1-Naphthalenamine, 5-nitro- → 1-Fluoro-5-nitronaphthalene

HRID 880471Notes

Reaction equation

HRID 880471 reaction equation
N([O-])=O.[Na+].[N+:5]([C:8]1[CH:17]=[CH:16][CH:15]=[C:14]2[C:9]=1[CH:10]=[CH:11][CH:12]=[C:13]2N)([O-:7])=[O:6].[F:19][P-](F)(F)(F)(F)F.[H+]>O>[F:19][C:13]1[C:14]2[C:9](=[C:8]([N+:5]([O-:7])=[O:6])[CH:17]=[CH:16][CH:15]=2)[CH:10]=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 767591-Naphthalenamine, 5-nitro-HCID 16211447Hexafluorophosphoric acidHCID 23668193Sodium Nitrite

Product 1

HCID 217302841-Fluoro-5-nitronaphthaleneYield 37%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
-5 °C

Procedure

Sodium nitrite (660 mg, 9.57 mmol) was added portionwise to a suspension of 5-nitronaphthalen-1-amine (1.2 g, 6.38 mmol) in a 1:1 mixture of water/concentrated hydrochloric acid (10 mL) at −5° C. The mixture was stirred for 15 min at −5° C. and a 60% w/w hexafluoro phosphoric acid solution (6 mL) was added. The brown precipitate was filtered and washed with cold water and diethyl ether and then allowed to dry in vacuo. The resulting solid was suspended in toluene and heated to 110° C. for 2 h before the mixture was then allowed to cool to ambient temperature and the solvent removed in vacuo to afford the crude product. Purification by column chromatography over silica gel (100-200 mesh) using petroleum ether as eluent afforded 1-fluoro-5-nitro-naphthalene (450 mg, 37%) as a yellow solid.

Workup

  1. filtrationThe brown precipitate was filtered
  2. washwashed with cold water and diethyl ether
  3. customto dry in vacuo
  4. temperatureheated to 110° C. for 2 h before the mixture
  5. temperatureto cool to ambient temperature
  6. customthe solvent removed in vacuo
  7. customto afford the crude product
  8. customPurification by column chromatography over silica gel (100-200 mesh)

Sources & evidence

ORD record
ord-e7c74a2612ca4b13a40f0adf05f393d4
Source dataset
uspto-grants-2015_03
Patent number
US08993574B2

Reaction notes

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