Methanesulfonic Acid → 7-Bromo-1,2,3,4-tetrahydroquinolin-2-one

HRID 1256263Notes

Reaction equation

HRID 1256263 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][C:8]2=[O:11])=[CH:4][CH:3]=1.CS(O)(=O)=O.[N-:17]=[N+]=[N-].[Na+].O.N>CCOC(C)=O.CCCCCC.O.C(Cl)(Cl)Cl>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][C:8](=[O:11])[NH:17]2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 6395Methanesulfonic AcidHCID 33557Sodium AzideHCID 1397781-Indanone, 6-bromo-HCID 12896473Azane;hydrate

Product 1

HCID 272818447-Bromo-1,2,3,4-tetrahydroquinolin-2-one

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To the CHCl3 solution (560 mL) of the compound (39.5 g) obtained in Step 1-1 and methanesulfonic acid (122 mL), sodium azide (36.5 g) was added separately in parts under ice cooling, and then the mixture was heated to reflux for 2.5 hours. To H2O (400 mL), the reaction mixture was added under ice cooling, adjusted to pH 9 with 28% ammonia water and extracted with CHCl3 three times. The combined organic layers were dried over Na2SO4 and concentrated under reduced pressure. Thereafter, the residue was purified by column chromatography (silica gel 60 N, mobile phase: EtOAc/hexane=50/50 to 75/25; v/v). The solid substance obtained was suspended in a solution of EtOAc/hexane (1/1; v/v) and the mixture was stirred at room temperature for one hour. A solid substance was obtained by filtration to give 7-bromo-3,4-dihydroquinolin-2(1H)-one (15.5 g, a light yellow solid).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 2.5 hours
  3. extractionextracted with CHCl3 three times
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThereafter, the residue was purified by column chromatography (silica gel 60 N, mobile phase: EtOAc/hexane=50/50 to 75/25; v/v)
  7. customThe solid substance obtained
  8. customA solid substance was obtained by filtration

Sources & evidence

ORD record
ord-e71850db1c1547f9aa2619a1438969a6
Source dataset
uspto-grants-2013_06
Patent number
US08461182B2

Reaction notes

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