Fluorene → 4,7-Difluoro-9H-fluoren-2-amine

HRID 2294447Notes

Reaction equation

HRID 2294447 reaction equation
C1C2CC3C(=CC=CC=3)C=2C=CC=1.[F:14][C:15]1[C:27]2[C:26]3[C:21](=[CH:22][C:23]([F:28])=[CH:24][CH:25]=3)[C:20](=O)[C:19]=2[CH:18]=[C:17]([NH2:30])[CH:16]=1.I>C(O)(=O)C>[F:14][C:15]1[C:27]2[C:26]3[C:21](=[CH:22][C:23]([F:28])=[CH:24][CH:25]=3)[CH2:20][C:19]=2[CH:18]=[C:17]([NH2:30])[CH:16]=1

Participants

5

Reactant 3

HCID 6853Fluorene2×HCID 24841Hydrogen iodideHCID 2650624,7-difluoro-9-oxo-2-fluorenamine

Product 1

HCID 2650634,7-Difluoro-9H-fluoren-2-amineYield 85.2%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

(Namkung, M. J.; Fletcher, T. L.; Wetzel, W. H. Derivatives of Fluorene. XX. Fluorofluorenes. V. New Difluoro-2-acetamidofluorenes for the Study of Carcinogenic Mechanisms. J. Med. Chem. 1965, 8, 551-554, the disclosure of which is herein incorporated by reference). To a 25 mL round-bottomed flask containing 4,7-difluoro-9-oxo-2-fluorenamine (EXAMPLE 32) (158.5 mg, 0.686 mmol) in 4.25 mL glacial acetic acid was added red phosphorous (425 mg, 13.7 mmol, 20 equiv) and 57% aqueous HI (0.51 mL). The mixture was heated to reflux for 40 h, then evaporated to near-dryness by distillation. Boiling water (5 mL) was added, and the hot mixture was filtered. Upon addition of 10% NH4OH (20 mL), a white precipitate formed, and was filtered, washed with water, and dried under vacuum to afford 127 mg (85%) of 4,7-difluoro-2-fluorenamine as a white solid, mp 119°-120° C. (lit. mp 119.5°-121° C.). Data for 4,7-difluoro-2-fluorenamine: 1H NMR (400 MHz, CDCl3) 7.70 (dd, J=8.4, 5.2, 1H), 7.15 (dd, J=9.0, 2.0, 1H), 7.03 (app dt, J=9.0, 2.0,1H), 6.63 (s, 1H), 6.39 (dd, J=11.6, 1.7, 1H), 3.83 (s, 2H), 3.80 (br s, 2H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 40 h
  3. customevaporated to near-dryness by distillation
  4. additionBoiling water (5 mL) was added
  5. filtrationthe hot mixture was filtered
  6. additionUpon addition of 10% NH4OH (20 mL)
  7. customa white precipitate formed
  8. filtrationwas filtered
  9. washwashed with water
  10. customdried under vacuum

Sources & evidence

ORD record
ord-8c3e3710e2d64f68ac24bbfa18c35416
Source dataset
uspto-grants-1997_11
Patent number
US05688810

Reaction notes

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