Sodium Hydroxide → 6-Bromo-(2-nitrophenyl)-1,2,3,4-tetrahydroquinoline

HRID 4039Notes

Reaction equation

HRID 4039 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[N:10]1[C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:13][CH2:12][CH2:11]1)([O-:3])=[O:2].[Br:20]N1C(=O)CCC1=O.[OH-].[Na+]>CN(C)C=O>[Br:20][C:16]1[CH:15]=[C:14]2[C:19](=[CH:18][CH:17]=1)[N:10]([C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=1[N+:1]([O-:3])=[O:2])[CH2:11][CH2:12][CH2:13]2

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 138129261-(2-Nitrophenyl)-1,2,3,4-tetrahydroquinoline

Product 1

HCID 138129286-Bromo-(2-nitrophenyl)-1,2,3,4-tetrahydroquinolineYield 82.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A stirred solution, under nitrogen, of 1-(2-nitrophenyl)-1,2,3,4-tetrahydroquinoline (76.3 g, 0.30 mole) in dimethylformamide (1000 ml) was cooled to -10° C. A solution of of N-bromosuccinimide (58.7 g, 0.33 mole) in dimethylformamide (250 ml) was added dropwise at such a rate as to keep the reaction temperature below 0° C. (1.5 hours). Half-an hour after the addition was completed, the reaction mixture was poured into 7 liters of 2N-sodium hydroxide solution/ice, with stirring. The product separated as an oil. The quench fluids were decanted and the oil was rinsed several times with water. The oil was dissolved in dichloromethane (1.5 l). The organic solution was extracted once with 2N-sodium hydroxide solution, thrice with water, dried over sodium sulfate and concentrated. The residue was dissolved in 1:1 hexane:toluene (250 ml) and the solution was absorbed on a chromatography column containing 2 kg of silica gel packed in 1:1 hexane:toluene. Elution with this solvent mixture provided 82.7 g (82%) of product, as an oil. For analysis, a sample was Kugelrohr distilled at a vessel temperature of 166°-168° C. (0.2 mm Hg).

Workup

  1. customthe reaction temperature below 0° C. (1.5 hours)
  2. additionHalf-an hour after the addition
  3. customThe product separated as an oil
  4. customThe quench fluids were decanted
  5. washthe oil was rinsed several times with water
  6. dissolutionThe oil was dissolved in dichloromethane (1.5 l)
  7. extractionThe organic solution was extracted once with 2N-sodium hydroxide solution, thrice with water
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated
  10. dissolutionThe residue was dissolved in 1:1 hexane
  11. customtoluene (250 ml) and the solution was absorbed on a chromatography column
  12. additioncontaining 2 kg of silica gel
  13. washElution with this solvent mixture

Sources & evidence

ORD record
ord-c2f682b48eea413db9b847972f11227f
Source dataset
uspto-grants-1988_02
Patent number
US04723007

Reaction notes

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