1,1-Dichloroethane → 3-Azidomethyl-7-chloro-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamide

HRID 1887793Notes

Reaction equation

HRID 1887793 reaction equation
[CH3:1][N:2]([CH3:24])[C:3]([C:5]1[N:6]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:7]2[C:12]([C:13](=[O:16])[C:14]=1[CH3:15])=[CH:11][CH:10]=[C:9]([Cl:17])[CH:8]=2)=[O:4].BrN1C(=O)CCC1=O.CC(N=NC(C#N)(C)C)(C#N)C.ClC(Cl)C.[N-:49]=[N+:50]=[N-:51].[Na+]>>[CH3:24][N:2]([CH3:1])[C:3]([C:5]1[N:6]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:7]2[C:12]([C:13](=[O:16])[C:14]=1[CH2:15][N:49]=[N+:50]=[N-:51])=[CH:11][CH:10]=[C:9]([Cl:17])[CH:8]=2)=[O:4]

Participants

6

Reactant 5

HCID 63651,1-DichloroethaneHCID 6547AzobisisobutyronitrileHCID 33557Sodium AzideHCID 67184N-bromobutanimideHCID 712089157-Chloro-3-methyl-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamide

Product 1

HCID 712090383-Azidomethyl-7-chloro-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamideYield 43.1%

Procedure

In a 50 mL round bottom flask, 7-chloro-3-methyl-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamide (0.54 g, 1.58 mmol), N-bromosuccinimide (0.367 g, 2.06 mmol) and AIBN (78 mg, 0.475 mmol) were added to dichloroethane (6.0 mL). The reaction mixture was heated to reflux for 5 hr. The mixture was concentrated to dryness and the crude (containing 3-bromomethyl-7-chloro-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamide) was redissolved in DMF (6.0 mL). To the reaction mixture was added sodium azide (0.515 g, 7.92 mmol). The reaction was stirred at room temperature overnight. The mixture was partitioned between ethyl acetate and water and the organic layer was washed with aqueous sodium bicarbonate solution. The organic layer was dried, evaporated to dryness and purified by flash chromatography using 40% ethyl acetate-hexane to afford 3-azidomethyl-7-chloro-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamide (260 mg, 43% yield).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 5 hr
  3. concentrationThe mixture was concentrated to dryness
  4. additionthe crude (containing 3-bromomethyl-7-chloro-4-oxo-1-phenyl-1,4-dihydro-quinoline-2-carboxylic acid dimethylamide)
  5. dissolutionwas redissolved in DMF (6.0 mL)
  6. customThe mixture was partitioned between ethyl acetate and water
  7. washthe organic layer was washed with aqueous sodium bicarbonate solution
  8. customThe organic layer was dried
  9. customevaporated to dryness
  10. custompurified by flash chromatography

Sources & evidence

ORD record
ord-927c0d178852409b94eaaae9706ca1df
Source dataset
uspto-grants-2013_08
Patent number
US08501732B2

Reaction notes

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