Hydrochloric Acid → 1-Bromophenanthrene

HRID 68504Notes

Reaction equation

HRID 68504 reaction equation
N[C:2]1[CH:15]=[CH:14][C:13]2[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[CH:6]=[CH:5][C:4]=2[C:3]=1[Br:16].Cl.N([O-])=O.[Na+].[PH2](=O)O>C1COCC1.O>[Br:16][C:3]1[C:4]2[CH:5]=[CH:6][C:7]3[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=3)[C:13]=2[CH:14]=[CH:15][CH:2]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 2850291-Bromophenanthren-2-amineHCID 4124402Phosphinic AcidHCID 23668193Sodium Nitrite

Product 1

HCID 139338801-BromophenanthreneYield 66.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 8028TetrahydrofuranSolvent

Procedure

First, 120 g of 2-amino-1-bromophenanthrene were dissolved in 750 mL of THF, and then 4.5 L of concentrated hydrochloric acid and 1.5 L of water were added to the solution. The reaction solution was cooled with ice, and then a solution of 45 g of sodium nitrite in 230 mL of water was dropped to the solution. After the mixture had been stirred for 1 hour under ice cooling, 2.25 L of a 50% aqueous solution of phosphinic acid were added to the mixture. The reaction solution was stirred for 30 minutes under ice cooling, and was then continuously stirred at room temperature for 17 hours. Subsequently, 10 L of water were added to the solution, and a solid was obtained through separation by filtration. The resultant solid was purified by silica gel column chromatography. Thus, 75 g of 1-bromophenanthrene were obtained (in 66% yield).

Workup

  1. temperatureThe reaction solution was cooled with ice
  2. stirringThe reaction solution was stirred for 30 minutes under ice cooling
  3. stirringwas then continuously stirred at room temperature for 17 hours
  4. customa solid was obtained through separation by filtration
  5. customThe resultant solid was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-17e9cecdc643483e972f7c4663a6ac3e
Source dataset
uspto-grants-2014_09
Patent number
US08822041B2

Reaction notes

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