified by column chromatography to give the title compound. 1H NMR (500 MHz, CDCl3) δ 6.84-6.90 (m, 2H), 6.51-6.57 (m, 2H), 3.90-3.97 (m, 1H), 3.50-3.64 (m, 3H), 3.35-3.45 (m, 2H), 2.61 (s, 1H), 1.95-2.04 (m, 1H), 1.32-1.75 (m, 8H). HRMS (ES) m/z M+H cal'd: 266.1551. found: 266.1548.

Workup

  1. temperatureThe mixture was warmed
  2. washrinse)
  3. additionwas then added
  4. temperatureThe reaction was cooled to 0° C.
  5. additiontreated with 50% NaOH (1 mL)
  6. additionwater (1 mL) The mixture was diluted with more water
  7. extractionextracted 3× with CH2Cl2
  8. dry with materialThe combined organics were dried (anhd. Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-92409a60ae7d47e085907fc1f6291ae9
Source dataset
uspto-grants-2014_09
Patent number
US08829196B2

Reaction notes

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