Hydrochloric Acid → 3-Bromo-7-hydroxy-1-naphthonitrile

HRID 1830673Notes

Reaction equation

HRID 1830673 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][CH:8]=[C:9]2[C:12]#[N:13])=[CH:4][CH:3]=1.[Br:14]Br.Cl.Cl[Sn]Cl>O.C(O)(=O)C>[Br:14][C:7]1[CH:8]=[C:9]([C:12]#[N:13])[C:10]2[C:5]([CH:6]=1)=[CH:4][CH:3]=[C:2]([OH:1])[CH:11]=2

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24408BromineHCID 24479Stannous ChlorideHCID 220481627-Hydroxynaphthalene-1-carbonitrile

Product 1

HCID 113225983-Bromo-7-hydroxy-1-naphthonitrileYield 38.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

To a mixture of 7-hydroxy-1-naphthonitrile (26.03 g, 154.0 mmol) and glacial acetic acid (400 mL) was added bromine (51.8 g, 323 mmol). The mixture was stirred at 100° C. for 6 hr. HCl (400 mL of 12 N solution) and SnCl2 (69 g, 308 mmol) were added and the mixture was stirred at 100° C. for 1 hour. The resulting solution was cooled to room temperature and poured into water (1 I). The resulting yellow precipitate was collected by filtration, dried under vacuum, and triturated with ethyl acetate to yield 14.68 g (38%) of the title compound as an off-white solid. An analytical sample was prepared by preparative reverse phase HPLC to yield the title compound as a white solid: mp 222–224° C.;1H NMR (DMSO-d6): δ 7.28–7.35 (2H, m), 7.97 (1H, d, J=8.73 Hz), 8.26 (1H, s), 8.47 (1H, s), 10.65 (1H, s); MS (ESI) m/z 246/247 (M−H)−.

Workup

  1. stirringthe mixture was stirred at 100° C. for 1 hour
  2. temperatureThe resulting solution was cooled to room temperature
  3. filtrationThe resulting yellow precipitate was collected by filtration
  4. customdried under vacuum
  5. customtriturated with ethyl acetate

Sources & evidence

ORD record
ord-6577db0e42ee4f4b86e87e32b5c57631
Source dataset
uspto-grants-2006_06
Patent number
US07067524B2

Reaction notes

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